| This paper consists of three part main contents. First, a brief overview of the synthesis and properties of carbamoylsilane. Second, we examined the reactions of electron-deficient aromatics respectively with N,N-dimethylcarbamoyl(trimethyl)silane 1, N-methoxymethyl-N-methylcarbamoyl(trimethyl)silane 2,N-methyl-N-(1-phenyl)ethylcarbamoyl(trimethyl)silane 3, and through the choice of temperature, solvents, proportion, reaction conditions were optimized. Third, we studied the reaction of N,N-dimethylcarbamoyl-(trimethyl)silane 1 with ?-nitro-arylacrylat-es, at the same time, we have also investigated the influence of the electric effect and steric hindrance effect of the substituents to the yields and regioselectivity under the condition of same temperature, solvent.Amine and its derivatives is a good solvent for ionization, a very stable chemical properties, and is completely miscible in water and a variety of other organic compounds, inorganic, is a good solvent for many inorganic salts, polymers and natural products, is also a variety of bio-active materials, polymers and natural products and intermediates. In the past decades, organic workers have been working on aminocarbonyl reaction, developed many of the preparation of amides, the most commonly used is the acid chloride, mixed acid anhydride, an activated ester reacts with an amino amide bond, since Heck and his collaborators are using CO as a substrate to amide, more and more researchers are using CO as carbonylation agent, but the drawback of this approach is also evident, CO great harm to the human body, and the reaction often require high temperature and pressure conditions, high operating costs, actual production has been greatly restricted. So it is very necessary to explore a simple and practical method of raw material.When N,N-dimethylcarbamoyl(trimethyl)silane 1 reacts with 3-acetylphenylisocyanate 4,3-nitro-benzonitril 5,1,3-dinitrobenzen 6,3-nitro-4-fluoro-threefluorinetoluene 7,3-cyano-pyridine 8,3-acet-ylpyridine 9,2-chloro-5-nitropyridine 10,2-chloro-5-(trifluoromethy-l)pyridine 11,2-bromine-5-fluoridepyridine 12,2-bromine-3-chloro-5-(trifluoromethyl)pyridine 13,2,4-dichloro-3-nitropyridine 14,2-cyan-o-3-nitro-5-bromidepyrid-ine 15, pyrazine 16,2-cyanopyrazine 17. Among these reaction 1,3-dinitrobenzene 6,3-acetylpyridine 9, 2-chloro-5-(trifluoromethyl)pyridine 11,2-bromine-5-fluoridepyridin-e 12, pyrazine 16 not action, other products are 2-(3-acetylphenyl)-isocyanate(N,N-dimethyl)carbinolamine 18,2-(3-nitro)benzonitril-(N,N-dimethyl)carbinolamine 19,2-(3-nitro-4-fluoro)threefluorinetol-uene(N,N-Mdimethyl)carbinolamine 21,2-(3-cyano)pyridine(N,N-dime-thyl)carbinolamine 22,2-(2-chloro-5-nitro)pyridine(N,N-dimethyl)-formamide 24,2-(2-bromine-3-chloro-5-trifluoromethyl)pyridine-(N,N-dimethyl)carbinolamine 27,2-(2,4-dichloro-3-nitro)pyridine-(N,N-dimethyl)f or ma mide 28,2-(2-cyano-3-nitro-5bromide)pyridine (N,N-dimethyl)formamide 29,2-(2-cyano)pyrazine(N,N-dimethyl) carbinolamine 31. The experimental results show that the substituents on the electron-deficient aromatics ability stronger, shorter reaction time, higher yield.When N-methoxymethyl-N-methylcarbamoyl(trimethyl)silane 2 react with 3-acetylphenylisocyanate 4,3-nitro-benzonitril 5,3-nitro-4-fluoro-threefluorinetoluene 7,3-cyanopyridine 8,2-chloro-5-nitro pyridine 10, we could afford the products 2-(3-acetylphenyl)isocya-nate(N-methoxymethyl-N-methyl)carbinolamin 32,2-(3-nitro)benzo-nitril(N-methoxymethyl-N-methyl)carbinolamine 33,2-(3-nitro-4-fluoro)threefluorinetoluene(N-methoxymethyl-N-methyl)carbinolam ine 34,2-(3-cyano)pyridine(N-methyl)carbinolamine 35,2-(2-chloro-5-nitro)pyridine(N-methyl)formamide 36. In the experiment, we found that the substrate 8,10, a product of the reaction is not stable and easy to decompose, directly after the reaction of hydrochloric acid hydrolysis of the processed by secondary amide 35,36 secondary alcohol amine, so the substrate 4,5,7 and carbamoylsilane resulting from the reaction of tertiary alcohol amine,32,33 and 34 after hydrolysis can form secondary alcohol amine, the establishment of this method for the preparation of secondary amide (secondary alcohol amine) provides a new way of thinking.When N-methyl-N-(1-phenyl)ethylcarbamoyl(trimethyl)silane 3 react with 3-acetylphenylisocyanate 4,3-nitro-benzonitril 5,3-nitro-4-fluoro-threefluorinetoluene 7,3-cyanopyridine 8,2-chloro-5-nitro-pyridine 10, we could afford the products 2-(3-acetylphenyl)isocya-nate(N-methyl-N-(1-phenyl)ethyl)carbinolamine 37,2-(3-nitro)benzo-nitril(N-methyl-N-(1-phenyl)ethyl)formamide 38,2-(3-nitro-4-fluoro) threefluorinetoluene(N-methyl-N-(1-phenyl)ethyl)carbinolamine 39, 2-(3-cyano)pyridine(N-methyl-N-(1-phenyl)ethyl)formamide 40,2-(2-chloro-5-nitro)pyridine(N-methyl-N-(1-phenyl)ethyl)formamide 41. The experiment mild reaction conditions, no catalysts, the operation is simple in the synthesis of asymmetric amide has very important significance.N,N-dimethylcarbamoyl(trimethyl)silane 1 was used to react of ?-nitro-2-hexene acid ethyl ester 42, ?-nitro-2-isopropylacrylic acid ethyl ester 43,?-nitro-2-(4-dimethylamino)phenylacrylate 44, ?-nitro-2-(4-methoxyl)phenylacrylate 45,?-nitro-2-(4-methyl)phenyl-acrylate 46, ?-nitro-2-phenylacrylate 47,?-nitro-2-(4-chloro)phenyl-acrylate 48, ?-nitro-2-(3-nitro)phenylacrylate 49, ?-nitro-4-benzene-pentenyl acid ethyl ester 50, ?-nitro-2-furylacrylate 51, ?-nitro-2-thienylacrylate 52,?-nitro-2-pyridylacrylate 53 to afford 2-nitro-3-(N,N-dimethyl) ammonia acyl ethyl caproate 54, 2-nitro-3-(N,N-dimethyl) ammonia acyl alien acid ethyl ester 55, 2-nitro-3-(N,N-dimethyl)ammonia acyl of dimethyl aminobenzoic acid ethyl 56,2-nitro-3-(N,N-dimethyl)ammonia acyl of methoxy benzoic acid ethyl 57,2-nitro-3-(N,N-dimethyl)ammonia acyl methyl benzoic acid ethyl ester 58,2-nitro-3-(N,N-dimethyl)ammonia acyl benzoic acid ethyl ester 59,2-nitro-3-(N,N-dimethyl)ammonia acyl of chlorobenzoic acid ethyl ester 60,2-nitro-3-(N,N-dimethyl)between ammonia acyl nitrobenzene acid ethyl ester 61,2-nitro-3-(N,N-dimet-hyl)ammoniacyl-4-benzene pentene acid ethyl ester 62,2-nitro-3-(N,N-dimethyl)ammonia acyl furan acid ethyl ester 63, 2-nitro-3-(N,N-dimethyl)ammonia acyl thiophene acid ethyl ester 64, 2-nitro-3-(N,N-dimethyl)ammonia acyl pyridine acid ethyl ester 65.The experiment found that the electronic effect of substituent, space steric hindrance and conjugation effect will be different degrees of effects on the reaction. When the ? of ethyl acrylate on even a fat chain, space steric hindrance is the main factors influencing the reaction, and the greater the space steric hindrance of substituent reaction time longer, but does not affect the production rate; When the ? of ethyl acrylate with aromatic ring, electronic effect are the main factors influencing the reaction, strong electron-withdrawing ability of the substituents, shorter reaction time, higher yield, and vice versa. |
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