二芳基二硫醚與硝基芳烴的反應(yīng)

李術(shù)艷，孫莉娜，沈淑君，程天行，程雙華，陳久喜

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二芳基二硫醚與硝基芳烴的反應(yīng)

李術(shù)艷1,2，孫莉娜1,2，沈淑君1,2，程天行3，程雙華3，陳久喜3

（1漳州職業(yè)技術(shù)學(xué)院食品與生物工程系，福建漳州 363000；2農(nóng)產(chǎn)品深加工及安全福建省高校應(yīng)用技術(shù)工程中心，福建 漳州 363000；3溫州大學(xué)化學(xué)與材料工程學(xué)院，浙江溫州 325035）

以二芳基二硫醚（ArSSAr）和硝基芳烴（ArNO2）為原料，在廉價(jià)易得的甲醛次硫酸氫鈉（Rongalite?）和碳酸鉀（K2CO3）共同促進(jìn)下，以二甲亞砜（DMSO）為溶劑，50℃下合成了一系列非對(duì)稱二芳基硫醚衍生物，產(chǎn)物結(jié)構(gòu)經(jīng)1H NMR和13C NMR確證。該方法具有反應(yīng)條件溫和、原料易得和操作簡(jiǎn)單等優(yōu)點(diǎn)。

二芳基二硫醚；硝基芳烴；甲醛次硫酸氫鈉；二芳基硫醚；反應(yīng)機(jī)理

引 言

二芳基硫醚是一類非常重要的含硫化合物，被廣泛應(yīng)用于藥物設(shè)計(jì)與開(kāi)發(fā)[1-4]。許多含有芳基硫醚官能團(tuán)的化合物具有多種生物活性。因此，二芳基硫醚衍生物的合成備受關(guān)注。早在1984年，Lindley等[5-6]報(bào)道了在六甲基磷酰胺等極性溶劑中高溫條件下（＞200℃）進(jìn)行芳基鹵化物與硫醇銅鹽或硫酚（醇）的反應(yīng)。近年來(lái)，過(guò)渡金屬催化的鹵代芳烴與硫酚的偶聯(lián)反應(yīng)制備硫醚的策略成為研究熱點(diǎn)[7-11]。最近，Bahekara等[12]報(bào)道了硝基芳烴與硫酚的偶聯(lián)反應(yīng)，實(shí)現(xiàn)了C—S的形成反應(yīng)以構(gòu)建二芳基硫醚衍生物（圖1）。

雖然近年來(lái)芳基硫醚的合成取得重要進(jìn)展[13-30]，但這些方法仍存在一些缺點(diǎn)，如使用過(guò)量的具有惡臭味液態(tài)狀的硫醇或硫酚，較長(zhǎng)的反應(yīng)時(shí)間，計(jì)量甚至過(guò)量的不穩(wěn)定的催化劑，苛刻的反應(yīng)條件等。因此，開(kāi)發(fā)一種簡(jiǎn)便的合成方法制備芳基硫醚仍然具有重要意義。

甲醛次硫酸氫鈉（Rongalite?），也稱雕白粉，是一種非常廉價(jià)的還原性試劑，被廣泛應(yīng)用于化工醫(yī)藥中間體的合成[31]。本課題組已報(bào)道了雕白粉促進(jìn)二硫醚的活化，與環(huán)氧化合物的開(kāi)環(huán)反應(yīng)[32]、,-不飽和羰基化合物的Michael反應(yīng)[33]。而甲醛次硫酸氫鈉促進(jìn)的二硫醚與硝基芳烴的反應(yīng)至今沒(méi)有報(bào)道。本文使用甲醛次硫酸氫鈉為促進(jìn)劑活化二芳基二硫醚（替代具有惡臭味的硫酚），進(jìn)而與硝基芳烴通過(guò)加成-消除反應(yīng)制備非對(duì)稱芳基硫醚衍生物。

1 實(shí)驗(yàn)部分

1.1 實(shí)驗(yàn)藥品

對(duì)硝基苯甲醛（分析純）、對(duì)二硝基苯（分析純）、對(duì)硝基苯乙酮（分析純）、4,4′-二甲基二苯基二硫醚（分析純）、4,4′-二羥基二苯基二硫醚（分析純）、二苯基二硫醚（分析純）均購(gòu)于百靈威科技有限公司；二甲亞砜（分析純）、碳酸鉀（分析純）、碳酸鈉（分析純）、碳酸氫鈉（分析純）、碳酸銫（分析純）、,-二甲基甲酰胺（分析純）均購(gòu)于上海阿拉丁生化科技股份有限公司；環(huán)己烷（分析純）、甲苯（分析純）、甲醇（分析純）、三乙胺（分析純）、二水合氟化鉀（分析純）均購(gòu)于天津市科密歐化學(xué)試劑有限公司；薄層層析硅膠板(2.5 cm×8 cm) 購(gòu)于煙臺(tái)江友硅膠開(kāi)發(fā)有限公司。

1.2 反應(yīng)及分析測(cè)試儀器

AVANCE-300型或ADVANCE-500型核磁共振儀，TMS為內(nèi)標(biāo)，CDCl3為溶劑，Bruker公司；MicrOTOF-QII高分辨質(zhì)譜，Bruker公司；WRS-1B數(shù)字熔點(diǎn)儀，上海精密科學(xué)儀器有限公司；ZF-20D型暗箱式紫外分析儀，河南愛(ài)博特科技發(fā)展有限公司；DSB-2100型旋轉(zhuǎn)蒸發(fā)儀，上海愛(ài)朗儀器有限公司；智能恒溫磁力攪拌器（ZNCL-QS 130-60），河南愛(ài)博特科技發(fā)展有限公司；TLE104E/02型電子天平，梅特勒-托利多儀器（上海）有限公司。

1.3 非對(duì)稱二芳基硫醚化合物的合成

在裝有磁力攪拌器的干燥的Schlenk管中加入硝基芳烴（0.4 mmol）、二芳基二硫醚（0.3 mmol）、甲醛次硫酸氫鈉（0.6 mmol）、K2CO3（0.45 mmol）和DMSO（2 ml），常溫?cái)嚢枞芙夂?，升溫?0℃充分?jǐn)嚢? h。整個(gè)實(shí)驗(yàn)過(guò)程用高效薄層色譜板（TLC）進(jìn)行監(jiān)測(cè)，反應(yīng)完畢后，反應(yīng)液用20ml水洗，然后再用乙醚30 ml分3次萃取，合并有機(jī)相，無(wú)水硫酸鎂干燥，過(guò)濾后濃縮，所得的粗產(chǎn)物用0.037～0.048 mm硅膠柱層析分離純化制得非對(duì)稱二芳基硫醚。

當(dāng)使用對(duì)硝基苯甲醛作為反應(yīng)底物時(shí)，反應(yīng)在氮?dú)夥諊羞M(jìn)行。

2 實(shí)驗(yàn)結(jié)果與討論

2.1 反應(yīng)條件篩選

選用如圖2所示的對(duì)硝基苯乙酮（1a）和二苯基二硫醚（2a）作為模板反應(yīng)，考察不同條件（如溶劑、堿、配比等）對(duì)反應(yīng)結(jié)果的影響。

2.1.1 溶劑的篩選 首先考察了溶劑對(duì)反應(yīng)的影響。如表1所示，溶劑對(duì)反應(yīng)的影響較大，當(dāng)選用環(huán)己烷、甲苯或甲醇作為溶劑時(shí)，只得到非常少量的目標(biāo)產(chǎn)物4-(苯硫基)苯甲醛(3a)。然而，當(dāng)反應(yīng)在,-二甲基甲酰胺（DMF）中進(jìn)行時(shí)，3a的收率提高至52%。當(dāng)選用二甲亞砜（DMSO）為溶劑，3a的收率進(jìn)一步提高至77%。因此，在接下來(lái)的反應(yīng)條件篩選選取DMSO作為溶劑。

表1 溶劑篩選

Note: Reaction conditions: 1a (0.4 mmol ), 2a (0.3 mmol)，K2CO3(0.45 mmol) and Rongalite?(0.6 mmol), solvent (2 ml), 3 h, 50℃.

2.1.2 堿的篩選 如表2所示，堿對(duì)該反應(yīng)也有一定的影響。在所有被考察的堿性化合物中，當(dāng)選用KF·2H2O作為堿時(shí)，反應(yīng)只得到痕量目標(biāo)產(chǎn)物3a。

表2 堿篩選

Note: Reaction conditions: 1a (0.4 mmol ), 2a (0.3 mmol)，base (0.45 mmol) and Rongalite?(0.6 mmol), DMSO (2 ml), 3 h, 50℃.

當(dāng)使用其他的無(wú)機(jī)堿（如NaHCO3、Cs2CO3和Na2CO3）或有機(jī)堿（如三乙胺，NEt3），3a的收率分別為60%、62%、67%和50%。以K2CO3作為堿時(shí)的收率可達(dá)77%。

2.1.3 堿及甲醛次硫酸氫鈉的用量對(duì)反應(yīng)的影響

以DMSO為反應(yīng)溶劑，K2CO3為堿性條件，考察了堿和甲醛次硫酸氫鈉（Rongalite?）的用量對(duì)反應(yīng)的影響。由表3可見(jiàn)，堿和甲醛次硫酸氫鈉對(duì)該反應(yīng)至關(guān)重要，不加兩者中任意一種，該反應(yīng)無(wú)法進(jìn)行。首先篩選K2CO3的用量，當(dāng)反應(yīng)體系中加入0.15 mmol的K2CO3時(shí)，產(chǎn)物3a的收率為30%；當(dāng)K2CO3的量增至0.3 mmol，產(chǎn)物3a的收率提高至65%；當(dāng)K2CO3的量為0.45 mmol時(shí)，產(chǎn)物3a的收率最高（77%）；繼續(xù)K2CO3的量增至0.6 mmol時(shí)，產(chǎn)率并沒(méi)有明顯的提高。另一方面，通過(guò)篩選Rongalite?的用量發(fā)現(xiàn)當(dāng)反應(yīng)體系中加入0.6 mmol的Rongalite?時(shí)，產(chǎn)物3a的收率為77%。

表3 堿及促進(jìn)劑的用量對(duì)反應(yīng)的影響

Note: Reaction conditions: 1a (0.4 mmol ), 2a (0.3 mmol)，DMSO (2 ml), 3 h, 50℃.

2.2 底物范圍

通過(guò)以上的篩選，獲得較佳的反應(yīng)條件如下：對(duì)硝基苯乙酮（0.4 mmol）、二苯基二硫醚（0.3 mmol）、Rongalite?（0.6 mmol），K2CO3（0.45 mmol），DMSO (2 ml)，50℃，3 h。為進(jìn)一步研究該反應(yīng)條件的普適性，探討了含其他取代基團(tuán)硝基芳烴與二芳基二硫醚的反應(yīng)情況。

如表4所示，對(duì)硝基苯乙酮（1a）與二對(duì)甲苯基二硫醚（2b）、二對(duì)羥基苯基二硫醚（2c）的反應(yīng)都能平穩(wěn)地進(jìn)行，相應(yīng)的目標(biāo)產(chǎn)物3b和3c收率分別為61% 和72%。有趣的是，當(dāng)使用1,4-二硝基苯（1b）為底物時(shí)，反應(yīng)也能順利進(jìn)行；如序號(hào)4～6所示，選擇性地合成了目標(biāo)產(chǎn)物3d～3f，收率分別是67%、61%和66%。值得一提的是，當(dāng)使用對(duì)硝基苯甲醛（1c）為底物時(shí)，采用在N2保護(hù)條件下、降低反應(yīng)溫度（25℃）的策略避免對(duì)硝基苯甲醛的甲酰基（CHO）被氧化。如序號(hào)7～9所示，1c與二苯基二硫醚（2a）、二對(duì)甲苯基二硫醚（2b）和二對(duì)羥基苯基二硫醚（2c）的反應(yīng)，所得的目標(biāo)產(chǎn)物3g～3i的收率分別為79%、70%和73%。當(dāng)然，該方法也存在底物使用范圍窄的局限性。例如，當(dāng)使用富電子的硝基芳烴作為底物時(shí)，該反應(yīng)無(wú)法進(jìn)行。

表4 底物范圍

Table 4 Substrates scope

EntryR (1)Ar (2)ProductYield /% 1COCH3 (1a)Ph (2a)3a77① 21ap-MeC6H4 (2b)3b61① 31ap-OHC6H4(2c)3c72① 4NO2 (1b)2a3d67① 51b2b3e61① 61b2c3f66① 7CHO (1c)2a3g79② 81c2b3h70② 91c2c3i73②

① Reaction conditions: 1 (0.4 mmol ), 2 (0.3 mmol), K2CO3(0.45 mmol) and Rongalite?(0.6 mmol), DMSO (2 ml), 3 h, 50℃. ②At 25℃ under N2atmosphere.

2.3 產(chǎn)物結(jié)構(gòu)表征

1-(4-苯硫基)苯乙酮(3a): 熔點(diǎn): 62～63℃;1H NMR (CDCl3, 300 MHz): 2.55 (s, 3H), 7.83～7.19 (m, 9H);13C NMR (CDCl3, 125 MHz):26.5,127.5, 128.8, 128.9, 129.7, 132.1, 133.9, 134.5, 144.9, 197.1。HRMS (/): [M+H]+calcd. for C14H13OS: 229.0682; found: 229.0677。

1-(對(duì)甲苯硫基)苯乙酮(3b): 熔點(diǎn): 92～93℃;1H NMR (CDCl3, 300 MHz): 2.39 (s, 3H), 2.53 (s, 3H), 7.13～7.23 (m, 4H), 7.39～7.80 (m, 4H);13C NMR (CDCl3, 125 MHz):21.1, 26.3, 126.5, 127.8, 128.7, 130.4, 134.0, 134.3, 139.2, 145.8, 196.9。HRMS (/): [M+H]+calcd. for C15H15OS: 243.0838; found: 243.0835。

1-(對(duì)羥基苯硫基)苯乙酮(3c): 油狀物;1H NMR (CDCl3, 300 MHz):2.55 (s, 3H), 5.20 (s, 1H), 6.90～7.81 (m, 8H);13C NMR (CDCl3, 125 MHz):25.8, 117.0, 120.8, 125.8, 130.1, 133.1, 137.2, 149.1, 157.2, 191.4。HRMS (/): [M+H]+calcd. for C14H13O2S: 245.0631; found: 245.0638。

4-(對(duì)硝基苯基)苯基硫醚(3d): 熔點(diǎn): 53～54℃;1H NMR (CDCl3, 300 MHz): 7.16～8.08 (m, 9H);13C NMR (CDCl3, 125 MHz):124.1, 126.7, 129.7, 130.1, 130.5, 134.8, 145.4, 148.5。HRMS (/): [M+H]+calcd. for C12H10NO2S: 232.0427; found: 232.0423。

4-(對(duì)硝基苯基)(對(duì)甲基苯基)硫醚(3e): 熔點(diǎn): 83～84℃;1H NMR (CDCl3, 300 MHz): 2.42 (s, 3H), 7.12～8.07 (m, 8H);13C NMR (CDCl3, 125 MHz):21.3, 124.0, 126.1, 126.5, 130.9, 135.1, 140.2, 142.2, 149.3。HRMS (/): [M+H]+calcd. for C13H12NO2S: 246.0583; found: 246.0588。

4-(對(duì)硝基苯硫基)苯酚(3f): 油狀物;1H NMR (CDCl3, 300 MHz): 5.21 (s, 1H), 6.933～7.10 (m, 4H), 7.43～8.06 (m, 4H);13C NMR (CDCl3, 125 MHz):117.2, 120.2, 124.0, 125.6, 137.4, 145.0, 150.1, 157.6。HRMS (/): [M+H]+calcd. for C12H10NO3S: 248.0376; found: 248.0379。

4-(苯硫基)苯甲醛(3g): 熔點(diǎn): 53～54℃;1H NMR (CDCl3, 300 MHz): 7.23～7.45 (m, 5H), 7.52～7.74 (m, 4H), 9.91 (s, 1H);13C NMR (CDCl3, 125 MHz):127.2, 129.2, 129.8, 130.2, 131.3, 133.7, 134.4, 147.3, 191.3。HRMS (/): [M+H]+calcd. for C13H11OS: 215.0525; found: 215.0529。

4-(對(duì)甲基苯硫基)苯甲醛(3h): 熔點(diǎn): 54～55℃;1H NMR (CDCl3, 300 MHz): 2.41 (s, 3H), 7.17～7.26 (m, 4H), 7.42～7.71 (m, 4H), 9.89 (s, 1H);13C NMR (CDCl3, 125 MHz):21.3, 126.5, 127.2, 130.0, 130.6, 133.4, 134.8, 139.7, 148.1, 191.1。HRMS (/): [M+H]+calcd. for C14H13OS: 229.0682; found: 229.0689。

4-(對(duì)羥基苯硫基)苯甲醛(3i): 油狀物;1H NMR (CDCl3, 300 MHz): 5.20 (s, 1H), 6.93～7.15 (m, 4H), 7.42～7.71 (m, 4H), 9.88 (s, 1H);13C NMR (CDCl3, 125 MHz):116.9, 125.8, 128.8, 133.8, 137.1, 146.9, 157.0, 196.0。HRMS (/): [M+H]+calcd. for C13H11O2S: 231.0474; found: 231.0479。

3 結(jié) 論

本文研究了以廉價(jià)的甲醛次硫酸氫鈉為反應(yīng)促進(jìn)劑，利用低毒無(wú)臭而且易于操作的二芳基二硫醚替代硫酚與硝基芳烴的反應(yīng)，在溫和的反應(yīng)條件下實(shí)現(xiàn)了非對(duì)稱二芳基硫醚的制備。所得產(chǎn)物采用1H NMR和13C NMR進(jìn)行確證。該方法具有反應(yīng)條件溫和、原料易得和操作簡(jiǎn)單等優(yōu)點(diǎn)，為非對(duì)稱二芳基硫醚衍生物的制備提供了新策略。

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Reaction of diaryl disulfides with nitroarenes

LI Shuyan1,2, SUN Lina1,2, SHEN Shujun1,2, CHENG Tianxing3, CHENG Shuanghua3, CHEN Jiuxi3

(1Department of Food and Biology Engineering, Zhangzhou Institute of Technology, Zhangzhou 363000, Fujian, China;2The Applied Technical Engineering Center of Further Processing and Safety of Agriculture Products, Higher Education Institution in Fujian Province, Zhangzhou 363000, Fujian, China;3College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou 325035, Zhejiang, China)

The cheap and readily available Rongalite?/K2CO3promoted the reaction of diaryl disulfides with nitroarenes in DMSO at 50 ℃, providing a convenient route to the synthesis of unsymmetrica diaryl sulfide. The structures of all products were characterized by1H NMR and13C NMR. This protocol had some distinct advantages of mild conditions, readily available starting materials and simple work-up.

diaryl sulfide; nitroarenes; sodium formaldehyde sulfoxylate; diaryl sulfide; reaction mechanism

10.11949/j.issn.0438-1157.20161755

O 6

A

0438—1157（2017）06—2394—05

程天行。

李術(shù)艷（1981—），女，碩士研究生，講師。

浙江省自然科學(xué)基金項(xiàng)目（LY16B020012）；福建省教育廳科技計(jì)劃項(xiàng)目（JA13388）。

2016-12-15收到初稿，2017-03-15收到修改稿。

2016-12-15.

CHENG Tianxing, ctx@wzu.edu.cn

supported by the Natural Science Foundation of Zhejiang Province (LY16B020012) and the Educational Foundation of Fujian Province (JA13388).