Metal-Free Aromatic Carbon–Phosphorus Bond Formation via a Sandmeyer-Type Reaction

英文原文与中文译文逐段对照 · English original with Chinese translation

Shuai Wang, Di Qiu, Fanyang Mo, Yan Zhang, and Jianbo Wang

王帅，邱迪，莫凡洋，张燕，王剑波

J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.66b01820 • Publication Date (Web): 28 Oct 2016 Downloaded from http://pubs.acs.org on October 28, 2016

《有机化学杂志》，刚接受的稿件 • DOI: 10.1021/acs.joc.66b01820 • 网络出版日期:2016年10月28日 于2016年10月28日从http://pubs.acs.org下载

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ACS Publications

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The Journal of Organic Chemistry is published by the American Chemical Society.

《有机化学杂志》由美国化学会出版。

Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course

由美国化学会出版。版权所有 © 美国化学会。然而，对于美国政府的原始作品或任何英联邦王国政府雇员在工作过程中创作的作品，不主张版权。

Metal-Free Aromatic Carbon-Phosphorus Bond Formation via a Sandmeyer-Type Reaction

通过桑德迈尔型反应实现无金属芳香碳-磷键的形成

Shuai Wang, Di Qiu, Fanyang Mo, Yan Zhang and Jianbo Wang*

王帅，邱迪，莫凡洋，张燕，王建波*

Beijing National Laboratory of Molecular Sciences (BNLMS), Key Laboratory of Bioorganic

北京分子科学国家实验室(BNLMS)，生物有机化学重点实验室

Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking

教育部生物有机与分子工程重点实验室，化学与分子工程学院，北京大学

University, Beijing 100871, China

中国北京 100871

RECEIVED DATE (to be automatically inserted after your manuscript is accepted if required according to the journal that you are submitting your paper to)

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ABSTRACT. An efficient metal-free phosphorylation process based on a Sandmeyer-type transformation with arylamines as the starting materials is developed. The transformation proceeds smoothly at room temperature without the exclusion of moisture or air. This phosphorylation reaction tolerates wide range of functional groups and affords the phosphorylation products in moderate to good yields, thus providing a valuable method for the formation of aromatic carbon-phosphorus bonds.

摘要。开发了一种以芳胺为起始原料，基于桑德迈尔型转化的高效无金属磷酸化方法。该转化在室温下顺利进行，无需排除水分或空气。这种磷酸化反应能耐受多种官能团，并以中等至良好的产率提供磷酸化产物，从而为芳香碳-磷键的形成提供了一种有价值的方法。

INTRODUCTION

引言

Aryl phosphonates belong to an important class of organophosphorus compounds due to their applications in medicinal chemistry, ${}^{1}$ material sciences, ${}^{2}$ and organic synthesis, ${}^{3}$ which makes the synthesis of this type of compounds of significant importance. The traditional methods to construct the aromatic carbon-phosphorus bonds in these compounds involve nucleophilic substitution reaction of organometallic reagent with electrophilic phosphine reagent (Scheme 1a), ${}^{4}$ Michaelis-Arbuzov reaction ${}^{5}$ and Friedel-Crafts reaction. ${}^{6}$ Additionally, the transition-metal-catalyzed cross-coupling reaction of aryl (pseudo)halides or some other compounds, such as aryltriflates, tosylates, boronic acids and hydrazine with phosphorus(III) compounds has been explored extensively since Hirao and co-workers’ pioneering work in ${1980}.{}^{7,8}$ Due to the excellent efficiency and remarkable functional group tolerance, the transition-metal-catalyzed coupling strategy has been widely utilized in carbon-phosphorus bond formation (Scheme 1b). Despite of the significant progresses, these methods still suffer from some limitations, such as the use of metal reagents and the requirement of relatively high temperature. Further efforts were made to construct aromatic carbon-phosphorus bonds under mild conditions, for example, Xiao and co-workers have recently reported that the employment of visible-light-induced photoredox catalysis achieves the nickel-catalyzed cross-coupling of aryl halide with diarylphosphine oxides at room temperature; ${}^{9}$ Toste and co-workers reported that, by employing dual gold and photoredox catalysis, aryldiazonium salts could react with $H$ -phosphonates at room temperature to form carbon-phosphorus bonds. ${}^{10}$ In spite of these remarkable improvements, highly efficient approaches for the construction of aromatic carbon-phosphorus bond under metal-free mild conditions, which could be served as alternative and supplementary methods for the synthesis of aryl phosphonate compounds, is still limited.

芳基膦酸酯由于在药物化学、${}^{1}$材料科学、${}^{2}$和有机合成${}^{3}$中的应用，属于一类重要的有机磷化合物，这使得这类化合物的合成具有重要意义。在这些化合物中构建芳族碳 - 磷键的传统方法包括有机金属试剂与亲电膦试剂的亲核取代反应(方案1a)、${}^{4}$米氏 - 阿尔布佐夫反应${}^{5}$和傅克反应。${}^{6}$此外，自平尾及其同事在${1980}.{}^{7,8}$的开创性工作以来，芳基(伪)卤化物或一些其他化合物(如芳基三氟甲磺酸酯、甲苯磺酸酯、硼酸和肼)与磷(III)化合物的过渡金属催化交叉偶联反应已得到广泛研究。由于其优异的效率和显著的官能团耐受性，过渡金属催化的偶联策略已广泛用于碳 - 磷键的形成(方案1b)。尽管取得了重大进展，但这些方法仍然存在一些局限性，例如使用金属试剂和需要相对较高的温度。人们进一步努力在温和条件下构建芳族碳 - 磷键，例如，肖及其同事最近报道，使用可见光诱导的光氧化还原催化在室温下实现了芳基卤化物与二芳基氧化膦的镍催化交叉偶联；${}^{9}$托斯特及其同事报道了，通过使用双金和光氧化还原催化，芳基重氮盐可以在室温下与$H$ - 膦酸酯反应形成碳 - 磷键。${}^{10}$尽管有这些显著改进，但在无金属温和条件下构建芳族碳 - 磷键的高效方法，作为芳基膦酸酯化合物合成的替代和补充方法，仍然有限。

Scheme 1. Synthetic Methods for the Construction of Aromatic Carbon-Phosphorus Bonds

方案1. 构建芳族碳 - 磷键的合成方法

The common C-P bond forming methods

常见的碳-磷键形成方法

(a)

(X = halogen, OTf, B(OH)2, etc.; R = alkyl, aryl, alkoxy, aryloxy)

(X = 卤素、三氟甲磺酸酯、硼酸等；R = 烷基、芳基、烷氧基、芳氧基)

Metal-free approach: this work

无金属方法:本研究

On the other hand, the transformation of aryldiazonium salts into various functional groups, such as halogen, hydroxyl group, cyano group, and sulfonates groups, known as Sandmeyer-type reactions, has been applied broadly both in laboratory research and industrial production. ${}^{11}$ The aryldiazonium salt intermediates, which could be in situ generated from aromatic amines, ${}^{12}$ has been recently explored in several new transformations. ${}^{{13},{14}}$ We have recently reported new approaches for the synthesis of arylboronic pinacol esters, arylstannane compounds, and trifluoromethylated arenes by using readily available arylamines as the starting materials. ${}^{14}$ Aryldiazonium salts have been previously reported to react with phosphorus trihalides since ${1950}\mathrm{\;s},{}^{15}$ but these transformations often suffer from poor yields and limited functional group tolerance. In view of the importance of aryl phosphonates compounds and our continued interest in the development of the transformations with aryldiazonium salts, we report herein an efficient approach for the metal-free C-P Bond formation through a similar Sandmeyer-type transformation. The important feature of this method is the use of triarylphosphites, which are stable and easy to handle, rather than the air-sensitive phosphorus trihalides, as the phosphorylation reagents.

另一方面，芳基重氮盐向各种官能团的转化，如卤素、羟基、氰基和磺酸酯基，即所谓的桑德迈尔型反应，已在实验室研究和工业生产中广泛应用。${}^{11}$ 芳基重氮盐中间体可由芳香胺原位生成，${}^{12}$ 最近已在几种新的转化反应中得到探索。${}^{{13},{14}}$ 我们最近报道了以易得的芳香胺为起始原料合成芳基硼酸频哪醇酯、芳基锡烷化合物和三氟甲基化芳烃的新方法。${}^{14}$ 芳基重氮盐此前已报道可与三卤化磷反应，因为${1950}\mathrm{\;s},{}^{15}$ 但这些转化反应往往产率低且官能团耐受性有限。鉴于芳基膦酸酯化合物的重要性以及我们对芳基重氮盐转化反应开发的持续兴趣，我们在此报告一种通过类似桑德迈尔型转化实现无金属C-P键形成的有效方法。该方法的重要特点是使用稳定且易于处理的亚磷酸三芳基酯，而不是对空气敏感的三卤化磷作为磷酰化试剂。

RESULTS AND DISCUSSIONS

结果与讨论

We began the study of the phosphorylation reaction with ethyl 4-aminobenzoate (1a) as the starting material. The arylamine 1a was firstly reacted with $t$ -BuONO (tert-butyl nitrite) in MeCN to form the corresponding aryldiazonium salt at $0{}^{ \circ }\mathrm{C}$ , and then trimethyl phosphite (2a) was added in sequence. To our delight, the expected phosphorylation product 3aa was obtained in a yield of 44% (Table 1, entry 1). As detected by GC-MS, the major by-products were ethyl benzoate, which was generated by the reduction of aryldiazonium salt species, and trimethyl phosphate. Since our previous study has indicated that acid can promote the generation of diazonium intermediate, ${}^{14c}$ we thus proceed to study the effect of acid additives. Indeed, the reaction proceeded more efficiently when TsOH was added (Table 1, entry 2), however, $\mathrm{{HCl}}$ and ${\mathrm{H}}_{2}{\mathrm{{SO}}}_{4}$ were found not suitable for this transformation (Table 1, entries 3 and 4), and the reaction failed to give 3aa when typical Lewis acid ${\mathrm{{BF}}}_{3}{\mathrm{{Et}}}_{2}\mathrm{O}$ was added (Table 1, entry 5). The product 3aa was formed in a lower yield when the reaction was carried out in DCM (dichloromethane) or DCE (dichloroethane) (Table 1, entries 6 and 7). No apparent improvement was observed when the reaction temperature was raised to ${80}{}^{ \circ }\mathrm{C}$ (Table 1, entry 8). Some other phosphorylation reagents were then explored. Triethyl phosphite (2b) gave only trace amount of the corresponding product 3ab (detected by GC-MS, Table 1, entry 9). Besides, only trace amount of ethyl benzoate was observed, because aryldiazonium salt was mainly transformed into some non-volatile species under this condition. To our delight, when triphenyl phosphite (2c) was employed as the phosphorus source, the corresponding product 3ac was produced in a yield of 78% (Table 1, entry 10). The increase of concentration showed almost no influence on the transformation (Table 1, entry 11). A low loading of $t$ -BuONO and $2\mathrm{c}$ led to the diminish of the yields of 3ac (Table 1, entries 12 and 13). The yield of 3ac could be further improved with a higher loading of 2c (Table 1, entry 14). One likely explanation for this result is that the higher equivalent of $3\mathrm{c}$ accelerates the phosphorylation process so that the generation of ethyl benzoate is inhibited.

我们以4-氨基苯甲酸乙酯(1a)为起始原料开始了磷酸化反应的研究。芳胺1a首先在MeCN中与$t$叔丁基亚硝酸酯(tert-butyl nitrite)在$0{}^{ \circ }\mathrm{C}$反应形成相应的芳基重氮盐，然后依次加入亚磷酸三甲酯(2a)。令我们高兴的是，预期的磷酸化产物3aa的产率为44%(表1，条目1)。通过GC-MS检测，主要副产物是由芳基重氮盐物种还原生成的苯甲酸乙酯和磷酸三甲酯。由于我们之前的研究表明酸可以促进重氮中间体的生成，${}^{14c}$因此我们继续研究酸添加剂的影响。事实上，加入对甲苯磺酸(TsOH)时反应进行得更有效(表1，条目2)，然而，$\mathrm{{HCl}}$和${\mathrm{H}}_{2}{\mathrm{{SO}}}_{4}$被发现不适用于这种转化(表1，条目3和4)，当加入典型的路易斯酸${\mathrm{{BF}}}_{3}{\mathrm{{Et}}}_{2}\mathrm{O}$时反应未能得到3aa(表1，条目5)。当反应在二氯甲烷(DCM)或二氯乙烷(DCE)中进行时，产物3aa的产率较低(表1，条目6和7)。当反应温度升至${80}{}^{ \circ }\mathrm{C}$时未观察到明显改善(表1，条目8)。然后探索了一些其他的磷酸化试剂。亚磷酸三乙酯(2b)仅得到痕量的相应产物3ab(通过GC-MS检测，表1，条目9)。此外，仅观察到痕量的苯甲酸乙酯，因为在此条件下芳基重氮盐主要转化为一些不挥发的物种。令我们高兴的是，当使用亚磷酸三苯酯(2c)作为磷源时，相应的产物3ac的产率为78%(表1，条目10)。浓度的增加对转化几乎没有影响(表1，条目11)。$t$ -BuONO和$2\mathrm{c}$的低用量导致3ac的产率降低(表1，条目12和13)。使用更高用量的2c可以进一步提高3ac的产率(表更多解释。一种可能的解释是更高当量的$3\mathrm{c}$加速了磷酸化过程，从而抑制了苯甲酸乙酯的生成。

Table 1. Optimization of Reaction Conditions ${}^{a}$

表1. 反应条件的优化${}^{a}$

${}^{a}$ Unless otherwise noted, the reaction conditions are as following: arylamine ( ${0.2}\mathrm{{mmol}}$ ), $t$ -BuONO

${}^{a}$除非另有说明，反应条件如下:芳胺(${0.2}\mathrm{{mmol}}$)，$t$ -BuONO

(0.3 mmol), P(OR)3 (0.4 mmol), acid (0.24 mmol), solvent (1.0 mL). Arylamine firstly reacted with

(0.3 mmol)，P(OR)3(0.4 mmol)，酸(0.24 mmol)，溶剂(1.0 mL)。芳胺首先与

$t$ -BuONO and acid at $0{}^{ \circ }\mathrm{C}$ for ${15}\mathrm{\;{min}}$ , and then the reaction system was allowed to warm to room temperature and $\mathrm{P}{\left( \mathrm{{OR}}\right) }_{3}$ was added. ${}^{b}$ Isolated yield. ${}^{c}{0.5}\mathrm{\;{mL}}$ solvent was used. ${}^{d}{0.3}\mathrm{{mmol}}\mathrm{P}{\left( \mathrm{{OR}}\right) }_{3}$ was added. ${}^{e}{0.24}\mathrm{{mmol}}t$ -BuONO was added. ${}^{f}{0.6}\mathrm{{mmol}}\mathrm{P}{\left( \mathrm{{OR}}\right) }_{3}$ was added.

$t$ -BuONO和酸在$0{}^{ \circ }\mathrm{C}$反应${15}\mathrm{\;{min}}$，然后使反应体系升温至室温并加入$\mathrm{P}{\left( \mathrm{{OR}}\right) }_{3}$。${}^{b}$分离产率。${}^{c}{0.5}\mathrm{\;{mL}}$使用了溶剂。加入了${}^{d}{0.3}\mathrm{{mmol}}\mathrm{P}{\left( \mathrm{{OR}}\right) }_{3}$。加入了${}^{e}{0.24}\mathrm{{mmol}}t$ -BuONO。加入了${}^{f}{0.6}\mathrm{{mmol}}\mathrm{P}{\left( \mathrm{{OR}}\right) }_{3}$。

With the optimized reaction conditions in hand, we then examined the substrate scope of this transformation with a series of functionalized arylamines using $2\mathbf{c}$ as the phosphorylation reagent (Scheme 2). The phosphorylation process has shown good functional group tolerance to both electron-withdrawing and electron-donating groups on the aromatic ring, including nitro (3b), cyano (3c), methyl (3d), halogen (3e and 3f), phenyl (3g), methylthio (3h), methoxy (3ic), acetyl (3j), alkynyl (3ra and 3rb), alkenyl (3w), azo group (3v), hydrogen (3z). In all the cases, the corresponding products were obtained in 40-98% yields. It is noteworthy that the tolerance of bromo and chloro groups, which is normally not compatible in transition-metal-catalyzed C-P bond construction approaches, makes possible of further transformation of the products with cross-coupling reactions.

在掌握了优化的反应条件后，我们接着使用$2\mathbf{c}$作为磷酰化试剂，用一系列官能化芳胺考察了该转化反应的底物范围(方案2)。磷酰化过程对芳环上的吸电子基团和供电子基团均表现出良好的官能团耐受性，包括硝基(3b)、氰基(3c)、甲基(3d)、卤素(3e和3f)、苯基(3g)、甲硫基(3h)、甲氧基(3ic)、乙酰基(3j)、炔基(3ra和3rb)、烯基(3w)、偶氮基(3v)、氢(3z)。在所有情况下，相应产物的产率为40 - 98%。值得注意的是，溴基和氯基的耐受性在过渡金属催化的C - P键构建方法中通常是不兼容的，这使得产物通过交叉偶联反应进行进一步转化成为可能。

Scheme 2. Substrate Scope of the Aniline Derivatives

方案2. 苯胺衍生物的底物范围

Reaction conditions: arylamine (0.2 mmol), t-BuONO (0.3 mmol), P(OPh)3 (0.6 mmol), TsOH ${\mathrm{H}}_{2}\mathrm{O} \; \left( {{0.24}\mathrm{{mmol}}}\right)$ , MeCN $\left( {{1.0}\mathrm{\;{mL}}}\right)$ . Arylamine was first reacted with $t$ -BuONO and acid at $0{}^{ \circ }\mathrm{C}$ for 15 min, and then the reaction system was warmed to room temperature and $\mathrm{P}{\left( \mathrm{{OPh}}\right) }_{3}$ was added. ${}^{a}$ Isolated yield after column chromatography. ${}^{b}$ The reaction of arylamine with $t$ -BuONO was carried out at room temperature for ${10}\mathrm{\;{min}}.{}^{c}{3.0}\mathrm{\;{mL}}$ MeCN was added.

反应条件:芳基胺(0.2 mmol)，叔丁基亚硝酸酯(0.3 mmol)，三苯基膦(0.6 mmol)，对甲苯磺酸${\mathrm{H}}_{2}\mathrm{O} \; \left( {{0.24}\mathrm{{mmol}}}\right)$，乙腈$\left( {{1.0}\mathrm{\;{mL}}}\right)$。芳基胺首先与$t$-叔丁基亚硝酸酯和酸在$0{}^{ \circ }\mathrm{C}$下反应15分钟，然后将反应体系升温至室温并加入$\mathrm{P}{\left( \mathrm{{OPh}}\right) }_{3}$。${}^{a}$柱色谱分离后的产率。${}^{b}$芳基胺与$t$-叔丁基亚硝酸酯的反应在室温下进行${10}\mathrm{\;{min}}.{}^{c}{3.0}\mathrm{\;{mL}}$，加入乙腈。

The para-substituted aryl amines with electron-withdrawing groups could gave relatively higher yields; while the substrate with electron-donating para-methyl substituent afforded a moderate yield of 66% (3d). The $p$ -OMe substituted aniline gave a low yield of 40% (3ic). Similar yield could be achieved with ortho- and meta-substituted anilines (3k-q), indicating that the phosphorylation is not sensitive to the steric effect. For the naphthylamine 1sa and 1sb, the diminished yield might be attributed to the poor solubility of the corresponding diazonium salts.

带有吸电子基团的对取代芳基胺能给出相对较高的产率；而带有供电子对甲基取代基的底物产率适中，为66%(3d)。$p$-甲氧基取代的苯胺产率较低，为40%(3ic)。邻位和间位取代的苯胺(3k-q)也能得到类似的产率，这表明磷酸化对空间效应不敏感。对于萘胺1sa和1sb，产率降低可能归因于相应重氮盐的溶解度较差。

We then expended the substrate scope of this phosphorylation reaction to the aromatic heterocyclic amine derivatives. The results shown in Scheme 3 indicate that the phosphorylation of some aromatic heterocyclic amine derivatives also works, but giving the phosphorylation products in low yields (5a-e). However, the phosphorylation reaction with some other aromatic heterocyclic amine derivatives did not occur (5f-h).

然后我们将该磷酸化反应的底物范围扩展到芳香杂环胺衍生物。方案3所示结果表明，一些芳香杂环胺衍生物的磷酸化反应也能进行，但磷酸化产物的产率较低(5a-e)。然而，与其他一些芳香杂环胺衍生物的磷酸化反应未发生(5f-h)。

Scheme 3. Substrate Scope of Aromatic Heterocyclic Amine Derivatives

方案3. 芳香杂环胺衍生物的底物范围

Unless otherwise noted, the reaction conditions are as following: arylamine ( ${0.2}\mathrm{{mmol}}$ ), t-BuONO $\left( {{0.3}\mathrm{{mmol}}}\right) ,\mathrm{P}{\left( \mathrm{{OPh}}\right) }_{3}\left( {{0.6}\mathrm{{mmol}}}\right) ,{\mathrm{{TsOH}}}_{2}\mathrm{O}\left( {{0.24}\mathrm{{mmol}}}\right)$ , MeCN $\left( {{1.0}\mathrm{\;{mL}}}\right)$ . Arylamine firstly reacted with $t$ -BuONO and acid at $0{}^{ \circ }\mathrm{C}$ for ${15}\mathrm{\;{min}}$ , and then the reaction system was warmed to room temperature and $\mathrm{P}{\left( \mathrm{{OPh}}\right) }_{3}$ was added. ${}^{a}$ Isolated yield with column chromatography. ${}^{b}$ The reaction of arylamine with $t$ -BuONO was carried out at room temperature for ${10}\mathrm{\;{min}}$ .

除非另有说明，反应条件如下:芳基胺(${0.2}\mathrm{{mmol}}$)，叔丁基亚硝酸酯$\left( {{0.3}\mathrm{{mmol}}}\right) ,\mathrm{P}{\left( \mathrm{{OPh}}\right) }_{3}\left( {{0.6}\mathrm{{mmol}}}\right) ,{\mathrm{{TsOH}}}_{2}\mathrm{O}\left( {{0.24}\mathrm{{mmol}}}\right)$，乙腈$\left( {{1.0}\mathrm{\;{mL}}}\right)$。芳基胺首先与$t$-叔丁基亚硝酸酯和酸在$0{}^{ \circ }\mathrm{C}$下反应${15}\mathrm{\;{min}}$，然后将反应体系升温至室温并加入$\mathrm{P}{\left( \mathrm{{OPh}}\right) }_{3}$。${}^{a}$柱色谱分离产率。${}^{b}$芳基胺与$t$-叔丁基亚硝酸酯的反应在室温下进行${10}\mathrm{\;{min}}$。

Next, the scope of a series of substituted triaryl phosphites (6a-d) was investigated and the results are summarized in Scheme 4. Good yields were achieved for the chloro- (7a) and bromo- (7b) substituted products, which could be convenient for further modifications. The tert-butyl substituted phosphite also gave a good yield of ${89}\% \left( {7\mathbf{d}}\right)$ , but the reaction with methoxy substituted substrate gave only diminished yield (7c).

接下来，研究了一系列取代亚磷酸三芳基酯(6a-d)的范围，结果总结在方案4中。氯代(7a)和溴代(7b)取代产物产率良好，便于进一步修饰。叔丁基取代的亚磷酸酯产率也良好，为${89}\% \left( {7\mathbf{d}}\right)$，但与甲氧基取代底物的反应产率仅降低(7c)。

Scheme 4. Substrate Scope of the Triaryl Phosphites

方案4. 亚磷酸三芳基酯的底物范围

Reaction conditions: arylamine $\left( {{0.2}\mathrm{{mmol}}}\right) , t$ -BuONO $\left( {{0.3}\mathrm{{mmol}}}\right) ,\mathrm{P}{\left( \mathrm{{OAr}}\right) }_{3}\left( {{0.6}\mathrm{{mmol}}}\right) ,{\mathrm{{TsOH}}}_{2}\mathrm{O} \; \left( {{0.24}\mathrm{{mmol}}}\right) ,\mathrm{{MeCN}}\left( {{1.0}\mathrm{\;{mL}}}\right)$ . Arylamine firstly reacted with $t$ -BuONO and acid at $0{}^{ \circ }\mathrm{C}$ for 15 minutes, and then the reaction system was warmed to room temperature and $\mathrm{P}{\left( \mathrm{{OPh}}\right) }_{3}$ was added. ${}^{a}$ Isolated yield after column chromatography.

反应条件:芳基胺$\left( {{0.2}\mathrm{{mmol}}}\right) , t$ -叔丁基亚硝酸酯$\left( {{0.3}\mathrm{{mmol}}}\right) ,\mathrm{P}{\left( \mathrm{{OAr}}\right) }_{3}\left( {{0.6}\mathrm{{mmol}}}\right) ,{\mathrm{{TsOH}}}_{2}\mathrm{O} \; \left( {{0.24}\mathrm{{mmol}}}\right) ,\mathrm{{MeCN}}\left( {{1.0}\mathrm{\;{mL}}}\right)$。芳基胺首先与$t$ -叔丁基亚硝酸酯和酸在$0{}^{ \circ }\mathrm{C}$下反应15分钟，然后将反应体系升温至室温并加入$\mathrm{P}{\left( \mathrm{{OPh}}\right) }_{3}$。${}^{a}$柱色谱分离后的产率。

For a further demonstration of the practical application of this method, the phosphorylation reaction of three substrates was carried out in 20 mmol-scale for the gram-scale synthesis of products 3ac, 3d, and 3ic, as shown in Scheme 5. To our delight, the reaction offered the corresponding products with comparable yields.

为了进一步证明该方法的实际应用，对三种底物进行了20 mmol规模的磷酸化反应，用于克级合成产物3ac、3d和3ic，如图方案5所示。令我们高兴的是，该反应以相当的产率提供了相应的产物。

Scheme 5. Gram-Scale Synthesis

方案5. 克级合成

${}^{a}$ Isolated yield, the numbers in the brackets are the yields for the reaction carried out in 0.2 mmol-scale. ${}^{b}$ The reaction of arylamine with $t$ -BuONO was carried out at room temperature for 10 min.

${}^{a}$分离产率，括号中的数字是0.2 mmol规模反应的产率。${}^{b}$芳基胺与$t$ -叔丁基亚硝酸酯的反应在室温下进行10分钟。

It is worth mentioning that the reaction using trialkyl phosphite (Table 1, 2a, b) as the phosphorylation reagent could only give a low yield, which might be a potential limit for the practical usefulness of this phosphorylation reaction. However, it was shown that the diphenyl phosphonates could be easily transferred to various dialkyl phosphonates through ester exchange as demonstrated by the example shown in eq 1, ${}^{16}$ which could circumvent such limitation.

值得一提的是，使用亚磷酸三烷基酯(表1，2a，b)作为磷酸化试剂的反应只能得到较低的产率，这可能是该磷酸化反应实际应用的一个潜在限制。然而，如式1所示的例子表明，二苯基膦酸酯可以通过酯交换轻松转化为各种二烷基膦酸酯，${}^{16}$这可以规避此类限制。

The mechanism of the reaction between arenediazonium salts and some phosphorus (III) compounds was previously investigated by Yasui and co-workers in ${1995.}^{17}$ In their study, it was reported that a small amount of arylphosphonate was formed via a phosphonium ion intermediate when arenediazonium salts were reacted with trialkyl phosphites in an alcoholic solvent under an argon atmosphere at ${20}{}^{ \circ }\mathrm{C}$ . Interestingly, according to the report 4-nitrobenzenediazonium fluoroborate gave a lower yield of arylphosphonate than 4-methylbenzenediazonium fluoroborate, which showed an opposite electronic preference as compared with our phosphorylation reaction. Also, the addition of acetonitrile, which is the best solvent in our phosphorylation reaction, was reported to make the coupling of aryl radical generated from arenediazonium salts with phosphorus species less favorable in Yasui’s work. The observation of the opposite results indicates that our phosphorylation reaction may proceed with a different pathway. To gain insights into the mechanistic details of our transformation, the reaction of 1a in the presence of radical scavenger TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl) was carried out (Scheme 6). When 10 mol% of TEMPO was added, the yield of 3ac dropped from 94% to 83%. Moreover, the reaction was almost blocked completely when 100 mol% or 150 mol% of TEMPO was added. These results indicate the possibility that a radical process may be involved in this transformation.

芳基重氮盐与一些磷(III)化合物之间反应的机理先前由安井及其同事在${1995.}^{17}$中进行了研究。在他们的研究中，据报道，当芳基重氮盐在氩气气氛下于${20}{}^{ \circ }\mathrm{C}$的醇溶剂中与亚磷酸三烷基酯反应时，会通过鏻离子中间体形成少量的芳基膦酸酯。有趣的是，根据报道，4-硝基苯重氮氟硼酸盐生成芳基膦酸酯的产率低于4-甲基苯重氮氟硼酸盐，这与我们的磷酸化反应显示出相反的电子偏好。此外，据报道添加乙腈(我们磷酸化反应中最好的溶剂)会使芳基重氮盐产生的芳基自由基与磷物种的偶联在安井的工作中不太有利。观察到相反的结果表明我们的磷酸化反应可能以不同的途径进行。为了深入了解我们转化反应的机理细节，在自由基清除剂TEMPO(2,2,6,6-四甲基哌啶-1-氧基)存在下进行了1a的反应(方案6)。当加入10 mol%的TEMPO时，3ac的产率从94%降至83%。此外，当加入100 mol%或150 mol%的TEMPO时，反应几乎完全受阻。这些结果表明该转化反应可能涉及自由基过程。

Scheme 6. Radical Trapping Experiments

方案6. 自由基捕获实验

Furthermore, experiments were carried out in order to reveal the influence of electronic effects of the reaction. Thus, a 1:1 mixture of electron-withdrawing group substituted aniline 1a and aniline 1z was reacted under the optimized conditions and the reaction was stopped in 2 min in order to keep the reaction at low conversion of aryl amines. A 1.5:1 ratio of $3\mathbf{{ac}}$ and $3\mathbf{z}$ was observed (Scheme 7a), indicating that the electron-deficient $\mathbf{{1a}}$ was more reactive. A 1.3:1 ratio of $\mathbf{{3z}}$ and $\mathbf{{3i}}$ was observed in the similar competition experiment of $\mathbf{{1z}}$ and methyl-substituted aniline $\mathbf{{1d}}$ (Scheme 7b). The electronic preferences suggest that the decrease of positive charge on the active center occurs during the transformation, which is in accordance with the generation of a radical species from a cationic intermediate.

此外，为了揭示反应的电子效应的影响，进行了实验。因此，将吸电子基团取代的苯胺1a和苯胺1z的1:1混合物在优化条件下反应，并在2分钟内停止反应，以使芳基胺的转化率保持较低。观察到$3\mathbf{{ac}}$与$3\mathbf{z}$的比例为1.5:1(方案7a)，表明缺电子的$\mathbf{{1a}}$更具反应性。在$\mathbf{{1z}}$与甲基取代的苯胺$\mathbf{{1d}}$的类似竞争实验中，观察到$\mathbf{{3z}}$与$\mathbf{{3i}}$的比例为1.3:1(方案7b)。电子偏好表明，在转化过程中活性中心的正电荷减少，这与从阳离子中间体生成自由基物种一致。

Scheme 7. Studies on Electronic Effects

方案7. 电子效应研究

Based on the general understanding on Sandmeyer-type reaction, ${}^{18}$ and our previous mechanistic investigation on Sandmeyer-type borylation and stannylation, ${}^{14}$ we have proposed a mechanism as shown in Scheme 8. First, arylamine reacts with $t$ -BuONO to generate diazonium salt intermediate $\mathbf{A}$ . Then single electron transfer (SET) between $\mathbf{A}$ and triphenyl phosphite generates radical anion species $\mathbf{B}$ and radical cation species $\mathbf{C}$ . Subsequently, phosphorous radical $\mathbf{D}$ is formed from $\mathbf{C}$ , followed by the reaction with $\mathbf{B}$ to afford the final phosphorylation product, along with the release of nitrogen.

基于对桑德迈尔型反应的一般理解，${}^{18}$ 以及我们之前对桑德迈尔型硼化和锡化反应的机理研究，${}^{14}$ 我们提出了如图8所示的机理。首先，芳胺与 $t$ -丁基亚硝酸酯反应生成重氮盐中间体 $\mathbf{A}$ 。然后，$\mathbf{A}$ 与亚磷酸三苯酯之间发生单电子转移(SET)，生成自由基阴离子物种 $\mathbf{B}$ 和自由基阳离子物种 $\mathbf{C}$ 。随后，$\mathbf{C}$ 形成磷自由基 $\mathbf{D}$ ，接着与 $\mathbf{B}$ 反应得到最终的磷酸化产物，同时释放出氮气。

Scheme 8.Proposed Reaction Mechanism

方案8. 提出的反应机理

${\mathrm{{Ar}}}^{\prime }\mathrm{O}\overset{+ \cdot }{\overset{\mathrm{P} - {\mathrm{{OAr}}}^{\prime } + {\mathrm{H}}_{2}\mathrm{O}}{\mathrm{{OAr}}{}^{\prime }}} \rightarrow \overset{\mathrm{O} \rightarrow }{\mathrm{{OAr}}{}^{\prime }} + {\mathrm{{Ar}}}^{\prime } - \mathrm{{OH}} + {\mathrm{H}}^{ \oplus }$(c)

$\mathrm{{Ar}} - {\mathrm{N}}_{2} \cdot \mathrm{O}\overrightarrow{{\mathrm{{Ts}}}^{\prime }} + \cdot \overset{\mathrm{O}}{\overbrace{\overset{1 - }{\mathrm{P}} - \mathrm{{OA}{r}^{\prime }}}} \rightarrow \mathrm{{Ar}} - \overset{\mathrm{O}}{\overbrace{\mathrm{P} - \mathrm{{OA}{r}^{\prime }}}} + {\mathrm{N}}_{2} + \mathrm{O}{\mathrm{{Ts}}}^{\prime }$(d)

CONCLUSION

结论

In summary, we have developed a Sandmeyer-type phosphorylation method to synthesize aryl phosphonates from easily available aryl amines. This metal-free transformation can be conducted under mild conditions without the exclusion of moisture or air. The reaction tolerates wide range of functional groups and affords the phosphorylation products in moderate to good yields. In view of the importance of aryl phosphonate compounds, we expect that this novel phosphorylation method will find practical applications in the synthesis of these compounds and will be a supplementary method for the construction of aromatic carbon-phosphorus bond. Detailed mechanistic study and further expansion of the substrate scope are currently under investigation in our laboratory.

总之，我们开发了一种桑德迈尔型磷酸化方法，可从易于获得的芳基胺合成芳基膦酸酯。这种无金属转化可以在温和条件下进行，无需排除水分或空气。该反应对多种官能团具有耐受性，并以中等至良好的产率提供磷酸化产物。鉴于芳基膦酸酯化合物的重要性，我们预计这种新型磷酸化方法将在这些化合物的合成中找到实际应用，并将成为构建芳族碳 - 磷键的补充方法。目前我们实验室正在进行详细的机理研究和底物范围的进一步扩展。

EXPERIMENTAL SECTION

实验部分

General Methods. P(OMe) ${}_{3}$ , P(OEt) ${}_{3}$ , P(OPh) ${}_{3}$ and the aniline derivatives were purchased from commercial suppliers and were used without further purifications. The solvents were all distilled prior to use. 200-300 mesh silica gels for the chromatography were used. Chemical shifts for ${}^{1}\mathrm{H}$ NMR (400 MHz) and ${}^{13}\mathrm{{CNMR}}$ (100 MHz) are reported relative to the chemical shift of tetramethylsilane (TMS): chemical shifts $\left( \delta \right)$ were reported in ppm, and coupling constants $\left( J\right)$ are in Hertz (Hz). For ${}^{31}\mathrm{P}$ NMR (162 MHz) spectra 85% phosphoric acid $\left( {\delta = 0}\right)$ was served as external standard. IR spectra are reported in wave numbers, ${\mathrm{{cm}}}^{-1}$ . For HRMS measurements, the mass analyzer is FT-ICR. The substituted triaryl phosphites (6a-d) were prepared following the literature procedure. ${}^{19}$

通用方法。P(OMe) ${}_{3}$、P(OEt) ${}_{3}$、P(OPh) ${}_{3}$ 和苯胺衍生物购自商业供应商，无需进一步纯化即可使用。所有溶剂在使用前均进行蒸馏。使用 200 - 300 目硅胶进行色谱分离。${}^{1}\mathrm{H}$ NMR(400 MHz)和 ${}^{13}\mathrm{{CNMR}}$(100 MHz)的化学位移相对于四甲基硅烷(TMS)的化学位移报告:化学位移 $\left( \delta \right)$ 以 ppm 为单位报告，耦合常数 $\left( J\right)$ 以赫兹(Hz)为单位。对于 ${}^{31}\mathrm{P}$ NMR(162 MHz)光谱，85% 磷酸 $\left( {\delta = 0}\right)$ 用作外标。红外光谱以波数 ${\mathrm{{cm}}}^{-1}$ 报告。对于高分辨质谱(HRMS)测量，质量分析器为傅里叶变换离子回旋共振(FT - ICR)。取代的三芳基亚磷酸酯(6a - d)按照文献方法制备。${}^{19}$

General procedure for the phosphorylation reaction.Arylamine $\left( {{0.2}\mathrm{{mmol}}}\right)$ and ${\mathrm{{TsOH} \cdot H}}_{2}\mathrm{O}$ (46 mg, 0.24 mmol) were added into a ${10}\mathrm{\;{mL}}$ reaction tube. After the addition of MeCN ( ${1.0}\mathrm{\;{mL}}$ ), the turbid solution was stirred at ${0}^{ \circ }\mathrm{C}$ . $t$ -BuONO (31 mg, ${0.3}\mathrm{{mmol}}$ ) was then added and the reaction solution was stirred at ${0}^{ \circ }\mathrm{C}$ for ${15}\mathrm{\;{min}}$ , followed by the addition of $\mathrm{P}{\left( \mathrm{{OR}}\right) }_{3}\left( {{0.6}\mathrm{{mmol}}}\right)$ , the resulting reaction solution was stirred for $8\mathrm{\;h}$ at room temperature (around ${25}^{ \circ }\mathrm{C}$ ). The solution was then concentrated under reduced pressure, and the crude residue was purified by silica gel column chromatography to afford the pure products.

磷酸化反应的一般步骤。将芳胺 $\left( {{0.2}\mathrm{{mmol}}}\right)$ 和 ${\mathrm{{TsOH} \cdot H}}_{2}\mathrm{O}$(46 mg，0.24 mmol)加入到一个 ${10}\mathrm{\;{mL}}$ 反应管中。加入 MeCN( ${1.0}\mathrm{\;{mL}}$ )后，将浑浊溶液在 ${0}^{ \circ }\mathrm{C}$ 下搅拌。然后加入 $t$ -BuONO(31 mg， ${0.3}\mathrm{{mmol}}$ )，并将反应溶液在 ${0}^{ \circ }\mathrm{C}$ 下搅拌 ${15}\mathrm{\;{min}}$ ，接着加入 $\mathrm{P}{\left( \mathrm{{OR}}\right) }_{3}\left( {{0.6}\mathrm{{mmol}}}\right)$ ，所得反应溶液在室温(约 ${25}^{ \circ }\mathrm{C}$ )下搅拌 $8\mathrm{\;h}$ 。然后将溶液减压浓缩，粗残渣通过硅胶柱色谱法纯化，得到纯产物。

General procedure for gram scale phosphorylation reaction. Arylamine (1a, 1d, or 1i, 20 mmol) and $\mathrm{{TsOH}} \cdot {\mathrm{H}}_{2}\mathrm{O}\left( {{4.56}\mathrm{\;g},{24}\mathrm{{mmol}}}\right)$ were added into a ${200}\mathrm{\;{mL}}$ reaction bulb. After the addition of $\mathrm{{MeCN}}\left( {{40}\mathrm{\;{mL}}}\right)$ , the turbid solution was stirred at ${0}^{ \circ }\mathrm{C}$ . t-BuONO (3.09 g,30 mmol) was then added dropwise and the reaction solution was stirred at $0{}^{ \circ }\mathrm{C}$ for ${15}\mathrm{\;{min}}$ , followed by the addition of $\mathrm{P}{\left( \mathrm{{OPh}}\right) }_{3}\left( {{18.06}\mathrm{\;g},{60}\mathrm{{mmol}}}\right)$ , the resulting reaction solution was stirred for $8\mathrm{\;h}$ at room temperature $\left( {{25}^{ \circ }\mathrm{C}}\right)$ . The solution was then concentrated under reduced pressure, and the crude residue was purified by silica gel column chromatography to afford the pure product.

克级磷酸化反应的一般步骤。将芳胺(1a、1d或1i，20毫摩尔)和$\mathrm{{TsOH}} \cdot {\mathrm{H}}_{2}\mathrm{O}\left( {{4.56}\mathrm{\;g},{24}\mathrm{{mmol}}}\right)$加入到一个${200}\mathrm{\;{mL}}$反应烧瓶中。加入$\mathrm{{MeCN}}\left( {{40}\mathrm{\;{mL}}}\right)$后，将浑浊溶液在${0}^{ \circ }\mathrm{C}$搅拌。然后滴加叔丁基亚硝酸酯(3.09克，30毫摩尔)，反应溶液在$0{}^{ \circ }\mathrm{C}$搅拌${15}\mathrm{\;{min}}$，接着加入$\mathrm{P}{\left( \mathrm{{OPh}}\right) }_{3}\left( {{18.06}\mathrm{\;g},{60}\mathrm{{mmol}}}\right)$，所得反应溶液在室温$\left( {{25}^{ \circ }\mathrm{C}}\right)$下搅拌$8\mathrm{\;h}$。然后将溶液减压浓缩，粗产物通过硅胶柱色谱纯化得到纯产物。

The ester exchange experiment. ${}^{16}$ The solution of sodium ( ${{130}\mathrm{{mg}}},{5.7}\mathrm{{mmol}}$ ) dissolved in ${3.0}\mathrm{\;{mL}}$ ethanol was added into a solution of $3\mathrm{{ic}}\left( {{340}\mathrm{{mg}},{1.0}\mathrm{{mmol}}}\right)$ dissolved in $3\mathrm{\;{mL}}$ ethanol, the reaction solution was stirred at room temperature for $2\mathrm{\;h}$ . Then the mixture was transferred into a ${125}\mathrm{\;{mL}}$ separating funnel and ${40}\mathrm{\;{mL}}$ diethyl ether was added. The solution was washed by $1\mathrm{M}\mathrm{{NaOH}}$ (40 $\mathrm{{mL}}$ ), and then the water phase was extracted with ${20}\mathrm{\;{mL}}$ ethanol. The organic phase was then washed by brine $\left( {{30}\mathrm{\;{mL}}}\right)$ . After drying by ${\mathrm{{Na}}}_{2}{\mathrm{{SO}}}_{4}$ and evaporation, the product 3ib was obtained (215 mg, 88%) as an orange liquid.

酯交换实验。${}^{16}$ 将溶解于${3.0}\mathrm{\;{mL}}$乙醇中的钠(${{130}\mathrm{{mg}}},{5.7}\mathrm{{mmol}}$)溶液加入到溶解于$3\mathrm{\;{mL}}$乙醇中的$3\mathrm{{ic}}\left( {{340}\mathrm{{mg}},{1.0}\mathrm{{mmol}}}\right)$溶液中，反应溶液在室温下搅拌$2\mathrm{\;h}$。然后将混合物转移至${125}\mathrm{\;{mL}}$分液漏斗中，并加入${40}\mathrm{\;{mL}}$乙醚。溶液用$1\mathrm{M}\mathrm{{NaOH}}$(40 $\mathrm{{mL}}$)洗涤，然后水相用${20}\mathrm{\;{mL}}$乙醇萃取。有机相再用盐水$\left( {{30}\mathrm{\;{mL}}}\right)$洗涤。经${\mathrm{{Na}}}_{2}{\mathrm{{SO}}}_{4}$干燥并蒸发后，得到橙色液体产物3ib(215 mg，88%)。

3ia was obtained as an orange liquid (205 mg, 84%) by using methanol as solvent under similar conditions. For 3id (orange liquid, 134 mg, 55%), i-PrOH was used instead of ethanol and the reaction was carried out at ${60}^{ \circ }\mathrm{C}$ for $2\mathrm{\;h}$ .

在相似条件下，以甲醇为溶剂得到橙色液体3ia(205 mg，84%)。对于3id(橙色液体，134 mg，55%)，用异丙醇代替乙醇，并在${60}^{ \circ }\mathrm{C}$下反应$2\mathrm{\;h}$。

The competition experiment. Arylamine 1a ( ${{83}\mathrm{{mg}}},\;{{0.5}\mathrm{{mmol}}}$ ), $\mathbf{{1z}}\left( {{47}\mathrm{{mg}},\;{0.5}\mathrm{{mmol}}}\right)$ and $\mathrm{{TsOH}} \cdot {\mathrm{H}}_{2}\mathrm{O}\left( {{228}\mathrm{{mg}},{1.2}\mathrm{{mmol}}}\right)$ were added into a ${50}\mathrm{\;{mL}}$ reaction bulb. After the addition of MeCN $\left( {{10}\mathrm{\;{mL}}}\right)$ , the turbid solution was stirred at ${0}^{ \circ }\mathrm{C}$ . $t$ -BuONO (155 mg, ${1.5}\mathrm{\;{mmol}}$ ) was then added and the reaction solution was stirred at ${0}^{ \circ }\mathrm{C}$ for ${15}\mathrm{\;{min}}$ , followed by the addition of $\mathrm{P}{\left( \mathrm{{OPh}}\right) }_{3}({341}\mathrm{{mg}},{1.1}$ mmol). The resulting reaction solution was stirred for $2\mathrm{\;{min}}$ at room temperature $\left( {{25}^{ \circ }\mathrm{C}}\right)$ . The reaction was quenched by filtering the mixture through a short column of silica gel (eluent: ethyl acetate). The solution was then concentrated under reduced pressure, and the crude residue was purified by silica gel column chromatography to afford the pure product 3ac (38mg, 20%) and 3z (20 mg, 13%).

竞争实验。将芳胺1a(${{83}\mathrm{{mg}}},\;{{0.5}\mathrm{{mmol}}}$)、$\mathbf{{1z}}\left( {{47}\mathrm{{mg}},\;{0.5}\mathrm{{mmol}}}\right)$和$\mathrm{{TsOH}} \cdot {\mathrm{H}}_{2}\mathrm{O}\left( {{228}\mathrm{{mg}},{1.2}\mathrm{{mmol}}}\right)$加入到${50}\mathrm{\;{mL}}$反应瓶中。加入乙腈$\left( {{10}\mathrm{\;{mL}}}\right)$后，将浑浊溶液在${0}^{ \circ }\mathrm{C}$下搅拌。然后加入$t$ -丁基亚硝酸酯(155 mg，${1.5}\mathrm{\;{mmol}}$)，反应溶液在${0}^{ \circ }\mathrm{C}$下搅拌${15}\mathrm{\;{min}}$，接着加入$\mathrm{P}{\left( \mathrm{{OPh}}\right) }_{3}({341}\mathrm{{mg}},{1.1}$ mmol)。所得反应溶液在室温下搅拌$2\mathrm{\;{min}}$ $\left( {{25}^{ \circ }\mathrm{C}}\right)$。通过硅胶短柱过滤混合物(洗脱剂:乙酸乙酯)淬灭反应。然后将溶液减压浓缩，粗残余物通过硅胶柱色谱法纯化，得到纯产物3ac(38mg，20%)和3z(20 mg，13%)。

Ethyl 4-(dimethoxyphosphoryl)benzoate (3aa). ${}^{20}$ Flash chromatography (silica gel, petroleum ether:ethyl acetate $= 2 : 1)$ afforded 3aa (28 mg,54%); yellow oil. ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta \; {8.16} - {8.13}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{7.91} - {7.86}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{4.41}\left( {\mathrm{q}, J = {7.1}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{3.79}\left( {\mathrm{\;d}, J = {11.1}\mathrm{\;{Hz}},6\mathrm{H}}\right) ,{1.42}(\mathrm{t}, J =$

4-(二甲氧基磷酰基)苯甲酸乙酯(3aa)。${}^{20}$ 快速柱色谱法(硅胶，石油醚:乙酸乙酯 $= 2 : 1)$ 得到3aa(28毫克，54%);黄色油状物。${}^{1}\mathrm{H}$ 核磁共振(400兆赫，${\mathrm{{CDCl}}}_{3}$ ) $\delta \; {8.16} - {8.13}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{7.91} - {7.86}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{4.41}\left( {\mathrm{q}, J = {7.1}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{3.79}\left( {\mathrm{\;d}, J = {11.1}\mathrm{\;{Hz}},6\mathrm{H}}\right) ,{1.42}(\mathrm{t}, J =$

7.1 Hz, 3H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl3) $\delta$ 165.7, 134.1 (d, $J = {3.4}\mathrm{\;{Hz}}$ ), 131.9 (d, $J = {9.9}\mathrm{\;{Hz}}$ ), 131.6 (d, $J = {187.2}\mathrm{\;{Hz}}$ ),129.4 (d, $J = {15.2}\mathrm{\;{Hz}}$ ),61.5,52.9 (d, $J = {5.6}\mathrm{\;{Hz}}$ ),14.3; ${}^{31}\mathrm{P}$ NMR (CDCl, 162 MHz) $\delta$ 20.6; IR (film): 1721,1273,1104,1020,830,763 ${\mathrm{\;{cm}}}^{-1}$ ; EI-MS ( $m/z$ , relative intensity): ${257}\left( {20}\right) ,{230}\left( {24}\right) ,{213}\left( {100}\right) ,{185}\left( {26}\right) ,{136}\left( {20}\right) ,{91}\left( {16}\right) ;$ HRMS (ESI) calcd for ${\mathrm{C}}_{11}{\mathrm{H}}_{16}{\mathrm{O}}_{5}\mathrm{P} \; {\left\lbrack {\mathrm{M}}^{ + }\mathrm{H}\right\rbrack }^{ + }$ 259.0730; found 259.0728.

7.1赫兹，3H);${}^{13}\mathrm{C}$ 核磁共振(100兆赫，CDCl3) $\delta$ 165.7, 134.1(双峰，$J = {3.4}\mathrm{\;{Hz}}$ )，131.9(双峰，$J = {9.9}\mathrm{\;{Hz}}$ )，131.6(双峰，$J = {187.2}\mathrm{\;{Hz}}$ )，129.4(双峰，$J = {15.2}\mathrm{\;{Hz}}$ )，61.5,52.9(双峰，$J = {5.6}\mathrm{\;{Hz}}$ )，14.3;${}^{31}\mathrm{P}$ 核磁共振(CDCl，162兆赫) $\delta$ 20.6;红外光谱(薄膜):1721,1273,1104,1020,830,763 ${\mathrm{\;{cm}}}^{-1}$ ;电子轰击质谱($m/z$ ，相对强度):${257}\left( {20}\right) ,{230}\left( {24}\right) ,{213}\left( {100}\right) ,{185}\left( {26}\right) ,{136}\left( {20}\right) ,{91}\left( {16}\right) ;$ 高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{11}{\mathrm{H}}_{16}{\mathrm{O}}_{5}\mathrm{P} \; {\left\lbrack {\mathrm{M}}^{ + }\mathrm{H}\right\rbrack }^{ + }$ 259.0730;实测值为259.0728。

Ethyl 4-(diphenoxyphosphoryl)benzoate (3ac). ${}^{21}$ Flash chromatography (silica gel, petroleum ether:ethyl acetate $= 5 : 1)$ afforded 3ac $\left( {{72}\mathrm{{mg}},{94}\% }\right)$ ; yellow oil. ${}^{1}\mathrm{H}$ NMR $\left( {{400}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta \; {8.17} - {8.14}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{8.07} - {8.01}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{7.31} - {7.26}\left( {\mathrm{\;m},4\mathrm{H}}\right) ,{7.19} - {7.14}\left( {\mathrm{\;m},6\mathrm{H}}\right) ,{4.41}\left( {\mathrm{q}, J = {7.1}\mathrm{\;{Hz}}}\right)$ , 2H), 1.39 (t, $J = {7.1}\mathrm{\;{Hz}},3\mathrm{H}$ ); ${}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) ${\delta 165.5},{150.1}$ (d, $J = {7.7}\mathrm{\;{Hz}}$ ), 134.7 (d, $J = {3.19}\mathrm{\;{Hz}}),{132.3}\left( {\mathrm{\;d}, J = {10.6}\mathrm{\;{Hz}}}\right) ,{131.3}\left( {\mathrm{\;d}, J = {192.93}\mathrm{\;{Hz}}}\right) ,{129.8},{129.6},{129},5,{120.6}(\mathrm{\;d}, J = {4.6}$ Hz), 61.6, 14.3; ${}^{31}\mathrm{P}$ NMR (CDCl3, 162 MHz) δ 10.6; IR (film): 1721, 1489, 1272, 1186, 1103, 932, 762 cm ${}^{-1}$ ; EI-MS ( $m/z$ , relative intensity): 381 (100),337 (15),289 (35),242 (24),170 (17),77 (76); HRMS (ESI) calcd for ${\mathrm{C}}_{21}{\mathrm{H}}_{20}{\mathrm{O}}_{5}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 383.1043; found 383.1043.

4-(二苯氧基磷酰基)苯甲酸乙酯(3ac)。${}^{21}$ 快速柱色谱法(硅胶，石油醚:乙酸乙酯 $= 5 : 1)$ 得到3ac $\left( {{72}\mathrm{{mg}},{94}\% }\right)$ ；黄色油状物。${}^{1}\mathrm{H}$ 核磁共振 $\left( {{400}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta \; {8.17} - {8.14}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{8.07} - {8.01}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{7.31} - {7.26}\left( {\mathrm{\;m},4\mathrm{H}}\right) ,{7.19} - {7.14}\left( {\mathrm{\;m},6\mathrm{H}}\right) ,{4.41}\left( {\mathrm{q}, J = {7.1}\mathrm{\;{Hz}}}\right)$ ，2H)，1.39(t，$J = {7.1}\mathrm{\;{Hz}},3\mathrm{H}$ )；${}^{13}\mathrm{C}$ 核磁共振(100兆赫，${\mathrm{{CDCl}}}_{3}$ )${\delta 165.5},{150.1}$ (d，$J = {7.7}\mathrm{\;{Hz}}$ )，134.7(d，$J = {3.19}\mathrm{\;{Hz}}),{132.3}\left( {\mathrm{\;d}, J = {10.6}\mathrm{\;{Hz}}}\right) ,{131.3}\left( {\mathrm{\;d}, J = {192.93}\mathrm{\;{Hz}}}\right) ,{129.8},{129.6},{129},5,{120.6}(\mathrm{\;d}, J = {4.6}$ 赫兹)，61.6，14.3；${}^{31}\mathrm{P}$ 核磁共振(CDCl3，162兆赫)δ10.6；红外光谱(薄膜):1721，1489，1272，1186，1103，932，762厘米${}^{-1}$ ；电子轰击质谱($m/z$ ，相对强度):381(100)，337(15)，289(35)，242(24)，170(17)，77(76)；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{21}{\mathrm{H}}_{20}{\mathrm{O}}_{5}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 383.1043；实测值为383.1043。

Diphenyl (4-nitrophenyl)phosphonate (3b). ${}^{16}$ Flash chromatography (silica gel, petroleum ether:ethyl acetate $= {10} : 1)$ afforded $\mathbf{{3b}}\left( {{68}\mathrm{{mg}},{95}\% }\right)$ ; yellow liquid. ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 8.35-8.32 $\left( {\mathrm{m},2\mathrm{H}}\right) ,{8.19} - {8.14}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{7.34} - {7.30}\left( {\mathrm{\;m},4\mathrm{H}}\right) ,{7.19} - {7.18}\left( {\mathrm{\;m},6\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR $\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta$ 150.7 (d, $J = {4.0}\mathrm{\;{Hz}}$ ), ${149.9}\left( {\mathrm{\;d}, J = {7.6}\mathrm{\;{Hz}}}\right) ,{133.8}\left( {\mathrm{\;d}, J = {191.8}\mathrm{\;{Hz}}}\right) ,{133.6}\left( {\mathrm{\;d}, J = {11.1}\mathrm{\;{Hz}}}\right) ,{130.0}$ , 125.7,123.6 $\left( {\mathrm{d}, J = {16.2}\mathrm{\;{Hz}}}\right) ,{120.5}\left( {\mathrm{\;d}, J = {4.6}\mathrm{\;{Hz}}}\right) ;{}^{31}\mathrm{P}$ NMR (CDC ${\mathrm{l}}_{3},{162}\mathrm{{MHz}}$ ) $\delta$ 8.2; IR (film): 1589,1516,1267,1187,945,932,777 ${\mathrm{\;{cm}}}^{-1}$ ; EI-MS $\left( {m/z}\right.$ , relative intensity): ${354}\left( {89}\right) ,{308}\left( {14}\right) ,{262}$ (14),215 (34),170 (16),94 (19),77 (100); HRMS (ESI) calcd for ${\mathrm{C}}_{18}{\mathrm{H}}_{15}{\mathrm{{NO}}}_{5}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 356.0682; found 356.0682.

二苯基(4-硝基苯基)膦酸酯(3b)。${}^{16}$ 快速柱色谱法(硅胶，石油醚:乙酸乙酯 $= {10} : 1)$ 得到 $\mathbf{{3b}}\left( {{68}\mathrm{{mg}},{95}\% }\right)$；黄色液体。${}^{1}\mathrm{H}$ 核磁共振(400兆赫，${\mathrm{{CDCl}}}_{3}$) $\delta$ 8.35 - 8.32 $\left( {\mathrm{m},2\mathrm{H}}\right) ,{8.19} - {8.14}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{7.34} - {7.30}\left( {\mathrm{\;m},4\mathrm{H}}\right) ,{7.19} - {7.18}\left( {\mathrm{\;m},6\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ 核磁共振 $\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta$ 150.7(双峰，$J = {4.0}\mathrm{\;{Hz}}$)，${149.9}\left( {\mathrm{\;d}, J = {7.6}\mathrm{\;{Hz}}}\right) ,{133.8}\left( {\mathrm{\;d}, J = {191.8}\mathrm{\;{Hz}}}\right) ,{133.6}\left( {\mathrm{\;d}, J = {11.1}\mathrm{\;{Hz}}}\right) ,{130.0}$，125.7，123.6 $\left( {\mathrm{d}, J = {16.2}\mathrm{\;{Hz}}}\right) ,{120.5}\left( {\mathrm{\;d}, J = {4.6}\mathrm{\;{Hz}}}\right) ;{}^{31}\mathrm{P}$ 核磁共振(CDCl${\mathrm{l}}_{3},{162}\mathrm{{MHz}}$) $\delta$ 8.2；红外光谱(薄膜):1589，1516，1267，1187，945，932，777 ${\mathrm{\;{cm}}}^{-1}$；电子轰击质谱 $\left( {m/z}\right.$，相对强度):${354}\left( {89}\right) ,{308}\left( {14}\right) ,{262}$ (14)，215(34)，170(16)，94(19)，77(100)；高分辨质谱(电喷雾电离)计算值为 ${\mathrm{C}}_{18}{\mathrm{H}}_{15}{\mathrm{{NO}}}_{5}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 356.0682；实测值为356.0682。

Diphenyl (4-cyanophenyl)phosphonate (3c). ${}^{16}$ Flash chromatography (silica gel, petroleum ether:ethyl acetate $= {10} : 1)$ afforded $3\mathrm{c}\left( {{66}\mathrm{{mg}},{98}\% }\right)$ ; red liquid. ${}^{1}\mathrm{H}$ NMR $\left( {{400}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta$ 8.11-8.05 (m, 2H), 7.80-7.77 (m, 2H), 7.33-7.26 (m, 4H), 7.20-7.16 (m, 6H); ${}^{13}\mathrm{C}\mathrm{{NMR}}$ (100 MHz, ${\mathrm{{CDCl}}}_{3})\delta$ 149.9 $\left( {\mathrm{d}, J = {7.8}\mathrm{\;{Hz}}}\right) ,{132.8}\left( {\mathrm{\;d}, J = {10.4}\mathrm{\;{Hz}}}\right) ,{132.2}\left( {\mathrm{\;d}, J = {15.8}\mathrm{\;{Hz}}}\right) ,{132.0}(\mathrm{\;d}, J = {192.4}$ Hz), 130.0, 125.6, 120.5 (d, J = 4.6 Hz), 117.6, 116.9 (d, J = 3.68 Hz); ${}^{31}\mathrm{P}$ NMR (CDC1, 162 MHz) $\delta$ 8.4; IR (film): 2233,1590,1489,1271,1185,935,767 ${\mathrm{\;{cm}}}^{-1}$ ; EI-MS $\left( {m/z}\right.$ , relative intensity): 334 (91), 242 (19), 195 (42), 170 (18), 94 (20), 77 (100); HRMS (ESI) calcd for ${\mathrm{C}}_{19}{\mathrm{H}}_{15}{\mathrm{{NO}}}_{3}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 336.0784; found 336.0786.

二苯基(4-氰基苯基)膦酸酯(3c)。${}^{16}$ 快速柱色谱法(硅胶，石油醚:乙酸乙酯 $= {10} : 1)$ 得到 $3\mathrm{c}\left( {{66}\mathrm{{mg}},{98}\% }\right)$；红色液体。${}^{1}\mathrm{H}$ 核磁共振 $\left( {{400}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta$ 8.11 - 8.05(多重峰，2H)，7.80 - 7.77(多重峰，2H)，7.33 - 7.26(多重峰，4H)，7.20 - 7.16(多重峰，6H)；${}^{13}\mathrm{C}\mathrm{{NMR}}$ (100兆赫兹，${\mathrm{{CDCl}}}_{3})\delta$ 149.9 $\left( {\mathrm{d}, J = {7.8}\mathrm{\;{Hz}}}\right) ,{132.8}\left( {\mathrm{\;d}, J = {10.4}\mathrm{\;{Hz}}}\right) ,{132.2}\left( {\mathrm{\;d}, J = {15.8}\mathrm{\;{Hz}}}\right) ,{132.0}(\mathrm{\;d}, J = {192.4}$ 赫兹)，130.0，125.6，120.5(耦合常数J = 4.6赫兹，双峰)，117.6，116.9(耦合常数J = 3.68赫兹，双峰)；${}^{31}\mathrm{P}$ 核磁共振(氘代氯仿，162兆赫兹) $\delta$ 8.4；红外光谱(薄膜):2233、1590、1489、1271、1185、935、767 ${\mathrm{\;{cm}}}^{-1}$；电子轰击质谱 $\left( {m/z}\right.$，相对强度):334(91)，242(19)，195(42)，170(18)，94(20)，77(100)；高分辨质谱(电喷雾电离)计算值为 ${\mathrm{C}}_{19}{\mathrm{H}}_{15}{\mathrm{{NO}}}_{3}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 336.0784；实测值为336.0786。

Diphenyl p-tolylphosphonate (3d). ${}^{16}$ Flash chromatography (silica gel, petroleum ether:ethyl acetate $= {20} : 1)$ afforded $\mathbf{{3d}}\left( {{43}\mathrm{{mg}},{66}\% }\right)$ ; yellow liquid. ${}^{1}\mathrm{H}$ NMR $\left( {{400}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 7.87} - {7.82}\left( {\mathrm{\;m},2\mathrm{H}}\right)$ , 7.30-7.25 (m, 6H), 7.19-7.17 (m, 4H), 7.14-7.11 (m, 2H), 2.40 (s, 3H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl3) $\delta$ 150.5 $\left( {\mathrm{d}, J = {7.4}\mathrm{\;{Hz}}}\right) ,{144.0}\left( {\mathrm{\;d}, J = {3.1}\mathrm{\;{Hz}}}\right) ,{132.3}\left( {\mathrm{\;d}, J = {10.9}\mathrm{\;{Hz}}}\right) ,{129.7},{129.4}\left( {\mathrm{\;d}, J = {16.4}\mathrm{\;{Hz}}}\right)$ , 125.1,123.5 $\left( {\mathrm{d}, J = {195.1}\mathrm{\;{Hz}}}\right) ,{120.7}\left( {\mathrm{\;d}, J = {4.5}\mathrm{\;{Hz}}}\right) ,{21.8};{}^{31}\mathrm{P}$ NMR $\left( {{\mathrm{{CDCl}}}_{3},{162}\mathrm{{MHz}}}\right) {\delta 12.48}$ ; IR (film): 1592,1490,1269,1188,1129,926,769 ${\mathrm{{cm}}}^{-1}$ ; EI-MS $\left( {m/z\text{ , relative intensity): 323 (100),231 }}\right)$ (77),213 (13),184 (22),170 (20),77 (77); HRMS (ESI) calcd for ${\mathrm{C}}_{19}{\mathrm{H}}_{18}{\mathrm{O}}_{3}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 325.0988; found 325.0994.

对甲苯基二苯基膦酸酯(3d)。${}^{16}$ 快速柱色谱法(硅胶，石油醚:乙酸乙酯 $= {20} : 1)$ 得到 $\mathbf{{3d}}\left( {{43}\mathrm{{mg}},{66}\% }\right)$ ；黄色液体。${}^{1}\mathrm{H}$ 核磁共振 $\left( {{400}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 7.87} - {7.82}\left( {\mathrm{\;m},2\mathrm{H}}\right)$ ，7.30 - 7.25(m，6H)，7.19 - 7.17(m，4H)，7.14 - 7.11(m，2H)，2.40(s，3H)；${}^{13}\mathrm{C}$ 核磁共振(100 MHz，CDCl₃)$\delta$ 150.5 $\left( {\mathrm{d}, J = {7.4}\mathrm{\;{Hz}}}\right) ,{144.0}\left( {\mathrm{\;d}, J = {3.1}\mathrm{\;{Hz}}}\right) ,{132.3}\left( {\mathrm{\;d}, J = {10.9}\mathrm{\;{Hz}}}\right) ,{129.7},{129.4}\left( {\mathrm{\;d}, J = {16.4}\mathrm{\;{Hz}}}\right)$ ，125.1，123.5 $\left( {\mathrm{d}, J = {195.1}\mathrm{\;{Hz}}}\right) ,{120.7}\left( {\mathrm{\;d}, J = {4.5}\mathrm{\;{Hz}}}\right) ,{21.8};{}^{31}\mathrm{P}$ 核磁共振 $\left( {{\mathrm{{CDCl}}}_{3},{162}\mathrm{{MHz}}}\right) {\delta 12.48}$ ；红外光谱(薄膜):1592，1490，1269，1188，1129，926，769 ${\mathrm{{cm}}}^{-1}$ ；电子轰击质谱 $\left( {m/z\text{ , relative intensity): 323 (100),231 }}\right)$ (77)，213(13)，184(22)，170(20)，77(77)；高分辨质谱(电喷雾电离)计算值为 ${\mathrm{C}}_{19}{\mathrm{H}}_{18}{\mathrm{O}}_{3}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 325.0988；实测值为325.0994。

Diphenyl (4-chlorophenyl)phosphonate (3e). ${}^{16}$ Flash chromatography (silica gel, petroleum ether:ethyl acetate $= {30} : 1)$ afforded 3e ( ${59}\mathrm{{mg}},{86}\%$ ); yellow liquid. ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 7.92-7.87 (m, 2H), 7.50-7.47 (m, 2H), 7.35-7.26 (m, 4H), 7.21-7.14 (m, 6H); ${}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3})\delta$ 150.2 (d, $J = {7.5}\mathrm{\;{Hz}}),{140.0}$ (d, $J = {4.2}\mathrm{\;{Hz}}),{133.7}$ (d, $J = {11.4}\mathrm{\;{Hz}}),{129.8},{129.1}$ (d, $J = \; {16.6}\mathrm{\;{Hz}}$ ), ${125.4}\left( {\mathrm{\;d}, J = {195.9}\mathrm{\;{Hz}}}\right) ,{125.4},{120.6}\left( {\mathrm{\;d}, J = {4.5}\mathrm{\;{Hz}}}\right) ;{}^{31}\mathrm{P}\mathrm{{NMR}}\left( {{\mathrm{{CDCl}}}_{3},{162}\mathrm{{MHz}}}\right) \delta$ 11.1; IR (film): 1590,1489,1280,1187,1088,930,772 ${\mathrm{{cm}}}^{-1}$ ; EI-MS $(m/z$ , relative intensity): 343 (78), 251 (33), 233 (7), 204 (25), 170 (22), 77(100); HRMS (ESI) calcd for ${\mathrm{C}}_{18}{\mathrm{H}}_{15}{\mathrm{{ClO}}}_{3}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 345.0442; found 345.0444.

二苯基(4-氯苯基)膦酸酯(3e)。${}^{16}$ 快速柱色谱法(硅胶，石油醚:乙酸乙酯 $= {30} : 1)$ 得到3e( ${59}\mathrm{{mg}},{86}\%$ );黄色液体。${}^{1}\mathrm{H}$ 核磁共振氢谱(400兆赫，${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 7.92 - 7.87(多重峰，2H)，7.50 - 7.47(多重峰，2H)，7.35 - 7.26(多重峰，4H)，7.21 - 7.14(多重峰，6H);${}^{13}\mathrm{C}$ 核磁共振碳谱(100兆赫，${\mathrm{{CDCl}}}_{3})\delta$ 150.2(双峰，$J = {7.5}\mathrm{\;{Hz}}),{140.0}$ (双峰，$J = {4.2}\mathrm{\;{Hz}}),{133.7}$ (双峰，$J = {11.4}\mathrm{\;{Hz}}),{129.8},{129.1}$ (双峰，$J = \; {16.6}\mathrm{\;{Hz}}$ )，${125.4}\left( {\mathrm{\;d}, J = {195.9}\mathrm{\;{Hz}}}\right) ,{125.4},{120.6}\left( {\mathrm{\;d}, J = {4.5}\mathrm{\;{Hz}}}\right) ;{}^{31}\mathrm{P}\mathrm{{NMR}}\left( {{\mathrm{{CDCl}}}_{3},{162}\mathrm{{MHz}}}\right) \delta$ 11.1;红外光谱(薄膜):1590,1489,1280,1187,1088,930,772 ${\mathrm{{cm}}}^{-1}$ ;电子轰击质谱 $(m/z$ ，相对强度):343(78)，251(33)，233(7)，204(2,5)，170(22)，77(100);高分辨质谱(电喷雾电离)计算值为 ${\mathrm{C}}_{18}{\mathrm{H}}_{15}{\mathrm{{ClO}}}_{3}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 345.0442;实测值为345.0444。

Diphenyl (4-bromophenyl)phosphonate (3f). Flash chromatography (silica gel, petroleum ether:ethyl acetate $= {30} : 1)$ afforded $\mathbf{{3f}}\left( {{60}\mathrm{{mg}},{77}\% }\right)$ ; yellow liquid. ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl ${}_{3}$ ) δ 7.84-7.79 (m, 2H), 7.65-7.62 (m, 2H), 7.31-7.27 (m, 4H), 7.18-7.13 (m, 6H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) δ 150.2 $\left( {\mathrm{d}, J = {7.6}\mathrm{\;{Hz}}}\right) ,{133.8}\left( {\mathrm{\;d}, J = {11.2}\mathrm{\;{Hz}}}\right) ,{132.1}\left( {\mathrm{\;d}, J = {16.4}\mathrm{\;{Hz}}}\right) ,{129.8},{128.6}\left( {\mathrm{\;d}, J = {4.2}\mathrm{\;{Hz}}}\right) ,{125.9}(\mathrm{\;d}$ , $J = {195.3}\mathrm{\;{Hz}}),{125.3},{120.6}\left( {\mathrm{\;d}, J = {4.5}\mathrm{\;{Hz}}}\right) ;{}^{31}\mathrm{P}$ NMR (CDCl3,162 MHz) $\delta$ 11.4; IR (film) 1581, 1483,1266,1186,1162,930,771 ${\mathrm{{cm}}}^{-1}$ ; EI-MS $\left( {m/z\text{ , relative intensity }}\right) : {389}\left( {63}\right) ,{295}\left( {29}\right) ,{248}\left( {16}\right)$ , 170 (21), 77 (100), 51 (16); HRMS (ESI) calcd for ${\mathrm{C}}_{18}{\mathrm{H}}_{15}{\mathrm{{BrO}}}_{3}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 388.9937; found 388.9939. Diphenyl [1,1’-biphenyl]-4-ylphosphonate (3g). ${}^{22}$ Flash chromatography (silica gel, petroleum ether:ethyl acetate $= {20} : 1)$ afforded $3\mathbf{g}\left( {{39}\mathrm{{mg}},{51}\% }\right)$ ; yellow liquid. ${}^{1}\mathrm{H}$ NMR $\left( {{400}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta \; {8.06} - {8.00}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{7.73} - {7.70}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{7.62}\left( {\mathrm{\;d}, J = {7.4}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.49} - {7.45}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{7.42} - {7.39}(\mathrm{m}$ , 1H), 7.32-7.29 (m, 4H), 7.23-7.21 (m, 4H), 7.17-7.13 (m, 2H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) δ 150.4 $\left( {\mathrm{d}, J = {7.6}\mathrm{\;{Hz}}}\right) ,{146.0}\left( {\mathrm{\;d}, J = {3.4}\mathrm{\;{Hz}}}\right) ,{139.7},{132.8}\left( {\mathrm{\;d}, J = {10.8}\mathrm{\;{Hz}}}\right) ,{129.8},{129.0},{128.4},{127.3}$ , ${127.3}\left( {\mathrm{\;d}, J = {16.1}\mathrm{\;{Hz}}}\right) ,{125.3}\left( {J = {194.7}\mathrm{\;{Hz}}}\right) ,{125.2},{120.7}\left( {\mathrm{\;d}, J = {4.5}\mathrm{\;{Hz}}}\right) ;{}^{31}\mathrm{P}\mathrm{{NMR}}\left( {{\mathrm{{CDCl}}}_{3},{162}}\right)$ MHz) $\delta$ 12.6; IR (film): ${1591},{1488},{1274},{1188},{1133},{928},{761}{\mathrm{\;{cm}}}^{-1}$ ; HRMS (ESI) calcd for ${\mathrm{C}}_{24}{\mathrm{H}}_{20}{\mathrm{O}}_{3}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{387.1145}$ ; found 387.1146.

二苯基(4 - 溴苯基)膦酸酯(3f)。快速柱色谱法(硅胶，石油醚:乙酸乙酯 $= {30} : 1)$ 得到 $\mathbf{{3f}}\left( {{60}\mathrm{{mg}},{77}\% }\right)$ ；黄色液体。 ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl ${}_{3}$ ) δ 7.84 - 7.79 (m, 2H)，7.65 - 7.62 (m, 2H)，7.31 - 7.27 (m, 4H)，7.18 - 7.13 (m, 6H)； ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) δ 150.2 $\left( {\mathrm{d}, J = {7.6}\mathrm{\;{Hz}}}\right) ,{133.8}\left( {\mathrm{\;d}, J = {11.2}\mathrm{\;{Hz}}}\right) ,{132.1}\left( {\mathrm{\;d}, J = {16.4}\mathrm{\;{Hz}}}\right) ,{129.8},{128.6}\left( {\mathrm{\;d}, J = {4.2}\mathrm{\;{Hz}}}\right) ,{125.9}(\mathrm{\;d}$ ， $J = {195.3}\mathrm{\;{Hz}}),{125.3},{120.6}\left( {\mathrm{\;d}, J = {4.5}\mathrm{\;{Hz}}}\right) ;{}^{31}\mathrm{P}$ NMR (CDCl3, 162 MHz) $\delta$ 11.4；红外光谱(液膜)1581、1483、1266、1186、1162、930、771 ${\mathrm{{cm}}}^{-1}$ ；电子轰击质谱 $\left( {m/z\text{ , relative intensity }}\right) : {389}\left( {63}\right) ,{295}\left( {29}\right) ,{248}\left( {16}\right)$ ，170 (21)，77 (100)，51 (16)；高分辨质谱(电喷雾电离)计算值 ${\mathrm{C}}_{18}{\mathrm{H}}_{15}{\mathrm{{BrO}}}_{3}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 388.9937；实测值 388.9939。二苯基[1,1’-联苯]-4 - 基膦酸酯(3g)。 ${}^{22}$ 快速柱色谱法(硅胶，石油醚:乙酸乙酯 $= {20} : 1)$ 得到 $3\mathbf{g}\left( {{39}\mathrm{{mg}},{51}\% }\right)$ ；黄色液体。 ${}^{1}\mathrm{H}$ NMR $\left( {{400}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta \; {8.06} - {8.00}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{7.73} - {7.70}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{7.62}\left( {\mathrm{\;d}, J = {7.4}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.49} - {7.45}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{7.42} - {7.39}(\mathrm{m}$ ，1H)，7.32 - 7.29 (m, 4H)，7.23 - 7.21 (m, 4H)，7.17 - 7.13 (m, 2H)； ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) δ 150.4 $\left( {\mathrm{d}, J = {7.6}\mathrm{\;{Hz}}}\right) ,{146.0}\left( {\mathrm{\;d}, J = {3.4}\mathrm{\;{Hz}}}\right) ,{139.7},{132.8}\left( {\mathrm{\;d}, J = {10.8}\mathrm{\;{Hz}}}\right) ,{129.8},{129.0},{128.4},{127.3}$ ， ${127.3}\left( {\mathrm{\;d}, J = {16.1}\mathrm{\;{Hz}}}\right) ,{125.3}\left( {J = {194.7}\mathrm{\;{Hz}}}\right) ,{125.2},{120.7}\left( {\mathrm{\;d}, J = {4.5}\mathrm{\;{Hz}}}\right) ;{}^{31}\mathrm{P}\mathrm{{NMR}}\left( {{\mathrm{{CDCl}}}_{3},{162}}\right)$ MHz) $\delta$ 12.6；红外光谱(液膜): ${1591},{1488},{1274},{1188},{1133},{928},{761}{\mathrm{\;{cm}}}^{-1}$ ；高分辨质谱(电喷雾电离)计算值 ${\mathrm{C}}_{24}{\mathrm{H}}_{20}{\mathrm{O}}_{3}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{387.1145}$ ；实测值 387.1146。

Diphenyl (4-(methylthio)phenyl)phosphonate (3h). Flash chromatography (silica gel, petroleum ether:ethyl acetate = 20:1) afforded 3h (37 mg, 52%); yellow liquid. ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta \; {7.86} - {7.80}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{7.30} - {7.26}\left( {\mathrm{\;m},6\mathrm{H}}\right) ,{7.19} - {7.12}\left( {\mathrm{\;m},6\mathrm{H}}\right) ,{2.45}\left( {\mathrm{\;s},3\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR $\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \; \delta$ 150.4 $\left( {\mathrm{d}, J = {7.5}\mathrm{\;{Hz}}}\right) ,{146.2}\left( {\mathrm{\;d}, J = {3.6}\mathrm{\;{Hz}}}\right) ,{132.5}\left( {\mathrm{\;d}, J = {11.1}\mathrm{\;{Hz}}}\right) ,{129.8},{125.2},{125.1}(\mathrm{\;d}, J = {16.1} \; \mathrm{{Hz}}),{122.0}\left( {\mathrm{\;d}, J = {197.5}\mathrm{\;{Hz}}}\right) ,{120.6}\left( {\mathrm{\;d}, J = {4.7}\mathrm{\;{Hz}}}\right) ,{14.6};{}^{31}\mathrm{P}$ NMR $\left( {{\mathrm{{CDCl}}}_{3},{162}\mathrm{{MHz}}}\right) \delta$ 12.7; IR (film): 1589, 1489, 1278, 1187, 1085, 927, 773 cm ${}^{-1}$ ; EI-MS $(m/z$ , relative intensity): 356 (100), 263 (94), 216 (23), 170 (12), 139 (9), 77 (68); HRMS (ESI) calcd for ${\mathrm{C}}_{19}{\mathrm{H}}_{18}{\mathrm{O}}_{3}\mathrm{{PS}}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 357.0709; found 357.0708.

二苯基(4-(甲硫基)苯基)膦酸酯(3h)。通过快速柱色谱法(硅胶，石油醚:乙酸乙酯 = 20:1)得到3h(37 mg，52%)；黄色液体。${}^{1}\mathrm{H}$核磁共振(400 MHz，${\mathrm{{CDCl}}}_{3}$)$\delta \; {7.86} - {7.80}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{7.30} - {7.26}\left( {\mathrm{\;m},6\mathrm{H}}\right) ,{7.19} - {7.12}\left( {\mathrm{\;m},6\mathrm{H}}\right) ,{2.45}\left( {\mathrm{\;s},3\mathrm{H}}\right) ;{}^{13}\mathrm{C}$核磁共振$\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \; \delta$ 150.4 $\left( {\mathrm{d}, J = {7.5}\mathrm{\;{Hz}}}\right) ,{146.2}\left( {\mathrm{\;d}, J = {3.6}\mathrm{\;{Hz}}}\right) ,{132.5}\left( {\mathrm{\;d}, J = {11.1}\mathrm{\;{Hz}}}\right) ,{129.8},{125.2},{125.1}(\mathrm{\;d}, J = {16.1} \; \mathrm{{Hz}}),{122.0}\left( {\mathrm{\;d}, J = {197.5}\mathrm{\;{Hz}}}\right) ,{120.6}\left( {\mathrm{\;d}, J = {4.7}\mathrm{\;{Hz}}}\right) ,{14.6};{}^{31}\mathrm{P}$核磁共振$\left( {{\mathrm{{CDCl}}}_{3},{162}\mathrm{{MHz}}}\right) \delta$ 12.7；红外光谱(薄膜):1589、1489、1278、1187、1085、927、773 cm${}^{-1}$；电子轰击质谱$(m/z$，相对强度):356(100)、263(94)、216(23)、170(12)、139(9)、77(68)；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{19}{\mathrm{H}}_{18}{\mathrm{O}}_{3}\mathrm{{PS}}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 357.0709；实测值为357.0708。

Dimethyl (4-methoxyphenyl)phosphonate (3ia) ${}^{10}$ Orange liquid (205 mg,84%). ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 7.74 (dd, $J = {12.7},{8.7}\mathrm{\;{Hz}},2\mathrm{H}$ ),6.98 (dd, $J = {8.7},{3.3}\mathrm{\;{Hz}},2\mathrm{H}$ ),3.85 (s,3H),3.74 (d, $J =$ 11.1 Hz, 6H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) δ 163.0 (d, $J = {3.5}\mathrm{\;{Hz}}$ ), 133.9 (d, $J = {11.2}\mathrm{\;{Hz}}$ ), 117.9 (d, $J = {196.1}\mathrm{\;{Hz}}),{114.1}\left( {\mathrm{\;d}, J = {16.1}\mathrm{\;{Hz}}}\right) ,{55.3},{52.5}\left( {\mathrm{\;d}, J = {5.5}\mathrm{\;{Hz}}}\right) ;{}^{31}\mathrm{P}$ NMR (CDC ${\mathrm{l}}_{3},{162}\mathrm{{MHz}}$ ) $\delta$ 23.1IR (film): 2955,1600,1507,1244,1132,1024,812 ${\mathrm{\;{cm}}}^{-1}$ ;EI-MS ( $m/z$ , relative intensity): 77 (15), 108 (30), 121 (69), 171 (80), 185 (24), 216 (100).

二甲基(4-甲氧基苯基)膦酸酯(3ia) ${}^{10}$ 橙色液体(205毫克，产率84%)。 ${}^{1}\mathrm{H}$ 核磁共振(400兆赫，${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 7.74(双重峰，$J = {12.7},{8.7}\mathrm{\;{Hz}},2\mathrm{H}$ )，6.98(双重峰，$J = {8.7},{3.3}\mathrm{\;{Hz}},2\mathrm{H}$ )，3.85(单峰，3H)，3.74(双重峰，$J =$ 11.1赫兹，6H)； ${}^{13}\mathrm{C}$ 核磁共振(100兆赫，CDCl${}_{3}$ ) δ 163.0(双重峰，$J = {3.5}\mathrm{\;{Hz}}$ )，133.9(双重峰，$J = {11.2}\mathrm{\;{Hz}}$ )，117.9(双重峰，$J = {196.1}\mathrm{\;{Hz}}),{114.1}\left( {\mathrm{\;d}, J = {16.1}\mathrm{\;{Hz}}}\right) ,{55.3},{52.5}\left( {\mathrm{\;d}, J = {5.5}\mathrm{\;{Hz}}}\right) ;{}^{31}\mathrm{P}$ 核磁共振(CDC${\mathrm{l}}_{3},{162}\mathrm{{MHz}}$ ) $\delta$ 23.1红外(薄膜):2955，1600，1507，1244，1132，1024，812 ${\mathrm{\;{cm}}}^{-1}$ ；电子轰击质谱($m/z$ ，相对强度):77(15)，108(30)，121(69)，171(80)，185(24)，216(100)。

Diethyl (4-methoxyphenyl)phosphonate (3ib). ${}^{16}$ Orange liquid (215 mg,88%). ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 7.78-7.72 $\left( {\mathrm{m},2\mathrm{H}}\right) ,{6.98} - {6.95}\left( {\mathrm{m},2\mathrm{H}}\right) ,{4.17} - {4.00}\left( {\mathrm{m},4\mathrm{H}}\right) ,{3.85}\left( {\mathrm{\;s},3\mathrm{H}}\right) ,{1.31}(\mathrm{t}, J = {7.0}\mathrm{\;{Hz}}$ , 6H); ${}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 162.8 (d, $J = {3.3}\mathrm{\;{Hz}}$ ),133.7(d, $J = {11.3}\mathrm{\;{Hz}}$ ), ${119.5}(\mathrm{\;d}, J = {195.0}$ Hz), 114.0 (d, $J = {16.1}\mathrm{\;{Hz}}),{61.9}$ (d, $J = {5.3}\mathrm{\;{Hz}}),{55.3},{16.3}$ (d, $J = {6.6}\mathrm{\;{Hz}});{}^{31}\mathrm{P}$ NMR (CDCl ${}_{3},{162}$ MHz) $\delta$ 20.3; IR (film): 1600,1243,1132,1022,962,807 ${\mathrm{\;{cm}}}^{-1}$ ; EI-MS $\left( {m/z\text{ , relative intensity): 244 }}\right)$ (39),216 (43),188 (100),171 (54),135 (24),108 (59); HRMS (ESI) calcd for ${\mathrm{C}}_{11}{\mathrm{H}}_{18}{\mathrm{O}}_{4}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 245.0937; found 245.0930.

(4-甲氧基苯基)膦酸二乙酯(3ib)。${}^{16}$ 橙色液体(215毫克，产率88%)。${}^{1}\mathrm{H}$ 核磁共振氢谱(400兆赫兹，${\mathrm{{CDCl}}}_{3}$)$\delta$ 7.78 - 7.72 $\left( {\mathrm{m},2\mathrm{H}}\right) ,{6.98} - {6.95}\left( {\mathrm{m},2\mathrm{H}}\right) ,{4.17} - {4.00}\left( {\mathrm{m},4\mathrm{H}}\right) ,{3.85}\left( {\mathrm{\;s},3\mathrm{H}}\right) ,{1.31}(\mathrm{t}, J = {7.0}\mathrm{\;{Hz}}$，6H)；${}^{13}\mathrm{C}$ 核磁共振碳谱(100兆赫兹，${\mathrm{{CDCl}}}_{3}$)$\delta$ 162.8(d，$J = {3.3}\mathrm{\;{Hz}}$)，133.7(d，$J = {11.3}\mathrm{\;{Hz}}$)，${119.5}(\mathrm{\;d}, J = {195.0}$赫兹)，114.0(d，$J = {16.1}\mathrm{\;{Hz}}),{61.9}$(d，$J = {5.3}\mathrm{\;{Hz}}),{55.3},{16.3}$(d，$J = {6.6}\mathrm{\;{Hz}});{}^{31}\mathrm{P}$ 核磁共振氢谱(CDCl${}_{3},{162}$兆赫兹)$\delta$ 20.3；红外光谱(薄膜):1600、1243、1132、1022、962、807 ${\mathrm{\;{cm}}}^{-1}$；电子轰击质谱$\left( {m/z\text{ , relative intensity): 244 }}\right)$(39)，216(43)，188(100)，171(54)，135(24)，108(59)；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{11}{\mathrm{H}}_{18}{\mathrm{O}}_{4}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 245.0937；实测值为245.0930。

Diphenyl (4-methoxyphenyl)phosphonate (3ic). ${}^{16}$ Flash chromatography (silica gel, petroleum ether:ethyl acetate $= {10} : 1)$ afforded 3ic (27 mg,40%); orange liquid. ${}^{1}\mathrm{H}$ NMR (400 MHz, CDC ${\mathrm{l}}_{3}$ ) $\delta \; {7.88}\left( {\mathrm{{dd}}, J = {13.4},{8.8}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.30} - {7.26}\left( {\mathrm{\;m},4\mathrm{H}}\right) ,{7.19} - {7.11}\left( {\mathrm{\;m},6\mathrm{H}}\right) ,{6.98}\left( {\mathrm{{dd}}, J = {8.8},{3.8}\mathrm{\;{Hz}},2\mathrm{H}}\right)$ , ${3.85}\left( {\mathrm{\;s},3\mathrm{H}}\right) {;}^{13}\mathrm{C}\mathrm{{NMR}}\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 163.5}\left( {\mathrm{\;d}, J = {3.6}\mathrm{\;{Hz}}}\right) ,{150.5}\left( {\mathrm{\;d}, J = {7.4}\mathrm{\;{Hz}}}\right) ,{134.4}(\mathrm{\;d}, J =$ 11.9 Hz), 129.7, 125.0, 120.7 (d, J = 4.5 Hz), 117.8 (d, J = 200.4 Hz), 114.2 (d, J = 16.9 Hz), 55.3; ${}^{31}\mathrm{P}$ NMR (CDCl ${}_{3},{162}\mathrm{{MHz}}$ ) $\delta$ 13.3; IR (film): 1597,1489,1257,1187,1130,926,770 ${\mathrm{\;{cm}}}^{-1}$ ; EI-MS $\left( {m/z\text{ , relative intensity }}\right) : {339}\left( {72}\right) ,{247}\left( {100}\right) ,{229}\left( 8\right) ,{200}\left( {16}\right) ,{170}\left( {18}\right) ,{77}\left( {67}\right)$ ; HRMS (ESI) calcd for ${\mathrm{C}}_{19}{\mathrm{H}}_{18}{\mathrm{O}}_{4}\mathrm{\;P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{341.0937}$ ; found 341.0943.

二苯基(4-甲氧基苯基)膦酸酯(3ic)。${}^{16}$ 快速柱色谱法(硅胶，石油醚:乙酸乙酯 $= {10} : 1)$ 得到3ic(27毫克，40%);橙色液体。${}^{1}\mathrm{H}$ 核磁共振(400兆赫，CDC ${\mathrm{l}}_{3}$ ) $\delta \; {7.88}\left( {\mathrm{{dd}}, J = {13.4},{8.8}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.30} - {7.26}\left( {\mathrm{\;m},4\mathrm{H}}\right) ,{7.19} - {7.11}\left( {\mathrm{\;m},6\mathrm{H}}\right) ,{6.98}\left( {\mathrm{{dd}}, J = {8.8},{3.8}\mathrm{\;{Hz}},2\mathrm{H}}\right)$ ，${3.85}\left( {\mathrm{\;s},3\mathrm{H}}\right) {;}^{13}\mathrm{C}\mathrm{{NMR}}\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 163.5}\left( {\mathrm{\;d}, J = {3.6}\mathrm{\;{Hz}}}\right) ,{150.5}\left( {\mathrm{\;d}, J = {7.4}\mathrm{\;{Hz}}}\right) ,{134.4}(\mathrm{\;d}, J =$ 11.9赫兹)，129.7，125.0，120.7(双峰，J = 4.5赫兹)，117.8(双峰，J = 200.4赫兹)，114.2(双峰，J = 16.9赫兹)，55.3; ${}^{31}\mathrm{P}$ 核磁共振(CDCl ${}_{3},{162}\mathrm{{MHz}}$ ) $\delta$ 13.3;红外光谱(薄膜):1597,1489,1257,1187,1130,926,770 ${\mathrm{\;{cm}}}^{-1}$ ;电子轰击质谱 $\left( {m/z\text{ , relative intensity }}\right) : {339}\left( {72}\right) ,{247}\left( {100}\right) ,{229}\left( 8\right) ,{200}\left( {16}\right) ,{170}\left( {18}\right) ,{77}\left( {67}\right)$ ;高分辨质谱(电喷雾电离)计算值为 ${\mathrm{C}}_{19}{\mathrm{H}}_{18}{\mathrm{O}}_{4}\mathrm{\;P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{341.0937}$ ;实测值341.0943。

Diisopropyl (4-methoxyphenyl)phosphonate (3id) ${}^{10}$ Orange liquid (134 mg,55%). ${}^{1}$ H NMR (400 MHz, CDCl ${}_{3}$ ) $\delta$ 7.75 (dd, $J = {12.5},{8.6}\mathrm{\;{Hz}},2\mathrm{H}$ ), 8.96-8.94 (m, 2H), 4.69-4.61 (m, 2H), 3.84 (s, 3H), ${1.36}\left( {\mathrm{\;d}, J = {6.0}\mathrm{\;{Hz}},6\mathrm{H}}\right) ,{1.21}\left( {\mathrm{\;d}, J = {6.0}\mathrm{\;{Hz}},6\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR $\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 162.6}(\mathrm{\;d}, J = {3.2}$ Hz), 133.7 (d, $J = {11.4}\mathrm{\;{Hz}}$ ), 121.2 (d, $J = {195.3}\mathrm{\;{Hz}}$ ), 113.8 (d, $J = {16.1}\mathrm{\;{Hz}}$ ), 70.4 (d, $J = {5.3}\mathrm{\;{Hz}}$ ), 55.3, 23.9 (dd, $J = {24.1},{3.9}\mathrm{\;{Hz}}$ ); ${}^{31}\mathrm{P}$ NMR (CDCl ${}_{3},{162}\mathrm{{MHz}}$ ) $\delta$ 18.0; IR (film): 2979,2923,1601, 1242,1133,1016,979 ${\mathrm{\;{cm}}}^{-1}$ ; EI-MS $\left( {m/z}\right.$ , relative intensity $) : {77}\left( {14}\right) ,{108}\left( {37}\right) ,{171}\left( {55}\right) ,{188}\left( {100}\right)$ , 230 (24), 272 (16).

二异丙基(4-甲氧基苯基)膦酸酯(3id) ${}^{10}$橙色液体(134毫克，55%)。${}^{1}$氢核磁共振(400兆赫，CDCl ${}_{3}$ ) $\delta$ 7.75(双重峰，$J = {12.5},{8.6}\mathrm{\;{Hz}},2\mathrm{H}$ )，8.96 - 8.94(多重峰，2H)，4.69 - 4.61(多重峰，2H)，3.84(单峰，3H)，${1.36}\left( {\mathrm{\;d}, J = {6.0}\mathrm{\;{Hz}},6\mathrm{H}}\right) ,{1.21}\left( {\mathrm{\;d}, J = {6.0}\mathrm{\;{Hz}},6\mathrm{H}}\right) ;{}^{13}\mathrm{C}$核磁共振$\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 162.6}(\mathrm{\;d}, J = {3.2}$赫兹)，133.7(双重峰，$J = {11.4}\mathrm{\;{Hz}}$ )，121.2(双重峰，$J = {195.3}\mathrm{\;{Hz}}$ )，113.8(双重峰，$J = {16.1}\mathrm{\;{Hz}}$ )，70.4(双重峰，$J = {5.3}\mathrm{\;{Hz}}$ )，55.3，23.9(双重峰，$J = {24.1},{3.9}\mathrm{\;{Hz}}$ ); ${}^{31}\mathrm{P}$核磁共振(CDCl ${}_{3},{162}\mathrm{{MHz}}$ ) $\delta$ 18.0;红外(薄膜):2979,2923,1601,1242,1133,1016,979 ${\mathrm{\;{cm}}}^{-1}$ ;电子轰击质谱$\left( {m/z}\right.$，相对强度$) : {77}\left( {14}\right) ,{108}\left( {37}\right) ,{171}\left( {55}\right) ,{188}\left( {100}\right)$，230(24)，272(16)。

Diphenyl (4-acetylphenyl)phosphonate (3j). Flash chromatography (silica gel, petroleum ether:ethyl acetate = 5:1) afforded 3j (62 mg, 89%); orange liquid. ${}^{1}$ H NMR (400 MHz, CDCl3) δ 8.08-8.05 (m, 4H), 7.32-7.28 (m, 4H), 7.19-7.16 (m, 6H), 2.64 (s, 3H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl3) δ 197.3, ${150.1}\left( {\mathrm{\;d}, J = {7.5}\mathrm{\;{Hz}}}\right) ,{140.4}\left( {\mathrm{\;d}, J = {3.1}\mathrm{\;{Hz}}}\right) ,{132.7}\left( {\mathrm{\;d}, J = {10.4}\mathrm{\;{Hz}}}\right) ,{131.6}\left( {\mathrm{\;d}, J = {191.0}\mathrm{\;{Hz}}}\right) ,{129.8}$ , ${128.2}\left( {\mathrm{\;d}, J = {16.0}\mathrm{\;{Hz}}}\right) ,{125.4},{120.6}\left( {\mathrm{\;d}, J = {4.6}\mathrm{\;{Hz}}}\right) ,{26.8};{}^{31}\mathrm{P}$ NMR $\left( {{\mathrm{{CDCl}}}_{3},{162}\mathrm{{MHz}}}\right) {\delta 10.5};\mathrm{{IR}}$ (film): 1691,1590,1489,1263,1186,930,764 ${\mathrm{\;{cm}}}^{-1}$ ; EI-MS $\left( {m/z\text{ , relative intensity): 353 (100),337 }}\right)$ (17),259 (39),212 (17),170 (15),77 (94); HRMS (ESI) calcd for ${\mathrm{C}}_{20}{\mathrm{H}}_{18}{\mathrm{O}}_{4}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 353.0937; found 353.0939.

二苯基(4-乙酰苯基)膦酸酯(3j)。通过快速柱色谱法(硅胶，石油醚:乙酸乙酯 = 5:1)得到3j(62 mg，89%);橙色液体。${}^{1}$ 氢核磁共振(400兆赫，氘代氯仿)δ 8.08 - 8.05(多重峰，4H)，7.32 - 7.28(多重峰，4H)，7.19 - 7.16(多重峰，6H)，2.64(单峰，3H);${}^{13}\mathrm{C}$ 核磁共振(100兆赫，氘代氯仿)δ 197.3，${150.1}\left( {\mathrm{\;d}, J = {7.5}\mathrm{\;{Hz}}}\right) ,{140.4}\left( {\mathrm{\;d}, J = {3.1}\mathrm{\;{Hz}}}\right) ,{132.7}\left( {\mathrm{\;d}, J = {10.4}\mathrm{\;{Hz}}}\right) ,{131.6}\left( {\mathrm{\;d}, J = {191.0}\mathrm{\;{Hz}}}\right) ,{129.8}$ ，${128.2}\left( {\mathrm{\;d}, J = {16.0}\mathrm{\;{Hz}}}\right) ,{125.4},{120.6}\left( {\mathrm{\;d}, J = {4.6}\mathrm{\;{Hz}}}\right) ,{26.8};{}^{31}\mathrm{P}$ 核磁共振$\left( {{\mathrm{{CDCl}}}_{3},{162}\mathrm{{MHz}}}\right) {\delta 10.5};\mathrm{{IR}}$ (薄膜):1691,1590,1489,1263,1186,930,764 ${\mathrm{\;{cm}}}^{-1}$ ;电子轰击质谱$\left( {m/z\text{ , relative intensity): 353 (100),337 }}\right)$ (17)，259(39)，212(17)，170(15)，77(94);高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{20}{\mathrm{H}}_{18}{\mathrm{O}}_{4}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 353.0937;实测值为353.0939。

Diphenyl o-tolylphosphonate (3k). ${}^{16}$ Flash chromatography (silica gel, petroleum ether:ethyl acetate $= {30} : 1)$ afforded $3\mathbf{k}\left( {{45}\mathrm{{mg}},{69}\% }\right)$ ; yellow liquid. ${}^{1}\mathrm{H}$ NMR $\left( {{400}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 8.08}\left( {\mathrm{{dd}}, J = {15.2}}\right)$ , ${7.6}\mathrm{\;{Hz}},1\mathrm{H}),{7.52} - {7.28}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{7.34} - {7.27}\left( {\mathrm{\;m},6\mathrm{H}}\right) ,{7.23} - {7.12}\left( {\mathrm{\;m},6\mathrm{H}}\right) ,{2.76}\left( {\mathrm{\;s},3\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 149.3 (d, $J = {7.9}\mathrm{\;{Hz}}),{141.1}$ (d, $J = {10.7}\mathrm{\;{Hz}}),{133.5}$ (d, $J = {11.1}\mathrm{\;{Hz}}$ ),132.3 (d, $J = \; {3.1}\mathrm{\;{Hz}}),{130.5}\left( {\mathrm{\;d}, J = {15.9}\mathrm{\;{Hz}}}\right) ,{128.7},{124.7}\left( {\mathrm{\;d}, J = {15.8}\mathrm{\;{Hz}}}\right) ,{124.5}\left( {\mathrm{\;d}, J = {188.7}\mathrm{\;{Hz}}}\right) ,{124.1},{119.4} \; \left( {\mathrm{d}, J = {4.7}\mathrm{\;{Hz}}}\right) ,{20.5}\left( {\mathrm{\;d}, J = {3.6}\mathrm{\;{Hz}}}\right) ;{}^{31}\mathrm{P}\mathrm{N}\mathrm{{MR}}\left( {{\mathrm{{CDCl}}}_{3},{162}\mathrm{{MHz}}}\right) {\delta 13.1};\mathrm{{IR}}$ (film): 1593,1490, 1187,1163,1025,928,757 ${\mathrm{{cm}}}^{-1}$ ; EI-MS $\left( {m/z\text{ , relative intensity }}\right) : {324}\left( {100}\right) ,{288}\left( {19}\right) ,{231}\left( {22}\right) ,{212}$ (29), 165 (22), 94 (27), 77 (72); HRMS (ESI) calcd for ${\mathrm{C}}_{19}{\mathrm{H}}_{18}{\mathrm{O}}_{3}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 325.0988; found 325.0988.

二苯基邻甲苯基膦酸酯(3k)。${}^{16}$ 快速柱色谱法(硅胶，石油醚:乙酸乙酯 $= {30} : 1)$ 得到 $3\mathbf{k}\left( {{45}\mathrm{{mg}},{69}\% }\right)$；黄色液体。${}^{1}\mathrm{H}$ 核磁共振 $\left( {{400}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 8.08}\left( {\mathrm{{dd}}, J = {15.2}}\right)$，${7.6}\mathrm{\;{Hz}},1\mathrm{H}),{7.52} - {7.28}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{7.34} - {7.27}\left( {\mathrm{\;m},6\mathrm{H}}\right) ,{7.23} - {7.12}\left( {\mathrm{\;m},6\mathrm{H}}\right) ,{2.76}\left( {\mathrm{\;s},3\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ 核磁共振(100兆赫，${\mathrm{{CDCl}}}_{3}$) $\delta$ 149.3(双峰，$J = {7.9}\mathrm{\;{Hz}}),{141.1}$ (双峰，$J = {10.7}\mathrm{\;{Hz}}),{133.5}$ (双峰，$J = {11.1}\mathrm{\;{Hz}}$)，132.3(双峰，$J = \; {3.1}\mathrm{\;{Hz}}),{130.5}\left( {\mathrm{\;d}, J = {15.9}\mathrm{\;{Hz}}}\right) ,{128.7},{124.7}\left( {\mathrm{\;d}, J = {15.8}\mathrm{\;{Hz}}}\right) ,{124.5}\left( {\mathrm{\;d}, J = {188.7}\mathrm{\;{Hz}}}\right) ,{124.1},{119.4} \; \left( {\mathrm{d}, J = {4.7}\mathrm{\;{Hz}}}\right) ,{20.5}\left( {\mathrm{\;d}, J = {3.6}\mathrm{\;{Hz}}}\right) ;{}^{31}\mathrm{P}\mathrm{N}\mathrm{{MR}}\left( {{\mathrm{{CDCl}}}_{3},{162}\mathrm{{MHz}}}\right) {\delta 13.1};\mathrm{{IR}}$ (薄膜):1593,1490,1187,1163,1025,928,757 ${\mathrm{{cm}}}^{-1}$；电子轰击质谱 $\left( {m/z\text{ , relative intensity }}\right) : {324}\left( {100}\right) ,{288}\left( {19}\right) ,{231}\left( {22}\right) ,{212}$ (29)，165(22)，94(27)，77(72)；高分辨质谱(电喷雾电离)计算值为 ${\mathrm{C}}_{19}{\mathrm{H}}_{18}{\mathrm{O}}_{3}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 325.0988；实测值为325.0988。

Diphenyl (2-cyanophenyl)phosphonate (3l). Flash chromatography (silica gel, petroleum ether:ethyl acetate = 5:1) afforded 31 (58 mg, 87%); yellow liquid. ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl3) δ 8.30-8.24 (m, 1H), 7.91-7.87 (m, 1H), 7.74-7.71 (m, 2H), 7.33-7.28 (m, 8H), 7.20-7.14 (m, 2H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDC ${\mathrm{D}}_{1}$ ) $\delta$ 150.0 (d, $J = {8.0}\mathrm{\;{Hz}}),{135.7}$ (d, $J = {9.4}\mathrm{\;{Hz}}),{134.8}$ (d, $J = {11.6}\mathrm{\;{Hz}}),{133.4}$ (d, $J = {2.6}$ Hz), 132.5 (d, J = 14.8 Hz), 129.9 (d, J = 192.9 Hz), 129.9, 125.6, 120.6 (d, J = 4.6 Hz), 117.0 (d, J $= {5.9}\mathrm{\;{Hz}}),{114.9}\left( {\mathrm{\;d}, J = {4.6}\mathrm{\;{Hz}}}\right) ;{}^{31}\mathrm{P}$ NMR (CDC ${\mathrm{l}}_{3},{162}\mathrm{{MHz}}$ ) $\delta$ 6.1; IR (film): 2231,1589,1489, 1278,1184,944,764 ${\mathrm{{cm}}}^{-1}$ ; EI-MS (m/z, relative intensity): 335 (100),242 (39),224 (22),195 (62), 170 (20), 77 (97); HRMS (ESI) calcd for ${\mathrm{C}}_{19}{\mathrm{H}}_{15}{\mathrm{{NO}}}_{3}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 336.0784; found 336.0787.

二苯基(2-氰基苯基)膦酸酯(3l)。通过快速柱色谱法(硅胶，石油醚:乙酸乙酯=5:1)得到31(58mg，87%)；黄色液体。${}^{1}\mathrm{H}$核磁共振(400兆赫，CDCl3)δ8.30 - 8.24(多重峰，1H)，7.91 - 7.87(多重峰，1H)，7.74 - 7.71(多重峰，2H)，7.33 - 7.28(多重峰，8H)，7.20 - 7.14(多重峰，2H)；${}^{13}\mathrm{C}$核磁共振(100兆赫，CDC${\mathrm{D}}_{1}$)$\delta$150.0(双重峰，$J = {8.0}\mathrm{\;{Hz}}),{135.7}$(双重峰，$J = {9.4}\mathrm{\;{Hz}}),{134.8}$(双重峰，$J = {11.6}\mathrm{\;{Hz}}),{133.4}$(双重峰，$J = {2.6}$赫兹)，132.5(双重峰，J = 14.8赫兹)，129.9(双重峰，J = 192.9赫兹)，129.9，125.6，120.6(双重峰，J = 4.6赫兹)，117.0(双重峰，J$= {5.9}\mathrm{\;{Hz}}),{114.9}\left( {\mathrm{\;d}, J = {4.6}\mathrm{\;{Hz}}}\right) ;{}^{31}\mathrm{P}$核磁共振(CDC${\mathrm{l}}_{3},{162}\mathrm{{MHz}}$)$\delta$6.1；红外光谱(薄膜):2231,1589,1489,1278,1184,944,764${\mathrm{{cm}}}^{-1}$；电子轰击质谱(质荷比，相对强度):335(1 hundred)，242(39)，224(22)，195(62)，170(20)，77(97)；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{19}{\mathrm{H}}_{15}{\mathrm{{NO}}}_{3}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$336.078 f；实测值为336.0787。

Diphenyl (2-chlorophenyl)phosphonate (3m). Flash chromatography (silica gel, petroleum ether:ethyl acetate $= {30} : 1)$ afforded $3\mathbf{m}\left( {{55}\mathrm{{mg}},{80}\% }\right)$ ; yellow liquid. ${}^{1}\mathrm{H}$ NMR $\left( {{400}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta \; {8.17} - {8.11}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{7.54} - {7.50}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{7.39} - {7.32}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{7.31} - {7.23}\left( {\mathrm{\;m},8\mathrm{H}}\right) ,{7.16} - {7.12}\left( {\mathrm{\;m},2\mathrm{H}}\right) {;}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) $\delta$ 150.2 (d, $J = {7.4}\mathrm{\;{Hz}}$ ),137.0,136.9 (d, $J = {8.8}\mathrm{\;{Hz}}$ ),134.6,131.1 (d, $J = \; {10.6}\mathrm{\;{Hz}}),{129.8},{126.7}\left( {\mathrm{\;d}, J = {14.7}\mathrm{\;{Hz}}}\right) ,{125.9}\left( {\mathrm{\;d}, J = {196.4}\mathrm{\;{Hz}}}\right) ,{125.3},{120.6}\left( {\mathrm{\;d}, J = {4.5}\mathrm{\;{Hz}}}\right) ;{}^{31}\mathrm{P}$ NMR (CDCl3,162 MHz) $\delta$ 8.2; IR (film): 1587,1489,1268,1186,1052,940,757 ${\mathrm{\;{cm}}}^{-1}$ ; EI-MS (m/z, relative intensity): 344 (100), 309 (71), 251 (21), 215 (83), 168 (37), 77 (88); HRMS (ESI) calcd for ${\mathrm{C}}_{18}{\mathrm{H}}_{15}{\mathrm{{ClO}}}_{3}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{345.0442}$ ; found 345.0441.

二苯基(2-氯苯基)膦酸酯(3m)。快速柱色谱法(硅胶，石油醚:乙酸乙酯$= {30} : 1)$得到$3\mathbf{m}\left( {{55}\mathrm{{mg}},{80}\% }\right)$；黄色液体。${}^{1}\mathrm{H}$核磁共振$\left( {{400}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta \; {8.17} - {8.11}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{7.54} - {7.50}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{7.39} - {7.32}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{7.31} - {7.23}\left( {\mathrm{\;m},8\mathrm{H}}\right) ,{7.16} - {7.12}\left( {\mathrm{\;m},2\mathrm{H}}\right) {;}^{13}\mathrm{C}$核磁共振(100兆赫, CDCl${}_{3}$)$\delta$150.2(双峰, $J = {7.4}\mathrm{\;{Hz}}$),137.0,136.9(双峰, $J = {8.8}\mathrm{\;{Hz}}$),134.6,131.1(双峰, $J = \; {10.6}\mathrm{\;{Hz}}),{129.8},{126.7}\left( {\mathrm{\;d}, J = {14.7}\mathrm{\;{Hz}}}\right) ,{125.9}\left( {\mathrm{\;d}, J = {196.4}\mathrm{\;{Hz}}}\right) ,{125.3},{120.6}\left( {\mathrm{\;d}, J = {4.5}\mathrm{\;{Hz}}}\right) ;{}^{31}\mathrm{P}$核磁共振(CDCl3,162兆赫)$\delta$8.2；红外光谱(薄膜):1587,1489,1268,1186,1052,940,757${\mathrm{\;{cm}}}^{-1}$；电子轰击质谱(质荷比，相对强度):344(100),309(71),251(21),215(83),168(37),77(88)；高分辨质谱(电喷雾电离)计算得到${\mathrm{C}}_{18}{\mathrm{H}}_{15}{\mathrm{{ClO}}}_{3}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{345.0442}$；实测值345.0441。

Diphenyl (3-nitrophenyl)phosphonate (3n). ${}^{23}$ Flash chromatography (silica gel, petroleum ether:ethyl acetate $= {20} : 1)$ afforded $\mathbf{{3n}}\left( {{59}\mathrm{{mg}},{69}\% }\right)$ ; yellow liquid. ${}^{1}\mathrm{H}$ NMR $\left( {{400}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 8.82}(\mathrm{\;d}, J = \; {13.3}\mathrm{\;{Hz}},1\mathrm{H}),{8.46}\left( {\mathrm{\;d}, J = {8.3}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{8.29}\left( {\mathrm{\;{dd}}, J = {13.2},{7.6}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.76} - {7.70}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{7.34} - {7.30} \; \left( {\mathrm{m},4\mathrm{H}}\right) ,{7.21} - {7.17}\left( {\mathrm{\;m},6\mathrm{H}}\right) ;{}^{13}\mathrm{C}\mathrm{{NMR}}\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 149.9}\left( {\mathrm{\;d}, J = {7.9}\mathrm{\;{Hz}}}\right) ,{148.1}(\mathrm{\;d}, J = {19.1}$ Hz), 138.0 (d, J = 10.3 Hz), 130.1 (d, J = 16.5 Hz), 130.0, 129.5 (d, J = 196.5 Hz), 127.8 (d, J $= {2.9}$ Hz),127.2 (d, $J = {12.1}\mathrm{\;{Hz}}$ ),125.7,120.5 (d, $J = {4.7}\mathrm{\;{Hz}}$ ); ${}^{31}\mathrm{P}$ NMR (CDCl ${}_{3},{162}\mathrm{{MHz}}$ ) δ 8.1; IR (film): 1590, 1532, 1489, 1362, 1185, 936, 762 cm ${}^{-1}$ ; EI-MS (m/z, relative intensity): 355 (100), 338 (17), 308 (308 (47), 170 (25), 94 (17), 77 (89); HRMS (ESI) calcd for ${\mathrm{C}}_{18}{\mathrm{H}}_{15}{\mathrm{{NO}}}_{5}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 356.0682; found 356.0685.

二苯基(3-硝基苯基)膦酸酯(3n)。${}^{23}$ 快速柱色谱法(硅胶，石油醚:乙酸乙酯 $= {20} : 1)$ 得到 $\mathbf{{3n}}\left( {{59}\mathrm{{mg}},{69}\% }\right)$；黄色液体。${}^{1}\mathrm{H}$ 核磁共振 $\left( {{400}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 8.82}(\mathrm{\;d}, J = \; {13.3}\mathrm{\;{Hz}},1\mathrm{H}),{8.46}\left( {\mathrm{\;d}, J = {8.3}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{8.29}\left( {\mathrm{\;{dd}}, J = {13.2},{7.6}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.76} - {7.70}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{7.34} - {7.30} \; \left( {\mathrm{m},4\mathrm{H}}\right) ,{7.21} - {7.17}\left( {\mathrm{\;m},6\mathrm{H}}\right) ;{}^{13}\mathrm{C}\mathrm{{NMR}}\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 149.9}\left( {\mathrm{\;d}, J = {7.9}\mathrm{\;{Hz}}}\right) ,{148.1}(\mathrm{\;d}, J = {19.1}$ 赫兹)，138.0(双峰，J = 10.3赫兹)，130.1(双峰，J = 16.5赫兹)，130.0，129.5(双峰，J = 196.5赫兹)，127.8(双峰，J $= {2.9}$ 赫兹)，127.2(双峰，$J = {12.1}\mathrm{\;{Hz}}$)，125.7，120.5(双峰，$J = {4.7}\mathrm{\;{Hz}}$)；${}^{31}\mathrm{P}$ 核磁共振(CDCl ${}_{3},{162}\mathrm{{MHz}}$)δ 8.1；红外光谱(薄膜):1590、1532、1489、1362、1185、936、762厘米${}^{-1}$；电子轰击质谱(质荷比，相对强度):355(100)，338(17)，308(308(47)，170(25)，94(17)，77(89)；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{18}{\mathrm{H}}_{15}{\mathrm{{NO}}}_{5}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 356.0682；实测值为: 356.0685。

Diphenyl (3-acetamidophenyl)phosphonate (30). Flash chromatography (silica gel, petroleum ether:ethyl acetate $= 2 : 1)$ afforded ${30}\left( {{31}\mathrm{{mg}},{42}\% }\right)$ ; orange liquid. ${}^{1}\mathrm{H}$ NMR $\left( {{400}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta \; {9.30}\left( {\mathrm{\;s},1\mathrm{H}}\right) ,{8.41}\left( {\mathrm{\;d}, J = {8.2}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.92}\left( {\mathrm{\;d}, J = {15.9}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.59}\left( {\mathrm{\;{dd}}, J = {13.4},{7.6}\mathrm{\;{Hz}},1\mathrm{H}}\right)$ , ${7.48} - {7.43}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{7.26} - {7.21}\left( {\mathrm{\;m},4\mathrm{H}}\right) ,{7.14} - {7.10}\left( {\mathrm{\;m},6\mathrm{H}}\right) ,{1.82}\left( {\mathrm{\;s},3\mathrm{H}}\right) ;{}^{13}\mathrm{C}\mathrm{{NMR}}\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \; {\delta 169.4},{150.0}\left( {\mathrm{\;d}, J = {7.7}\mathrm{\;{Hz}}}\right) ,{139.7}\left( {\mathrm{\;d}, J = {20.2}\mathrm{\;{Hz}}}\right) ,{129.8},{129.6},{126.3}\left( {\mathrm{\;d}, J = {194.0}\mathrm{\;{Hz}}}\right) ,{126.2}\left( {\mathrm{\;d},}\right) \; J = {8.6}\mathrm{\;{Hz}}),{125.5},{124.5}\left( {\mathrm{\;d}, J = {3.0}\mathrm{\;{Hz}}}\right) ,{123.2}\left( {\mathrm{\;d}, J = {13.6}\mathrm{\;{Hz}}}\right) ,{120.7}\left( {\mathrm{\;d}, J = {4.3}\mathrm{\;{Hz}}}\right) ,{24.0};{}^{31}\mathrm{P}$ NMR (CDCl3,162 MHz) $\delta$ 12.8; IR (film): 3295,2926,1549,1488,1185,935,771 cm ${}^{-1}$ ; HRMS (ESI) calcd for ${\mathrm{C}}_{20}{\mathrm{H}}_{19}{\mathrm{{NO}}}_{4}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{368.1046}$ ; found 368.1051.

二苯基(3-乙酰氨基苯基)膦酸酯(30)。快速柱色谱法(硅胶，石油醚:乙酸乙酯$= 2 : 1)$得到${30}\left( {{31}\mathrm{{mg}},{42}\% }\right)$；橙色液体。${}^{1}\mathrm{H}$核磁共振$\left( {{400}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta \; {9.30}\left( {\mathrm{\;s},1\mathrm{H}}\right) ,{8.41}\left( {\mathrm{\;d}, J = {8.2}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.92}\left( {\mathrm{\;d}, J = {15.9}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.59}\left( {\mathrm{\;{dd}}, J = {13.4},{7.6}\mathrm{\;{Hz}},1\mathrm{H}}\right)$，${7.48} - {7.43}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{7.26} - {7.21}\left( {\mathrm{\;m},4\mathrm{H}}\right) ,{7.14} - {7.10}\left( {\mathrm{\;m},6\mathrm{H}}\right) ,{1.82}\left( {\mathrm{\;s},3\mathrm{H}}\right) ;{}^{13}\mathrm{C}\mathrm{{NMR}}\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \; {\delta 169.4},{150.0}\left( {\mathrm{\;d}, J = {7.7}\mathrm{\;{Hz}}}\right) ,{139.7}\left( {\mathrm{\;d}, J = {20.2}\mathrm{\;{Hz}}}\right) ,{129.8},{129.6},{126.3}\left( {\mathrm{\;d}, J = {194.0}\mathrm{\;{Hz}}}\right) ,{126.2}\left( {\mathrm{\;d},}\right) \; J = {8.6}\mathrm{\;{Hz}}),{125.5},{124.5}\left( {\mathrm{\;d}, J = {3.0}\mathrm{\;{Hz}}}\right) ,{123.2}\left( {\mathrm{\;d}, J = {13.6}\mathrm{\;{Hz}}}\right) ,{120.7}\left( {\mathrm{\;d}, J = {4.3}\mathrm{\;{Hz}}}\right) ,{24.0};{}^{31}\mathrm{P}$核磁共振(CDCl3，162兆赫)$\delta$12.8；红外光谱(薄膜):3295、2926、1549、1488、1185、935、771厘米${}^{-1}$；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{20}{\mathrm{H}}_{19}{\mathrm{{NO}}}_{4}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{368.1046}$；实测值为368.1051。

3-(Diphenoxyphosphoryl)phenyl acetate (3p). Flash chromatography (silica gel, petroleum ether:ethyl acetate = 10:1) afforded 3p (59 mg,81%); yellow liquid. ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta \; {7.82}\left( {\mathrm{{dd}}, J = {13.6},{7.6}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.72}\left( {\mathrm{\;d}, J = {15.1}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.54} - {7.49}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{7.36} - {2.28}\left( {\mathrm{\;m},5\mathrm{H}}\right)$ , ${7.19} - {7.13}\left( {\mathrm{\;m},6\mathrm{H}}\right) ,{2.31}\left( {\mathrm{\;s},3\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR $\;\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta$ 169.0,150.7 $\left( {\mathrm{d}, J = {21.3}\mathrm{\;{Hz}}}\right)$ , ${150.2}\left( {\mathrm{\;d}, J = {7.8}\mathrm{\;{Hz}}}\right) ,{130.0}\left( {\mathrm{\;d}, J = {18.1}\mathrm{\;{Hz}}}\right) ,{129.8},{129.6}\left( {\mathrm{\;d}, J = {9.8}\mathrm{\;{Hz}}}\right) ,{128.6}\left( {\mathrm{\;d}, J = {194.5}\mathrm{\;{Hz}}}\right)$ , 126.7 (d, $J = {3.4}\mathrm{\;{Hz}}$ ),125.4 (d, $J = {11.1}\mathrm{\;{Hz}}$ ),125.3,120.6 (d, $J = {4.5}\mathrm{\;{Hz}}$ ),21.1; ${}^{31}\mathrm{P}$ NMR (CDC ${\mathrm{l}}_{3}$ , ${162}\mathrm{{MHz}})\delta$ 10.6; IR (film): 1770,1590,1489,1277,1187,933,771 ${\mathrm{\;{cm}}}^{-1}$ ; EI-MS $(m/z$ , relative intensity): 368 (14), 326 (100), 233 (14), 186 (7), 170 (9), 94 (6), 77 (29); HRMS (ESI) calcd for ${\mathrm{C}}_{20}{\mathrm{H}}_{18}{\mathrm{O}}_{5}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 369.0886; found 369.0889.

乙酸3-(二苯氧基磷酰基)苯酯(3p)。通过快速柱色谱法(硅胶，石油醚:乙酸乙酯 = 10:1)得到3p(59 mg，81%);黄色液体。${}^{1}\mathrm{H}$核磁共振(400 MHz，${\mathrm{{CDCl}}}_{3}$) $\delta \; {7.82}\left( {\mathrm{{dd}}, J = {13.6},{7.6}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.72}\left( {\mathrm{\;d}, J = {15.1}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.54} - {7.49}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{7.36} - {2.28}\left( {\mathrm{\;m},5\mathrm{H}}\right)$，${7.19} - {7.13}\left( {\mathrm{\;m},6\mathrm{H}}\right) ,{2.31}\left( {\mathrm{\;s},3\mathrm{H}}\right) ;{}^{13}\mathrm{C}$核磁共振$\;\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta$ 169.0,150.7 $\left( {\mathrm{d}, J = {21.3}\mathrm{\;{Hz}}}\right)$，${150.2}\left( {\mathrm{\;d}, J = {7.8}\mathrm{\;{Hz}}}\right) ,{130.0}\left( {\mathrm{\;d}, J = {18.1}\mathrm{\;{Hz}}}\right) ,{129.8},{129.6}\left( {\mathrm{\;d}, J = {9.8}\mathrm{\;{Hz}}}\right) ,{128.6}\left( {\mathrm{\;d}, J = {194.5}\mathrm{\;{Hz}}}\right)$，126.7(d，$J = {3.4}\mathrm{\;{Hz}}$)，125.4(d，$J = {11.1}\mathrm{\;{Hz}}$)，125.3,120.6(d，$J = {4.5}\mathrm{\;{Hz}}$)，21.1; ${}^{31}\mathrm{P}$核磁共振(CDCl${\mathrm{l}}_{3}$，${162}\mathrm{{MHz}})\delta$ 10.6;红外光谱(薄膜):1770,1590,1489,1277,1187,933,771 ${\mathrm{\;{cm}}}^{-1}$;电子轰击质谱$(m/z$，相对强度):368(14)，326(100)，233(14)，186(7)，170(9)，94(6)，77(29);高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{20}{\mathrm{H}}_{18}{\mathrm{O}}_{5}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 369.0886;实测值为369.0889。

Diphenyl (3-bromophenyl)phosphonate (3q). Flash chromatography (silica gel, petroleum ether:ethyl acetate $= {30} : 1)$ afforded ${3q}$ ( ${67}\mathrm{{mg}},{86}\%$ ); yellow liquid. ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 8.11 (d, $J = \; {14.3}\mathrm{\;{Hz}},1\mathrm{H}),{7.89}\left( {\mathrm{{dd}}, J = {13.6},{7.6}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.74} - {7.32}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{7.41} - {7.37}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{7.33} - {7.29}(\mathrm{\;m}$ , 4H), 7.19- 7.15 (m, 6H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl3) δ 150.1 (d, $J = {7.7}\mathrm{\;{Hz}}$ ), 136.3 (d, $J = {2.9}\mathrm{\;{Hz}}$ ), 135.0 (d, $J = {11.1}\mathrm{\;{Hz}}$ ), ${130.7}\left( {\mathrm{\;d}, J = {9.7}\mathrm{\;{Hz}}}\right) ,{130.3}\left( {\mathrm{\;d}, J = {16.9}\mathrm{\;{Hz}}}\right) ,{129.9},{129.4}\left( {\mathrm{\;d}, J = {192.7}\mathrm{\;{Hz}}}\right)$ , 125.4,123.0 $\left( {\mathrm{d}, J = {20.7}\mathrm{\;{Hz}}}\right) ,{120.6}\left( {\mathrm{\;d}, J = {4.6}\mathrm{\;{Hz}}}\right) ;{}^{31}\mathrm{P}$ NMR (CDCl3,162 MHz) $\delta$ 9.6; IR (film): 1590,1488,1275,1186,1137,932,763 ${\mathrm{{cm}}}^{-1}$ ; EI-MS $(m/z$ , relative intensity): 389 (56),310 (16), 295 (24), 248 (16), 170 (28), 77 (100); HRMS (ESI) calcd for ${\mathrm{C}}_{18}{\mathrm{H}}_{15}{\mathrm{{BrO}}}_{3}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 388.9937; found 388.9936.

二苯基(3-溴苯基)膦酸酯(3q)。快速柱色谱法(硅胶，石油醚:乙酸乙酯$= {30} : 1)$得到${3q}$(${67}\mathrm{{mg}},{86}\%$);黄色液体。${}^{1}\mathrm{H}$核磁共振(400兆赫，${\mathrm{{CDCl}}}_{3}$)$\delta$8.11(d，$J = \; {14.3}\mathrm{\;{Hz}},1\mathrm{H}),{7.89}\left( {\mathrm{{dd}}, J = {13.6},{7.6}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.74} - {7.32}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{7.41} - {7.37}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{7.33} - {7.29}(\mathrm{\;m}$，4H)，7.19 - 7.15(m，6H);${}^{13}\mathrm{C}$核磁共振(100兆赫，CDCl₃)δ150.1(d，$J = {7.7}\mathrm{\;{Hz}}$)，136.3(d，$J = {2.9}\mathrm{\;{Hz}}$)，135.0(d，$J = {11.1}\mathrm{\;{Hz}}$)，${130.7}\left( {\mathrm{\;d}, J = {9.7}\mathrm{\;{Hz}}}\right) ,{130.3}\left( {\mathrm{\;d}, J = {16.9}\mathrm{\;{Hz}}}\right) ,{129.9},{129.4}\left( {\mathrm{\;d}, J = {192.7}\mathrm{\;{Hz}}}\right)$，125.4，123.0$\left( {\mathrm{d}, J = {20.7}\mathrm{\;{Hz}}}\right) ,{120.6}\left( {\mathrm{\;d}, J = {4.6}\mathrm{\;{Hz}}}\right) ;{}^{31}\mathrm{P}$核磁共振(CDCl₃，162兆赫)$\delta$9.6;红外光谱(薄膜):1590,1488,1275,1186,1137,932,763${\mathrm{{cm}}}^{-1}$;电子轰击质谱$(m/z$，相对强度):389(56)，310(16)，295(24)，248(16)，170(28)，77(百);高分辨质谱(电喷雾电离)计算得到${\mathrm{C}}_{18}{\mathrm{H}}_{15}{\mathrm{{BrO}}}_{3}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$388.9937;实测值388.9936。

Diphenyl (4-((triisopropylsilyl)ethynyl)phenyl)phosphonate (3ra). Flash chromatography (silica gel, petroleum ether:ethyl acetate = 50:1) afforded 3ra (64 mg, 65%); yellow liquid. ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 7.89 (d, $J = {13.8},{8.1}\mathrm{\;{Hz}},2\mathrm{H}$ ),7.59-7.56 (m,2H),7.31-7.27 (m,4H),7.18-7.13 (m,6H), ${1.13}\left( {\mathrm{\;s},{21}\mathrm{H}}\right) {;}^{13}\mathrm{C}\mathrm{{NMR}}\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 150.2}\left( {\mathrm{\;d}, J = {7.3}\mathrm{\;{Hz}}}\right) ,{132.2}\left( {\mathrm{\;d}, J = {6.6}\mathrm{\;{Hz}}}\right) ,{132.0}(\mathrm{\;d}, J \; = {12.2}\mathrm{\;{Hz}}),{129.8},{128.5}\left( {\mathrm{\;d}, J = {3.7}\mathrm{\;{Hz}}}\right) ,{126.3}\left( {\mathrm{\;d}, J = {193.4}\mathrm{\;{Hz}}}\right) ,{125.3},{120.6}\left( {\mathrm{\;d}, J = {4.6}\mathrm{\;{Hz}}}\right) ,{105.7}$ , 95.0, 18.6, 11.3; ${}^{31}\mathrm{P}$ NMR (CDCl3, 162 MHz) δ 11.5; IR (film): 2943, 2866, 1596, 1490, 1187, 1127, 932 cm ${}^{-1}$ ; EI-MS ( $m/z$ , relative intensity): 490 (3),447 (100),419 (24),405 (26),391 (33),377 (44), 77 (26); HRMS (ESI) calcd for ${\mathrm{C}}_{29}{\mathrm{H}}_{36}{\mathrm{O}}_{3}\mathrm{{PSi}}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 491.2166; found 491.2165.

二苯基(4-((三异丙基甲硅烷基)乙炔基)phenyl)膦酸酯(3ra)。快速柱色谱法(硅胶，石油醚:乙酸乙酯 = 50:1)得到3ra(64毫克，65%);黄色液体。${}^{1}\mathrm{H}$核磁共振(400兆赫，${\mathrm{{CDCl}}}_{3}$) $\delta$ 7.89(双峰，$J = {13.8},{8.1}\mathrm{\;{Hz}},2\mathrm{H}$)，7.59 - 7.56(多重峰，2H)，7.31 - 7.27(多重峰，4H)，7.18 - 7.13(多重峰，6H)，${1.13}\left( {\mathrm{\;s},{21}\mathrm{H}}\right) {;}^{13}\mathrm{C}\mathrm{{NMR}}\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 150.2}\left( {\mathrm{\;d}, J = {7.3}\mathrm{\;{Hz}}}\right) ,{132.2}\left( {\mathrm{\;d}, J = {6.6}\mathrm{\;{Hz}}}\right) ,{132.0}(\mathrm{\;d}, J \; = {12.2}\mathrm{\;{Hz}}),{129.8},{128.5}\left( {\mathrm{\;d}, J = {3.7}\mathrm{\;{Hz}}}\right) ,{126.3}\left( {\mathrm{\;d}, J = {193.4}\mathrm{\;{Hz}}}\right) ,{125.3},{120.6}\left( {\mathrm{\;d}, J = {4.6}\mathrm{\;{Hz}}}\right) ,{105.7}$，95.0，18.6，11.3; ${}^{31}\mathrm{P}$核磁共振(CDCl3，162兆赫)δ 11.5;红外(薄膜):2943，2866，1596，1490，1187，1127，932厘米${}^{-1}$;电子轰击质谱($m/z$ ,相对强度):490(3)，447(100)，419(24)，405(26)，391(33)，377(44)，77(26);高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{29}{\mathrm{H}}_{36}{\mathrm{O}}_{3}\mathrm{{PSi}}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 491.2166;实测值为491.2165。

Diphenyl (4-ethynylphenyl)phosphonate (3rb). Flash chromatography (silica gel, petroleum ether:ethyl acetate $= {20} : 1)$ afforded 3rb $\left( {{32}\mathrm{{mg}},{48}\% }\right)$ ; pale yellow liquid. ${}^{1}\mathrm{H}$ NMR $({400}\mathrm{{MHz}}$ , ${\mathrm{{CDCl}}}_{3}){\delta 7.87} - {7.81}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{7.54} - {7.51}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{7.24} - {7.18}\left( {\mathrm{\;m},4\mathrm{H}}\right) ,{7.11} - {7.06}\left( {\mathrm{\;m},6\mathrm{H}}\right) ,{3.17}\left( {\mathrm{\;s},1\mathrm{H}}\right)$ ; ${}^{13}\mathrm{C}$ NMR $\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 150.2}\left( {\mathrm{\;d}, J = {7.5}\mathrm{\;{Hz}}}\right) ,{132.3}\left( {\mathrm{\;d}, J = {2.3}\mathrm{\;{Hz}}}\right) ,{132.1}\left( {\mathrm{\;d}, J = {3.0}\mathrm{\;{Hz}}}\right)$ , ${129.8},{127.2}\left( {\mathrm{\;d}, J = {3.7}\mathrm{\;{Hz}}}\right) ,{127.2}\left( {\mathrm{\;d}, J = {193.6}\mathrm{\;{Hz}}}\right) ,{125.3},{120.6}\left( {\mathrm{\;d}, J = {4.5}\mathrm{\;{Hz}}}\right) ,{82.4},{80.5};{}^{31}\mathrm{P}$ NMR (CDCl3,162 MHz) $\delta$ 11.1; IR (film): 1593,1489,1186,1125,930,767 cm ${}^{-1}$ ; EI-MS (m/z, relative intensity): 333 (100), 241 (60), 223 (16), 194 (46), 170 (20), 77 (97); HRMS (ESI) calcd for ${\mathrm{C}}_{20}{\mathrm{H}}_{16}{\mathrm{O}}_{3}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{335.0832}$ ; found 335.0840.

二苯基(4-乙炔基苯基)膦酸酯(3rb)。快速柱色谱法(硅胶，石油醚:乙酸乙酯$= {20} : 1)$得到3rb$\left( {{32}\mathrm{{mg}},{48}\% }\right)$；浅黄色液体。${}^{1}\mathrm{H}$核磁共振$({400}\mathrm{{MHz}}$，${\mathrm{{CDCl}}}_{3}){\delta 7.87} - {7.81}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{7.54} - {7.51}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{7.24} - {7.18}\left( {\mathrm{\;m},4\mathrm{H}}\right) ,{7.11} - {7.06}\left( {\mathrm{\;m},6\mathrm{H}}\right) ,{3.17}\left( {\mathrm{\;s},1\mathrm{H}}\right)$；${}^{13}\mathrm{C}$核磁共振$\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 150.2}\left( {\mathrm{\;d}, J = {7.5}\mathrm{\;{Hz}}}\right) ,{132.3}\left( {\mathrm{\;d}, J = {2.3}\mathrm{\;{Hz}}}\right) ,{132.1}\left( {\mathrm{\;d}, J = {3.0}\mathrm{\;{Hz}}}\right)$，${129.8},{127.2}\left( {\mathrm{\;d}, J = {3.7}\mathrm{\;{Hz}}}\right) ,{127.2}\left( {\mathrm{\;d}, J = {193.6}\mathrm{\;{Hz}}}\right) ,{125.3},{120.6}\left( {\mathrm{\;d}, J = {4.5}\mathrm{\;{Hz}}}\right) ,{82.4},{80.5};{}^{31}\mathrm{P}$核磁共振(CDCl3，162兆赫)$\delta$11.1；红外光谱(薄膜):1593、1489、1186、1125、930、767厘米${}^{-1}$；电子轰击质谱(质荷比，相对强度):333(100)、241(60)、223(16)、194(46)、170(20)、77(97)；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{20}{\mathrm{H}}_{16}{\mathrm{O}}_{3}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{335.0832}$；实测值为335.0840。

Diphenyl naphthalen-1-ylphosphonate (3sa). Flash chromatography (silica gel, petroleum ether:ethyl acetate $= {20} : 1)$ afforded 3sa (25 mg, 35%); red liquid. ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) δ 8.78 (d, $J = {8.6} \; \mathrm{{Hz}},1\mathrm{H}),{8.40} - {8.34}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{8.09}\left( {\mathrm{\;d}, J = {8.3}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.94}\left( {\mathrm{\;d}, J = {8.2}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.74} - {7.69}\left( {\mathrm{\;m},1\mathrm{H}}\right)$ , ${7.63} - {7.59}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{7.56} - {7.51}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{7.31} - {7.24}\left( {\mathrm{\;m},4\mathrm{H}}\right) ,{7.20} - {7.16}\left( {\mathrm{\;m},4\mathrm{H}}\right) ,{7.14} - {7.10}\left( {\mathrm{\;m},2\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) $\delta$ 150.4 (d, $J = {7.6}\mathrm{\;{Hz}}$ ), 135.8 (d, $J = {10.0}\mathrm{\;{Hz}}$ ), 134.6 (d, $J = {3.6}\mathrm{\;{Hz}}$ ), 133.6 $\left( {\mathrm{d}, J = {13.6}\mathrm{\;{Hz}}}\right) ,{132.5}\left( {\mathrm{\;d}, J = {11.1}\mathrm{\;{Hz}}}\right) ,{129.7},{129.1},{128.0},{126.7},{126.5}\left( {\mathrm{\;d}, J = {4.3}\mathrm{\;{Hz}}}\right) ,{125.2}, \; {124.6}\left( {\mathrm{\;d}, J = {17.6}\mathrm{\;{Hz}}}\right) ,{123.2}\left( {\mathrm{\;d}, J = {187.8}\mathrm{\;{Hz}}}\right) ,{120.6}\left( {\mathrm{\;d}, J = {4.8}\mathrm{\;{Hz}}}\right) ;{}^{31}\mathrm{P}\mathrm{{NMR}}\left( {{\mathrm{{CDCl}}}_{3},{162}\mathrm{{MHz}}}\right) \delta$ 12.7; IR (film): 1591,1489,1272,1187,996,928,774 ${\mathrm{{cm}}}^{-1}$ ; EI-MS $\left( {m/z}\right.$ , relative intensity): 360 (99),267 (100),249 (42),202 (26),173 (26),127 (28),77 (59); HRMS (ESI) calcd for ${\mathrm{C}}_{22}{\mathrm{H}}_{18}{\mathrm{O}}_{3}\mathrm{P} \; {\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 361.0988; found 361.0990.

二苯基萘-1-基膦酸酯(3sa)。快速柱色谱法(硅胶，石油醚:乙酸乙酯$= {20} : 1)$)得到3sa(25毫克，35%)；红色液体。${}^{1}\mathrm{H}$核磁共振(400兆赫兹，${\mathrm{{CDCl}}}_{3}$)δ8.78(d，$J = {8.6} \; \mathrm{{Hz}},1\mathrm{H}),{8.40} - {8.34}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{8.09}\left( {\mathrm{\;d}, J = {8.3}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.94}\left( {\mathrm{\;d}, J = {8.2}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.74} - {7.69}\left( {\mathrm{\;m},1\mathrm{H}}\right)$，${7.63} - {7.59}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{7.56} - {7.51}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{7.31} - {7.24}\left( {\mathrm{\;m},4\mathrm{H}}\right) ,{7.20} - {7.16}\left( {\mathrm{\;m},4\mathrm{H}}\right) ,{7.14} - {7.10}\left( {\mathrm{\;m},2\mathrm{H}}\right) ;{}^{13}\mathrm{C}$核磁共振(100兆赫兹，CDCl${}_{3}$)$\delta$150.4(d，$J = {7.6}\mathrm{\;{Hz}}$)，135.8(d，$J = {10.0}\mathrm{\;{Hz}}$)，134.6(d，$J = {3.6}\mathrm{\;{Hz}}$)，133.6$\left( {\mathrm{d}, J = {13.6}\mathrm{\;{Hz}}}\right) ,{132.5}\left( {\mathrm{\;d}, J = {11.1}\mathrm{\;{Hz}}}\right) ,{129.7},{129.1},{128.0},{126.7},{126.5}\left( {\mathrm{\;d}, J = {4.3}\mathrm{\;{Hz}}}\right) ,{125.2}, \; {124.6}\left( {\mathrm{\;d}, J = {17.6}\mathrm{\;{Hz}}}\right) ,{123.2}\left( {\mathrm{\;d}, J = {187.8}\mathrm{\;{Hz}}}\right) ,{120.6}\left( {\mathrm{\;d}, J = {4.8}\mathrm{\;{Hz}}}\right) ;{}^{31}\mathrm{P}\mathrm{{NMR}}\left( {{\mathrm{{CDCl}}}_{3},{162}\mathrm{{MHz}}}\right) \delta$12.7；红外光谱(薄膜):1591、1489、1272、1187、996、928、774${\mathrm{{cm}}}^{-1}$；电子轰击质谱$\left( {m/z}\right.$，相对强度):360(99)，267(100)，249(42)，202(26)，173(26)，127(2)，77(59)；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{22}{\mathrm{H}}_{18}{\mathrm{O}}_{3}\mathrm{P} \; {\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$361.0988；实测值为361.0990。

Diphenyl naphthalen-2-ylphosphonate (3sb). Flash chromatography (silica gel, petroleum ether:ethyl acetate = 20:1) afforded 3sb (32 mg,44%); orange solid, m.p. = 84-85°C. ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}){\delta 8.57}\left( {\mathrm{\;d}, J = {16.4}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.95} - {7.87}\left( {\mathrm{\;m},4\mathrm{H}}\right) ,{7.64} - {7.55}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{7.30} - {7.21}\left( {\mathrm{\;m},8\mathrm{H}}\right) ,{7.14} - \; {7.11}\left( {\mathrm{\;m},2\mathrm{H}}\right) {;}^{13}\mathrm{{CNMR}}\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 150.4}\left( {\mathrm{\;d}, J = {7.5}\mathrm{\;{Hz}}}\right) ,{135.3}\left( {\mathrm{\;d}, J = {2.8}\mathrm{\;{Hz}}}\right) ,{135.2}(\mathrm{\;d}, J \; = {11.0}\mathrm{\;{Hz}}),{132.3}\left( {\mathrm{\;d}, J = {17.7}\mathrm{\;{Hz}}}\right) ,{129.8},{129.2},{128.8},{128.6}\left( {\mathrm{\;d}, J = {15.0}\mathrm{\;{Hz}}}\right) ,{127.9},{127.2},{126.4}(\mathrm{\;d}$ , $J = {10.2}\mathrm{\;{Hz}}$ ),125.2 (d, $J = {1.0}\mathrm{\;{Hz}}$ ),123.8 (d, $J = {193.1}\mathrm{\;{Hz}}$ ),120.7 (d, $J = {4.5}\mathrm{\;{Hz}}$ ); ${}^{31}\mathrm{P}$ NMR (CDC ${\mathrm{l}}_{3}$ , ${162}\mathrm{{MHz}})\delta$ 12.6; IR (film): 1589,1489,1277,1187,1085,926,771 ${\mathrm{{cm}}}^{-1}$ ; EI-MS $(m/z$ , relative intensity): 360 (100), 267 (73), 220 (22), 204 (21), 170 (11), 127 (28), 77 (67); HRMS (ESI) calcd for ${\mathrm{C}}_{22}{\mathrm{H}}_{18}{\mathrm{O}}_{3}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{361.0988}$ ; found 361.0984.

二苯基萘-2-基膦酸酯(3sb)。通过快速柱色谱法(硅胶，石油醚:乙酸乙酯 = 20:1)得到 3sb(32 mg，44%)；橙色固体，熔点 = 84 - 85°C。${}^{1}\mathrm{H}$核磁共振(400 MHz，${\mathrm{{CDCl}}}_{3}){\delta 8.57}\left( {\mathrm{\;d}, J = {16.4}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.95} - {7.87}\left( {\mathrm{\;m},4\mathrm{H}}\right) ,{7.64} - {7.55}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{7.30} - {7.21}\left( {\mathrm{\;m},8\mathrm{H}}\right) ,{7.14} - \; {7.11}\left( {\mathrm{\;m},2\mathrm{H}}\right) {;}^{13}\mathrm{{CNMR}}\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 150.4}\left( {\mathrm{\;d}, J = {7.5}\mathrm{\;{Hz}}}\right) ,{135.3}\left( {\mathrm{\;d}, J = {2.8}\mathrm{\;{Hz}}}\right) ,{135.2}(\mathrm{\;d}, J \; = {11.0}\mathrm{\;{Hz}}),{132.3}\left( {\mathrm{\;d}, J = {17.7}\mathrm{\;{Hz}}}\right) ,{129.8},{129.2},{128.8},{128.6}\left( {\mathrm{\;d}, J = {15.0}\mathrm{\;{Hz}}}\right) ,{127.9},{127.2},{126.4}(\mathrm{\;d}$，$J = {10.2}\mathrm{\;{Hz}}$)，125.2(d，$J = {1.0}\mathrm{\;{Hz}}$)，123.8(d，$J = {193.1}\mathrm{\;{Hz}}$)，120.7(d，$J = {4.5}\mathrm{\;{Hz}}$)；${}^{31}\mathrm{P}$核磁共振(CD${\mathrm{l}}_{3}$，${162}\mathrm{{MHz}})\delta$ 12.6；红外(薄膜):1589,1489,憨窨7,1187,1085,926,771 ${\mathrm{{cm}}}^{-1}$；电子轰击质谱$(m/z$，相对强度):360(100)，267(73)，220(22)，204(21)，170(11)，127(28)，77(67)；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{22}{\mathrm{H}}_{18}{\mathrm{O}}_{3}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{361.0988}$；实测值为 361.0984。

Diphenyl (4-nitronaphthalen-1-yl)phosphonate(3t). Flash chromatography (silica gel, petroleum ether:ethyl acetate = 10:1) afforded 3t (81 mg, 99%); yellow solid, m. p. = 106-109 °C. ${}^{1}\mathrm{H}$ NMR $\left( {{400}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 8.94}\left( {\mathrm{\;d}, J = {8.1}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{8.49} - {8.40}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{8.05}\left( {\mathrm{\;{dd}}, J = {7.6},{3.3}\mathrm{\;{Hz}},1\mathrm{H}}\right)$ , 7.88-7.80 (m, 2H), 7.31-7.21 (m, 4H), 7.19-7.14 (m, 6H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl3) δ 151.1 (d, J $= {4.4}\mathrm{\;{Hz}}),{150.0}\left( {\mathrm{\;d}, J = {7.4}\mathrm{\;{Hz}}}\right) ,{134.1}\left( {\mathrm{\;d}, J = {10.0}\mathrm{\;{Hz}}}\right) ,{133.9}\left( {\mathrm{\;d}, J = {12.0}\mathrm{\;{Hz}}}\right) ,{130.0},{129.6},{129.6} \; \left( {\mathrm{d}, J = {186.5}\mathrm{\;{Hz}}}\right) ,{129.3},{127.1}\left( {\mathrm{\;d}, J = {4.3}\mathrm{\;{Hz}}}\right) ,{125.6},{124.9}\left( {\mathrm{\;d}, J = {13.9}\mathrm{\;{Hz}}}\right) ,{123.6},{120.9},(\mathrm{d}, J =$ 18.0 Hz), 120.4 (d, J = 4.7 Hz); ${}^{31}\mathrm{P}$ NMR (CDCl3, 162 MHz) δ 9.5; IR (film): 1590,1257,1489, 1278,1184,937,766,689 ${\mathrm{{cm}}}^{-1}$ ; HRMS (ESI) calcd for ${\mathrm{C}}_{22}{\mathrm{H}}_{17}{\mathrm{{NO}}}_{5}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 406.0839; found 406.0844.

二苯基(4-硝基萘-1-基)膦酸酯(3t)。快速柱色谱法(硅胶，石油醚:乙酸乙酯 = 10:1)得到3t(81 mg，99%)；黄色固体，熔点 = 106 - 109 °C。${}^{1}\mathrm{H}$核磁共振$\left( {{400}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 8.94}\left( {\mathrm{\;d}, J = {8.1}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{8.49} - {8.40}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{8.05}\left( {\mathrm{\;{dd}}, J = {7.6},{3.3}\mathrm{\;{Hz}},1\mathrm{H}}\right)$，7.88 - 7.80(多重峰，2H)，7.31 - 7.21(多重峰，4H)，7.19 - 7.14(多重峰，6H)；${}^{13}\mathrm{C}$核磁共振(100 MHz，CDCl3)δ 151.1(双峰，J $= {4.4}\mathrm{\;{Hz}}),{150.0}\left( {\mathrm{\;d}, J = {7.4}\mathrm{\;{Hz}}}\right) ,{134.1}\left( {\mathrm{\;d}, J = {10.0}\mathrm{\;{Hz}}}\right) ,{133.9}\left( {\mathrm{\;d}, J = {12.0}\mathrm{\;{Hz}}}\right) ,{130.0},{129.6},{129.6} \; \left( {\mathrm{d}, J = {186.5}\mathrm{\;{Hz}}}\right) ,{129.3},{127.1}\left( {\mathrm{\;d}, J = {4.3}\mathrm{\;{Hz}}}\right) ,{125.6},{124.9}\left( {\mathrm{\;d}, J = {13.9}\mathrm{\;{Hz}}}\right) ,{123.6},{120.9},(\mathrm{d}, J =$ 18.0 Hz)，120.4(双峰，J = 4.7 Hz)；${}^{31}\mathrm{P}$核磁共振(CDCl3，162 MHz)δ 9.5；红外光谱(薄膜):1590,1257,1489,1278,1184,937,766,689 ${\mathrm{{cm}}}^{-1}$；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{22}{\mathrm{H}}_{17}{\mathrm{{NO}}}_{5}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 406.0839；实测值为406.0844。

Diphenyl (3-fluoro-4-nitrophenyl)phosphonate (3u). Flash chromatography (silica gel, petroleum ether:ethyl acetate = 10:1) afforded 3u (50 mg, 67%); yellow solid, m.p. = 81-84°C. ${}^{1}$ H NMR (400 MHz, CDCl3) δ 8.18-8.13 (m, 1H), 7.94-7.87 (m, 2H), 7.36-7.32 (m, 4H), 7.22-7.10 (m, 6H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) δ 154.9 (dd, J = 269.0, 22.82 Hz), 149.7 (d, J = 7.8 Hz), 140.2 (dd, J = 4.5, ${2.2}\mathrm{\;{Hz}}),{135.3}\left( {\mathrm{{dd}}, J = {185.9},{6.6}\mathrm{\;{Hz}}}\right) ,{130.1},{128.3}\left( {\mathrm{{dd}}, J = {9.5},{5.0}\mathrm{\;{Hz}}}\right) ,{126.5}(\mathrm{{dd}}, J = {17.7},{2.7}$ Hz), 125.9 (d, J = 0.9 Hz), 122.6 (dd, J = 22.2, 11.5 Hz), 120.4 (d, J = 4.5 Hz); ${}^{31}\mathrm{P}$ NMR (CDCl3, ${162}\mathrm{{MHz}})\delta$ 5.1; IR (film): ${1597},{1533},{1489},{1279},{1184},{942},{737}{\mathrm{\;{cm}}}^{-1}$ ; EI-MS $(m/z$ , relative intensity): ${373}\left( {98}\right) ,{326}\left( {20}\right) ,{280}\left( 8\right) ,{233}\left( {35}\right) ,{170}\left( {20}\right) ,{77}\left( {97}\right)$ ; HRMS (ESI) calcd for ${\mathrm{C}}_{18}{\mathrm{H}}_{14}{\mathrm{{FNO}}}_{5}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{374.0588}$ ; found 374.0592.

二苯基(3-氟-4-硝基苯基)膦酸酯(3u)。通过快速柱色谱法(硅胶，石油醚:乙酸乙酯 = 10:1)得到3u(50mg，67%)；黄色固体，熔点 = 81 - 84°C。${}^{1}$ 氢核磁共振谱(400兆赫兹，氘代氯仿)δ 8.18 - 8.13(多重峰，1H)，7.94 - 7.87(多重峰，2H)，7.36 - 7.32(多重峰，4H)，7.22 - 7.10(多重峰，6H)；${}^{13}\mathrm{C}$ 核磁共振谱(100兆赫兹，氘代氯仿${}_{3}$ )δ 154.9(双重双峰，J = 269.0，22.82赫兹)，149.7(双重峰，J = 7.8赫兹)，140.2(双重双峰，J = 4.5，${2.2}\mathrm{\;{Hz}}),{135.3}\left( {\mathrm{{dd}}, J = {185.9},{6.6}\mathrm{\;{Hz}}}\right) ,{130.1},{128.3}\left( {\mathrm{{dd}}, J = {9.5},{5.0}\mathrm{\;{Hz}}}\right) ,{126.5}(\mathrm{{dd}}, J = {17.7},{2.7}$ 赫兹)，125.9(双重峰，J = 0.9赫兹)，122.6(双重双峰，J = 22.2，11.5赫兹)，120.4(双重峰，J = 4.5赫兹)；${}^{31}\mathrm{P}$ 核磁共振谱(氘代氯仿，${162}\mathrm{{MHz}})\delta$ 5.1；红外光谱(薄膜):${1597},{1533},{1489},{1279},{1184},{942},{737}{\mathrm{\;{cm}}}^{-1}$ ；电子轰击质谱$(m/z$ ，相对强度):${373}\left( {98}\right) ,{326}\left( {20}\right) ,{280}\left( 8\right) ,{233}\left( {35}\right) ,{170}\left( {20}\right) ,{77}\left( {97}\right)$ ；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{18}{\mathrm{H}}_{14}{\mathrm{{FNO}}}_{5}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{374.0588}$ ；实测值为374.0592。

Diphenyl (E)-(4-(phenyldiazenyl)phenyl)phosphonate (3v). Flash chromatography (silica gel, petroleum ether:ethyl acetate $= {30} : 1)$ afforded $3\mathbf{v}\left( {{35}\mathrm{{mg}},{42}\% }\right)$ ; red liquid. ${}^{1}\mathrm{H}$ NMR $({400}\mathrm{{MHz}}$ , ${\mathrm{{CDCl}}}_{3}){\delta 8.15}$ - ${8.09}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{8.01} - {7.94}\left( {\mathrm{\;m},4\mathrm{H}}\right) ,{7.55} - {7.52}\left( {\mathrm{\;m},3\mathrm{H}}\right) ,{7.34} - {7.28}\left( {\mathrm{\;m},4\mathrm{H}}\right) ,{7.23} - {7.14}(\mathrm{\;m}$ , 6H); ${}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 155.2 (d, $J = {3.9}\mathrm{\;{Hz}}$ ),152.5,150.3 (d, $J = {7.5}\mathrm{\;{Hz}}$ ),133.4 (d, $J = \; {11.0}\mathrm{\;{Hz}}),{132.0},{129.8},{129.2},{128.9}\left( {\mathrm{\;d}, J = {202.1}\mathrm{\;{Hz}}}\right) ,{125.3},{123.2},{122.8}\left( {\mathrm{\;d}, J = {16.4}\mathrm{\;{Hz}}}\right) ,{120.6}(\mathrm{\;d}$ , $J = {4.5}\mathrm{\;{Hz}});{}^{31}\mathrm{P}\mathrm{{NMR}}\left( {{\mathrm{{CDCl}}}_{3},{162}\mathrm{{MHz}}}\right) \delta$ 11.0; IR (film): 1593,1489,1274,1187,1125,931,769 ${\mathrm{{cm}}}^{-1}$ ; HRMS (ESI) calcd for ${\mathrm{C}}_{24}{\mathrm{H}}_{20}{\mathrm{\;N}}_{2}{\mathrm{O}}_{3}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{415.1206}$ ; found 415.1212.

(E)-二苯基(4-(苯基重氮基)苯基)膦酸酯(3v)。快速柱色谱法(硅胶，石油醚:乙酸乙酯$= {30} : 1)$得到$3\mathbf{v}\left( {{35}\mathrm{{mg}},{42}\% }\right)$；红色液体。${}^{1}\mathrm{H}$核磁共振$({400}\mathrm{{MHz}}$，${\mathrm{{CDCl}}}_{3}){\delta 8.15}$ - ${8.09}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{8.01} - {7.94}\left( {\mathrm{\;m},4\mathrm{H}}\right) ,{7.55} - {7.52}\left( {\mathrm{\;m},3\mathrm{H}}\right) ,{7.34} - {7.28}\left( {\mathrm{\;m},4\mathrm{H}}\right) ,{7.23} - {7.14}(\mathrm{\;m}$，6H)；${}^{13}\mathrm{C}$核磁共振(100兆赫，${\mathrm{{CDCl}}}_{3}$)$\delta$ 155.2(d，$J = {3.9}\mathrm{\;{Hz}}$)，152.5，150.3(d，$J = {7.5}\mathrm{\;{Hz}}$)，133.4(d，$J = \; {11.0}\mathrm{\;{Hz}}),{132.0},{129.8},{129.2},{128.9}\left( {\mathrm{\;d}, J = {202.1}\mathrm{\;{Hz}}}\right) ,{125.3},{123.2},{122.8}\left( {\mathrm{\;d}, J = {16.4}\mathrm{\;{Hz}}}\right) ,{120.6}(\mathrm{\;d}$，$J = {4.5}\mathrm{\;{Hz}});{}^{31}\mathrm{P}\mathrm{{NMR}}\left( {{\mathrm{{CDCl}}}_{3},{162}\mathrm{{MHz}}}\right) \delta$ 11.0；红外光谱(薄膜):1593、1489、1274、1187、1125、931、769 ${\mathrm{{cm}}}^{-1}$；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{24}{\mathrm{H}}_{20}{\mathrm{\;N}}_{2}{\mathrm{O}}_{3}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{415.1206}$；实测值为415.1212。

Ethyl (E)-3-(4-(diphenoxyphosphoryl)phenyl)acrylate (3w). Flash chromatography (silica gel, petroleum ether:ethyl acetate $= {10} : 1)$ afforded $3\mathbf{w}\left( {{41}\mathrm{{mg}},{50}\% }\right)$ ; red liquid. ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 8.00-7.95 $\left( {\mathrm{m},2\mathrm{H}}\right) ,{7.70} - {7.62}\left( {\mathrm{m},3\mathrm{H}}\right) ,{7.32} - {7.26}\left( {\mathrm{m},4\mathrm{H}}\right) ,{7.20} - {7.14}\left( {\mathrm{\;m},6\mathrm{H}}\right) ,{6.53}\left( {\mathrm{d}, J = }\right) \; {16.0}\mathrm{\;{Hz}},1\mathrm{H}),{4.28}\left( {\mathrm{q}, J = {7.1}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{1.34}\left( {\mathrm{t}, J = {7.0}\mathrm{\;{Hz}},3\mathrm{H}}\right) ;{}^{13}\mathrm{C}\mathrm{{NMR}}\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta \; {166.4},{150.2}\left( {\mathrm{\;d}, J = {7.8}\mathrm{\;{Hz}}}\right) ,{142.8},{139.0}\left( {\mathrm{\;d}, J = {3.5}\mathrm{\;{Hz}}}\right) ,{132.8}\left( {\mathrm{\;d}, J = {10.6}\mathrm{\;{Hz}}}\right) ,{129.8},{128.4}(\mathrm{\;d}, J =$ 193.7 Hz), 128.0 (d, J = 16.1 Hz), 125.3, 121.3, 120.6 (d, J = 4.6 Hz), 60.8, 14.3; ${}^{31}\mathrm{P}$ NMR (CDCl3, 162 MHz) $\delta$ 11.3; IR (film): 2923,1713,1489,1276,1184,936,771,681 cm ${}^{-1}$ ; HRMS (ESI) calcd for ${\mathrm{C}}_{23}{\mathrm{H}}_{22}{\mathrm{O}}_{5}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{409.1199}$ ; found 409.1197.

(E)-3-(4-(二苯氧基磷酰基)苯基)丙烯酸乙酯(3w)。快速柱色谱法(硅胶，石油醚:乙酸乙酯$= {10} : 1)$得到$3\mathbf{w}\left( {{41}\mathrm{{mg}},{50}\% }\right)$；红色液体。${}^{1}\mathrm{H}$核磁共振(400兆赫，${\mathrm{{CDCl}}}_{3}$)$\delta$8.00 - 7.95$\left( {\mathrm{m},2\mathrm{H}}\right) ,{7.70} - {7.62}\left( {\mathrm{m},3\mathrm{H}}\right) ,{7.32} - {7.26}\left( {\mathrm{m},4\mathrm{H}}\right) ,{7.20} - {7.14}\left( {\mathrm{\;m},6\mathrm{H}}\right) ,{6.53}\left( {\mathrm{d}, J = }\right) \; {16.0}\mathrm{\;{Hz}},1\mathrm{H}),{4.28}\left( {\mathrm{q}, J = {7.1}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{1.34}\left( {\mathrm{t}, J = {7.0}\mathrm{\;{Hz}},3\mathrm{H}}\right) ;{}^{13}\mathrm{C}\mathrm{{NMR}}\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta \; {166.4},{150.2}\left( {\mathrm{\;d}, J = {7.8}\mathrm{\;{Hz}}}\right) ,{142.8},{139.0}\left( {\mathrm{\;d}, J = {3.5}\mathrm{\;{Hz}}}\right) ,{132.8}\left( {\mathrm{\;d}, J = {10.6}\mathrm{\;{Hz}}}\right) ,{129.8},{128.4}(\mathrm{\;d}, J =$193.7赫兹)，128.0(d，J = 16.1赫兹)，125.3，121.3，120.6(d，J = 4.6赫兹)，60.8，14.3；${}^{31}\mathrm{P}$核磁共振(CDCl3，162兆赫)$\delta$11.3；红外光谱(薄膜):2923,1713,1489,1276,1184,936,771,681厘米${}^{-1}$；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{23}{\mathrm{H}}_{22}{\mathrm{O}}_{5}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{409.1199}$；实测值为409.1197。

Diphenyl (3-(benzyloxy)phenyl)phosphonate (3x). Flash chromatography (silica gel, petroleum ether:ethyl acetate = 20:1) afforded 3x (51 mg, 61%); yellow liquid. ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 7.58-7.53 (m, 2H), 7.43-7.34 (m, 6H), 7.31-7.27 (m, 4H), 7.21-7.13 (m, 7H), 5.08 (s, 2H); ${}^{13}\mathrm{C}$ NMR $\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 158.6}\left( {\mathrm{\;d}, J = {20.1}\mathrm{\;{Hz}}}\right) ,{150.4}\left( {\mathrm{\;d}, J = {7.5}\mathrm{\;{Hz}}}\right) ,{136.3},{130.0}\left( {\mathrm{\;d}, J = {18.7}\mathrm{\;{Hz}}}\right)$ , 129.8,128.7,128.2,128.0 $\left( {\mathrm{d}, J = {191.9}\mathrm{\;{Hz}}}\right) ,{127.6},{125.2},{124.8}\left( {\mathrm{\;d}, J = {9.7}\mathrm{\;{Hz}}}\right) ,{120.6}(\mathrm{\;d}, J = {4.5} \; \mathrm{{Hz}}),{120.5}\left( {\mathrm{\;d}, J = {3.2}\mathrm{\;{Hz}}}\right) ,{117.8}\left( {\mathrm{\;d}, J = {12.0}\mathrm{\;{Hz}}}\right) ,{70.3};{}^{31}\mathrm{P}$ NMR $\left( {{\mathrm{{CDCl}}}_{3},{162}\mathrm{{MHz}}}\right) {\delta 12.1}$ ; IR (film): ${1592},{1488},{1230},{1185},{1025},{938},{755}{\mathrm{\;{cm}}}^{-1}$ ; HRMS (ESI) calcd for ${\mathrm{C}}_{25}{\mathrm{H}}_{22}{\mathrm{O}}_{4}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 417.1250; found 417.1248.

二苯基(3-(苄氧基)苯基)膦酸酯(3x)。通过快速柱色谱法(硅胶，石油醚:乙酸乙酯 = 20:1)得到3x(51 mg，61%)；黄色液体。${}^{1}\mathrm{H}$核磁共振(400 MHz，${\mathrm{{CDCl}}}_{3}$) $\delta$ 7.58 - 7.53(多重峰，2H)，7.43 - 7.34(多重峰，6H)，7.31 - 7.27(多重峰，4H)，7.21 - 7.13(多重峰，7H)，5.08(单峰，2H)；${}^{13}\mathrm{C}$核磁共振$\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 158.6}\left( {\mathrm{\;d}, J = {20.1}\mathrm{\;{Hz}}}\right) ,{150.4}\left( {\mathrm{\;d}, J = {7.5}\mathrm{\;{Hz}}}\right) ,{136.3},{130.0}\left( {\mathrm{\;d}, J = {18.7}\mathrm{\;{Hz}}}\right)$，129.8，128.7，128.2，128.0 $\left( {\mathrm{d}, J = {191.9}\mathrm{\;{Hz}}}\right) ,{127.6},{125.2},{124.8}\left( {\mathrm{\;d}, J = {9.7}\mathrm{\;{Hz}}}\right) ,{120.6}(\mathrm{\;d}, J = {4.5} \; \mathrm{{Hz}}),{120.5}\left( {\mathrm{\;d}, J = {3.2}\mathrm{\;{Hz}}}\right) ,{117.8}\left( {\mathrm{\;d}, J = {12.0}\mathrm{\;{Hz}}}\right) ,{70.3};{}^{31}\mathrm{P}$核磁共振$\left( {{\mathrm{{CDCl}}}_{3},{162}\mathrm{{MHz}}}\right) {\delta 12.1}$；红外(薄膜):${1592},{1488},{1230},{1185},{1025},{938},{755}{\mathrm{\;{cm}}}^{-1}$；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{25}{\mathrm{H}}_{22}{\mathrm{O}}_{4}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 417.1250；实测值为417.1248。

Diphenyl (3,5-difluorophenyl)phosphonate (3ya). Flash chromatography (silica gel, petroleum ether:ethyl acetate = 30:1) afforded 3ya (42 mg, 61%); yellow liquid. ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) ${\delta 7.52} - {7.46}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{7.34} - {7.30}\left( {\mathrm{\;m},4\mathrm{H}}\right) ,{7.20} - {7.16}\left( {\mathrm{\;m},6\mathrm{H}}\right) ,{7.07} - {7.02}\left( {\mathrm{\;m},1\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 162.9 (ddd, $J = {253.8},{26.8},{8.9}\mathrm{\;{Hz}}),{150.0}\left( {\mathrm{\;d}, J = {7.7}\mathrm{\;{Hz}}}\right) ,{130.8}\left( {\mathrm{\;d}, J = {196.2}\mathrm{\;{Hz}}}\right) ,{129.9}$ , ${125.6},{120.5}\left( {\mathrm{\;d}, J = {4.5}\mathrm{\;{Hz}}}\right) ,{115.3}\left( {\mathrm{\;{dd}}, J = {26.6},{10.5}\mathrm{\;{Hz}}}\right) ,{108.9}\left( {\mathrm{{dt}}, J = {24.8},{2.5}\mathrm{\;{Hz}}}\right) ;{}^{31}\mathrm{P}$ NMR $\left( {{\mathrm{{CDCl}}}_{3},{162}\mathrm{{MHz}}}\right) \delta$ 8.2; IR (film): ${1593},{1489},{1430},{1304},{1185},{936},{768}{\mathrm{\;{cm}}}^{-1}$ ; EI-MS (m/z, relative intensity): 345 (100), 253 (18), 206 (34), 170 (20), 94 (15), 77 (86); HRMS (ESI) calcd for ${\mathrm{C}}_{18}{\mathrm{H}}_{14}{\mathrm{\;F}}_{2}{\mathrm{O}}_{3}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{347.0643}$ ; found 347.0641.

二苯基(3,5-二氟苯基)膦酸酯(3ya)。通过快速柱色谱法(硅胶，石油醚:乙酸乙酯 = 30:1)得到3ya(42 mg，61%)；黄色液体。${}^{1}\mathrm{H}$核磁共振(400 MHz，${\mathrm{{CDCl}}}_{3}$) ${\delta 7.52} - {7.46}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{7.34} - {7.30}\left( {\mathrm{\;m},4\mathrm{H}}\right) ,{7.20} - {7.16}\left( {\mathrm{\;m},6\mathrm{H}}\right) ,{7.07} - {7.02}\left( {\mathrm{\;m},1\mathrm{H}}\right) ;{}^{13}\mathrm{C}$核磁共振(100 MHz，${\mathrm{{CDCl}}}_{3}$) $\delta$ 162.9(ddd，$J = {253.8},{26.8},{8.9}\mathrm{\;{Hz}}),{150.0}\left( {\mathrm{\;d}, J = {7.7}\mathrm{\;{Hz}}}\right) ,{130.8}\left( {\mathrm{\;d}, J = {196.2}\mathrm{\;{Hz}}}\right) ,{129.9}$，${125.6},{120.5}\left( {\mathrm{\;d}, J = {4.5}\mathrm{\;{Hz}}}\right) ,{115.3}\left( {\mathrm{\;{dd}}, J = {26.6},{10.5}\mathrm{\;{Hz}}}\right) ,{108.9}\left( {\mathrm{{dt}}, J = {24.8},{2.5}\mathrm{\;{Hz}}}\right) ;{}^{31}\mathrm{P}$核磁共振$\left( {{\mathrm{{CDCl}}}_{3},{162}\mathrm{{MHz}}}\right) \delta$ 8.2；红外光谱(薄膜):${1593},{1489},{1430},{1304},{1185},{936},{768}{\mathrm{\;{cm}}}^{-1}$；电子轰击质谱(m/z，相对强度):345(100)，253(18)，206(34)，170(20)，94(15)，77(86)；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{18}{\mathrm{H}}_{14}{\mathrm{\;F}}_{2}{\mathrm{O}}_{3}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{347.0643}$；实测值为347.0641。

Diphenyl (3,4-difluorophenyl)phosphonate (3yb). Flash chromatography (silica gel, petroleum ether:ethyl acetate = 20:1) afforded 3yb (56 mg, 81%); yellow solid, m.p. = 89-90 ${}^{ \circ }\mathrm{C}$ . ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl ${}_{3}$ ) $\delta$ 7.82-7.70 $\left( {\mathrm{m},2\mathrm{H}}\right) ,{7.32} - {7.28}\left( {\mathrm{\;m},5\mathrm{H}}\right) ,{7.19} - {7.14}\left( {\mathrm{\;m},6\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3})\delta$ 153.7 (ddd, $J = {257.5},{12.5},{3.8}\mathrm{\;{Hz}}$ ),150.4 (ddd, $J = {253.1},{24.0},{12.7}\mathrm{\;{Hz}}$ ),150.1 (d, $J = \; {7.5}\mathrm{\;{Hz}}),{129.9},{129.6}\left( {\mathrm{{ddd}}, J = {10.3},{7.4},{4.1}\mathrm{\;{Hz}}}\right) ,{125.5},{124.1}\left( {\mathrm{{dt}}, J = {198.3},{4.5}\mathrm{\;{Hz}}}\right) ,{121.7}(\mathrm{{ddd}}, J \; = {18.4},{11.9},{1.2}\mathrm{\;{Hz}}),{120.5}\left( {\mathrm{\;d}, J = {4.5}\mathrm{\;{Hz}}}\right) ,{118.3}\left( {\mathrm{t}, J = {18.3}\mathrm{\;{Hz}}}\right) ;{}^{31}\mathrm{P}\mathrm{{NMR}}\left( {{\mathrm{{CDCl}}}_{3},{162}\mathrm{{MHz}}}\right) \delta$ 9.1; IR (film): 1590, 1489, 1278, 1186, 1093, 934, 769 cm ${}^{-1}$ ; EI-MS ( $m/z$ , relative intensity): 345 (95),254 (29),206 (30),170 (22),77 (100),51 (19); HRMS (ESI) calcd for ${\mathrm{C}}_{18}{\mathrm{H}}_{14}{\mathrm{\;F}}_{2}{\mathrm{O}}_{3}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 347.0643; found 347.0647.

二苯基(3,4-二氟苯基)膦酸酯(3yb)。通过快速柱色谱法(硅胶，石油醚:乙酸乙酯 = 20:1)得到3yb(56 mg，81%)；黄色固体，熔点 = 89 - 90${}^{ \circ }\mathrm{C}$。${}^{1}\mathrm{H}$核磁共振(400 MHz，CDCl${}_{3}$) $\delta$ 7.82 - 7.70$\left( {\mathrm{m},2\mathrm{H}}\right) ,{7.32} - {7.28}\left( {\mathrm{\;m},5\mathrm{H}}\right) ,{7.19} - {7.14}\left( {\mathrm{\;m},6\mathrm{H}}\right) ;{}^{13}\mathrm{C}$核磁共振(100 MHz，${\mathrm{{CDCl}}}_{3})\delta$ 153.7(ddd，$J = {257.5},{12.5},{3.8}\mathrm{\;{Hz}}$)，150.4(ddd，$J = {253.1},{24.0},{12.7}\mathrm{\;{Hz}}$)，150.1(d，$J = \; {7.5}\mathrm{\;{Hz}}),{129.9},{129.6}\left( {\mathrm{{ddd}}, J = {10.3},{7.4},{4.1}\mathrm{\;{Hz}}}\right) ,{125.5},{124.1}\left( {\mathrm{{dt}}, J = {198.3},{4.5}\mathrm{\;{Hz}}}\right) ,{121.7}(\mathrm{{ddd}}, J \; = {18.4},{11.9},{1.2}\mathrm{\;{Hz}}),{120.5}\left( {\mathrm{\;d}, J = {4.5}\mathrm{\;{Hz}}}\right) ,{118.3}\left( {\mathrm{t}, J = {18.3}\mathrm{\;{Hz}}}\right) ;{}^{31}\mathrm{P}\mathrm{{NMR}}\left( {{\mathrm{{CDCl}}}_{3},{162}\mathrm{{MHz}}}\right) \delta$ 9.1；红外光谱(薄膜):1590、1489、1278、1186、1093、934、769 cm${}^{-1}$；电子轰击质谱($m/z$，相对强度):345(95)，254(29)，206(30)，170(22)，77(100)，51(19)；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{18}{\mathrm{H}}_{14}{\mathrm{\;F}}_{2}{\mathrm{O}}_{3}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 347.0643；实测值为$347.0647。

Diphenyl phenylphosphonate (3z). ${}^{16}$ Flash chromatography (silica gel, petroleum ether:ehtyl acetate = 20:1) afforded 3z (49 mg,79%); yellow solid, m.p. = 70-72°C. ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta \; {8.00} - {7.94}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{7.62} - {7.59}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{7.52} - {7.49}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{7.31} - {7.27}\left( {\mathrm{\;m},4\mathrm{H}}\right) ,{7.20} - {7.12}\left( {\mathrm{\;m},6\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) δ 150.4 (d, J = 7.5 Hz), 133.2 (d, J = 3.2 Hz), 132.3 (d, J = 10.4 Hz), 129.7, 128.7 (d, $J = {15.9}\mathrm{\;{Hz}}$ ),126.9 (d, $J = {192.8}\mathrm{\;{Hz}}$ ),125.1,120.6 (d, $J = {4.5}\mathrm{\;{Hz}}$ ); ${}^{31}\mathrm{P}$ NMR (CDCl ${}_{3},{162}$ MHz) $\delta$ 12.3; IR (film): 1591,1489,1270,1187,1131,926,773,689 ${\mathrm{{cm}}}^{-1}$ ; EI-MS $(m/z$ , relative intensity): 309 (100), 217 (43), 199 (11), 170 (34), 152 (8), 77(57); HRMS (ESI) calcd for ${\mathrm{C}}_{18}{\mathrm{H}}_{16}{\mathrm{O}}_{3}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 311.0832; found 311.0827.

二苯基苯基膦酸酯(3z)。${}^{16}$ 快速柱色谱法(硅胶,石油醚:乙酸乙酯=20:1)得到3z(49mg,79%);黄色固体,熔点=70 - 72°C。${}^{1}\mathrm{H}$ 核磁共振氢谱(400MHz,${\mathrm{{CDCl}}}_{3}$) $\delta \; {8.00} - {7.94}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{7.62} - {7.59}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{7.52} - {7.49}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{7.31} - {7.27}\left( {\mathrm{\;m},4\mathrm{H}}\right) ,{7.20} - {7.12}\left( {\mathrm{\;m},6\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ 核磁共振碳谱(100MHz, CDCl${}_{3}$) δ 150.4(d, J = 7.5Hz),133.2(d, J = 3.2Hz),132.3(d, J = 10.4Hz),129.7,128.7(d,$J = {15.9}\mathrm{\;{Hz}}$),126.9(d,$J = {192.8}\mathrm{\;{Hz}}$),125.1,120.6(d,$J = {4.5}\mathrm{\;{Hz}}$);${}^{31}\mathrm{P}$ 核磁共振氢谱(CDCl${}_{3},{162}$MHz) $\delta$ 12.3;红外光谱(薄膜):1591,1489,1270,1187,1131,926,773,689 ${\mathrm{{cm}}}^{-1}$;电子轰击质谱$(m/z$,相对强度):309(100),217(43),199(11),170(34),152(8),77(57);高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{18}{\mathrm{H}}_{16}{\mathrm{O}}_{3}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 311.0832;实测值为311.0827。

Ethyl 5-(diphenoxyphosphoryl)benzofuran-2-carboxylate (5a). Flash chromatography (silica gel, petroleum ether:ethyl acetate $= 5 : 1)$ afforded $\mathbf{{5a}}\left( {{49}\mathrm{{mg}},{58}\% }\right)$ ; orange liquid. ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 8.38(d, $J = {14.63}\mathrm{\;{Hz}},1\mathrm{H}$ ),8.06-8.00 (m,1H),7.74-7.70 (m,1H),7.58 (s,1H),7.31-7.26 $\left( {\mathrm{m},4\mathrm{H}}\right) ,{7.20} - {7.13}\left( {\mathrm{\;m},6\mathrm{H}}\right) ,{4.46}\left( {\mathrm{q}, J = {7.1}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{1.43}\left( {\mathrm{t}, J = {7.1}\mathrm{\;{Hz}},3\mathrm{H}}\right) ;{}^{13}\mathrm{C}\mathrm{{NMR}}\left( {{100}\mathrm{{MHz}}}\right.$ , ${\mathrm{{CDCl}}}_{3})\delta$ 159.0,157.8,150.3 (d, $J = {7.5}\mathrm{\;{Hz}}$ ),147.3,130.7 (d, $J = {12.2}\mathrm{\;{Hz}}$ ),129.8,128.8 (d, $J = {12.1} \; \mathrm{{Hz}}),{127.2}\left( {\mathrm{\;d}, J = {10.0}\mathrm{\;{Hz}}}\right) ,{125.3},{122.4}\left( {\mathrm{\;d}, J = {195.5}\mathrm{\;{Hz}}}\right) ,{120.6}\left( {\mathrm{\;d}, J = {4.5}\mathrm{\;{Hz}}}\right) ,{113.6},{113.1}(\mathrm{\;d}, J \; = {16.9}\mathrm{\;{Hz}}),{61.9},{14.3};{}^{31}\mathrm{P}\mathrm{{NMR}}\left( {{\mathrm{{CDCl}}}_{3},{162}\mathrm{{MHz}}}\right) \delta$ 12.3; IR (film): 1728,1590,1489,1186,1087, 932,767 ${\mathrm{\;{cm}}}^{-1}$ ; EI-MS $(m/z$ , relative intensity): 421 (100),377 (9),329 (58),207 (11),170 (12),77 (60); HRMS (ESI) calcd for ${\mathrm{C}}_{23}{\mathrm{H}}_{20}{\mathrm{O}}_{6}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{423.0992}$ ; found 423.0996.

5-(二苯氧基磷酰基)苯并呋喃-2-羧酸乙酯(5a)。快速柱色谱法(硅胶，石油醚:乙酸乙酯$= 5 : 1)$得到$\mathbf{{5a}}\left( {{49}\mathrm{{mg}},{58}\% }\right)$；橙色液体。${}^{1}\mathrm{H}$核磁共振(400兆赫，${\mathrm{{CDCl}}}_{3}$)$\delta$8.38(双峰，$J = {14.63}\mathrm{\;{Hz}},1\mathrm{H}$)，8.06 - 8.00(多重峰，1H)，7.74 - 7.70(多重峰，1H)，7.58(单峰，1H)，7.31 - 7.26$\left( {\mathrm{m},4\mathrm{H}}\right) ,{7.20} - {7.13}\left( {\mathrm{\;m},6\mathrm{H}}\right) ,{4.46}\left( {\mathrm{q}, J = {7.1}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{1.43}\left( {\mathrm{t}, J = {7.1}\mathrm{\;{Hz}},3\mathrm{H}}\right) ;{}^{13}\mathrm{C}\mathrm{{NMR}}\left( {{100}\mathrm{{MHz}}}\right.$，${\mathrm{{CDCl}}}_{3})\delta$159.0，157.8，150.3(双峰，$J = {7.5}\mathrm{\;{Hz}}$)，147.3，130.7(双峰，$J = {12.2}\mathrm{\;{Hz}}$)，129.8，128.8(双峰，$J = {12.1} \; \mathrm{{Hz}}),{127.2}\left( {\mathrm{\;d}, J = {10.0}\mathrm{\;{Hz}}}\right) ,{125.3},{122.4}\left( {\mathrm{\;d}, J = {195.5}\mathrm{\;{Hz}}}\right) ,{120.6}\left( {\mathrm{\;d}, J = {4.5}\mathrm{\;{Hz}}}\right) ,{113.6},{113.1}(\mathrm{\;d}, J \; = {16.9}\mathrm{\;{Hz}}),{61.9},{14.3};{}^{31}\mathrm{P}\mathrm{{NMR}}\left( {{\mathrm{{CDCl}}}_{3},{162}\mathrm{{MHz}}}\right) \delta$12.3；红外光谱(薄膜):1728，1590，1489，1186，1087，932，767${\mathrm{\;{cm}}}^{-1}$；电子轰击质谱$(m/z$，相对强度):421(100)，377(9)，329(58)，207(11)，170(12)，77(60)；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{23}{\mathrm{H}}_{20}{\mathrm{O}}_{6}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{423.0992}$；实测值为423.0996。

Diphenyl (5-bromopyridin-3-yl)phosphonate (5b). Flash chromatography (silica gel, petroleum ether:ethyl acetate = 15:1) afforded 5b (21 mg, 27%); white solid, m.p. = 138-141 °C. ${}^{1}$ H NMR (400 MHz, CDCl ${}_{3}$ ) $\delta$ 9.03 (d, $J = {5.6}\mathrm{\;{Hz}},1\mathrm{H}),{8.88}$ (s,1H),8.31(d, $J = {14.2}\mathrm{\;{Hz}},1\mathrm{H}),{7.35} - {7.31}$ (m,4H), 7.20-7.18 (m,6 H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) δ 154.9,150.5 (d, $J = {11.8}\mathrm{\;{Hz}}$ ),149.8 (d, $J = {7.7} \; \mathrm{{Hz}}),{142.1}\left( {\mathrm{\;d}, J = {9.1}\mathrm{\;{Hz}}}\right) ,{130.0},{125.7},{125.3}\left( {\mathrm{\;d}, J = {191.7}\mathrm{\;{Hz}}}\right) ,{121.1}\left( {\mathrm{\;d}, J = {14.9}\mathrm{\;{Hz}}}\right) ,{120.5}(\mathrm{\;d}, J \; = {4.5}\mathrm{\;{Hz}});{}^{31}\mathrm{P}\mathrm{{NMR}}\left( {{\mathrm{{CDCl}}}_{3},{162}\mathrm{{MHz}}}\right) {\delta 6.8};\mathrm{{IR}}$ (film): 1589,1488,1265,1185,1160,943,770 ${\mathrm{{cm}}}^{-1}$ ; EI-MS (m/z, relative intensity): 389 (56),310 (31),296 (36),251 (8),170 (16),77 (100); HRMS (ESI) calcd for ${\mathrm{C}}_{17}{\mathrm{H}}_{14}{\mathrm{{BrNO}}}_{3}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 389.9889; found 389.9892.

二苯基(5-溴吡啶-3-基)膦酸酯(5b)。通过快速柱色谱法(硅胶，石油醚:乙酸乙酯 = 15:1)得到5b(21 mg，27%)；白色固体，熔点 = 138 - 141 °C。${}^{1}$ 氢谱(400 MHz，CDCl ${}_{3}$ ) $\delta$ 9.03 (d，$J = {5.6}\mathrm{\;{Hz}},1\mathrm{H}),{8.88}$ (s，1H)，8.31(d，$J = {14.2}\mathrm{\;{Hz}},1\mathrm{H}),{7.35} - {7.31}$ (m，4H)，7.20 - 7.18 (m，6H)；${}^{13}\mathrm{C}$ 碳谱(100 MHz，CDCl ${}_{3}$ ) δ 154.9，150.5 (d，$J = {11.8}\mathrm{\;{Hz}}$ )，149.8 (d，$J = {7.7} \; \mathrm{{Hz}}),{142.1}\left( {\mathrm{\;d}, J = {9.1}\mathrm{\;{Hz}}}\right) ,{130.0},{125.7},{125.3}\left( {\mathrm{\;d}, J = {191.7}\mathrm{\;{Hz}}}\right) ,{121.1}\left( {\mathrm{\;d}, J = {14.9}\mathrm{\;{Hz}}}\right) ,{120.5}(\mathrm{\;d}, J \; = {4.5}\mathrm{\;{Hz}});{}^{31}\mathrm{P}\mathrm{{NMR}}\left( {{\mathrm{{CDCl}}}_{3},{162}\mathrm{{MHz}}}\right) {\delta 6.8};\mathrm{{IR}}$ (薄膜):1589，1488，1265，1185，1160，943，770 ${\mathrm{{cm}}}^{-1}$ ；电子轰击质谱(EI-MS)(m/z，相对强度):389 (56)，310 (31)，296 (36)，251 (8)，170 (16)，77 (100)；高分辨质谱(ESI)计算值为${\mathrm{C}}_{17}{\mathrm{H}}_{14}{\mathrm{{BrNO}}}_{3}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 389.9889；实测值为389.9892。

Diphenyl (6-methoxypyridin-3-yl)phosphonate (5c). Flash chromatography (silica gel, petroleum ether:ethyl acetate = 10:1) afforded 5c (17 mg, 25%); yellow oil. ${}^{1}$ H NMR (400 MHz, CDC1 ${}_{3}$ ) δ 8.72 $\left( {\mathrm{{dd}}, J = {7.0},{1.9}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{8.02}\left( {\mathrm{{ddd}}, J = {12.2},{8.6},{2.2}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.33} - {7.29}\left( {\mathrm{\;m},4\mathrm{H}}\right) ,{7.21} - {7.14}\left( {\mathrm{\;m},6\mathrm{H}}\right)$ , ${6.82}\left( {\mathrm{\;{dd}}, J = {8.6},{2.9}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{3.99}\left( {\mathrm{\;s},3\mathrm{H}}\right) ;{}^{13}\mathrm{C}\mathrm{{NMR}}\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 167.0},{152.4}(\mathrm{\;d}, J = {15.4}$ Hz), 150.2 (d, $J = {7.5}\mathrm{\;{Hz}}$ ), 141.7 (d, $J = {10.4}\mathrm{\;{Hz}}$ ), 129.8, 125.3, 120.6 (d, $J = {4.7}\mathrm{\;{Hz}}$ ), 115.3 (d, $J =$ 201.5 Hz), 111.3 (d, J = 13.3 Hz), 54.0; ${}^{31}\mathrm{P}$ NMR (CDCl3, 162 MHz) δ 11.2; IR (film) 1592, 1488, 1275,1187,1024,929,770,689 cm ${}^{-1}$ ; EI-MS (m/z, relative intensity): 340 (100),325 (9), 248 (75), 207 (12),170 (14),77 (46); HRMS (ESI) calcd for ${\mathrm{C}}_{18}{\mathrm{H}}_{17}{\mathrm{{NO}}}_{4}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{342.0890}$ ; found 342.0893. Diphenyl (6-(trifluoromethyl)pyridin-3-yl)phosphonate (5d). Flash chromatography (silica gel, petroleum ether:ethyl acetate = 15:1) afforded 5d (47 mg,63%); white solid, m.p. = 129-132 °C. ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl3) ${\delta 9.17}\left( {\mathrm{\;d}, J = {5.7}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{8.37}\left( {\mathrm{\;{dd}}, J = {13.4},{8.1}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.75}(\mathrm{\;{dd}}, J =$

二苯基(6-甲氧基吡啶-3-基)膦酸酯(5c)。通过快速柱色谱法(硅胶，石油醚:乙酸乙酯 = 10:1)得到5c(17毫克，25%)；黄色油状物。${}^{1}$ 氢核磁共振(400兆赫兹，CDC1 ${}_{3}$ ) δ 8.72 $\left( {\mathrm{{dd}}, J = {7.0},{1.9}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{8.02}\left( {\mathrm{{ddd}}, J = {12.2},{8.6},{2.2}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.33} - {7.29}\left( {\mathrm{\;m},4\mathrm{H}}\right) ,{7.21} - {7.14}\left( {\mathrm{\;m},6\mathrm{H}}\right)$ ，${6.82}\left( {\mathrm{\;{dd}}, J = {8.6},{2.9}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{3.99}\left( {\mathrm{\;s},3\mathrm{H}}\right) ;{}^{13}\mathrm{C}\mathrm{{NMR}}\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 167.0},{152.4}(\mathrm{\;d}, J = {15.4}$ 赫兹)，150.2(双峰，$J = {7.5}\mathrm{\;{Hz}}$ )，141.7(双峰，$J = {10.4}\mathrm{\;{Hz}}$ )，129.8，125.3，120.6(双峰，$J = {4.7}\mathrm{\;{Hz}}$ )，115.3(双峰，$J =$ 201.5赫兹)，111.3(耦合常数J = 13.3赫兹)，54.0；${}^{31}\mathrm{P}$ 核磁共振(CDCl3，162兆赫兹)δ 11.2；红外光谱(薄膜)1592，1488，1275，1187，1024，929，770，689厘米${}^{-1}$ ；电子轰击质谱(质荷比，相对强度):340(100)，325(9)，248(75)，207(12)，170(14)，77(46)；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{18}{\mathrm{H}}_{17}{\mathrm{{NO}}}_{4}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{342.0890}$ ；实测值342.0893。二苯基(6-(三氟甲基)吡啶-3-基)膦酸酯(5d)。通过快速柱色谱法(硅胶，石油醚:乙酸乙酯 = 15:1)得到5d(47毫克，63%)；白色固体，熔点 = 129 - 132°C。${}^{1}\mathrm{H}$ 核磁共振(400兆赫兹，CDCl3) ${\delta 9.17}\left( {\mathrm{\;d}, J = {5.7}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{8.37}\left( {\mathrm{\;{dd}}, J = {13.4},{8.1}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.75}(\mathrm{\;{dd}}, J =$

7.8,2.5Hz,1H),7.28-7.24 (m,4H),7.13-7.11 (m,6H); ${}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 152.7 (d, $J =$ 12.9 Hz), 149.7 (d, J = 7.7 Hz), 141.9 (d, J = 9.4 Hz), 130.1, 127.0 (d, J = 193.2 Hz), 125.8, 120.9 (q, $J = {276.6}\mathrm{\;{Hz}}),{120.4}\left( {\mathrm{\;d}, J = {4.7}\mathrm{\;{Hz}}}\right) ,{120.3}\left( {\mathrm{\;d}, J = {9.9}\mathrm{\;{Hz}}}\right) ;{}^{31}\mathrm{P}$ NMR (CDCl3,162 MHz) $\delta$ 6.6; IR (film): 2928,1590,1485,1335,1184,1160,1078,945 ${\mathrm{{cm}}}^{-1}$ ; EI-MS $(m/z$ , relative intensity): 378 (100), 286 (33), 239 (20), 170 (12), 94 (9), 77 (68); HRMS (ESI) calcd for ${\mathrm{C}}_{18}{\mathrm{H}}_{14}{\mathrm{\;F}}_{3}{\mathrm{{NO}}}_{3}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 380.0658; found 380.0658.

7.8, 2.5赫兹, 1H), 7.28 - 7.24 (多重峰, 4H), 7.13 - 7.11 (多重峰, 6H); ${}^{13}\mathrm{C}$ 核磁共振 (100兆赫, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 152.7 (双峰, $J =$ 12.9赫兹), 149.7 (J = 7.7赫兹的双峰), 141.9 (J = 9.4赫兹的双峰), 130.1, 127.0 (J = 193.2赫兹的双峰), 125.8, 120.9 (四重峰, $J = {276.6}\mathrm{\;{Hz}}),{120.4}\left( {\mathrm{\;d}, J = {4.7}\mathrm{\;{Hz}}}\right) ,{120.3}\left( {\mathrm{\;d}, J = {9.9}\mathrm{\;{Hz}}}\right) ;{}^{31}\mathrm{P}$ 核磁共振 (CDCl3, 162兆赫) $\delta$ 6.6; 红外 (薄膜): 2928, 1590, 1485, 1335, 1184, 1160, 1078, 945 ${\mathrm{{cm}}}^{-1}$ ; 电子轰击质谱 $(m/z$ , 相对强度): 378 (100), 286 (33), 239 (20), 170 (12), 94 (9), 77 (68); 高分辨质谱 (电喷雾电离) 计算值为 ${\mathrm{C}}_{18}{\mathrm{H}}_{14}{\mathrm{\;F}}_{3}{\mathrm{{NO}}}_{3}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 380.0658; 实测值为380.0658。

Diphenyl (2-methylbenzo[d]thiazol-5-yl)phosphonate (5e). Flash chromatography (silica gel, petroleum ether:ethyl acetate $= 5 : 1)$ afforded $\mathbf{{5e}}\left( {{23}\mathrm{{mg}},{30}\% }\right)$ ; orange solid, m.p. $= {102} - {105}^{ \circ }\mathrm{C} \cdot {}^{1}\mathrm{H}$ NMR (400 MHz, CDCl ${}_{3}$ ) $\delta$ 8.54 (d, $J = {15.3}\mathrm{\;{Hz}},1\mathrm{H}$ ), 7.97-7.88 (m, 2H), 7.30-7.26 (m, 4H), 7.22-7.18 (m,4H),7.16-7.12 (m,2H),2.87 (s,3H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) $\delta$ 168.9,153.0 (d, $J = {21.1}\mathrm{\;{Hz}}),{150.3}\left( {\mathrm{\;d}, J = {7.6}\mathrm{\;{Hz}}}\right) ,{141.1},{129.8},{127.5}\left( {\mathrm{\;d}, J = {11.7}\mathrm{\;{Hz}}}\right) ,{126.8}\left( {\mathrm{\;d}, J = {11.1}\mathrm{\;{Hz}}}\right)$ , 125.2,124.4 $\left( {\mathrm{d}, J = {195.0}\mathrm{\;{Hz}}}\right) ,{122.0}\left( {\mathrm{\;d}.J = {18.1}\mathrm{\;{Hz}}}\right) ,{120.6}\left( {\mathrm{\;d}, J = {4.6}\mathrm{\;{Hz}}}\right) ,{20.3};{}^{31}\mathrm{P}\mathrm{N}\mathrm{{MR}}\left( {\mathrm{C}{\mathrm{{DCl}}}_{3}}\right.$ , 162 MHz) $\delta$ 12.1; IR (film): ${1592},{1489},{1274},{1187},{1059},{931},{772},{689}{\mathrm{\;{cm}}}^{-1}$ ; HRMS (ESI) calcd for ${\mathrm{C}}_{20}{\mathrm{H}}_{17}{\mathrm{{NO}}}_{3}\mathrm{{PS}}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{382.0661}$ ; found 382.0663.

二苯基(2-甲基苯并[d]噻唑-5-基)膦酸酯(5e)。快速柱色谱法(硅胶，石油醚:乙酸乙酯$= 5 : 1)$得到$\mathbf{{5e}}\left( {{23}\mathrm{{mg}},{30}\% }\right)$；橙色固体，熔点$= {102} - {105}^{ \circ }\mathrm{C} \cdot {}^{1}\mathrm{H}$核磁共振(400兆赫，CDCl${}_{3}$)$\delta$8.54(双峰，$J = {15.3}\mathrm{\;{Hz}},1\mathrm{H}$)，7.97 - 7.88(多重峰，2H)，7.30 - 7.26(多重峰，4H)，7.22 - 7.18(多重峰，4H)，7.16 - 7.12(多重峰，2H)，2.87(单峰，3H)；${}^{13}\mathrm{C}$核磁共振(100兆赫，CDCl${}_{3}$)$\delta$168.9，153.0(双峰，$J = {21.1}\mathrm{\;{Hz}}),{150.3}\left( {\mathrm{\;d}, J = {7.6}\mathrm{\;{Hz}}}\right) ,{141.1},{129.8},{127.5}\left( {\mathrm{\;d}, J = {11.7}\mathrm{\;{Hz}}}\right) ,{126.8}\left( {\mathrm{\;d}, J = {11.1}\mathrm{\;{Hz}}}\right)$，125.2，124.4$\left( {\mathrm{d}, J = {195.0}\mathrm{\;{Hz}}}\right) ,{122.0}\left( {\mathrm{\;d}.J = {18.1}\mathrm{\;{Hz}}}\right) ,{120.6}\left( {\mathrm{\;d}, J = {4.6}\mathrm{\;{Hz}}}\right) ,{20.3};{}^{31}\mathrm{P}\mathrm{N}\mathrm{{MR}}\left( {\mathrm{C}{\mathrm{{DCl}}}_{3}}\right.$，162兆赫)$\delta$12.1；红外光谱(薄膜):${1592},{1489},{1274},{1187},{1059},{931},{772},{689}{\mathrm{\;{cm}}}^{-1}$；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{20}{\mathrm{H}}_{17}{\mathrm{{NO}}}_{3}\mathrm{{PS}}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }{382.0661}$；实测值为382.0663。

Ethyl 4-(bis(4-chlorophenoxy)phosphoryl)benzoate (7a). Flash chromatography (silica gel, petroleum ether:ethyl acetate = 15:1) afforded 7a (66 mg, 73%); yellow oil. ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 8.19-8.16 (m,2H),8.04-7.99 (m,2H),7.27-7.55 (m,4H),7.13-7.11 (m,4H),4.42 (q, $J = \; {7.1}\mathrm{\;{Hz}},2\mathrm{H}),{1.41}\left( {\mathrm{t}, J = {7.1}\mathrm{\;{Hz}},3\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR $\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 165.4},{148.5}\left( {\mathrm{\;d}, J = {7.6}\mathrm{\;{Hz}}}\right)$ , ${135.0}\left( {\mathrm{\;d}, J = {3.5}\mathrm{\;{Hz}}}\right) ,{132.3}\left( {\mathrm{\;d}, J = {10.8}\mathrm{\;{Hz}}}\right) ,{131.0},{130.4}\left( {\mathrm{\;d}, J = {191.1}\mathrm{\;{Hz}}}\right) ,{129.9},{129.7}(\mathrm{\;d}, J =$ 15.96 Hz), 121.9 (d, J = 4.6 Hz), 61.7, 14.3; ${}^{31}$ P NMR (CDCl3, 162 MHz) δ 11.2; IR (film): 1724, 1486,1273,1192,1102,926 ${\mathrm{{cm}}}^{-1}$ ; HRMS (ESI) calcd for ${\mathrm{C}}_{21}{\mathrm{H}}_{18}{\mathrm{{Cl}}}_{2}{\mathrm{O}}_{5}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 451.0263; found 451.0258. Ethyl 4-(bis(4-bromophenoxy)phosphoryl)benzoate (7b). Flash chromatography (silica gel, petroleum ether:ethyl acetate $= {30} : 1)$ afforded $7\mathbf{b}\left( {{80}\mathrm{{mg}},{74}\% }\right)$ ; yellow liquid. ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ 8.19-8.16 $\left( {\mathrm{m},2\mathrm{H}}\right) ,{8.04} - {7.98}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{7.42} - {7.40}\left( {\mathrm{m},4\mathrm{H}}\right) ,{7.08} - {7.05}\left( {\mathrm{\;m},4\mathrm{H}}\right) ,{4.42}(\mathrm{q}, J = \; {7.1}\mathrm{\;{Hz}},2\mathrm{H}),{1.41}\left( {\mathrm{t}, J = {7.1}\mathrm{\;{Hz}},3\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR $\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 165.4},{149.0}\left( {\mathrm{\;d}, J = {7.4}\mathrm{\;{Hz}}}\right)$ , 135.1 (d, $J = {3.3}\mathrm{\;{Hz}}$ ), ${132.9},{132.3}\left( {\mathrm{\;d}, J = {10.7}\mathrm{\;{Hz}}}\right) ,{130.3}\left( {\mathrm{\;d}, J = {191.0}\mathrm{\;{Hz}}}\right) ,{129.7}\left( {\mathrm{\;d}, J = {16.0}\mathrm{\;{Hz}}}\right)$ , 122.3 (d, $J = {4.7}\mathrm{\;{Hz}}$ ),118.6,61.7,14.3; ${}^{31}\mathrm{P}$ NMR (CDCl3,162 MHz) $\delta$ 10.8; IR (film): 1721,1482, 1273,1191,1012,926,830,759 ${\mathrm{{cm}}}^{-1}$ ; HRMS (ESI) calcd for ${\mathrm{C}}_{21}{\mathrm{H}}_{18}{\mathrm{{Br}}}_{2}{\mathrm{O}}_{5}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 538.9253; found 538.9248.

4-(双(4-氯苯氧基)磷酰基)苯甲酸乙酯(7a)。通过快速柱色谱法(硅胶，石油醚:乙酸乙酯 = 15:1)得到7a(66毫克，产率73%)；黄色油状物。${}^{1}\mathrm{H}$核磁共振(400兆赫兹，${\mathrm{{CDCl}}}_{3}$) $\delta$ 8.19 - 8.16(多重峰，2H)，8.04 - 7.99(多重峰，2H)，7.27 - 7.55(多重峰，4H)，7.13 - 7.11(多重峰，4H)，4.42(四重峰，$J = \; {7.1}\mathrm{\;{Hz}},2\mathrm{H}),{1.41}\left( {\mathrm{t}, J = {7.1}\mathrm{\;{Hz}},3\mathrm{H}}\right) ;{}^{13}\mathrm{C}$核磁共振$\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 165.4},{148.5}\left( {\mathrm{\;d}, J = {7.6}\mathrm{\;{Hz}}}\right)$，${135.0}\left( {\mathrm{\;d}, J = {3.5}\mathrm{\;{Hz}}}\right) ,{132.3}\left( {\mathrm{\;d}, J = {10.8}\mathrm{\;{Hz}}}\right) ,{131.0},{130.4}\left( {\mathrm{\;d}, J = {191.1}\mathrm{\;{Hz}}}\right) ,{129.9},{129.7}(\mathrm{\;d}, J =$ 15.96赫兹)，121.9(耦合常数J = 4.6赫兹的双峰)，61.7，14.3；${}^{31}$磷核磁共振(CDCl3，162兆赫兹)δ 11.2；红外光谱(薄膜):1724、1486、1273、1192、1102、926 ${\mathrm{{cm}}}^{-1}$；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{21}{\mathrm{H}}_{18}{\mathrm{{Cl}}}_{2}{\mathrm{O}}_{5}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 451.0263；实测值为451.0258。4-(双(4-溴苯氧基)磷酰基)苯甲酸乙酯(7b)。通过快速柱色谱法(硅胶，石油醚:乙酸乙酯$= {30} : 1)$得到$7\mathbf{b}\left( {{80}\mathrm{{mg}},{74}\% }\right)$；黄色液体。${}^{1}\mathrm{H}$核磁共振(400兆赫兹，${\mathrm{{CDCl}}}_{3}$) $\delta$ 8.19 - 8.16 $\left( {\mathrm{m},2\mathrm{H}}\right) ,{8.04} - {7.98}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{7.42} - {7.40}\left( {\mathrm{m},4\mathrm{H}}\right) ,{7.08} - {7.05}\left( {\mathrm{\;m},4\mathrm{H}}\right) ,{4.42}(\mathrm{q}, J = \; {7.1}\mathrm{\;{Hz}},2\mathrm{H}),{1.41}\left( {\mathrm{t}, J = {7.1}\mathrm{\;{Hz}},3\mathrm{H}}\right) ;{}^{13}\mathrm{C}$核磁共振$\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 165.4},{149.0}\left( {\mathrm{\;d}, J = {7.4}\mathrm{\;{Hz}}}\right)$，135.1(耦合常数为$J = {3.3}\mathrm{\;{Hz}}$的双峰)，${132.9},{132.3}\left( {\mathrm{\;d}, J = {10.7}\mathrm{\;{Hz}}}\right) ,{130.3}\left( {\mathrm{\;d}, J = {191.0}\mathrm{\;{Hz}}}\right) ,{129.7}\left( {\mathrm{\;d}, J = {16.0}\mathrm{\;{Hz}}}\right)$，122.3(耦合常数为$J = {4.7}\mathrm{\;{Hz}}$的双峰)，118.6，61.7，14.3；${}^{31}\mathrm{P}$磷核磁共振(CDCl3，162兆赫兹) $\delta$ 10.8；红外光谱(薄膜):1721、1482、1273、1191、1012、926、830、759 ${\mathrm{{cm}}}^{-1}$；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{21}{\mathrm{H}}_{18}{\mathrm{{Br}}}_{2}{\mathrm{O}}_{5}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 538.9253；实测值为538.9248。

Ethyl 4-(bis(4-methoxyphenoxy)phosphoryl)benzoate (7c). Flash chromatography (silica gel, petroleum ether:ethyl acetate $= {20} : 1)$ afforded $7\mathbf{c}\left( {{45}\mathrm{{mg}},{51}\% }\right)$ ; pale yellow liquid. ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl ${}_{3}$ ) δ 8.17-8.14 (m, 2H), 8.07-8.01 (m, 2H), 7.20-7.16 (m, 2H), 6.80-6.69 (m, 6H), 4.41 (q, $J = {7.1}\mathrm{\;{Hz}},2\mathrm{H}),{3.74}\left( {\mathrm{\;s},6\mathrm{H}}\right) ,{1.41}\left( {\mathrm{t}, J = {7.1}\mathrm{\;{Hz}},3\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR $\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 165.5},{160.7}$ , ${151.0}\left( {\mathrm{\;d}, J = {7.6}\mathrm{\;{Hz}}}\right) ,{134.6}\left( {\mathrm{\;d}, J = {3.3}\mathrm{\;{Hz}}}\right) ,{132.3}\left( {\mathrm{\;d}, J = {10.5}\mathrm{\;{Hz}}}\right) ,{131.3}\left( {\mathrm{\;d}, J = {191.6}\mathrm{\;{Hz}}}\right) ,{129.5}(\mathrm{\;d}$ , $J = {15.7}\mathrm{\;{Hz}}),{112.6}\left( {\mathrm{\;d}, J = {4.4}\mathrm{\;{Hz}}}\right) ,{111.3},{61.6},{55.4},{14.3};{}^{31}\mathrm{P}$ NMR $\left( {{\mathrm{{CDCl}}}_{3},{162}\mathrm{{MHz}}}\right) \delta$ 10.1; IR (film): ${1722},{1607},{1490},{1270},{1133},{961},{858}{\mathrm{\;{cm}}}^{-1}$ ; HRMS (ESI) calcd for ${\mathrm{C}}_{23}{\mathrm{H}}_{24}{\mathrm{O}}_{7}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$ 443.1254; found 443.1263.

4-(双(4-甲氧基苯氧基)磷酰基)苯甲酸乙酯(7c)。快速柱色谱法(硅胶，石油醚:乙酸乙酯$= {20} : 1)$得到$7\mathbf{c}\left( {{45}\mathrm{{mg}},{51}\% }\right)$；浅黄色液体。${}^{1}\mathrm{H}$核磁共振(400兆赫，CDCl${}_{3}$)δ8.17 - 8.14(m，2H)，8.07 - 8.01(m，2H)，7.20 - 7.16(m，2H)，6.80 - 6.69(m，6H)，4.41(q，$J = {7.1}\mathrm{\;{Hz}},2\mathrm{H}),{3.74}\left( {\mathrm{\;s},6\mathrm{H}}\right) ,{1.41}\left( {\mathrm{t}, J = {7.1}\mathrm{\;{Hz}},3\mathrm{H}}\right) ;{}^{13}\mathrm{C}$核磁共振$\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) {\delta 165.5},{160.7}$，${151.0}\left( {\mathrm{\;d}, J = {7.6}\mathrm{\;{Hz}}}\right) ,{134.6}\left( {\mathrm{\;d}, J = {3.3}\mathrm{\;{Hz}}}\right) ,{132.3}\left( {\mathrm{\;d}, J = {10.5}\mathrm{\;{Hz}}}\right) ,{131.3}\left( {\mathrm{\;d}, J = {191.6}\mathrm{\;{Hz}}}\right) ,{129.5}(\mathrm{\;d}$，$J = {15.7}\mathrm{\;{Hz}}),{112.6}\left( {\mathrm{\;d}, J = {4.4}\mathrm{\;{Hz}}}\right) ,{111.3},{61.6},{55.4},{14.3};{}^{31}\mathrm{P}$核磁共振$\left( {{\mathrm{{CDCl}}}_{3},{162}\mathrm{{MHz}}}\right) \delta$10.1；红外光谱(薄膜):${1722},{1607},{1490},{1270},{1133},{961},{858}{\mathrm{\;{cm}}}^{-1}$；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{23}{\mathrm{H}}_{24}{\mathrm{O}}_{7}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$443.1254；实测值为443.1263。

Ethyl 4-(bis(4-(tert-butyl)phenoxy)phosphoryl)benzoate (7d). Flash chromatography (silica gel, petroleum ether:ethyl acetate = 50:1) afforded 7d (88 mg, 89%); pale yellow liquid. ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl ${}_{3}$ ) δ 8.17-8.14 (m, 2H), 8.08-8.02 (m, 2H), 7.30-7.28 (m, 4H), 7.10-7.08 (m, 4H), 4.41 (q, $J = {7.1}\mathrm{\;{Hz}},2\mathrm{H}),{1.41}$ (t, $J = {7.1}\mathrm{\;{Hz}},3\mathrm{H}),{1.27}$ (s,18H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) δ 165.6,148.2, ${147.8}\left( {\mathrm{\;d}, J = {7.6}\mathrm{\;{Hz}}}\right) ,{134.5}\left( {\mathrm{\;d}, J = {3.2}\mathrm{\;{Hz}}}\right) ,{132.4}\left( {\mathrm{\;d}, J = {10.5}\mathrm{\;{Hz}}}\right) ,{131.7}(\mathrm{\;d}, J = {191.1}\mathrm{\;{Hz}}),{129.5}(\mathrm{\;d}$ , $J = {15.7}\mathrm{\;{Hz}}),{126.7},{119.9}\left( {\mathrm{\;d}, J = {4.4}\mathrm{\;{Hz}}}\right) ,{61.6},{34.4},{31.4},{14.3};{}^{31}\mathrm{P}$ NMR (CDC ${\mathrm{l}}_{3},{162}\mathrm{{MHz}}$ ) ${\delta 10.8}$ ; IR (film): ${2963},{1724},{1508},{1272},{1169},{947}{\mathrm{\;{cm}}}^{-1}$ ; HRMS (ESI) calcd for ${\mathrm{C}}_{29}{\mathrm{H}}_{36}{\mathrm{O}}_{5}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$

4-(双(4-(叔丁基)苯氧基)磷酰基)苯甲酸乙酯(7d)。快速柱色谱法(硅胶，石油醚:乙酸乙酯 = 50:1)得到7d(88毫克，89%)；浅黄色液体。${}^{1}\mathrm{H}$核磁共振(400兆赫，CDCl ${}_{3}$ )δ 8.17 - 8.14(多重峰，2H)，8.08 - 8.02(多重峰，2H)，7.30 - 7.28(多重峰，4H)，7.10 - 7.08(多重峰，4H)，4.41(四重峰，$J = {7.1}\mathrm{\;{Hz}},2\mathrm{H}),{1.41}$ (三重峰，$J = {7.1}\mathrm{\;{Hz}},3\mathrm{H}),{1.27}$ (单峰，18H)；${}^{13}\mathrm{C}$核磁共振(100兆赫，CDCl ${}_{3}$ )δ 165.6，148.2，${147.8}\left( {\mathrm{\;d}, J = {7.6}\mathrm{\;{Hz}}}\right) ,{134.5}\left( {\mathrm{\;d}, J = {3.2}\mathrm{\;{Hz}}}\right) ,{132.4}\left( {\mathrm{\;d}, J = {10.5}\mathrm{\;{Hz}}}\right) ,{131.7}(\mathrm{\;d}, J = {191.1}\mathrm{\;{Hz}}),{129.5}(\mathrm{\;d}$ ，$J = {15.7}\mathrm{\;{Hz}}),{126.7},{119.9}\left( {\mathrm{\;d}, J = {4.4}\mathrm{\;{Hz}}}\right) ,{61.6},{34.4},{31.4},{14.3};{}^{31}\mathrm{P}$核磁共振(CDC ${\mathrm{l}}_{3},{162}\mathrm{{MHz}}$ ) ${\delta 10.8}$ ；红外光谱(薄膜):${2963},{1724},{1508},{1272},{1169},{947}{\mathrm{\;{cm}}}^{-1}$ ；高分辨质谱(电喷雾电离)计算值为${\mathrm{C}}_{29}{\mathrm{H}}_{36}{\mathrm{O}}_{5}\mathrm{P}{\left\lbrack \mathrm{M} + \mathrm{H}\right\rbrack }^{ + }$

495.2295, found 495.2310.

495.2295,实测值495.2310。

ASSOCIATED CONTENT

相关内容

Supporting Information

支持信息

Copies of ${}^{1}\mathrm{H}$ and ${}^{13}\mathrm{C}$ spectra for all the products. This material is available free of charge via the Internet at http://pubs.acs.org.

所有产品的${}^{1}\mathrm{H}$和${}^{13}\mathrm{C}$光谱副本。该材料可通过互联网免费获取，网址为http://pubs.acs.org。

AUTHOR INFORMATION

作者信息

Corresponding Author

通讯作者

Notes

注释

The authors declare no competing financial interest.

作者声明不存在利益冲突。

ACKNOWLEDGMENTS

致谢

We are grateful to National Basic Research Program of China (973 Program, No. 2015CB856600) and Natural Science Foundation of China (Grant 21472004 and 21332002) for the financial support.

我们感谢中国国家基础研究计划(973计划，项目编号2015CB856600)以及中国国家自然科学基金(资助号21472004和21332002)提供的资金支持。

REFERENCES

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