Catalyst-Free Imidation of Allyl Sulfides with Chloramine-T and Subsequent [2,3]-Sigmatropic Rearrangement

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

Jiang, Yubo ${}^{a, b, c}$ (江玉波) Mo, Fanyang ${}^{c}$ (莫凡洋) Qiu, Dić(邱迪) Kuang, Chunxiang**(匡春香) Zhang, Yan ${}^{c}$ (张艳) Wang, Jianbo**(王剑波)

Jiang, Yubo ${}^{a, b, c}$ (江玉波) Mo, Fanyang ${}^{c}$ (莫凡洋) Qiu, Dić(邱迪) Kuang, Chunxiang**(匡春香) Zhang, Yan ${}^{c}$ (张艳) Wang, Jianbo**(王剑波)

${}^{a}$ Department of Chemistry, Tongji University, Shanghai 200092, China ${}^{b}$ Faculty of Science, Kunming University of Science and Technology, Kunming, Yunnan 650093, China ${}^{c}$ Beijing National Laboratory of Molecular Sciences (BNLMS) and Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871, China

${}^{a}$ 同济大学化学系，上海200092，中国 ${}^{b}$ 昆明理工大学理学院，昆明，云南650093，中国 ${}^{c}$ 北京分子科学国家实验室(BNLMS)及北京大学化学与分子工程学院生物有机化学与分子工程教育部重点实验室，北京100871，中国

A facile synthesis of various allyl sulfonamides based on imidation of allyl sulfides with chloramine-T and subsequent [2,3]-sigmatropic rearrangement has been achieved without metal catalysts. The reaction completes smoothly within ${10}\mathrm{\;{min}}$ , providing excellent yields in environment friendly solvent of alcohol. Functional groups such as bromine, hydroxyl, protected amido and aldehyde are tolerant under this condition.

基于烯丙基硫醚与氯胺 -T的亚胺化反应及后续的[2,3]-σ迁移重排，已实现了各种烯丙基磺酰胺的简便合成，且无需金属催化剂。该反应在${10}\mathrm{\;{min}}$内顺利完成，在环境友好的醇类溶剂中提供了优异的产率。在此条件下，溴、羟基、保护的酰胺基和醛等官能团具有耐受性。

Keywords allyl sulfonamide, allyl sulfide, transition-metal-free reaction, sigmatropic rearrangement, nitrene

关键词 烯丙基磺酰胺，烯丙基硫醚，无过渡金属反应，σ迁移重排，氮烯

Introduction

引言

The construction of carbon-nitrogen bond is one of the major topics in organic synthesis as the nitrogen is ubiquitous in natural products and biologically active agents. Similar to the related carbene species, nitrene is highly reactive species and can undergo various transformations, such as C-H bond insertions and aziridina-tions. ${}^{\left\lbrack 1\right\rbrack }$ These reactions can serve as useful approaches toward carbon-nitrogen bond formation. The reaction of nitrene with sulfides affords sulfilimines, which have diverse reactivities. ${}^{\left\lbrack 2\right\rbrack }$ When allylsulfides are employed in this reaction, the corresponding sulfilimines bearing allylic substituent will undergo [2,3]-sigmatropic rearrangement to afford allylic amides. ${}^{\left\lbrack 3\right\rbrack }$ This unique transformation is considered as an interesting method for the synthesis of allylic amine derivatives.

碳 - 氮键的构建是有机合成中的主要课题之一，因为氮在天然产物和生物活性剂中普遍存在。与相关的卡宾物种类似，氮烯是高活性物种，可进行各种转化，如C - H键插入和氮杂环丙烷化反应。${}^{\left\lbrack 1\right\rbrack }$ 这些反应可作为形成碳 - 氮键的有用方法。氮烯与硫化物反应生成亚磺酰亚胺，其具有多种反应活性。${}^{\left\lbrack 2\right\rbrack }$ 当烯丙基硫化物用于该反应时，相应的带有烯丙基取代基的亚磺酰亚胺将进行[2,3] - 迁移重排以得到烯丙基酰胺。${}^{\left\lbrack 3\right\rbrack }$ 这种独特的转化被认为是合成烯丙基胺衍生物的一种有趣方法。

Copper-catalyzed formation of sulfimides and se-lenimides and subsequent [2,3]-sigmatropic rearrangement to the corresponding allylic sulfonamides using [ $N$ -( $p$ -tolylsulfonyl)imino] phenyliodinane (TsN = IPh) as nitrogen source has been reported by Uemura and coworkers. ${}^{\left\lbrack 4\right\rbrack }$ The iron-catalyzed imidation of sulfides with tert-butoxycarbonyl azide and [2,3]-sigmatropic rearrangement has been investigated by ${\operatorname{Bach}}^{\left\lbrack 5\right\rbrack }$ and van Vranken ${}^{\left\lbrack 6\right\rbrack }$ respectively. Very recently, the synthesis of allenamides has been achieved by Armstrong ${}^{\left\lbrack 7\right\rbrack }$ through this rearrangement by employing CbzNHOTf as the nitrene precursor.

Uemura及其同事报道了使用[$N$ - ($p$ - 甲苯磺酰基)亚氨基]苯基碘鎓盐(TsN = IPh)作为氮源，铜催化形成亚磺酰亚胺和亚硒酰亚胺，随后进行[2,3] - 迁移重排生成相应的烯丙基亚磺酰胺。${}^{\left\lbrack 4\right\rbrack }$ ${\operatorname{Bach}}^{\left\lbrack 5\right\rbrack }$和van Vranken ${}^{\left\lbrack 6\right\rbrack }$分别研究了铁催化的硫化物与叔丁氧羰基叠氮化物的亚胺化反应及[2,3] - 迁移重排。最近，Armstrong ${}^{\left\lbrack 7\right\rbrack }$通过使用CbzNHOTf作为氮烯前体，通过这种重排反应实现了丙二烯酰胺的合成。

As the continuation of our own interest in [2,3]- sigmatropic rearrangement of sulfide ylides ${}^{\left\lbrack 8\right\rbrack }$ and transition-metal-free transformations, ${}^{\left\lbrack 9\right\rbrack }$ we have investigated the metal-free imidation of allyl sulfides 1 by using chloramine-T (TsNClNa) as the nitrogen source. ${}^{\left\lbrack 3\right\rbrack }$ The subsequent [2,3]-sigmatropic rearrangement affords allyl sulfonamides 2 in good yields (Scheme 1).

作为我们自身对硫化物叶立德的[2,3] - 迁移重排${}^{\left\lbrack 8\right\rbrack }$和无过渡金属转化${}^{\left\lbrack 9\right\rbrack }$兴趣的延续，我们研究了使用氯胺 - T(TsNClNa)作为氮源对烯丙基硫化物1进行无金属亚胺化反应。${}^{\left\lbrack 3\right\rbrack }$ 随后的[2,3] - 迁移重排以良好的产率得到烯丙基亚磺酰胺2(方案1)。

Scheme 1 Imidation/[2,3]-sigmatropic rearrangement

方案1 亚胺化/[2,3] - 迁移重排

The products contains sulfonamide segment which serves as one of the common structural features in drugs. ${}^{\left\lbrack {10}\right\rbrack }$ Furthermore, they can also be converted to allyl sulfonamides and allyl amides by removal of the protecting group (Ts). ${}^{\left\lbrack 5,{11}\right\rbrack }$

产物含有磺酰胺片段，这是药物中常见的结构特征之一。${}^{\left\lbrack {10}\right\rbrack }$ 此外，通过去除保护基(Ts)，它们还可以转化为烯丙基亚磺酰胺和烯丙基酰胺。${}^{\left\lbrack 5,{11}\right\rbrack }$

Results and Discussion

结果与讨论

The allyl sulfides were prepared and their reactions with chloramine-T were investigated. The allyl(phenyl)- sulfane 1a was selected to optimize the reaction conditions (Table 1). Initially, only trace of product could be detected when we conducted the reaction in toluene as the solvent under room temperature (Table 1, Eentry 1).

制备了烯丙基硫醚并研究了它们与氯胺 -T 的反应。选择烯丙基(苯基)硫醚 1a 来优化反应条件(表 1)。最初，当我们在室温下以甲苯为溶剂进行反应时，只能检测到痕量产物(表 1，条目 1)。

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Received June 20, 2012; accepted July 4, 2012.

2012 年 6 月 收到；2012 年 7 月 4 日 接受。

Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/cjoc.201200604 or from the author.

本文的支持信息可在网页 http://dx.doi.org/10.1002/cjoc.201200604 上获取，或向作者索取。

Dedicated to the 80th Anniversary of Chinese Chemical Society.

献给中国化学会成立 80 周年。

The yield was increased to 50% when we elevated the reaction temperature to ${70}{}^{ \circ }\mathrm{C}$ (Table 2, Eentry 1). We continued to tried other solvents and found that DCE, THF, DMF and dioxane could afford moderate yields (Table 2, Entries 3-6), while MeCN and EtOH afforded excellent yields (Table 2, Entries 7-12). Moderate yields can also be obtained when ${\mathrm{H}}_{2}\mathrm{O}$ was used as the solvent under heating or microwave conditions (Table 1, Entries 14-16). Notably, more favored yields can be achieved under room temperature other than 70 C when MeCN or EtOH was chosen as the medium (Table 1, Entries 10, 12).

当将反应温度升至${70}{}^{ \circ }\mathrm{C}$时，产率提高到了 50%(表 2，条目 1)。我们继续尝试其他溶剂，发现二氯乙烷、四氢呋喃、N, N - 二甲基甲酰胺和二氧六环能提供中等产率(表 2，条目 3 - 6)，而乙腈和乙醇能提供优异产率(表 2，条目 7 - 12)。当${\mathrm{H}}_{2}\mathrm{O}$用作加热或微波条件下的溶剂时，也能获得中等产率(表 1，条目 14 - 16)。值得注意的是，当选择乙腈或乙醇作为介质时，在室温下比 70℃能获得更有利的产率(表 1，条目 10、12)。

Table 1 Optimization of the reaction conditions with 1a

表 1 用 1a 优化反应条件

${}^{a}$ Determined by TLC. ${}^{b}$ Isolated yields. ${}^{c}$ Yield using anhydrous chloramine-T was given in parentheses. ${}^{d}$ Amount of recovered staring material was not determined.

${}^{a}$ 通过薄层色谱法测定。${}^{b}$ 分离产率。${}^{c}$ 使用无水氯胺 -T 的产率列于括号内。${}^{d}$ 未测定回收原料的量。

The optimized reaction conditions (EtOH/room temperature) were then applied to a series of allyl sulfides $\mathbf{1}\mathbf{b} - \mathbf{1}\mathbf{q}$ and the results were summarized in Table 2. All aromatic allyl sulfides reacted smoothly with chloramines-T and afforded excellent yields. The sub-stituents on the aromatic ring had some influences on the reaction. When electron-donating aromatic allyl sulfides were subjected to the reaction, the yields slightly increased (Table 2, Entries 1, 2, 4, 9), while the yields decreased when the aromatic ring bears electron-withdrawing group (Table 2, Entries 3, 5). Various substituted and cyclic allyl sulfides could also be used for the construction of C-N bonds (Table 2, Entries 6-9). The benzyl and alkyl allyl sulfides react slowly at room temperature, they could work successfully when heated to 70 °C (Table 2, Entries 10, 11). Moreover, functional groups such as bromine, hydroxyl, protected amido and aldehyde on allyl part are tolerant in this system (Table 2, Entries 12-16). It is worth noting that this reaction proceeds very fast and could complete within 10 min in all cases.

然后将优化的反应条件(乙醇/室温)应用于一系列烯丙基硫醚$\mathbf{1}\mathbf{b} - \mathbf{1}\mathbf{q}$，结果总结在表 2 中。所有芳基烯丙基硫醚与氯胺 -T 反应顺利，产率优异。芳环上的取代基对反应有一些影响。当给电子的芳基烯丙基硫醚进行反应时，产率略有增加(表 2，条目 1、2、4、9)，而当芳环带有吸电子基团时，产率降低(表 2，条目 3、5)。各种取代的和环状的烯丙基硫醚也可用于构建 C - N 键(表 2，条目 6 - 9)。苄基和烷基烯丙基硫醚在室温下反应缓慢，加热至 70℃时能成功反应(表 2，条目 10、11)。此外，烯丙基部分的溴、羟基、保护的酰胺基和醛等官能团在该体系中是耐受的(表 2，条目 12 - 16)。值得注意的是，该反应进行得非常快，在所有情况下 10 分钟内即可完成。

Conclusions

结论

In summary, we have developed a process of metal-catalyst free imidation of allyl sulfides with Chlor-amines-T and subsequent [2,3]-sigmatropic rearrangement. Various substituted and functionalized allyl sul-fonamides or allyl amides can be easily obtained through this approach. It affords an efficient strategy for the construction of carbon-nitrogen bond. Compared to other procedures, this method has wider scope and higher efficiency.

总之，我们开发了一种无金属催化剂的方法，用氯胺 - T对烯丙基硫醚进行亚胺化反应，随后进行[2,3] - 迁移重排。通过这种方法可以轻松获得各种取代和官能化的烯丙基磺酰胺或烯丙基酰胺。它为构建碳 - 氮键提供了一种有效的策略。与其他方法相比，该方法具有更广泛的适用范围和更高的效率。

Experimental

实验

General

一般信息

Aryl mercaptans, bromides and chloramine-T were purchased from Alfa Aesar. Chloroform-d and dimethylsulfoxide- ${d}_{6}$ were purchased from Cambridge Isotope Laboratories. All solvents were distilled prior to use. THF was freshly distilled from Na before use. All reactions were performed in air atmosphere. For chromatography, 200—300 mesh silica gel (Qingdao, China) was employed. ${}^{1}\mathrm{H}$ NMR (300 or ${200}\mathrm{{MHz}}$ ) and ${}^{13}\mathrm{C}$ NMR (75 or ${50}\mathrm{{MHz}}$ ) spectra were measured on Varian ${300}\mathrm{{MHz}}$ spectrometers; ${}^{1}\mathrm{H}$ NMR (400 MHz) and ${}^{13}\mathrm{C}$ NMR (100 MHz) spectra were measured on Bruker ARX 400 MHz spectrometer. ${\mathrm{{CDCl}}}_{3}$ was used as solvent with tetramethylsilane (TMS) as internal standard. IR spectra were recorded with a Nicolet 5MX-S infrared spectrometer.

芳基硫醇、溴化物和氯胺 -T购自Alfa Aesar。氘代氯仿和二甲基亚砜 - ${d}_{6}$购自剑桥同位素实验室。所有溶剂在使用前均进行蒸馏。四氢呋喃(THF)在使用前用钠新鲜蒸馏。所有反应均在空气气氛中进行。柱色谱使用200 - 300目硅胶(中国青岛)。${}^{1}\mathrm{H}$核磁共振(300或${200}\mathrm{{MHz}}$)和${}^{13}\mathrm{C}$核磁共振(75或${50}\mathrm{{MHz}}$)光谱在Varian ${300}\mathrm{{MHz}}$光谱仪上测量；${}^{1}\mathrm{H}$核磁共振(400 MHz)和${}^{13}\mathrm{C}$核磁共振(100 MHz)光谱在Bruker ARX 400 MHz光谱仪上测量。${\mathrm{{CDCl}}}_{3}$用作溶剂，四甲基硅烷(TMS)作为内标。红外光谱用Nicolet 5MX - S红外光谱仪记录。

Table 2 Reaction of $1\mathrm{\;b} - 1\mathrm{q}$ with chloramine-T under qptimization conditions

表2 $1\mathrm{\;b} - 1\mathrm{q}$与氯胺 -T在优化条件下的反应

Entry	Allyl sulfide 1	Product 2	Yield ${}^{a}$ %
1	1b	2b	90
2	1c	2c	92

Continued

续表

Entry	Allyl sulfide 1	Product 2	Yield ${}^{a}/\%$
3	1d		72
4	1e	2e	97
5	1f	2f	78
6	1g	2g	78
7	1h	2h	77
8	1i	2i	93
9	1j		95
${10}^{b}$	1k	2k	45
${11}^{b}$	11	21	91
12	1m	2m	84
13	1n	2n	83
${14}^{c}$			82
	10	20

Continued

续表

Entry	Allyl sulfide 1	Product 2	Yield ${}^{a}/{}^{w}$
15	1p	2p	84
${16}^{b}$	1q	2q	68

${}^{a}$ Isolated yields. ${}^{b}$ The reaction was carried out at ${70}{}^{ \circ }\mathrm{C}{}^{c}$ d.r. $= {60} : {40}$ .

${}^{a}$ 分离产率。${}^{b}$ 反应在${70}{}^{ \circ }\mathrm{C}{}^{c}$ 下进行，非对映体过量率为$= {60} : {40}$ 。

Synthesis and spectral data for the substrates 1a-1q and 3-4

底物1a - 1q和3 - 4的合成及光谱数据

(E)-Ethyl 4-(phenylthio)but-2-enoate (3): ${}^{\left\lbrack {12}\right\rbrack }$ A 2.05 mL portion of thiophenol (2.2 g, 20 mmol) and 5.13 g of (E)-ethyl 4-bromobut-2-enoate (22 mmol) were dissolved in ${30}\mathrm{\;{mL}}$ of dry diethyl ether and cooled to-10 °C. A ${2.2}\mathrm{\;g}$ portion of triethylamine $\left( {{22}\mathrm{{mmol}}}\right)$ was added dropwise during ${0.5}\mathrm{\;h}$ . After being stirred at $- {10}{}^{ \circ }\mathrm{C}$ for ${30}\mathrm{\;{min}}$ , the mixture was refluxed for $1\mathrm{\;h}$ and stirred overnight at room temperature. The precipitate was removed by filtration and washed with diethyl ether. The filtrate was washed with aqueous $\mathrm{{NaOH}}$ and dried over ${\mathrm{{MgSO}}}_{4}$ . After the solvent was removed the residue was purified by column chromatography. ${4.35}\mathrm{\;g}$ (98%) of 3 was obtained as a colorless liquid.

(E)-4-(苯硫基)丁-2-烯酸乙酯(3):${}^{\left\lbrack {12}\right\rbrack }$ 将2.05 mL苯硫酚(2.2 g, 20 mmol)和5.13 g (E)-4-溴丁-2-烯酸乙酯(22 mmol)溶解于${30}\mathrm{\;{mL}}$无水乙醚中，冷却至 -10 °C。在${0.5}\mathrm{\;h}$期间逐滴加入${2.2}\mathrm{\;g}$份三乙胺$\left( {{22}\mathrm{{mmol}}}\right)$。在$- {10}{}^{ \circ }\mathrm{C}$搅拌${30}\mathrm{\;{min}}$后，混合物回流$1\mathrm{\;h}$并在室温下搅拌过夜。通过过滤除去沉淀，并用乙醚洗涤。滤液用水性$\mathrm{{NaOH}}$洗涤，并用${\mathrm{{MgSO}}}_{4}$干燥。除去溶剂后，残余物通过柱色谱法纯化。得到${4.35}\mathrm{\;g}$(98%)的3为无色液体。

(E)-4-(Phenylthio)but-2-enal (4): ${}^{\left\lbrack {13}\right\rbrack }$ A ${0.72}\mathrm{\;g}$ (4 mmol) portion of $\left( E\right)$ -ethyl-4-(phenylthio)but-2-enoate (3), ${0.672}\mathrm{\;g}{\mathrm{{NaHCO}}}_{3}$ and ${2.035}\mathrm{\;g}$ of DMP were added to ${20}\mathrm{\;{mL}}$ of ${\mathrm{{CH}}}_{2}{\mathrm{{Cl}}}_{2}$ under $0{}^{ \circ }\mathrm{C}$ and the reaction was conducted by TLC. Flash chromatography provided crude product which was further purified by column chromatography providing ${0.584}\mathrm{\;g}\left( {{82}\% }\right) 4$ as a colorless liquid.

(E)-4-(苯硫基)丁-2-烯醛(4):${}^{\left\lbrack {13}\right\rbrack }$ 将${0.72}\mathrm{\;g}$(4 mmol)份的$\left( E\right)$ - 乙基-4-(苯硫基)丁-2-烯酸乙酯(3)、${0.672}\mathrm{\;g}{\mathrm{{NaHCO}}}_{3}$和${2.035}\mathrm{\;g}$的DMP加入到${20}\mathrm{\;{mL}}$的${\mathrm{{CH}}}_{2}{\mathrm{{Cl}}}_{2}$中，在$0{}^{ \circ }\mathrm{C}$下进行反应，通过TLC监测。快速柱色谱法得到粗产物，再通过柱色谱法进一步纯化，得到${0.584}\mathrm{\;g}\left( {{82}\% }\right) 4$为无色液体。

General procedure for the preparation of 1a- 1m: ${}^{\left\lbrack {14} - {19}\right\rbrack }$ To a ${15}\mathrm{\;{mL}}$ of dry THF was added ${12}\mathrm{\;{mmol}}$ of NaH, 10 mmol of thiol (slowly added) and stirred at 0 °C for 15 min. To the system was then added 12 mmol of allyl bromide and stirred overnight at room temperature. The precipitate was removed by filtration and washed with diethyl ether. After the solvent was removed the residue was purified by column chromatography.

制备1a - 1m的通用方法:${}^{\left\lbrack {14} - {19}\right\rbrack }$ 向${15}\mathrm{\;{mL}}$无水THF中加入${12}\mathrm{\;{mmol}}$ NaH、10 mmol硫醇(缓慢加入)，并在0 °C搅拌15分钟。然后向体系中加入12 mmol烯丙基溴，并在室温下搅拌过夜。通过过滤除去沉淀，并用乙醚洗涤。除去溶剂后，残余物通过柱色谱法纯化。

(4-Chlorophenyl)(cyclohex-2-enyl)sulfane (1f): Colorless liquid; ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta : {7.34}(\mathrm{\;d}$ , $J = {8.4}\mathrm{\;{Hz}},2\mathrm{H}),{7.25}\left( {\mathrm{\;d}, J = {8.5}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{5.85}(\mathrm{\;{dd}}, J =$ 3.50,9.9 Hz,1H),5.74 (dd, $J = {1.8},{10.0}\mathrm{\;{Hz}},1\mathrm{H}$ ),3.81 (s, br, 1H), 2.04-1.58 (m, 6H); ${}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta : {134.3},{132.6},{130.7},{128.9},{126.5},{44.2},{28.7}$ , 24.8, 19.3; IR (film) v: 2933, 1476, 1096, 1013, 815 ${\mathrm{{cm}}}^{-1}$ ; EI-MS (relative intensity) $m/z\left( \% \right) : {224}\left( {11}\right) ,{143}$ (16), 108 (18), 81 (100), 53 (14); HRMS calcd for ${\mathrm{C}}_{12}{\mathrm{H}}_{13}\mathrm{{ClSK}}{\left( \mathrm{M} + \mathrm{{Na}}\right) }^{ + } : {263.0058}$ , found 263.0053.

(4-氯苯基)(环己-2-烯基)硫醚(1f):无色液体；${}^{1}\mathrm{H}$核磁共振(400兆赫兹，${\mathrm{{CDCl}}}_{3}$)$\delta : {7.34}(\mathrm{\;d}$，$J = {8.4}\mathrm{\;{Hz}},2\mathrm{H}),{7.25}\left( {\mathrm{\;d}, J = {8.5}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{5.85}(\mathrm{\;{dd}}, J =$ 3.50，9.9赫兹，1H)，5.74(dd，$J = {1.8},{10.0}\mathrm{\;{Hz}},1\mathrm{H}$)，3.81(s，宽峰，1H)，2.04 - 1.58(m，6H)；${}^{13}\mathrm{C}$核磁共振(100兆赫兹，${\mathrm{{CDCl}}}_{3}$)$\delta : {134.3},{132.6},{130.7},{128.9},{126.5},{44.2},{28.7}$，24.8，19.3；红外光谱(薄膜)v:2933，1476，1096，1013，815 ${\mathrm{{cm}}}^{-1}$；电子轰击质谱(相对强度)$m/z\left( \% \right) : {224}\left( {11}\right) ,{143}$(16)，108(18)，81(100)，53(14)；高分辨质谱计算值为${\mathrm{C}}_{12}{\mathrm{H}}_{13}\mathrm{{ClSK}}{\left( \mathrm{M} + \mathrm{{Na}}\right) }^{ + } : {263.0058}$，实测值为263.0053。

Cyclohex-2-enyl(4-methoxyphenyl)sulfane (1j): Colorless liquid; ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ :7.41 (d, $J = {8.7}\mathrm{\;{Hz}},2\mathrm{H}$ ), ${6.84}\left( {\mathrm{\;d}, J = {8.62}\mathrm{\;{Hz}},2\mathrm{H}}\right)$ , ${5.81} - {5.73}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{3.79}\left( {\mathrm{\;s},3\mathrm{H}}\right) ,{3.65}\left( {\text{ br }\mathrm{s},1\mathrm{H}}\right)$ , 2.00-1.54 (m, 6H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl3) $\delta : {159.3},{135.1},{130.0},{127.2},{125.7},{114.3},{55.2},{45.4}$ , 28.7, 24.9, 19.4; IR (film) v: 2933, 1492, 1243, 1029, ${823}{\mathrm{\;{cm}}}^{-1}$ ; EI-MS (relative intensity) $m/z\left( \% \right) : {220}\left( {21}\right)$ , 140 (100),81 (55); HRMS calcd for ${\mathrm{C}}_{13}{\mathrm{H}}_{15}\mathrm{{OS}}{\left( \mathrm{M} - \mathrm{H}\right) }^{ + }$ : 219.0838, found 219.0838.

环己-2-烯基(4-甲氧基苯基)硫醚(1j):无色液体；${}^{1}\mathrm{H}$核磁共振(400兆赫兹，${\mathrm{{CDCl}}}_{3}$)$\delta$:7.41(d，$J = {8.7}\mathrm{\;{Hz}},2\mathrm{H}$)，${6.84}\left( {\mathrm{\;d}, J = {8.62}\mathrm{\;{Hz}},2\mathrm{H}}\right)$，${5.81} - {5.73}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{3.79}\left( {\mathrm{\;s},3\mathrm{H}}\right) ,{3.65}\left( {\text{ br }\mathrm{s},1\mathrm{H}}\right)$，2.00 - 1.54(m，6H)；${}^{13}\mathrm{C}$核磁共振(100兆赫兹，氯仿)$\delta : {159.3},{135.1},{130.0},{127.2},{125.7},{114.3},{55.2},{45.4}$，28.7，24.9，19.4；红外光谱(薄膜)v:2933，1492，1243，1029，${823}{\mathrm{\;{cm}}}^{-1}$；电子轰击质谱(相对强度)$m/z\left( \% \right) : {220}\left( {21}\right)$，140(100)，81(55)；高分辨质谱计算值为${\mathrm{C}}_{13}{\mathrm{H}}_{15}\mathrm{{OS}}{\left( \mathrm{M} - \mathrm{H}\right) }^{ + }$:219.0838，实测值为219.0838。

(E)-4-(Phenylthio)but-2-en-1-ol (1n): ${}^{\left\lbrack {20}\right\rbrack }$ A 0.666 g (3 mmol) portion of (E)-ethyl-4-(phenylthio) but-2- enoate (3) was dissolved in ${10}\mathrm{\;{mL}}$ of dry THF and cooled to 0°C. A 6 mL portion of Dibal-H (6 mmol, 1n in hexane) was added, and after the mixture was stirred at $0{}^{ \circ }\mathrm{C}$ for $1\mathrm{\;h},2\mathrm{\;{mL}}$ of methanol, ${10}\mathrm{\;{mL}}$ of water,1 $\mathrm{{mL}}$ of saturated $\mathrm{{NaOH}}$ aqueous, and ${10}\mathrm{\;{mL}}$ of aqueous KNa tartrate $\left( {{30}\% , W/W}\right)$ were added successively. The mixture was stirred at room temperature for $1\mathrm{\;h}$ , and the layers were separated. The aqueous layer was extracted with ${30}\mathrm{\;{mL}}{\mathrm{{Et}}}_{2}\mathrm{O}$ for three times, and the combined organic layers were washed with water and brine and dried over ${\mathrm{{MgSO}}}_{4}$ . After evaporation of the solvent, the residue was purified by column chromatography. Compound $1\mathrm{n}\left( {{0.443}\mathrm{\;g},{82}\% }\right)$ was obtained as a colorless liquid. ${}^{1}\mathrm{H}$ NMR (300 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta : {7.34} - {7.16}(\mathrm{\;m}$ , 5H), 5.75-5.70 (m, 2H), 4.04 (d, J=4.2 Hz, 2H), 3.54 $\left( {\mathrm{d}, J = {5.8}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{1.73}\left( {\mathrm{\;s},1\mathrm{H}}\right) ;{}^{13}\mathrm{C}\mathrm{{NMR}}({75}\mathrm{{MHz}}$ , ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ :135.6,132.3,129.8,128.7,126.8,126.2,62.7, 35.7.

(E)-4-(苯硫基)丁-2-烯-1-醇(1n):${}^{\left\lbrack {20}\right\rbrack }$ 将0.666 g(3 mmol)(E)-4-(苯硫基)丁-2-烯酸乙酯(3)溶于${10}\mathrm{\;{mL}}$干燥四氢呋喃中并冷却至0°C。加入6 mL二异丁基氢化铝(6 mmol，己烷中1n)，混合物在$0{}^{ \circ }\mathrm{C}$搅拌$1\mathrm{\;h},2\mathrm{\;{mL}}$后，依次加入${10}\mathrm{\;{mL}}$甲醇、${10}\mathrm{\;{mL}}$水、1 $\mathrm{{mL}}$饱和$\mathrm{{NaOH}}$水溶液和${10}\mathrm{\;{mL}}$酒石酸钾钠水溶液$\left( {{30}\% , W/W}\right)$。混合物在室温搅拌$1\mathrm{\;h}$，分层。水层用${30}\mathrm{\;{mL}}{\mathrm{{Et}}}_{2}\mathrm{O}$萃取三次，合并有机层用水和盐水洗涤，经${\mathrm{{MgSO}}}_{4}$干燥。蒸发溶剂后，残余物用柱色谱法纯化。得到化合物$1\mathrm{n}\left( {{0.443}\mathrm{\;g},{82}\% }\right)$为无色液体。${}^{1}\mathrm{H}$核磁共振(300 MHz，${\mathrm{{CDCl}}}_{3}$) $\delta : {7.34} - {7.16}(\mathrm{\;m}$，5H)，5.75 - 5.70(m，2H)，4.04(d，J = 4.2 Hz，2H)，3.54 $\left( {\mathrm{d}, J = {5.8}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{1.73}\left( {\mathrm{\;s},1\mathrm{H}}\right) ;{}^{13}\mathrm{C}\mathrm{{NMR}}({75}\mathrm{{MHz}}$，${\mathrm{{CDCl}}}_{3}$) $\delta$:135.6，132.3，129.8，128.7，126.8，126.2，62.7，35.7。

(E)-1-Phenyl-4-(phenylthio)but-2-en-1-ol (1o): In a 25 mL round bottom flask a magnetic stir bar was placed and the apparatus was flame dried. Then, dried diethyl ether (10 mL), phenylmagnesium bromide (4.5 mmol,3 mol/L in diethyl ether) and 0.534 g (3 mmol) of $\left( E\right)$ -4-(phenylthio)-but-2-enal (4) were added to the flask under $0{}^{ \circ }\mathrm{C}$ . After stirred at room temperature for ${30}\mathrm{\;{min}}$ , the reaction was quenched by slow addition of a saturated ${\mathrm{{NH}}}_{4}\mathrm{{Cl}}$ solution followed by extraction with diethyl ether $\left( {{15}\mathrm{\;{mL}} \times 3}\right)$ . The combined organic layers were washed with brine, dried $\left( {{\mathrm{{Na}}}_{2}{\mathrm{{SO}}}_{4}}\right)$ , concentrated and the crude product was purified by column chromatography to afford ${0.66}\mathrm{\;g}$ of 10 as a light yellow oil, yield 86%. ${}^{1}\mathrm{H}$ NMR (300 MHz, CDCl3) $\delta : {7.33} - {7.14} \; \left( {\mathrm{m},{10}\mathrm{H}}\right) ,{5.85} - {5.62}\left( {\mathrm{m},2\mathrm{H}}\right) ,{5.09}\left( {\mathrm{\;d}, J = {5.4}\mathrm{\;{Hz}},1\mathrm{H}}\right)$ , ${3.52}\left( {\mathrm{\;d}, J = {6.8}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{1.97}\left( {\mathrm{\;d}, J = {2.8}\mathrm{\;{Hz}},1\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR (75 MHz, CDCl3) 6: 142.3, 135.3, 135.3, 130.4, 128.7, 128.4, 127.5, 126.6, 126.4, 126.1, 74.2, 36.0; IR (film) $v$ : 967,699,738 ${\mathrm{\;{cm}}}^{-1}$ ; EI-MS (relative intensity) m/z (%): 256 (27), 146 (49), 129 (29), 110 (100), 105 (80), 77 (52), 65 (15); HRMS calcd for ${\mathrm{C}}_{16}{\mathrm{H}}_{16}\mathrm{{OSNa}} \; {\left( \mathrm{M} + \mathrm{{Na}}\right) }^{ + } : {279.0814}$ , found 279.0807.

(E)-1-苯基-4-(苯硫基)丁-2-烯-1-醇(1o):在一个25 mL的圆底烧瓶中放入一根磁力搅拌棒，仪器经火焰干燥。然后，在$0{}^{ \circ }\mathrm{C}$条件下，向烧瓶中加入干燥的乙醚(10 mL)、苯基溴化镁(4.5 mmol，3 mol/L的乙醚溶液)和0.534 g(3 mmol)的$\left( E\right)$-4-(苯硫基)丁-2-烯醛(4)。在室温下搅拌${30}\mathrm{\;{min}}$后，通过缓慢加入饱和${\mathrm{{NH}}}_{4}\mathrm{{Cl}}$溶液淬灭反应，然后用乙醚$\left( {{15}\mathrm{\;{mL}} \times 3}\right)$萃取。合并的有机层用盐水洗涤，$\left( {{\mathrm{{Na}}}_{2}{\mathrm{{SO}}}_{4}}\right)$干燥，浓缩，粗产物通过柱色谱纯化，得到${0.66}\mathrm{\;g}$的10为浅黄色油状物，产率86%。${}^{1}\mathrm{H}$核磁共振(300 MHz，CDCl3)$\delta : {7.33} - {7.14} \; \left( {\mathrm{m},{10}\mathrm{H}}\right) ,{5.85} - {5.62}\left( {\mathrm{m},2\mathrm{H}}\right) ,{5.09}\left( {\mathrm{\;d}, J = {5.4}\mathrm{\;{Hz}},1\mathrm{H}}\right)$，${3.52}\left( {\mathrm{\;d}, J = {6.8}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{1.97}\left( {\mathrm{\;d}, J = {2.8}\mathrm{\;{Hz}},1\mathrm{H}}\right) ;{}^{13}\mathrm{C}$核磁共振(75 MHz，CDCl3)δ:142.3、135.3、135.3、130.4、128.7、128.4、127.5、126.6、126.4、126.1、74.2、36.0；红外光谱(薄膜)$v$:967、699、738${\mathrm{\;{cm}}}^{-1}$；电子轰击质谱(相对强度)m/z(%):256(27)、146(49)、129(29)、110(100)、105(80)、77(52)、65(15)；高分辨质谱计算值为${\mathrm{C}}_{16}{\mathrm{H}}_{16}\mathrm{{OSNa}} \; {\left( \mathrm{M} + \mathrm{{Na}}\right) }^{ + } : {279.0814}$，实测值为279.0807。

(E)-2-(4-(Phenylthio)but-2-enyl)isoindoline-1,3-dione (1p): Triphenylphosphane (1.179 g, 4.5 mmol) and phthalimide (0.529 g, 3.6 mmol) were added at room temperature to a solution of ${0.540}\mathrm{\;g}$ (3 mmol) of (E)-4-(phenylthio)but-2-en-1-ol (1n) in THF (10 mL). Diethyl azodicarboxylate $\left( {{0.783}\mathrm{{mg}},{4.5}\mathrm{{mmol}}}\right)$ was added dropwise to the reaction mixture at $0{}^{ \circ }\mathrm{C}$ . After complete consumption (the reaction was monitored by TLC), the solvent was removed in vacuo and the crude product was purified by column chromatography on silica gel to afford the corresponding $\mathbf{{1p}}$ as a white solid, 0.917 g, yield 99%. m.p. 114-115 °C; ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl3) δ: 7.84-7.82 (m, 2H), 7.73-7.71 (m, 2H), 7.30-7.26 (m, 2H), 7.17-7.14 (m, 2H), 7.06- 7.02 (m, 1H), 5.81-5.75 (m, 1H), 5.56-5.51 (m, 1H), ${4.18}\left( {\mathrm{\;d}, J = {6.3}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{3.46}\left( {\mathrm{\;d}, J = {7.0}\mathrm{\;{Hz}},2\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR (75 MHz, CDCl3) δ: 167.6, 135.0, 133.8, 132.0, 130.9, 129.7, 128.6, 126.5, 126.4, 123.2, 38.8, 36.2; IR (film) $v$ : 1709,1392,717 ${\mathrm{{cm}}}^{-1}$ ; EI-MS (relative intensity) $m/z\left( \% \right) : {309}\left( {36}\right) ,{200}\left( {100}\right) ,{182}\left( {40}\right) ,{130}\left( {38}\right)$ , 109 (35),53 (49); HRMS calcd for ${\mathrm{C}}_{18}{\mathrm{H}}_{15}{\mathrm{{NO}}}_{2}\mathrm{{SNa}} \; {\left( \mathrm{M} + \mathrm{{Na}}\right) }^{ + } : {332.0716}$ , found 332.0708.

(E)-2-(4-(苯硫基)丁-2-烯基)异吲哚啉-1,3-二酮(1p):在室温下，将三苯基膦(1.179 g，4.5 mmol)和邻苯二甲酰亚胺(0.529 g，3.6 mmol)加入到${0.540}\mathrm{\;g}$ (3 mmol)的(E)-4-(苯硫基)丁-2-烯-1-醇(1n)的四氢呋喃(10 mL)溶液中。在$0{}^{ \circ }\mathrm{C}$ 时，将偶氮二羧酸二乙酯$\left( {{0.783}\mathrm{{mg}},{4.5}\mathrm{{mmol}}}\right)$ 滴加到反应混合物中。完全消耗后(通过薄层层析监测反应)，在真空中除去溶剂，粗产物通过硅胶柱色谱法纯化，得到相应的$\mathbf{{1p}}$ ，为白色固体，0.917 g，产率99%。熔点114 - 115℃；${}^{1}\mathrm{H}$ 核磁共振(400 MHz，CDCl3)δ:7.84 - 7.82(m，2H)，7.73 - 7.71(m，2H)，7.30 - 7.26(m，2H)，7.17 - 7.14(m,2H)，7.06 - 7.02(m，1H)，5.81 - 5.75(m，1H)，5.56 - 5.51(m，1H)；${4.18}\left( {\mathrm{\;d}, J = {6.3}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{3.46}\left( {\mathrm{\;d}, J = {7.0}\mathrm{\;{Hz}},2\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ 核磁共振(75 MHz，CDCl3)δ:167.6，135.0，133.8，132.0，130.9，129.7，128.6，126.5，126.4，123.2，38.8，36.2；红外(薄膜) $v$ :1709，1392，717 ${\mathrm{{cm}}}^{-1}$ ；电子轰击质谱(相对强度) $m/z\left( \% \right) : {309}\left( {36}\right) ,{200}\left( {100}\right) ,{182}\left( {40}\right) ,{130}\left( {38}\right)$ ，109(35)，53(49)；高分辨质谱计算值为${\mathrm{C}}_{18}{\mathrm{H}}_{15}{\mathrm{{NO}}}_{2}\mathrm{{SNa}} \; {\left( \mathrm{M} + \mathrm{{Na}}\right) }^{ + } : {332.0716}$ ，实测值为332.0708。

(E)-2-(3-(Phenylthio)prop-1-enyl)-1,3-dioxolane (1q): To a 25 mL two-necked, round-bottomed flask, equipped with a Dean-Stark adapter and a condenser, containing the (E)-4-(phenylthio)but-2-enal (4) (0.534 g, 3 mmol), p-toluenesulfonic acid (14 mg, 0.075 mmol), in benzene (15 mL) was added ethylene glycol (0.279 g, 4.5 mmol) in benzene (10 mL). The reaction mixture was heated to reflux and was monitored by TLC until no starting aldehyde was detected. The reaction mixture was then filtered through a pad of anhydrous ${\mathrm{{NaHCO}}}_{3}$ , and the filter cake was washed with ${\mathrm{{CH}}}_{2}{\mathrm{{Cl}}}_{2}\left( {{10}\mathrm{\;{mL}} \times 3}\right)$ . Concentration of the filtrate gave the crude product which was further purified by column chromatography on silica gel to give 0.373 g of 1q as a light yellow oil, yield 56%. ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl ${}_{3}$ ) 5: 7.34-7.16 (m, 5H), 3.96-3.83 (m, 4H), 5.97 (td, J=6.93, 6.93, 15.17 Hz, 1H), 5.57 (dd, $J = {5.8},{15.40}\mathrm{\;{Hz}},1\mathrm{H}),{5.21}\left( {\mathrm{\;d}, J = {5.8}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{3.55}$ (d, $J = {6.9}\mathrm{\;{Hz}},2\mathrm{H}$ ); ${}^{13}\mathrm{C}\mathrm{{NMR}}\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \; \delta : {135.5},{131.3},{129.9},{129.4},{128.8},{126.3},{102.8},{64.7}$ , 35.5; EI-MS (relative intensity) $m/z\left( \% \right) : {222}\left( {24}\right) ,{112}$ (100), 73 (47), 41 (87); IR (film) v: 1141, 1404, 961, 738,687 ${\mathrm{{cm}}}^{-1}$ ; HRMS calcd for ${\mathrm{C}}_{12}{\mathrm{H}}_{14}{\mathrm{O}}_{2}\mathrm{{SK}}$ (M + Na) ${}^{ + }$ : 261.0556, found 261.0552.

(E)-2-(3-(苯硫基)丙-1-烯基)-1,3-二氧戊环(1q):向一个配备有迪安-斯塔克分水器和冷凝器的25 mL两口圆底烧瓶中，加入苯(15 mL)中的(E)-4-(苯硫基)丁-2-烯醛(4)(0.534 g，3 mmol)、对甲苯磺酸(14 mg，0.075 mmol)，再加入苯(10 mL)中的乙二醇(0.279 g，4.5 mmol)。将反应混合物加热至回流，并用薄层色谱法监测，直至未检测到起始醛。然后将反应混合物通过无水${\mathrm{{NaHCO}}}_{3}$垫过滤，滤饼用${\mathrm{{CH}}}_{2}{\mathrm{{Cl}}}_{2}\left( {{10}\mathrm{\;{mL}} \times 3}\right)$洗涤。滤液浓缩得到粗产物，再通过硅胶柱色谱进一步纯化，得到0.373 g浅黄色油状的1q，产率56%。${}^{1}\mathrm{H}$核磁共振(400 MHz，CDCl${}_{3}$)δ:7.34 - 7.16(多重峰，5H)，3.96 - 3.83(多重峰，4H)，5.97(三重二重峰，J = 6.93，6.93，15.17 Hz，1H)，5.57(双重峰，$J = {5.8},{15.40}\mathrm{\;{Hz}},1\mathrm{H}),{5.21}\left( {\mathrm{\;d}, J = {5.8}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{3.55}$(双重峰，$J = {6.9}\mathrm{\;{Hz}},2\mathrm{H}$)；${}^{13}\mathrm{C}\mathrm{{NMR}}\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \; \delta : {135.5},{131.3},{129.9},{129.4},{128.8},{126.3},{102.8},{64.7}$，35.5；电子轰击质谱(相对强度)$m/z\left( \% \right) : {222}\left( {24}\right) ,{112}$(100)，73(47)，41(87)；红外光谱(薄膜)ν:1141，1404，961，738，687${\mathrm{{cm}}}^{-1}$；高分辨质谱计算值为${\mathrm{C}}_{12}{\mathrm{H}}_{14}{\mathrm{O}}_{2}\mathrm{{SK}}$(M + Na)${}^{ + }$:261.0556，实测值为261.0552。

Synthesis and spectral data for products $2\mathrm{a} - 2\mathrm{q}$

产品$2\mathrm{a} - 2\mathrm{q}$的合成与光谱数据

General procedure for the reaction of allyl sulfides with chloramine-T: To a flask was added 1 mmol allyl sulfides (1), 1.3 mmol chloramine-T, 2 mL of EtOH and the system was stirred at the assigned temperature. After the reaction finished, the solvent was removed in vacuo and the residue was purified by column chromatography on silica gel to afford the corresponding product.

烯丙基硫醚与氯胺 - T反应的通用步骤:向烧瓶中加入1 mmol烯丙基硫醚(1)、1.3 mmol氯胺 - T、2 mL乙醇，体系在指定温度下搅拌。反应结束后，减压除去溶剂，残余物通过硅胶柱色谱法纯化得到相应产物。

$N$ -Allyl-4-methyl- $N$ -(phenylthio)benzenesulfonamide (2a): Colorless oil; ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl ${}_{3}$ ) δ: 7.80 $\left( {\mathrm{d}, J = {8.3}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.39}\left( {\mathrm{\;d}, J = {7.6}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.33} - {7.20} \; \left( {\mathrm{m},5\mathrm{H}}\right) ,{5.71}\left( {\mathrm{{tdd}}, J = {6.5},{6.47},{10.1},{16.7}\mathrm{\;{Hz}},1\mathrm{H}}\right)$ , ${5.15}\left( {\mathrm{t}, J = {14.1},{14.1}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{4.15}\left( {\mathrm{\;d}, J = {6.5}\mathrm{\;{Hz}},2\mathrm{H}}\right)$ , 2.42 (s, 3H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) δ: 144.0, 137.0, 136.1, 132.3, 129.6, 128.9, 127.8, 127.4, 126.3, 119.6, 56.9, 21.5; IR (film) v: 1349, 1160, 827, 812, 659 ${\mathrm{{cm}}}^{-1}$ ; EI-MS (relative intensity) $m/z\left( \% \right) : {319}\left( {{\mathrm{M}}^{ + },{13}}\right)$ , 164 (56), 109 (72), 91 (100), 65 (54), 56 (44), 41 (45); HRMS calcd for ${\mathrm{C}}_{16}{\mathrm{H}}_{17}{\mathrm{{NO}}}_{2}{\mathrm{\;S}}_{2}\mathrm{\;K}{\left( \mathrm{M} + \mathrm{{Na}}\right) }^{ + } : {358.0332}$ , found 358.0326.

$N$ -烯丙基-4-甲基-$N$ -(苯硫基)苯磺酰胺(2a):无色油状物；${}^{1}\mathrm{H}$ NMR(400 MHz, CDCl${}_{3}$ ) δ: 7.80$\left( {\mathrm{d}, J = {8.3}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.39}\left( {\mathrm{\;d}, J = {7.6}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.33} - {7.20} \; \left( {\mathrm{m},5\mathrm{H}}\right) ,{5.71}\left( {\mathrm{{tdd}}, J = {6.5},{6.47},{10.1},{16.7}\mathrm{\;{Hz}},1\mathrm{H}}\right)$,${5.15}\left( {\mathrm{t}, J = {14.1},{14.1}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{4.15}\left( {\mathrm{\;d}, J = {6.5}\mathrm{\;{Hz}},2\mathrm{H}}\right)$, 2.42 (s, 3H)；${}^{13}\mathrm{C}$ NMR(100 MHz, CDCl${}_{3}$ ) δ: 144.0, 137.0, 136.1, 132.3, 129.6, 128.9, 127.8, 127.4, 126.3, 119.6, 56.9, 21.5；IR(薄膜) v: 1349, 1160, 827, 812, 659${\mathrm{{cm}}}^{-1}$；EI - MS(相对强度)$m/z\left( \% \right) : {319}\left( {{\mathrm{M}}^{ + },{13}}\right)$, 164 (56), 109 (72), 91 (100), 65 (54), 56 (44), 41 (45)；HRMS计算值为${\mathrm{C}}_{16}{\mathrm{H}}_{17}{\mathrm{{NO}}}_{2}{\mathrm{\;S}}_{2}\mathrm{\;K}{\left( \mathrm{M} + \mathrm{{Na}}\right) }^{ + } : {358.0332}$, 实测值为358.0326。

$N$ -Allyl-4-methyl- $N$ -( $p$ -tolylthio)benzenesulfonamide (2b): Colorless oil; ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta : {7.80}$ (d, $J = {8.3}\mathrm{\;{Hz}},2\mathrm{H}),{7.35}$ (d, $J = {8.1}\mathrm{\;{Hz}},2\mathrm{H}),{7.29}$ (d, $J = {8.2}\mathrm{\;{Hz}},2\mathrm{H}),{7.12}\left( {\mathrm{\;d}, J = {8.1}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{5.71}(\mathrm{{tdd}}, J = \; {6.4},{6.4},{10.1},{16.7}\mathrm{\;{Hz}},1\mathrm{H}),{5.16}\left( {\mathrm{{dd}}, J = {5.2},{21.1}\mathrm{\;{Hz}}}\right.$ , 2H), 4.12 (d, J =6.4 Hz, 2H), 2.42 (s, 3H), 2.33 (s, 3H); ${}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) δ: 143.9,138.2,136.4, 133.1, 132.6, 129.6, 129.5, 128.3, 127.8, 119.4, 56.7, 21.5, 21.1; IR (film) v: 1352, 1160, 827, 809, 659 cm ${}^{-1}$ ; EI-MS (relative intensity) m/z (%): 333 (13), 178 (67), 123 (100), 91 (57), 65 (27); HRMS calcd for ${\mathrm{C}}_{17}{\mathrm{H}}_{19}\mathrm{\;N}$ - ${\mathrm{O}}_{2}{\mathrm{\;S}}_{2}\mathrm{{Na}}{\left( \mathrm{M} + \mathrm{{Na}}\right) }^{ + } : {356.0749}$ , found 356.0742 .

$N$-烯丙基-4-甲基-$N$-($p$-甲苯硫基)苯磺酰胺(2b):无色油状物；${}^{1}\mathrm{H}$核磁共振(400兆赫，${\mathrm{{CDCl}}}_{3}$)$\delta : {7.80}$(双峰，$J = {8.3}\mathrm{\;{Hz}},2\mathrm{H}),{7.35}$(双峰，$J = {8.1}\mathrm{\;{Hz}},2\mathrm{H}),{7.29}$(双峰，$J = {8.2}\mathrm{\;{Hz}},2\mathrm{H}),{7.12}\left( {\mathrm{\;d}, J = {8.1}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{5.71}(\mathrm{{tdd}}, J = \; {6.4},{6.4},{10.1},{16.7}\mathrm{\;{Hz}},1\mathrm{H}),{5.16}\left( {\mathrm{{dd}}, J = {5.2},{21.1}\mathrm{\;{Hz}}}\right.$，2H)，4.12(双峰，J = 6.4赫兹，2H)，2.42(单峰，3H)，2.33(单峰，3H)；${}^{13}\mathrm{C}$核磁共振(100兆赫，${\mathrm{{CDCl}}}_{3}$)δ:143.9，138.2，136.4，133.1，132.6，129.6，129.5，128.3，127.8，119.4，56.7，21.5，21.1；红外光谱(薄膜)v:1352，1160，827，809，659厘米${}^{-1}$；电子轰击质谱(相对强度)m/z(%):333(13)，178(67)，123(100)，91(57)，65(27)；高分辨质谱计算值为${\mathrm{C}}_{17}{\mathrm{H}}_{19}\mathrm{\;N}$-${\mathrm{O}}_{2}{\mathrm{\;S}}_{2}\mathrm{{Na}}{\left( \mathrm{M} + \mathrm{{Na}}\right) }^{ + } : {356.0749}$，实测值为356.0742。

$N$ -Allyl-4-methyl- $N$ -( $o$ -tolylthio)benzenesulfonamide (2c): Colorless oil; ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta : {7.82} \; \left( {\mathrm{d}, J = {8.3}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.47}\left( {\mathrm{\;d}, J = {7.8}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.30}(\mathrm{\;d}$ , $J = {8.1}\mathrm{\;{Hz}},2\mathrm{H}),{7.22} - {7.18}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{7.11} - {7.06}\left( {\mathrm{\;m},}\right)$ 2H),5.71 (tdd, $J = {6.5},{6.5},{10.1},{16.7}\mathrm{\;{Hz}},1\mathrm{H}$ ),5.13 (ddd, $J = {1.2},{13.6},{11.2}\mathrm{\;{Hz}},2\mathrm{H}$ ), ${4.16}(\mathrm{d}, J = {6.5}\mathrm{\;{Hz}}$ , 2H), 2.43 (s, 3H), 2.22 (s, 3H); ${}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta : {144.0},{136.2},{136.2},{132.8},{132.1},{130.1}$ , 129.6, 127.8, 126.6, 126.3, 124.4, 119.7, 56.9, 21.6, 18.8; IR (film) v: 1352,1166,827,812,659 cm ${}^{-1}$ ; EI-MS (relative intensity) m/z (%): 333 (27), 178 (80), 137 (40), 123 (74), 91 (100), 65 (46), 45 (69); HRMS calcd for ${\mathrm{C}}_{17}{\mathrm{H}}_{19}{\mathrm{{NO}}}_{2}{\mathrm{\;S}}_{2}\mathrm{{Na}}{\left( \mathrm{M} + \mathrm{{Na}}\right) }^{ + } : {356.0749}$ , found 356.0749.

$N$ -烯丙基-4-甲基- $N$ -( $o$ -甲苯硫基)苯磺酰胺(2c):无色油状物；${}^{1}\mathrm{H}$核磁共振(400兆赫，${\mathrm{{CDCl}}}_{3}$ ) $\delta : {7.82} \; \left( {\mathrm{d}, J = {8.3}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.47}\left( {\mathrm{\;d}, J = {7.8}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.30}(\mathrm{\;d}$ ，$J = {8.1}\mathrm{\;{Hz}},2\mathrm{H}),{7.22} - {7.18}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{7.11} - {7.06}\left( {\mathrm{\;m},}\right)$ 2H)，5.71(tdd，$J = {6.5},{6.5},{10.1},{16.7}\mathrm{\;{Hz}},1\mathrm{H}$ )，5.13(ddd，$J = {1.2},{13.6},{11.2}\mathrm{\;{Hz}},2\mathrm{H}$ )，${4.16}(\mathrm{d}, J = {6.5}\mathrm{\;{Hz}}$ ，2H)，2.43(s，3H)，2.22(s，3H)；${}^{13}\mathrm{C}$核磁共振(100兆赫，${\mathrm{{CDCl}}}_{3}$ ) $\delta : {144.0},{136.2},{136.2},{132.8},{132.1},{130.1}$ ，129.6，127.8，126.6，126.3，124.4，119.7，56.9，21.6，18.8；红外光谱(薄膜)v:1352，1166，827，812，659厘米${}^{-1}$ ；电子轰击质谱(相对强度)m/z(%):333(27)，178(80)，137(40)，123(74)，91(100)，65(46)，45(69)；高分辨质谱计算值为${\mathrm{C}}_{17}{\mathrm{H}}_{19}{\mathrm{{NO}}}_{2}{\mathrm{\;S}}_{2}\mathrm{{Na}}{\left( \mathrm{M} + \mathrm{{Na}}\right) }^{ + } : {356.0749}$ ，实测值为356.0749。

$N$ -Allyl- $N$ -(4-chlorophenylthio)-4-methylbenzenesul-fonamide (2d): White solid, m.p. 64-65°C; ${}^{1}\mathrm{H}$ NMR $\left. {\left( {{400}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta : {7.80}(\mathrm{\;d}, J = {8.3}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.36} - \; {7.26}\left( {\mathrm{\;m},6\mathrm{H}}\right) ,{5.70}\left( {\mathrm{{tdd}}, J = {6.5},{6.5},{10.1},{16.7}\mathrm{\;{Hz}},1\mathrm{H}}\right)$ , 5.19-5.13 (m,2H),4.13 (d, $J = {6.5}\mathrm{\;{Hz}},2\mathrm{H}),{2.44}(\mathrm{\;s}$ , 1H); ${}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta : {144.2},{136.0}$ , 135.6, 133.5, 132.2, 129.6, 129.0, 128.0, 127.7, 119.9, 77.3, 77.0, 76.7, 57.0, 21.5; IR (film) v: 1474, 1349, 1086,812,659 ${\mathrm{{cm}}}^{-1}$ ; EI-MS (relative intensity) $m/z\left( \% \right)$ : 353 (11), 198 (49), 143 (68), 91 (100), 108 (30), 65 (46); HRMS calcd for ${\mathrm{C}}_{16}{\mathrm{H}}_{16}{\mathrm{{ClNO}}}_{2}{\mathrm{\;S}}_{2}\mathrm{{Na}}{\left( \mathrm{M} + \mathrm{{Na}}\right) }^{ + }$ : 376.0202, found 376.0203.

$N$-烯丙基-$N$-(4-氯苯硫基)-4-甲基苯磺酰胺(2d):白色固体，熔点64 - 65°C；${}^{1}\mathrm{H}$核磁共振$\left. {\left( {{400}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta : {7.80}(\mathrm{\;d}, J = {8.3}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.36} - \; {7.26}\left( {\mathrm{\;m},6\mathrm{H}}\right) ,{5.70}\left( {\mathrm{{tdd}}, J = {6.5},{6.5},{10.1},{16.7}\mathrm{\;{Hz}},1\mathrm{H}}\right)$，5.19 - 5.13(多重峰，2H)，4.13(双峰，$J = {6.5}\mathrm{\;{Hz}},2\mathrm{H}),{2.44}(\mathrm{\;s}$，1H)；${}^{13}\mathrm{C}$核磁共振(100兆赫，${\mathrm{{CDCl}}}_{3}$)$\delta : {144.2},{136.0}$，135.6，133.5，132.2，129.6，129.0，128.0，127.7，119.9，77.3，77.0，76.7，57.0，21.5；红外光谱(薄膜)v:1474，1349，1086，812，659${\mathrm{{cm}}}^{-1}$；电子轰击质谱(相对强度)$m/z\left( \% \right)$:353(11)，198(49)，143(68)，91(100)，108(30)，65(46)；高分辨质谱计算值为${\mathrm{C}}_{16}{\mathrm{H}}_{16}{\mathrm{{ClNO}}}_{2}{\mathrm{\;S}}_{2}\mathrm{{Na}}{\left( \mathrm{M} + \mathrm{{Na}}\right) }^{ + }$:376.0202，实测值为376.0203。

$N$ -Allyl- $N$ -(4-methoxyphenylthio)-4-methylbenzene-sulfonamide (2e): Colorless oil; ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta : {7.79}\left( {\mathrm{\;d}, J = {8.3}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.52}(\mathrm{\;d}, J = {8.9}\mathrm{\;{Hz}}$ , 2H), 7.30 (d, $J = {8.0}\mathrm{\;{Hz}},2\mathrm{H}),{6.85}\left( {\mathrm{\;d}, J = {8.9}\mathrm{\;{Hz}},2\mathrm{H}}\right)$ , 5.72 (tdd, $J = {6.4},{6.4},{10.1},{16.5}\mathrm{\;{Hz}},1\mathrm{H}),{5.17}$ (ddd, $J = {1.3},{9.3},{7.1}\mathrm{\;{Hz}},2\mathrm{H}),{4.08}\left( {\mathrm{\;d}, J = {6.4}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{3.81}$ (s, 3H), 2.43 (s, 3H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl3) $\delta : {160.6},{143.7},{136.5},{133.6},{132.9},{129.5},{127.7},{126.5}$ , 119.1, 114.4, 56.3, 55.3, 21.5; IR (film) v: 1590, 1492, 1346,1245,1086,824,812,662 ${\mathrm{{cm}}}^{-1}$ ; EI-MS (relative intensity) $m/z\left( \% \right) : {349}\left( {12}\right) ,{194}\left( {56}\right) ,{139}\left( {100}\right) ,{91}$ (50); HRMS calcd for ${\mathrm{C}}_{17}{\mathrm{H}}_{19}{\mathrm{{NO}}}_{3}{\mathrm{\;S}}_{2}\mathrm{{Na}}{\left( \mathrm{M} + \mathrm{{Na}}\right) }^{ + }$ : 372.0698, found 372.0699.

$N$ -烯丙基- $N$ -(4-甲氧基苯硫基)-4-甲基苯磺酰胺 (2e):无色油状物；${}^{1}\mathrm{H}$ 核磁共振谱 (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta : {7.79}\left( {\mathrm{\;d}, J = {8.3}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.52}(\mathrm{\;d}, J = {8.9}\mathrm{\;{Hz}}$ , 2H)，7.30 (d, $J = {8.0}\mathrm{\;{Hz}},2\mathrm{H}),{6.85}\left( {\mathrm{\;d}, J = {8.9}\mathrm{\;{Hz}},2\mathrm{H}}\right)$ , 5.72 (tdd, $J = {6.4},{6.4},{10.1},{16.5}\mathrm{\;{Hz}},1\mathrm{H}),{5.17}$ (ddd, $J = {1.3},{9.3},{7.1}\mathrm{\;{Hz}},2\mathrm{H}),{4.08}\left( {\mathrm{\;d}, J = {6.4}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{3.81}$ (s, 3H)，2.43 (s, 3H)；${}^{13}\mathrm{C}$ 核磁共振谱 (100 MHz, CDCl3) $\delta : {160.6},{143.7},{136.5},{133.6},{132.9},{129.5},{127.7},{126.5}$ , 119.1, 114.4, 56.3, 55.3, 21.5；红外光谱 (薄膜) v:1590, 1492, 1346, 1245, 1086, 824, 812, 662 ${\mathrm{{cm}}}^{-1}$ ；电子轰击质谱 (相对强度) $m/z\left( \% \right) : {349}\left( {12}\right) ,{194}\left( {56}\right) ,{139}\left( {100}\right) ,{91}$ (50)；高分辨质谱计算值为 ${\mathrm{C}}_{17}{\mathrm{H}}_{19}{\mathrm{{NO}}}_{3}{\mathrm{\;S}}_{2}\mathrm{{Na}}{\left( \mathrm{M} + \mathrm{{Na}}\right) }^{ + }$ :372.0698，实测值:372.0699。

$N$ -(4-Chlorophenylthio)- $N$ -(cyclohex-2-enyl)-4-meth-ylbenzenesulfonamide (2f): White solid, m.p. 79-80 °C; ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta : {7.84}(\mathrm{\;d}, J = {8.3}\mathrm{\;{Hz}}$ , 2H), ${7.40}\left( {\mathrm{\;d}, J = {8.6}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.33} - {7.27}\left( {\mathrm{\;m},4\mathrm{H}}\right)$ , 5.77-5.73 (m, 1H), 4.92 (br s, 2H), 2.24 (s, 3H), 1.91-1.54 (m, 6H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl3) $\delta : {144.1},{132.6},{129.7},{128.8},{127.6},{126.8},{59.8},{24.2}$ , 21.5, 21.1; IR (film) v: 1474, 1355, 1166, 1086, 873, 814,729,665 ${\mathrm{{cm}}}^{-1}$ ; EI-MS (relative intensity) $m/z$ (%): 393 (12), 313 (66), 91 (100), 65 (44), 41 (42); HRMS calcd for ${\mathrm{C}}_{19}{\mathrm{H}}_{20}{\mathrm{{ClNO}}}_{2}{\mathrm{\;S}}_{2}\mathrm{{Na}}{\left( \mathrm{M} + \mathrm{{Na}}\right) }^{ + } : {416.0516}$ , found 416.0512.

$N$ -(4-氯苯硫基)- $N$ -(环己-2-烯基)-4-甲基苯磺酰胺(2f):白色固体，熔点79 - 80°C；${}^{1}\mathrm{H}$ 核磁共振(400兆赫兹，${\mathrm{{CDCl}}}_{3}$ ) $\delta : {7.84}(\mathrm{\;d}, J = {8.3}\mathrm{\;{Hz}}$ ，2H)，${7.40}\left( {\mathrm{\;d}, J = {8.6}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.33} - {7.27}\left( {\mathrm{\;m},4\mathrm{H}}\right)$ ，5.77 - 5.73(多重峰，1H)，4.92(宽单峰，2H)，2.24(单峰，3H)，1.91 - 1.54(多重峰，6H)；${}^{13}\mathrm{C}$ 核磁共振(100兆赫兹，CDCl₃) $\delta : {144.1},{132.6},{129.7},{128.8},{127.6},{126.8},{59.8},{24.2}$ ，21.5，21.1；红外光谱(薄膜)v:1474，1355，1166，1086，873，814，729，665 ${\mathrm{{cm}}}^{-1}$ ；电子轰击质谱(相对强度) $m/z$ (%):393(12)，313(66)，91(100)，65(44)，41(42)；高分辨质谱计算值为 ${\mathrm{C}}_{19}{\mathrm{H}}_{20}{\mathrm{{ClNO}}}_{2}{\mathrm{\;S}}_{2}\mathrm{{Na}}{\left( \mathrm{M} + \mathrm{{Na}}\right) }^{ + } : {416.0516}$ ，实测值为416.0512。

$N$ -(Cyclohex-2-enyl)-4-methyl- $N$ -(phenylthio)ben-zenesulfonamide (2i): White solid, m.p. 101-102 °C; ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta : {7.85}\left( {\mathrm{\;d}, J = {8.3}\mathrm{\;{Hz}},2\mathrm{H}}\right)$ , ${7.44}\left( {\mathrm{\;d}, J = {7.5}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.33} - {7.30}\left( {\mathrm{\;m},4\mathrm{H}}\right) ,{7.21} - \; {7.17}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{5.75} - {5.72}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{4.93} - {4.91}\left( {\mathrm{\;m},2\mathrm{H}}\right)$ , 2.24 (s, 3H), 1.90-1.57 (m, 6H); ${}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3})\delta$ :143.9,137.0,137.0,132.4,129.6,128.7, 127.6, 127.0, 126.6, 124.8, 59.8, 24.2, 21.5, 21.2; IR (film) $v$ : 1355,1163,873,854,812,665 ${\mathrm{{cm}}}^{-1}$ ; EI-MS (relative intensity) m/z (%): 359 (2), 279 (59), 124 (100), 109 (37), 91 (66), 81 (34), 65 (44); HRMS calcd for ${\mathrm{C}}_{19}{\mathrm{H}}_{21}{\mathrm{{NO}}}_{2}{\mathrm{\;S}}_{2}\mathrm{{Na}}{\left( \mathrm{M} + \mathrm{{Na}}\right) }^{ + } : {382.0906}$ , found 382.0905.

$N$ -(环己-2-烯基)-4-甲基-$N$ -(苯硫基)苯磺酰胺(2i):白色固体，熔点101 - 102°C；${}^{1}\mathrm{H}$ 核磁共振谱(400兆赫兹，${\mathrm{{CDCl}}}_{3}$ )$\delta : {7.85}\left( {\mathrm{\;d}, J = {8.3}\mathrm{\;{Hz}},2\mathrm{H}}\right)$ ，${7.44}\left( {\mathrm{\;d}, J = {7.5}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.33} - {7.30}\left( {\mathrm{\;m},4\mathrm{H}}\right) ,{7.21} - \; {7.17}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{5.75} - {5.72}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{4.93} - {4.91}\left( {\mathrm{\;m},2\mathrm{H}}\right)$ ，2.24(单峰，3H)，1.90 - 1.57(多重峰，6H)；${}^{13}\mathrm{C}$ 核磁共振谱(100兆赫兹，${\mathrm{{CDCl}}}_{3})\delta$ ):143.9，137.0，137.0，132.4，129.6，128.7，127.6，127.0，126.6，124.8，59.8，24.2，21.5，21.2；红外光谱(薄膜)$v$ :1355，1163，873，854，812，6,65${\mathrm{{cm}}}^{-1}$ ；电子轰击质谱(相对强度)m/z(%):359(2)，279(59)，124(100)，109(37)，91(66)，81(34)，65(44)；高分辨质谱计算值为${\mathrm{C}}_{19}{\mathrm{H}}_{21}{\mathrm{{NO}}}_{2}{\mathrm{\;S}}_{2}\mathrm{{Na}}{\left( \mathrm{M} + \mathrm{{Na}}\right) }^{ + } : {382.0906}$ ，实测值为382.0905。

$N$ -(Cyclohex-2-enyl)- $N$ -(4-methoxyphenylthio)-4- methylbenzenesulfonamide (2j): Colorless oil; ${}^{1}\mathrm{H}$ NMR $\left( {{400}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta : {7.83}\left( {\mathrm{\;d}, J = {8.3}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.57}(\mathrm{\;d}$ , $J = {8.8}\mathrm{\;{Hz}},2\mathrm{H}),{7.30}\left( {\mathrm{\;d}, J = {8.0}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{6.86}(\mathrm{\;d}, J = \; {8.9}\mathrm{\;{Hz}},2\mathrm{H}),{5.79} - {5.75}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{5.04}\left( {\mathrm{\;s},\mathrm{{br}},1\mathrm{H}}\right)$ , 4.83-4.81 $\left( {\mathrm{m},1\mathrm{H}}\right) ,{3.81}\left( {\mathrm{\;s},3\mathrm{H}}\right) ,{2.43}\left( {\mathrm{\;s},3\mathrm{H}}\right) ,{1.95} - \; {1.59}\left( {\mathrm{\;m},6\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR $\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta : {159.9}$ , 143.6, 137.4, 131.9, 129.5, 127.7, 127.6, 114.3, 59.7, 55.3, 24.3, 21.5, 21.3; IR (film) v: 1590, 1492, 1346, 1251, 1160, 1083, 1028, 873, 854, 812, 729, 665 cm ${}^{-1}$ ; EI-MS (relative intensity) $m/z\left( \% \right)$ : ${389}\left( 5\right) ,{309}\left( {36}\right)$ , 154 (100), 139 (74), 91 (56), 65 (26); HRMS calcd for ${\mathrm{C}}_{20}{\mathrm{H}}_{24}{\mathrm{{NO}}}_{3}{\mathrm{\;S}}_{2}{\left( \mathrm{M} + \mathrm{H}\right) }^{ + } : {390.1192}$ , found 390.1191.

$N$ -(环己-2-烯基)-$N$ -(4-甲氧基苯硫基)-4-甲基苯磺酰胺(2j):无色油状物；${}^{1}\mathrm{H}$ NMR $\left( {{400}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta : {7.83}\left( {\mathrm{\;d}, J = {8.3}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.57}(\mathrm{\;d}$ ，$J = {8.8}\mathrm{\;{Hz}},2\mathrm{H}),{7.30}\left( {\mathrm{\;d}, J = {8.0}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{6.86}(\mathrm{\;d}, J = \; {8.9}\mathrm{\;{Hz}},2\mathrm{H}),{5.79} - {5.75}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{5.04}\left( {\mathrm{\;s},\mathrm{{br}},1\mathrm{H}}\right)$ ，4.83 - 4.81 $\left( {\mathrm{m},1\mathrm{H}}\right) ,{3.81}\left( {\mathrm{\;s},3\mathrm{H}}\right) ,{2.43}\left( {\mathrm{\;s},3\mathrm{H}}\right) ,{1.95} - \; {1.59}\left( {\mathrm{\;m},6\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR $\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta : {159.9}$ ，143.6，137.4，131.9，129.5，127.7，127.6，114.3，59.7，55.3，24.3，21.5，21.3；IR(薄膜)v:1590，1492，1346，1251，1160，1083，1028，873，854，812，729，665 cm ${}^{-1}$ ；EI-MS(相对强度)$m/z\left( \% \right)$ :${389}\left( 5\right) ,{309}\left( {36}\right)$ ，154(100)，139(74)，91(56)，65(26)；HRMS计算值为${\mathrm{C}}_{20}{\mathrm{H}}_{24}{\mathrm{{NO}}}_{3}{\mathrm{\;S}}_{2}{\left( \mathrm{M} + \mathrm{H}\right) }^{ + } : {390.1192}$ ，实测值为390.1191。

$N$ -Allyl- $N$ -(butylthio)-4-methylbenzenesulfonamide (2k): Colorless oil; ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl ${}_{3}$ ) $\delta$ : 7.80 $\left( {\mathrm{d}, J = {8.3}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.30}\left( {\mathrm{\;d}, J = {8.2}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{5.77}(\mathrm{{tdd}}$ , $J = {6.5},{6.5},{10.08},{16.7}\mathrm{\;{Hz}},1\mathrm{H}),{5.19}(\mathrm{{ddd}}, J = {1.3}$ , ${10.9},{8.7}\mathrm{\;{Hz}},2\mathrm{H}),{4.04}\left( {\mathrm{\;d}, J = {6.5}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{2.88}(\mathrm{t}, J = \; {7.4}\mathrm{\;{Hz}},2\mathrm{H}),{2.43}\left( {\mathrm{\;s},3\mathrm{H}}\right) ,{1.59} - {1.52}\left( {\mathrm{\;m},2\mathrm{H}}\right)$ , ${1.43} - {1.36}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,\left( {\mathrm{t}, J = {7.33},{7.33}\mathrm{\;{Hz}},3\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) $\delta$ : 143.6, 136.0, 133.1, 129.4, 127.8, 119.1, 57.6, 39.8, 29.1, 21.8, 21.5, 13.6; IR (film) v: 1345, 1160, 1089, 912, 827, 812, 732, 662 cm ${}^{-1}$ ; EI-MS (relative intensity) m/z (%): 299 (30), 344 (52), 103 (70), 91 (100), 65 (44), 56 (97), 41 (70), 29 (53); HRMS calcd for ${\mathrm{C}}_{14}{\mathrm{H}}_{21}{\mathrm{{NO}}}_{2}{\mathrm{\;S}}_{2}\mathrm{{Na}}{\left( \mathrm{M} + \mathrm{{Na}}\right) }^{ + } : {322.0907}$ , found 322.0906.

$N$ -烯丙基- $N$ -(丁硫基)-4-甲基苯磺酰胺(2k):无色油状物；${}^{1}\mathrm{H}$ NMR(400 MHz, CDCl ${}_{3}$ ) $\delta$ :7.80 $\left( {\mathrm{d}, J = {8.3}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.30}\left( {\mathrm{\;d}, J = {8.2}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{5.77}(\mathrm{{tdd}}$ ，$J = {6.5},{6.5},{10.08},{16.7}\mathrm{\;{Hz}},1\mathrm{H}),{5.19}(\mathrm{{ddd}}, J = {1.3}$ ，${10.9},{8.7}\mathrm{\;{Hz}},2\mathrm{H}),{4.04}\left( {\mathrm{\;d}, J = {6.5}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{2.88}(\mathrm{t}, J = \; {7.4}\mathrm{\;{Hz}},2\mathrm{H}),{2.43}\left( {\mathrm{\;s},3\mathrm{H}}\right) ,{1.59} - {1.52}\left( {\mathrm{\;m},2\mathrm{H}}\right)$ ，${1.43} - {1.36}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,\left( {\mathrm{t}, J = {7.33},{7.33}\mathrm{\;{Hz}},3\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR(100 MHz, CDCl ${}_{3}$ ) $\delta$ :143.6, 136.0, 133.1, 129.4, 127.8, 119.1, 57.6, 39.8, 29.1, 21.8, 21.5, 13.6；IR(膜)v:1345, 1160, 1089, 912, 827, 812, 732, 662 cm ${}^{-1}$ ；EI-MS(相对强度)m/z(%):299(30)，344(52)，103(70)，91(100)，65(44)，56(97)，41(70)，29(53)；HRMS计算值为${\mathrm{C}}_{14}{\mathrm{H}}_{21}{\mathrm{{NO}}}_{2}{\mathrm{\;S}}_{2}\mathrm{{Na}}{\left( \mathrm{M} + \mathrm{{Na}}\right) }^{ + } : {322.0907}$ ，实测值为322.0906。

$N$ -Allyl- $N$ -(benzylthio)-4-methylbenzenesulfonamide (21): White solid, m.p. 52—53 °C; ${}^{1}$ H NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta : {7.82}\left( {\mathrm{\;d}, J = {8.3}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.32} - {7.26}\left( {\mathrm{\;m},7\mathrm{H}}\right)$ , ${5.52}\left( {\mathrm{{tdd}}, J = {6.5},{6.5},{10.4},{16.8}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{5.06} - {5.01} \; \left( {\mathrm{m},2\mathrm{H}}\right) ,{4.10}\left( {\mathrm{\;s},2\mathrm{H}}\right) ,{3.81}\left( {\mathrm{\;d}, J = {6.4}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{2.42}(\mathrm{\;s}$ , 3H); ${}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta : {143.7},{136.2}$ , 134.9, 132.7, 129.7, 129.4, 128.6, 127.8, 127.6, 118.9, 57.2,44.8,21.5; IR (film) $v : {1349},{1160},{1086},{925},{827}$ , ${812},{711},{699},{662}{\mathrm{\;{cm}}}^{-1}$ ; EI-MS (relative intensity) $m/z$ (%): 333 (10), 123 (20), 91 (100), 65 (19); HRMS calcd for ${\mathrm{C}}_{17}{\mathrm{H}}_{19}{\mathrm{{NO}}}_{2}{\mathrm{\;S}}_{2}\mathrm{{Na}}{\left( \mathrm{M} + \mathrm{{Na}}\right) }^{ + } : {356.0749}$ , found 356.0741.

$N$ -烯丙基- $N$ -(苄硫基)-4-甲基苯磺酰胺(21):白色固体，熔点52 - 53 °C；${}^{1}$ H核磁共振(400兆赫，${\mathrm{{CDCl}}}_{3}$ ) $\delta : {7.82}\left( {\mathrm{\;d}, J = {8.3}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.32} - {7.26}\left( {\mathrm{\;m},7\mathrm{H}}\right)$ ，${5.52}\left( {\mathrm{{tdd}}, J = {6.5},{6.5},{10.4},{16.8}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{5.06} - {5.01} \; \left( {\mathrm{m},2\mathrm{H}}\right) ,{4.10}\left( {\mathrm{\;s},2\mathrm{H}}\right) ,{3.81}\left( {\mathrm{\;d}, J = {6.4}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{2.42}(\mathrm{\;s}$ ，3H)；${}^{13}\mathrm{C}$ 核磁共振(100兆赫，${\mathrm{{CDCl}}}_{3}$ ) $\delta : {143.7},{136.2}$ ，134.9，132.7，129.7，129.4，128.6，127.8，127.6，118.9，57.2，44.8，21.5；红外(薄膜) $v : {1349},{1160},{1086},{925},{827}$ ，${812},{711},{699},{662}{\mathrm{\;{cm}}}^{-1}$ ；电子轰击质谱(相对强度) $m/z$ (%): 333(10)，123(20)，91(100)，65(19)；高分辨质谱计算值为${\mathrm{C}}_{17}{\mathrm{H}}_{19}{\mathrm{{NO}}}_{2}{\mathrm{\;S}}_{2}\mathrm{{Na}}{\left( \mathrm{M} + \mathrm{{Na}}\right) }^{ + } : {356.0749}$ ，实测值为356.0741。

$N$ -(1-Bromobut-3-en-2-yl)-4-methyl- $N$ -(phenylthio)- benzenesulfonamide (2m): White solid, m.p. 83-84 °C; ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl ${}_{3}$ ) $\delta : {7.83}\left( {\mathrm{\;d}, J = {8.3}\mathrm{\;{Hz}},2\mathrm{H}}\right)$ , ${7.52}\left( {\mathrm{\;d}, J = {7.4}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.34} - {7.23}\left( {\mathrm{\;m},5\mathrm{H}}\right) ,{5.64}(\mathrm{{ddd}}$ , $J = {7.8},{10.3},{17.3}\mathrm{\;{Hz}},1\mathrm{H}),{5.15}\left( {\mathrm{\;d}, J = {10.4}\mathrm{\;{Hz}},2\mathrm{H}}\right)$ , ${4.91}\left( {\mathrm{q}, J = {7.4},{7.4},{7.7}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{3.45}(\mathrm{{dd}}, J = {6.9},{10.4} \; \mathrm{{Hz}},1\mathrm{H}),{3.34}\left( {\mathrm{t}, J = {8.7},{8.7}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{2.42}\left( {\mathrm{\;s},3\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR (100 MHz, CDCl3) δ: 144.2, 137.7, 136.1, 133.2, 129.4, 128.9, 128.1, 127.7, 126.6, 120.6, 66.0, 32.1, 21.6; IR (film) v: 1358, 1163, 1086, 888, 836, 812, 741, ${668}{\mathrm{\;{cm}}}^{-1}$ ; EI-MS (relative intensity) $m/z\left( \% \right) : {413}\left( 8\right)$ , 411 (7), 258 (37), 256 (36), 124 (44), 109 (69), 91 (100), 65(63); HRMS calcd for ${\mathrm{C}}_{17}{\mathrm{H}}_{18}{\mathrm{{BrNO}}}_{2}{\mathrm{\;S}}_{2}\mathrm{{Na}}{\left( \mathrm{M} + \mathrm{{Na}}\right) }^{ + }$ : 433.9855, found 433.9847.

$N$ -(1-溴丁-3-烯-2-基)-4-甲基-$N$ -(苯硫基)-苯磺酰胺(2m):白色固体，熔点83 - 84°C；${}^{1}\mathrm{H}$ 核磁共振(400兆赫，CDCl${}_{3}$ ) $\delta : {7.83}\left( {\mathrm{\;d}, J = {8.3}\mathrm{\;{Hz}},2\mathrm{H}}\right)$ ，${7.52}\left( {\mathrm{\;d}, J = {7.4}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.34} - {7.23}\left( {\mathrm{\;m},5\mathrm{H}}\right) ,{5.64}(\mathrm{{ddd}}$ ，$J = {7.8},{10.3},{17.3}\mathrm{\;{Hz}},1\mathrm{H}),{5.15}\left( {\mathrm{\;d}, J = {10.4}\mathrm{\;{Hz}},2\mathrm{H}}\right)$ ，${4.91}\left( {\mathrm{q}, J = {7.4},{7.4},{7.7}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{3.45}(\mathrm{{dd}}, J = {6.9},{10.4} \; \mathrm{{Hz}},1\mathrm{H}),{3.34}\left( {\mathrm{t}, J = {8.7},{8.7}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{2.42}\left( {\mathrm{\;s},3\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ 核磁共振(100兆赫，CDCl3) δ:144.2，137.7，136.1，133.2，129.4，128.9，128.1，127.7，126.6，120.6，66.0，32.1，21.6；红外(薄膜) v:1358，1163，1086，888，836，812，741，${668}{\mathrm{\;{cm}}}^{-1}$ ；电子轰击质谱(相对强度) $m/z\left( \% \right) : {413}\left( 8\right)$ ，411(7)，258(37)，256(36)，124(44)，109(69)，91(100)，65(63)；高分辨质谱计算值为${\mathrm{C}}_{17}{\mathrm{H}}_{18}{\mathrm{{BrNO}}}_{2}{\mathrm{\;S}}_{2}\mathrm{{Na}}{\left( \mathrm{M} + \mathrm{{Na}}\right) }^{ + }$ :433.9855，实测值为433.9847。

$N$ -(1-Hydroxybut-3-en-2-yl)-4-methyl- $N$ -(phenyl-thio)benzenesulfonamide (2n): White solid, m.p. 107-108 °C; ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl ${}_{3}$ ) $\delta : {7.83}$ (d, $J = {8.3}\mathrm{\;{Hz}},2\mathrm{H}),{7.58}\left( {\mathrm{\;s},2\mathrm{H}}\right) ,{7.36} - {7.24}\left( {\mathrm{\;m},5\mathrm{H}}\right) ,{5.56} \; \left( {\mathrm{{ddd}}, J = {8.0},{10.0},{17.6}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{5.09}(\mathrm{\;d}, J = {10.5}\mathrm{\;{Hz}}$ , 2H), 4.81 (dt, $J = {5.3},{8.0},{7.7}\mathrm{\;{Hz}},1\mathrm{H}),{3.70}(\mathrm{t}, J = {10.0}$ ,

$N$ -(1-羟基丁-3-烯-2-基)-4-甲基-$N$ -(苯硫基)苯磺酰胺(2n):白色固体，熔点107 - 108°C；${}^{1}\mathrm{H}$ 核磁共振(400兆赫，CDCl${}_{3}$ ) $\delta : {7.83}$ (d，$J = {8.3}\mathrm{\;{Hz}},2\mathrm{H}),{7.58}\left( {\mathrm{\;s},2\mathrm{H}}\right) ,{7.36} - {7.24}\left( {\mathrm{\;m},5\mathrm{H}}\right) ,{5.56} \; \left( {\mathrm{{ddd}}, J = {8.0},{10.0},{17.6}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{5.09}(\mathrm{\;d}, J = {10.5}\mathrm{\;{Hz}}$ ，2H)，4.81(双重三重峰，$J = {5.3},{8.0},{7.7}\mathrm{\;{Hz}},1\mathrm{H}),{3.70}(\mathrm{t}, J = {10.0}$ ，10.0 Hz, 1H), 3.56 (s, 1H), 2.42 (s, 3H), 1.52 (s, 1H); ${}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta : {144.1},{137.9},{136.2}$ , 132.5, 129.4, 129.1, 128.0, 127.8, 126.7, 119.8, 66.5, 62.7, 21.5; IR (film) v: 1349, 1160, 1086, 1041, 870, 812,738,665 ${\mathrm{{cm}}}^{-1}$ ; EI-MS (relative intensity) $m/z\left( \% \right)$ : 349 (7), 318 (40), 164 (58), 124 (44), 109 (78), 91 (100), 65 (57); HRMS calcd for ${\mathrm{C}}_{17}{\mathrm{H}}_{19}{\mathrm{{NO}}}_{3}{\mathrm{\;S}}_{2}\mathrm{{Na}}{\left( \mathrm{M} + \mathrm{{Na}}\right) }^{ + }$ : 372.0699, found 372.0690.

$N$ -(1-Hydroxy-1-phenylbut-3-en-2-yl)-4-methyl- $N$ - (phenylthio) benzenesulfonamide (20): Colorless oil; ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl3) δ: 7.84 (d, J=8.2 Hz, 2H), 7.74-7.69 (m, 2H), 7.37-7.21 (m, 10H), 5.52 (ddd, $J = {8.4},{10.4},{17.2}\mathrm{\;{Hz}},1\mathrm{H}),\left( {\mathrm{d}, J = {10.1}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{4.70}(\mathrm{\;s}$ , 1H), 4.57 (s, 1H), 2.39 (s, 3H), 2.30 (s, 1H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) δ: 144.0, 139.6, 137.5, 136.0, 131.7, 129.2, 129.1, 128.3, 128.1, 128.1, 127.6, 127.4, 120.7, 74.0, 71.7, 21.5; IR (film) v: 1346, 1160, 1086, 1022, 906,812,732,699,668 cm ${}^{-1}$ ; EI-MS (relative intensity) $m/z\left( \% \right) : {318}\left( {32}\right) ,{210}\left( {98}\right) ,{163}\left( {69}\right) ,{155}\left( {48}\right) ,{109}$ (47), 91 (100), 79 (52), 65 (44); HRMS calcd for ${\mathrm{C}}_{23}{\mathrm{H}}_{23}{\mathrm{{NO}}}_{3}{\mathrm{\;S}}_{2}\mathrm{{Na}}{\left( \mathrm{M} + \mathrm{{Na}}\right) }^{ + } : {448.1011}$ , found 448.1003.

$N$ -(1-(1,3-Dioxoisoindolin-2-yl)but-3-en-2-yl)-4- methyl- $N$ -(phenylthio)benzenesulfonamide (2p): White solid, m.p. 183-185 °C; ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl3) $\delta : {7.78} - {7.75}\left( {\mathrm{\;m},4\mathrm{H}}\right) ,{7.71} - {7.68}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{7.46}\left( {\mathrm{\;s},2\mathrm{H}}\right)$ , 7.30-7.11 (m, 5H), 5.77-5.68 (m, 1H), 5.22-5.03 $\left( {\mathrm{m},3\mathrm{H}}\right) ,{3.83}\left( {\mathrm{\;d}, J = {13.4}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{2.26}\left( {\mathrm{\;s},3\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR (100 MHz, CDCl3) 5: 167.7, 143.8, 138.3, 133.9, 131.8, 129.4, 128.7, 127.8, 127.1, 125.8, 123.2, 120.4, 120.3, 62.4, 39.9, 21.5; EI-MS (relative intensity) $m/z$ (%): 478 (2), 318 (30), 200 (24), 160 (100), 91 (49); HRMS calcd for ${\mathrm{C}}_{25}{\mathrm{H}}_{22}{\mathrm{\;N}}_{2}{\mathrm{O}}_{4}{\mathrm{\;S}}_{2}\mathrm{{Na}}{\left( \mathrm{M} + \mathrm{{Na}}\right) }^{ + } : {501.0905}$ , found 501.0913.

$N$ -(1-(1,3-Dioxolan-2-yl)allyl)-4-methyl- $N$ -(phenyl-thio)benzenesulfonamide (2q): Colorless oil; ${}^{1}\mathrm{H}$ NMR $\left( {{400}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta : {7.82}\left( {\mathrm{\;d}, J = {8.2}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.47}(\mathrm{\;s}$ , 2H), 7.30-7.12 (m, 5H), 5.82 (ddd, J=7.8, 10.4, 17.9 Hz, 1H), 5.19 (d, J = 10.5 Hz, 2H), 5.01 (s, 1H), 5.01-4.69 (m, 1H), 3.86-3.83 (m, 4H), 2.41 (s, 3H); ${}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) 6: 143.8,138.2,136.3, 131.4, 129.2, 128.5, 128.2, 126.9, 125.6, 120.8, 103.1, 65.9, 65.3, 64.5, 21.5; IR (film) v: 1349, 1163, 1086, 866,814,665 ${\mathrm{{cm}}}^{-1}$ ; EI-MS (relative intensity) $m/z\left( \% \right)$ : 282 (8), 109 (11), 91 (14), 73 (100), 45 (23); HRMS calcd for ${\mathrm{C}}_{19}{\mathrm{H}}_{21}{\mathrm{{NO}}}_{4}{\mathrm{\;S}}_{2}\mathrm{{Na}}{\left( \mathrm{M} + \mathrm{{Na}}\right) }^{ + } : {414.0804}$ , found 414.0800.

Acknowledgement

致谢

The project is supported by NSFC (Nos. 20902005, 20832002, 20772003, 20821062) and 973 Program (No. 2012CB821600).

本项目受国家自然科学基金(项目编号:20902005、20832002、20772003、20821062)和国家重点基础研究发展计划(973计划，项目编号:2012CB821600)资助。

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