有机添加剂对抑制锌粉催化合成炔基硅烷副产物的影响

doi:10.11949/j.issn.0438-1157.20171603

摘要/Abstract

摘要：

锌粉催化苯乙炔与氯硅烷的硅烷化反应产物中会形成约33%端烯副产物。通过添加有机物作为H捕捉剂，利用气相色谱对产物进行分析，研究其对抑制端烯副产物形成的影响。实验结果表明，当使用吡啶和1，8-二氮杂二环十一碳-7-烯（DBU）时，可有效提高选择性。分别对有机添加剂的浓度、反应时间和温度进行了优化。浓度优化结果表明，添加6 mol吡啶或DBU时，副产物含量均明显降低，转化率相对提高，且添加吡啶时效果更显著。添加6 mol吡啶时，继续考察反应时间和温度的影响，结果发现，反应20 h后，转化率较高，延长反应时间不再明显提高反应的选择性和转化率；提高温度有利于提高转化率，但不利于提高选择性，110℃下反应转化率较高，100℃反应时选择性最好。

关键词: 锌粉, 硅烷化, 端烯副产物, 选择性, 催化, 化学反应

Abstract:

Silylation of phenylacetylene with trimethylchlorosilane (TMCS) in the presence of zinc powder catalyst will produce around 33% alkene by-product. Different organic additives were used as H scavengers to reduce the production of styrene (ST). From the results via GC analysis, pyridine and 1,8-diazabicyclo[5.4.0]undec-7-ene(DBU) were found to be effective to increase the selectivity but the conversion rate was decreased. The concentration of organic additives, reaction time and temperature were then optimized. The concentration optimization showed that 6 mol DBU was effective to decrease the generation of styrene but the yield of main product phenylethynyltrimethylchlorosilane (PT) dropped significantly. 6 mol pyridine was the optimal concentration for its relatively high conversion and selectivity. The yield of styrene decreased to around 13% while the yield of PT was 57%. The optimal reaction time was 20 h. Conversion and selectivity rarely changed with a longer reaction time. As for temperature, it was found that a higher temperature was beneficial to improve the conversion but unfavorable to selectivity. The results showed that the conversion was highest at 110℃ while the selectivity was best at 100℃ with 6 mol pyridine.

Key words: zinc powder, silylation, alkene by-product, selectivity, catalysis, chemical reaction

中图分类号:

TQ06

黄盼, 刘振, 邵云奇, 邓诗峰, 刘柏平. 有机添加剂对抑制锌粉催化合成炔基硅烷副产物的影响[J]. 化工学报, 2018, 69(7): 2993-3000.

HUANG Pan, LIU Zhen, SHAO Yunqi, DENG Shifeng, LIU Boping. Influences of organic additives on inhibiting by-products in zinc-catalyzed synthesis of alkynylsilane[J]. CIESC Journal, 2018, 69(7): 2993-3000.

参考文献 30

[1]	KHAN A, ASIRI A M, KOSA S A, et al. Catalytic stereoselective addition to alkynes. Borylation or silylation promoted by magnesiasupported iron oxide and cis-diboronation or silaboration by supported platinum nanoparticles[J]. Journal of Catalysis, 2015, 329(9):401-412.
[2]	SUGITA H, HATANAKA Y, HIYAMA T. Silylation of 1-alkynes with chlorosilanes promoted by zinc:preparation of alkynylsilanes in a single step[J]. Tetrahedron Letters, 1995, 36(16):2769-2772.
[3]	RAHAIM R J, SHAW J T. Zinc-catalyzed silylation of terminal alkynes[J]. Journal of Organic Chemistry, 2008, 73(7):2912-2915.
[4]	ITOH M, MITSUZUKA M, IWATA K, et al. A novel synthesis and extremely high thermal stability of poly[(phenylsilylene) ethynylene-1, 3-phenyleneethynylene] [J]. Macromolecules, 1994, 27(26):7917-7919.
[5]	ITOH M, INOUE K, IWATA K, et al. New highly heat-resistant polymers containing silicon:poly(silyleneethynylenephenyleneethynylene)s[J]. Macromolecules, 1997, 30(4):694-701.
[6]	JIANG Z Y, ZHOU Y, HUANG F R, et al. Characterization of a modified silicon-containing arylacetylene resin with POSS functionality[J]. Chinese Journal of Polymer Science, 2011, 29(6):726-731.
[7]	ALAZET S, ZIMMER L, BILLARD T. Base-catalyzed electrophilic trifluoromethylthiolation of terminal alkynes[J]. Angew. Chem. Int. Ed. Engl., 2013, 52(41):10814-10817.
[8]	TERAO J, KAMBE N. Transition metal catalyzed carbon-silicon bond forming reactions using chlorosilanes promoted by grignard reagents[J]. Chemical Record, 2007, 7(1):57.
[9]	王明明, 王子潇, 商明, 等. 过渡金属催化的C-H炔基化反应[J]. 有机化学, 2015, 35(3):570-577. WANG M M, WANG Z X, SHANG M, et al. Transition-metalcatalyzed C-H alkynylation[J]. Chinese Journal of Organic Chemistry, 2015, 35(3):570-577.
[10]	MARCINIEC B. Hydrosilylation:A Comprehensive Review on Recent Advances[M]. MATISONS J. Netherlands:Springer Science & Business Media, 2008:4-38.
[11]	KOWNACKI I, MARCINIEC B, DUDZIEC B, et al. Silylative coupling of terminal alkynes with iodosilanes:new catalytic activation of sp-hybridized carbon-hydrogen bonds[J]. Organometallics, 2011, 30(9):2539-2545.
[12]	KOWNACKI I, ORWAT B, MARCINIEC B. Iridium-promoted conversion of chlorosilanes to alkynyl derivatives in a one-pot reaction sequence[J]. Organometallics, 2014, 33(12):3051-3059.
[13]	KOWNACKI I, ORWAT B, MARCINIEC B, et al. A new and efficient route for the synthesis of alkynyl functionalized silicon derivatives[J]. Tetrahedron Letters, 2014, 55(2):548-550.
[14]	ANO Y, TOBISU M, CHATANI N. Ruthenium-catalyzed direct orthoalkynylation of arenes with chelation assistance[J]. Synlett, 2012, 23(19):2763-2767.
[15]	ANO Y, TOBISU M, CHATANI N. Palladium-catalyzed direct orthoalkynylation of aromatic carboxylic acid derivatives[J]. Organic Letters, 2012, 14(1):354-357.
[16]	XU Y H, ZHANG Q C, HE T, et al. Palladium-catalyzed direct alkynylation of N-vinylacetamides[J]. Advanced Synthesis & Catalysis, 2014, 356(7):1539-1543.
[17]	JIANG H L, ZHU S Z. Silylation of 1-alkynes with chlorosilanes promoted by Zn(OTf)2:an efficient way to the preparation of alkynylsilanes[J]. Tetrahedron Letters, 2005, 46(3):517-519.
[18]	KIYOKAWA K, TACHIKAKE N, YASUDA M, et al. Direct synthesis of alkynylstannanes:ZnBr2 catalyst for the reaction of tributyltin methoxide and terminal alkynes[J]. Angew. Chem. Int. Ed.Engl., 2011, 50(44):10393-10396.
[19]	YAMAGUCHI K, WANG Y, OISHI T, et al. Heterogeneously catalyzed aerobic cross-dehydrogenative coupling of terminal alkynes and monohydrosilanes by gold supported on OMS-2[J]. Angew. Chem. Int. Ed. Engl., 2013, 52(21):5627-30.
[20]	TORRENTE J P, NGUYEN D H, JIMÉNEZ M V, et al. Hydrosilylation of terminal alkynes catalyzed by a ONO-pincer iridium(Ⅲ) hydride compound:mechanistic insights into the hydrosilylation and dehydrogenative silylation catalysis[J]. Organometallics, 2016, 35(14):2410-2422.
[21]	CHALK A J, HARROD J F. Homogeneous catalysis(Ⅱ):The mechanism of the hydrosilation of olefins catalyzed by group Ⅷ metal complexes[J]. Journal of the American Chemical Society, 1965, 87(1):16-21.
[22]	HARROD J F, CHALK A J. Dicobalt octacarbonyl as a catalyst for hydrosilation of olefins[J]. Journal of the American Chemical Society, 1965, 87(5):1133-1133.
[23]	MEISTER T K, RIENER K, GIGLER P, et al. Platinum catalysis revisited-unraveling principles of catalytic olefin hydrosilylation[J]. ACS Catalysis, 2016, 6(2):1274-1284.
[24]	SHIMIZU R, FUCHIKAMI T. Dehydrogenative silylation of terminal alkynes by iridium catalyst[J]. Tetrahedron Letters, 2000, 41(6):907-910.
[25]	YONEKURA K, IKETANI Y, SEKINE M, et al. Zinc-catalyzed dehydrogenative silylation of indoles[J]. Organometallics, 2017, 36(17):3234-3249.
[26]	MÁEORG U, VⅡRLAID S, HAGU H, et al. On the in situ trimethylsilylation of zinc acetylides[J]. Journal of Organometallic Chemistry, 2000, 601(2):341-342.
[27]	沈浩, 蒋孝杰, 周燕, 等. 锌粉催化合成含硅芳炔树脂[J]. 过程工程学报, 2014, 14(2):329-334. SHEN H, JIANG X J, ZHOU Y, et al. Synthesis of silicon-containing arylacetylene resin catalyzed by zinc powder[J]. The Chinese Journal of Process Engineering, 2014, 14(2):329-334.
[28]	蒋孝杰. 含硅芳炔树脂的合成、共混改性及复合材料的性能研究[D]. 上海:华东理工大学, 2016. JIANG X J. Studies of synthesis, blend modification and performance of the composite of silicon-containing arylacetylene resin[D]. Shanghai:East China University of Science and Technology, 2016.
[29]	汪强, 杨建辉, 袁荞龙, 等. 硅烷芳炔-硅氧烷芳炔嵌段共聚物的合成与表征[J]. 化工学报, 2014, 65(10):4168-4175. WANG Q, YANG J H, YUAN Q L, et al. Synthesis and characterization of block copolymers of poly(silane arylacetylene) and poly(siloxane arylacetylene)[J]. CIESC Jorunal, 2014, 65(10):4168-4175.
[30]	姜欢, 邓诗峰, 阮湘政. 氯化锌催化合成含硅芳炔树脂[J]. 高分子材料科学与工程, 2017, 33(11):18-21. JIANG H, DENG S F, RUAN X Z. Synthesis of silicon-containing arylacetylene resin catalyzed by ZnCl2[J]. Polymer Materials Science & Engineering, 2017, 33(11):18-21.