1738-36-9Relevant articles and documents
Corresponding amine nitrile and method of manufacturing thereof
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Paragraph 0153; 0154; 0155; 0162; 0163, (2018/05/07)
The invention relates to a manufacturing method of nitrile. Compared with the prior art, the manufacturing method has the characteristics of significantly reduced using amount of an ammonia source, low environmental pressure, low energy consumption, low production cost, high purity and yield of a nitrile product and the like, and nitrile with a more complex structure can be obtained. The invention also relates to a method for manufacturing corresponding amine from nitrile.
Method for producing organic compounds by substituting halogen atoms
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Page 15; 21, (2008/06/13)
The invention pertains to a method in which a halogen atom of an organic compound is replaced with a group derived from a nucleophilic agent, at high yield and high efficiency, by the following method which includes a step of reacting the nucleophilic agent with an organic material having a halogen atom bonded to a carbon atom having four σ bonds, more specifically: a method for producing an organic compound having Q, the method including a step of reacting a compound represented by general formula (2) with an organic starting material having at least one halogen atom bonded to a carbon atom having four σ bonds so as to replace the halogen atom in the organic starting material with Q:MQa (wherein M represents an alkali metal atom, an alkali earth metal atom, or a rare earth metal atom; Q represents a moiety of an inorganic acid or an active hydrogen compound derived by eliminating a proton, wherein Q is a halogen atom different from the halogen atom in the organic starting material having the halogen atom bonded to the carbon atom having the four σ bonds; and a represents an integer of 1 to 3) in the presence of a compound represented by general formula (1) (wherein Z- represents an anion derived by eliminating a proton from an inorganic acid or an active hydrogen compound; R2 is the same or different; R2 each independently represent a C1-C10 hydrocarbon group or two R2 on the same nitrogen atom may be bonded with each other to form a ring with the nitrogen atom).
Synthesis of α-amino acids by addition of putative azido radicals to α-methoxy acrylonitriles derived from aldehydes and ketones
Clive, Derrick L. J.,Etkin, Nola
, p. 2459 - 2462 (2007/10/02)
α-Methoxy acrylonitriles, available from aldehydes and ketones, react with sodium azide in the presence of ceric ammonium nitrate to give azido nitrates; from these compounds, α-amino acids are obtained by sequential treatment with sodium acetate in acetic acid and then methanolic potassium carbonate, followed by hydrogenation.
CYANOTRIMETHYLSILANE AS A VERSATILE REAGENT FOR INTRODUCING CYANIDE FUNCTIONALITY
Utimoto, Kiitiro,Wakabayashi, Yukio,Horiie,Takafumi,Inoue, Masaharu,Shishiyama, Yuho,et al.
, p. 967 - 974 (2007/10/02)
Cyanotrimethylsilane adds to some α,β-unsaturated ketones in conjugate manner under the catalytic action of Lewis acids such as triethylaluminium, aluminium chloride, and SnCl2.Hydrolysis of the products gives β-cyano ketones which are identical to the hydrocyanated products of the starting enones.The title silicon reagent reacts with acetals and orthoesters under the catalytic action of SnCl2 or BF3*OEt2 affording 2-alkoxy- and 2,2-dialkoxyalkanenitriles.Application of the reaction to O-protected β-D-ribofuranoses gives selectively β-D-ribofuranosyl cyanide in excellent yield.
ZnCl2-catalysed cycloadditions between ketene acetals and α,β-unsaturated carbonyl compounds. A simple route to 2,2-dialkoxy-3,4-dihydropyrans
Bakker, C. G.,Scheeren, J. W.,Nivard, R. J. F.
, p. 13 - 20 (2007/10/02)
2,2-dialkoxy-3,4-dihydropyrans (3) can be obtained under mild conditions and in good yields from ketene acetals (1) and α,β-unsaturated carbonyl compounds (2) in the presence of ZnCl2.At low temperatures ( -20 deg C) the reaction between 1 and 2 proceeds as a (2 + 2)-cycloaddition, leading to an oxetane (4), which can sometimes be isolated by neutralisation of the Lewis acid.At higher temperatures, however, the oxetanes decompose into the starting compounds, eventually leading to the thermodynamically more stable dihydropyrans.The cycloadditions of tetramethoxyethene (1a) with 2, having no substituents at the β-carbon atom, yield a cyclobutane derivative as the low temperature product; in cycloadditions of α,β-unsaturated esters this is the final product.Cycloadditions of 2-chloroketene acetal (1e) lead in some cases to 2:1 adducts.The deviating behaviour of 1a and 1e is discussed.
2-ALKOXY AND 2,2-DIALKOXY NITRILES FROM ACETALS AND ORTHOESTERS --- EXCHANGE OF ALKOXY INTO CYANO GROUP BY MEANS OF CYANOTRIMETHYLSILANE
Utimoto, Kiitiro,Wakabayashi, Yukio,Shishiyama, Yuho,Inoue, Masaharu,Nozaki, Hitosi
, p. 4279 - 4280 (2007/10/02)
Title transformation is accomplished by the catalytic action of SnCl2 or BF3*OEt2.Lithio derivative of 2,2-dimethoxyacetonitrile is used as synthetic equivalent of methyl lithioformate.
Mechanism of Reactions of N-(Methoxymethyl)-N,N-dimethylanilinium Ions with Nucleophilic Reagents
Knier, Barry L.,Jencks, William P.
, p. 6789 - 6798 (2007/10/02)
The prediction that the oxocarbonium ion derived from formaldehyde should have a "lifetime" of ca. 10-15 s that gives rise to an enforced preassociation or concerted reaction mechanism has been tested by examining the reactions of N-(methoxymethyl)-N,N-dimethylanilinium ions in water in the presence of added nucleophilic reagents.These compounds undergo well-behaved second-order reactions with nucleophiles and give the amount of substitution product that is expected from the rate increase in the presence of nucleophile.Structure-reactivity correlations exhibit behavior intermediate between that expected for SN2 (Swain-Scott) and carbonium ion (N+) reactions.The small values of s = 0.3 and βnuc = 0.14 and large values of β1g = -0.7 to -0.9 indicate a transition state that can be described either as an open transition state for SN2 displacement or as an oxocarbonium ion that is stabilized by weak interactions with the entering and leaving groups.Secondary α-deuterium isotope effects for the second-order reactions range from (kH/kD)/D = 0.99 for fluoride ion to 1.18 for iodide ion.Solvolysis and the second-order reaction with n-propylamine exhibit values of ΔS(ex) = -1.2 and -2.1 cal K-1 mol-1, respectively, and display similar changes in rate in mixed water-alcohol solvents.It is suggested that the lifetime of the carbonium ion species in the presence of nucleophiles is so short that the reaction mechanism must be concerted.
