Synthesis of 1-cyclohexenylacetonitrile using cyclohexanone and acetonitrile under synergetic activation of CaC2 and CsF

doi:10.16085/j.issn.1000-6613.2019-0262

Abstract

Abstract:

CaC₂ is a commodity chemical, and is of potential use in some alkaline catalyzed reactions. The synergetic activation effect of CaC₂-CsF for the reaction of cyclohexanone (CYC) and acetonitrile (ACN) was reported for the first time. The effects of reaction time, temperature and dosage of activating agents on the reaction were investigated. The results show that the reactivity of CYC is enhanced by the strong complexation between CsF and CYC, and the nucleophilic reactivity of ACN is enhanced via its deprotonation by the strong basicity of CaC₂. The reaction proceeds efficiently at mild conditions under synergetic action of CaC₂ and CsF, yielding 1-cyclohexenylacetonitrile (1-CAC) and acetylene simultaneously. The present method is much superior to the reported other synthetic methods , 97.5% of CYC conversion and 87.9% of 1-CAC yield can be obtained in 3h at 100℃ (n _CsF∶n _CaC2∶n _CYC∶n _ACN=1∶5.7∶10∶35.5). This study provides a novel method for the efficient synthesis of 1-CAC, and the result is instructive for the utilization of CaC₂ as a strong base in promoting the reaction of ACN with other carbonyl compounds.

Key words: calcium carbide, chemical reaction, activation, synthesis, multiphase reaction

摘要：

电石是一种煤化工产品，其强碱性对很多碱催化反应具有潜在的促进作用。本文首次报道了电石和氟化铯对环己酮与乙腈反应的促进作用，考察了反应时间、温度和氟化铯用量对反应的影响。结果表明，氟化铯与环己酮具有强络合作用，可以提高羰基的反应活性；碳化钙不但可通过其去质子化作用来提高乙腈的亲核反应活性，还可促进目标产物的形成。在碳化钙和氟化铯的共同作用下，可实现环己烯乙腈的高效合成，而碳化钙则定量转化为乙炔。在100℃和物料比n _氟化铯∶n _碳化钙∶n _环己酮∶n _乙腈=1∶5.7∶10∶35.5条件下常压回流3h，环己酮的转化率和环己烯乙腈的收率分别达97.5%与87.9%，远高于其他合成方法。本研究提供了一种绿色、高效的1-环己烯乙腈合成新方法，对于研究电石作为强碱性物质促进乙腈与其他羰基化合物反应具有重要借鉴意义。

关键词: 碳化钙, 化学反应, 活化, 合成, 多相反应

CLC Number:

TQ203.9

Maoqiang JIANG,Hong MENG,Yingzhou LU,Chunxi LI. Synthesis of 1-cyclohexenylacetonitrile using cyclohexanone and acetonitrile under synergetic activation of CaC₂ and CsF[J]. Chemical Industry and Engineering Progress, 2019, 38(11): 4971-4977.

姜茂强,孟洪,陆颖舟,李春喜. CaC₂与CsF活化环己酮与乙腈反应合成环己烯乙腈[J]. 化工进展, 2019, 38(11): 4971-4977.

Figures/Tables 10

References 38

1	LI Y , LIU Q , LI W , et al . Efficient destruction of hexachlorobenzene by calcium carbide through mechanochemical reaction in a planetary ball mill[J]. Chemosphere, 2017, 166: 275-280.
2	江罗, 陈标华, 张吉瑞, 等 . 活性炭孔径分布对乙炔氢氯化低固汞催化剂性能的影响[J]. 化工学报, 2018, 69(1): 423-428.
	JIANG Luo , CHEN Biaohua , ZHANG Jirui , et al . Effect of activated carbon pore size distribution on low-mercury catalyst performance for acetylene hydrochlorination[J]. CIESC Journal, 2018, 69(1): 423-428.
3	白慧芳, 王娇娇 . 乙炔氢氯化反应无汞催化剂研究进展[J]. 当代化工, 2018, 47(10): 2169-2172.
	BAI HuiFang , WANG Jiaojiao . Research progress of mercury-free catalysts for hydrochlorination of acetylene[J]. Contemporary Chemical Industry, 2018, 47(10): 2169-2172.
4	张一科, 贾则琨, 甄彬, 等 . 纽兰德催化剂催化乙炔二聚反应过程[J]. 化工学报, 2016, 67(1): 294-299.
	ZHANG Yike , JIA Zekun , ZHEN Bin , et al . Acetylene dimerization catalyzed by Nieuwland catalyst[J]. CIESC Journal, 2016, 67(1): 294-299.
5	SCHOBERT H . Production of acetylene and acetylene-based chemicals from coal[J]. Chem. Rev., 2014, 114 (3): 1743-1760.
6	RODYGIN K S , WERNER G , KUCHEROV F , et al . Calcium carbide: a unique reagent for organic synthesis and nanotechnology[J]. Chemistry: An Asian J., 2016, 11(7): 965-976.
7	江玉波, 梁雪秋 . 碳化钙在有机合成中的应用进展[J]. 化学试剂, 2012, 34(10) :910-912.
	JIANG Yubo , LIANG Xueqiu . Progress in organic synthesis of calcium carbide[J]. Chemical Reagents, 2012, 34(10): 910-912.
8	刘青, 刘清雅, 王仁醒, 等 . 电石与醇的反应行为[J]. 化工学报, 2013, 64(7): 2573-2579.
	LIU Qing , LIU Qingya , WANG Renxing , et al . Reaction behavior of calcium carbide with alcohols[J]. CIESC Journal, 2013, 64(7): 2573-2579.
9	NOPPARAT T , MONGKOL S , SUMTIT W . Direct synthesis of poly (p-phenyleneethynylene)s from calcium carbide[J]. Poly. Chem., 2014, 5(1): 48-52.
10	LIN Z W , YU D Y , SUM Y, et al . Synthesis of functional acetylene derivatives from calcium carbide[J]. ChemSusChem, 2014, 5(4): 625-628.
11	TEONG S P , DENG S , LI X K , et al . Direct vinylation of natural alcohol and derivatives with calcium carbide[J]. Green Chem., 2017, 19(7): 1659-1662.
12	EAKKAPHON R , TIRAYUT V , MONGKOL S , et al . An atom-economic approach for vinylation of indoles and phenols using calcium carbide as acetylene surrogate[J]. Europ. J. Org. Chem., 2016, 25: 4347-4353.
13	RYOSUKE M , YUSUKE A , MATSUBARA H . Synthesis of vinyl ethers of alcohols using calcium carbide under superbasic catalytic conditions (KOH/DMSO)[J]. Green Chem., 2016, 18(9): 2614-2618.
14	RODYGIN K S , ANANIKOV V P . An efficient metal-free pathway to vinyl thioesters with calcium carbide as the acetylene source[J]. Green Chem., 2016, 18(2): 482-486.
15	ZHANG W , WU H , LIU Z , et al . The use of calcium carbide in one-pot synthesis of symmetric diaryl ethynes[J]. Chem. Commun., 2006, 38(46): 4826-4828.
16	CHUENTRAGOOL P , VONGNAM K , RASHATASAKHON P , et al . Calcium carbide as a cost-effective starting material for symmetrical diarylethynes via Pd-catalyzed coupling reaction[J]. Tetrahedron, 2011, 67: 8177-8182.
17	KAEWCHANGWAT N , SUKATO R , VCHIRAWONGKWIN V , et al . Direct synthesis of aryl substituted pyrroles from calcium carbide: an underestimated chemical feedstock[J]. Cheminform, 2014, 17(1):460-465.
18	HU D , WANG F , WANG J D . Bi/AC modified with phosphoric acid as catalyst in the hydrochlorination of acetylene[J]. RSC Adv., 2017, 7(13): 7567-7575.
19	ZHAO J , ZHANG T T , DI X X , et al . Nitrogen-modified activated carbon supported bimetallic gold-cesium(Ⅰ) as highly active and stable catalyst for the hydrochlorination of acetylene[J]. RSC Adv., 2015, 5 (5): 6925-6931.
20	SUM Y N, YU D Y , ZHANG Y . Synthesis of acetylenic alcohols with calcium carbide as the acetylene source[J]. Green Chem., 2013, 15(10):2718-2721.
21	LI A , SONG H , XU X , et al . Greener production process of acetylene and calcium diglyceroxide via mechanochemical reaction of CaC₂ and glycerol[J]. ACS Sustain. Chem. Eng., 2018, 6(8): 9560-9565.
22	ZHANG K , TAO S , XU X , et al . Preparation of mesoporous carbon materials through mechanochemical reaction of calcium carbide and transition metal chlorides[J]. Ind. Eng. Chem. Res., 2018, 57(18): 6180-6188.
23	LI Y , LIU Q , LI W , et al . Synthesis and supercapacitor application of alkynyl carbon materials derived from CaC₂ and polyhalogenated hydrocarbons by interfacial mechanochemical reactions[J]. ACS Appl. Mater. Interfaces, 2017, 9(4): 3895-3901.
24	LIU Q , CHENG L , XU X , et al . Greatly enhanced reactivity of CaC₂ with perchloro-hydrocarbons in a stirring ball mill for the manufacture of alkynyl carbon materials[J]. Chem. Eng. Process-Process Intensification, 2018, 124: 261-268.
25	LI W , LI Y , LIU Q , et al . Adsorptive desulfurization of diesel oil by alkynyl carbon materials derived from calcium carbide and polyhalohydrocarbons[J]. Energy Fuels, 2017, 31(9): 9035-9042.
26	DAI C , WANG X , WANG Y , et al . Synthesis of nanostructured carbon by chlorination of calcium carbide at moderate temperatures and its performance evaluation[J]. Mater. Chem. Phys., 2008, 112(2): 461-465.
27	LI Q , LI Y , CHEN Y , et al . Synthesis of g-graphyne by mechanochemistry and its electronic structure[J]. Carbon, 2018, 136:248-254.
28	LI Y J , MENG H , LU Y Z , et al . Efficient catalysis of calcium carbide for the synthesis of isophorone from acetone[J]. Ind. Eng. Chem. Res., 2016, 55 (18): 5257-5262.
29	GOSCINIAK D J . Ultraviolet radiation absorbing compositions of 1-cyclohexenylacetonitrile derivatives of aldehydes: US4935533[P].1990-06-19.
30	ZHANG W . Synthesis of 1-cyclohexenyl acetonitrile by heating reaction liquid of cyclohexanone, cyanoacetate, ammonium acetate, and n-hexane, carrying out dehydration reaction and carrying out decarboxylation reaction: CN104262197-A[P]. 2015-0107.
31	FRANKLIN S . The enamine as a cyclohexylidene source[J]. J. Org. Chem., 1973, 38 (2): 399-401.
32	KOZLOV N S , KOZINTSEV S I , KACHEROVSK F B . Production of cyclohexenyl acetonitrile by reacting cyclohexanone with excess of acetonitrile in presence of potassium or caesium hydroxide SU1498756-A[P]. 1987-07-06.
33	ZHANG W . Making 1-cyclohexenyl acetic acid by adding cyclohexanone and acetonitrile to vessel containing sodium-sodium hydroxide/gamma-alumina solid mixture, reacting, adding 1-cyclohexenyl acetonitrile to acid and liquid water and hydrolyzing: CN105152902-A[P]. 2015-12-06.
34	FOSTER R , HAMMICK D L L , WARDLEY A A . Interaction of polynitro-compounds with aromatic hydrocarbons and bases. Part XI. A new method for determining the association constants for certain interactions between nitro-compounds and bases in solution[J]. J. Chem. Soc., 1953: 3817-3820.
35	MEILLE V , SCHULZ E , VRINAT M , et al . A new route towards deep desulfurization: selective charge transfer complex formation[J]. Chem. Commun., 1998(3): 305-306.
36	XU X , MENG H , LU Y , et al . Aldol condensation of refluxing acetone on CaC₂ achieves efficient production of diacetone-alcohol, mesityl oxide and isophorone[J]. RSC Adv., 2018, 8：30610-30615..
37	LEDOVSKAYA M , RODYGIN K , ANANIKOV V . Calcium-mediated one-pot preparation of isoxazoles with deuterium incorporation[J]. Org. Chem. Front., 2018, 5： 226-231.
38	ABOLFAZL H , DANIEL S , ANDREAS M , et al . Fluoride-assisted activation of calcium carbide: a simple method for the ethynylation of aldehydes and ketones[J]. Org. Lett., 2015, 17： 2808-2811.

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Synthesis of 1-cyclohexenylacetonitrile using cyclohexanone and acetonitrile under synergetic activation of CaC₂ and CsF

CaC₂与CsF活化环己酮与乙腈反应合成环己烯乙腈

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Figures/Tables 10

References 38

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序号	反应物1	反应物2	促进剂	活化剂	环己酮转化率/%	1-环己烯乙腈产率/%
1	环己酮	乙腈	电石	—	0	0
2	环己酮	乙腈	—	氟化铯	0	0
3	环己酮	乙腈	电石	氟化铯	92.7	75.8
4	环己酮	乙腈	电石	氟化钾	0	0