【作者】 崔颖娜；

【导师】 尹静梅； 高大彬；

【作者基本信息】 大连大学 ， 有机化学， 2007， 硕士

【摘要】 羰基化反应是有机合成中重要的反应之一,常规羰基化反应的弊端是大多数反应要求高温、高压条件,或贵金属催化剂。近年来,光促进温和条件下的羰基化反应已成为化学工作者研究的热点之一。CO是羰基化反应中最常见的C₁源,但由于CO毒性高和较复杂的气体操作,使其应用受到了一定的限制。探索固体或液体化合物在反应中作为方便安全的C₁源的研究引起了人们的关注。本文研究了烯烃与甲酸甲酯在光促进温和条件下的羰基化反应。研究发现,对烯烃的光促进羰基化反应,钴络合物催化剂的催化活性很高;反应在弱碱性条件下进行较为有利,NaOAc是非常好的添加物;同时研究了卤离子对反应的影响,发现NaI对反应的促进效果较好;升高温度钴催化的光促进羰基化反应速度明显加快;但对直链端烯烃的羰基化反应而言,钴催化下反应产物的正异比不理想。铜络合物催化剂的催化活性较低,但对直链端烯烃羰基化而言,反应的异正比比较理想,产物的选择性很高,主要生成异构酯。碱性添加物对反应没有促进作用;卤离子对不同的烯烃表现出不同的促进效果,NaI对环己烯的羰基化反应有一定的促进作用,而NaBr对1-辛烯的羰基化反应有促进作用。本文通过IR分析,同位素(CD₃OD和CH₃¹⁸OH)实验对甲酸甲酯参与光促进羰基化反应的机理进行了研究,证实反应中HCOOCH₃是先分解为CO和CH₃OH,再与烯烃进行羰基化反应的。另外,对影响烯烃光促进羰基化反应的因素如烯烃的结构,醇的结构等进行了研究。研究表明烯烃双键碳上带有供电子官能团时更易进行羰基化反应,带有吸电子官能团时较难进行羰基化反应;烯烃的空间构型对反应活性的影响也较大,带有支链的烯烃反应速度比端烯烃要慢。不同结构醇的反应活性为伯醇>仲醇>叔醇,对伯醇而言,随醇碳链的增长,反应活性下降。本文利用紫外和红外光谱对以Co（OAc）₂为催化剂,光促进温和条件下CO参与的羰基化反应机理进行了初步研究。初步认为Co（OAc）₂可能不经过文献中推测的生成Co₂（CO）₈这条反应路径,而是可能经过其他途径进行催化反应。更多还原

【Abstract】 Carbonylation is one of the most important organic synthesis which usually takes place at high temperatures and high pressure with precious catalysts. In recent years, more and more attention has been paid to the photo-promoted carbonylation under ambient conditions.It is well known that carbon monoxide gas is the most commonly employed C1 source in the carbonylation. However, the use of carbon monoxide gas is limited due to high toxicity and complicated operation. The recent attention has been paid to the researches of using C1 source in liquid or solid state in place of CO gas.In this paper, the photo-promoted carbonylation of olefins with methyl formate catalyzed by non-precious metal catalysts has been studied under ambient conditions.The cobalt complexes catalysts show high catalytic activities for the photo-promoted carbonylation of olefins. Weak basicity is beneficial to this reaction and NaOAc is the most efficient additive. In addiation, NaI also can promote the reaction. The results indicate that the reaction activities of olefins increase with the increasing temperature under the catalysis of cobalt complexes. However, as for the carbonylation of straight chain terminal olefins, the ratio of n/i is not good as we expected.On the basis of the carbonylation with cobalt complexes catalysts, copper complexes are investigated. The catalytic activities of copper complexes are lower than cobalt complexes but the selectivity of ester for straight chain terminal olefins is high, the major product is isomeric ester. Base additives have no promoted effects on this reaction. On the other hand, halides have different promoted effects on different olefins. The activities of cyclohexene and 1-octene can be improved by additition of NaI and NaBr, respectively.The mechanism of methyl formate participating in the carbonylation is verified by the IR analysis and the labeling experiments of CD)3OD and CH₃¹⁸OH. The results indicate that methyl formate decomposes into CO and CH₃OH firstly under irradiation, and then the carbonylation of olefins proceed.The influences of some factors on the photo-promoted carbonylation of olefins are studied. The results are obtained that double bond with groups of donating electrons are beneficial to this reaction and double bond with groups of withdrawing electrons are unfavorable to this reaction. The space configuration of olefins also have some effects on the reaction, the activitiy of terminal olefin is better than branched olefin. The activity sequence of the alcohols is as follows: primary alcohol, secondary alcohol and tertiary alcohol. As for primary alcohol, the activity decreases with the increasing length of carbon chain.The mechanism of photopromoted carbonylation of olefin with carbon monoxide catalyzed by Co（OAc）₂ is investigated by UV and IR spectrograph. It is preliminary considered that Co₂（CO）₈ maybe is not the intermediate as some literature reported, Co（OAc）₂ is assumed to initiate the reaction via another catalytic cycle.更多还原