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以2-溴-3,3,3-三氟丙烯(1)为原料,经卤素-镁交换反应制得中间体三氟异丙烯基格氏试剂(2);2分别与CO2,正丁醛,苯甲醛和苯甲酰氯反应合成了2-三氟甲基丙烯酸(3a),2-三氟甲基-1-己烯-3-醇(3b),1-苯基-2-三氟甲基-2-丙烯-1-醇(3c)和1-苯基-4-三氟甲基-4-丁烯-1-酮(3d),其中3d为新化合物,其结构经1H NMR,13C NMR,IR,MS和元素分析表征。考察了交换试剂、物料比、温度和反应时间对3a产率的影响。在最优反应条件[以i-Pr Mg Br/Li Cl为交换试剂,1 50 mmol,n(2-溴丙烷)∶n(1)=1.25∶1.00,于-60℃反应2 h]下,3a收率64.3%。 相似文献
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3,3,3-三氟丙酸是一种新型三氟甲基合成切块,在医药、农药、染料及功能材料等精细化工领域有着广泛的应用。以3,3,3-三氟-1-氯丙烷和Cl2为原料,在紫外光照下经氯化反应合成了3,3,3-三氟-1,1,1-三氯丙烷,再与Oleum试剂经水解反应合成了3,3,3-三氟丙酸,收率47.7%,其结构经1H NMR, 13C NMR和MS确证。并对反应条件进行了优化。 相似文献
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Reaction of diethyl 2,2-difluoro-3-(a-methylbenzyl)imino-4,4,4-trifluoropropanephosphonate (3) with triethylamine afforded a mixture of normal [1,3]-proton shift reaction product 5 and its HF-eliminated compound 6Z in 1 : 1 ratio. Upon hydrolysis, this reaction mixture gave solely 1,3,3,3-tetrafluoro-2-dioxypropanephosphonate (9). Reaction of 3 with DBU provided only 6, in which the ratio of E/Z forms was dependent on the reaction conditions. Aqueous hydrolysis of 6 led to 9. Catalytic hydrogenation and hydrogenolysis of 6 gave geometric isomers of 11 as expected. The reaction mechanism involved was discussed. 相似文献
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本文对邻三氟甲基苯甲酸的合成工艺进行了研究。邻三氟甲基苯甲酸以邻氯三氟甲基苯为初始原料,通过Grignard,加成和水解三步反应得到。该反应条件温和可控,总收率41.3%,纯度高达99.5%以上。该方法所得目标产物邻三氟甲基苯甲酸纯度高、成本较低、易操作,相对比较适合工业化生产。 相似文献
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Ali Ramazani Nahid Shajari Amir Tofangchi Mahyari Mehdi Khoobi Yavar Ahmadi Ali Souldozi 《Phosphorus, sulfur, and silicon and the related elements》2013,188(12):2496-2502
Reactions of (N-isocyanimino)triphenylphosphorane with 1,1,1-trifluoroacetone in the presence of aromatic (or heteroaromatic) carboxylic acids (3-methylbenzoic acid, 1-naphthalenecarboxylic acid, 2-naphthalenecarboxylic acid, 2-furancarboxylic acid, and 2-thiophenecarboxylic acid) proceed smoothly at room temperature and in neutral conditions to afford sterically congested 1,1,1-trifluoro-2-(5-aryl-1,3,4-oxadiazol-2-yl)-2-propanol derivatives in high yields. The reaction proceeds smoothly and cleanly under mild conditions, and no side reactions were observed. Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file. 相似文献
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以甲基乙烯酮为原料,用乙炔基格氏试剂对其加成,然后水解得到目标物3-甲基-1-戊烯-4-炔-3-醇。研究了温度对反应的影响,发现在25℃的反应温度下,目标化合物的气相色谱产率为50%,减压蒸馏纯化后收率为30%。目标产物用1HNMR、IR进行了表征。 相似文献
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The purpose of the present investigation is to calculate partition functions and thermodynamic quantities, viz., entropy, enthalpy, heat capacity, and Gibbs free energies, for 1-butanol, 2-methyl-1-propanol, and butanal in the vapor phase. We employed the multi-structural (MS) anharmonicity method and electronic structure calculations including both explicitly correlated coupled cluster theory and density functional theory. The calculations are performed using all structures for each molecule and employing both the local harmonic approximation (MS-LH) and the inclusion of torsional anharmonicity (MS-T). The results obtained from the MS-T calculations are in excellent agreement with experimental data taken from the Thermodynamics Research Center data series and the CRC Handbook of Chemistry and Physics, where available. They are also compared with Benson's empirical group additivity values, where available; in most cases, the present results are more accurate than the group additivity values. In other cases, where experimental data (but not group additivity values) are available, we also obtain good agreement with experiment. This validates the accuracy of the electronic structure calculations when combined with the MS-T method for estimating the thermodynamic properties of systems with multiple torsions, and it increases our confidence in the predictions made with this method for molecules and temperatures where experimental or empirical data are not available. 相似文献
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Reaction of 2-pyridylmagnesium chlorides with N,N-dialkyl arylamides afford exclusively 2-(aroyl) pyridines in high yields and purity without the formation of any tertiary alcohol. This method employs easily available raw materials and avoids the use of hazardous lithium reagents and cryogenic conditions. Further, preferential reactivity of this Grignard reagent with N,N-dialkyl arylamides over its carbonitrile counterparts offers a variety of 2-(aroyl) pyridines including the ones containing carbonitrile groups on the aryl ring. 相似文献
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Masakazu Kogami 《合成通讯》2013,43(5):681-688
Lithium chloride was found to accelerate formation of the Grignard reagent from inactive 3-bromo-2-methylthiophene (1) and commercial magnesium metal. Based on this finding, a convenient and potentially scalable preparation of ethyl 2-methylthiophene-3-carboxylate (3) was achieved. In addition, this process has been found to provide a new, general approach to 3-substituted 2-methylthiophenes. 相似文献
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SHI Zhen WANG Luyao GU Huan LI Jianli BAI Yinjuan & YANG Bingqin Department of Chemistry Northwest University Xi''''an China 《中国科学B辑(英文版)》2005,48(Z1)
A facile and efficient method for the formylation of Grignard reagent was reported, and a new approach for the preparation of aldehydes from Grignard reagent and benzimida-zolium salts was provided. 相似文献
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α-Diazocarbonyl compounds react with methylmagnesium bromide at −78 °C generating the corresponding α-diazo-α-bromomagnesio species, which can be intercepted by various electrophilic reagents. For example, with alkyl chloroformates α-diazo-β-ketoesters or mixed esters of α-diazomalonate are obtained in good yields. 相似文献
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Andrei S. Batsanov Philip D. Bolton Royston C.B. Copley Matthew G. Davidson Judith A.K. Howard Christian Lustig Richard D. Price 《Journal of organometallic chemistry》1998,550(1-2)
Imino(triphenyl)phosphorane, Ph3P=NH 1a, is metallated by ethylmagnesium chloride to give the N-magnesioiminophosphorane complex [Ph3P=NMgCl·O=P(NMe2)3]2 4, whose X-ray structure has been determined. 相似文献