| 摘要 |
1341045 Pseudo-nitrosites; nitro-ketoximes; nitroketones; furoxanes; diamines; aminoacids; diacids SOC NATIONALE DES PETROLES D'AQUITAINE 22 Dec 1970 [24 Dec 1969] 60871/70 Heading C2C Aliphatic diamines, amino-carboxylic acids and dicarboxylic acids are prepared by reacting a cycloaliphatic hydrocarbon having one or more double bonds and 8 to 32 carbon atoms in the ring with a nitrogen oxide, in a liquid medium in which the hydrocarbon is soluble and from which the product 1-nitro-2-nitroso cycloaliphatic compound (pseudo-nitrosite) precipitates (as dimer) as it is formed and is removed before the conversion, based on the weight of hydrocarbon, exceeds 64%; isomerizing the pseudo-nitrosite to the cyclic 1-nitroketoxime by heating in a polar solvent at 80-160‹ C.; treating the nitro-ketoxime with a dehydrating acid, e.g. H 2 SO 4 , H 3 PO 4 or a polyphosphoric acid, to form the corresponding furoxane, and reducing the latter to yield an aliphatic diamine; or treating the 1-nitroketoxime with a strong non-oxidizing non- dehydrating aqueous acid, e.g. HCl, to give the 2-nitro cyclic ketone, and hydrolysing the latter either with an acid solution to give a dicarboxylic acid, or with an alkaline solution followed by acidification to give the #-nitro carboxylic acid and reducing this to the aminoacid. Examples start with cyclododecene to yield finally 1,12-diaminododecane, and 12- aminododecanoic acid; and cyclooctene to yield finally 1,8-diaminooctane, 8-aminocaprylic acid and suberic acid. Other specified starting materials are cyclooctadiene, cyclododecadiene and cyclododecatriene.
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