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METHOD FOR DIRECT AMINATION OF SECONDARY ALCOHOLS USING AMMONIA TO PRIMARY AMINES

机译:用氨直接稀释初级氨基的二级醇的方法

摘要

FIELD: chemistry.;SUBSTANCE: invention relates to an improved method of producing primary amines. Method involves the following stages: A) preparing a solution of secondary alcohol selected from a group comprising cyclic alcohols, 2-dodecanol, 4-phenyl-2-butanol, polypropylene glycol, OH-modified natural fatty acids and esters of OH-modified natural fatty acids, in fluid non-gaseous phase, B) bringing into interaction of said phase with free ammonia and homogeneous catalyst. Process step B) is carried out at excessive pressure of 20 to 50 bar and temperature of 80-220 °C in a two-phase system consisting of liquid phase and gaseous phase, where volume ratio of volume of liquid phase and volume of gas phase at process step B in greater than or equal to 0.25, and/or ammonia at step B) in terms of hydroxyl groups in secondary alcohol is used in molar ratio of at least 5 to 1. If necessary, method involves a step C) of separating primary amine, formed at step B). Homogeneous catalyst used is at least one catalyst selected from coordination compounds of one noble metal selected from among elements of ruthenium, osmium, rhodium, iridium, palladium and platinum. Alcohol used at step A) has at least two secondary hydroxy groups, and is selected preferably from 2-dodecanol, cyclododecanol, 4-phenyl-2-butanol, isosorbide, isomannide, isoidite, polypropylene glycol, mannitol, sorbitol, galactitol and alkyl glycoside. Preferably, at stage B) liquid ammonia is used and homogeneous catalyst used is at least one pincer catalyst. Preferable homogeneous catalyst is carbonylchlorohydrido[4,5-(diisopropylphosphinomethylacridino)ruthenium(II)].;EFFECT: method enables direct amination of secondary alcohols to obtain products with high output, eliminating an additional step of separation and purification of products produced on intermediate steps, and prevents formation of by-products.;8 cl, 1 dwg, 1 tbl, 9 ex
机译:伯胺的制备方法技术领域本发明涉及一种生产伯胺的改进方法。该方法包括以下步骤:A)制备选自以下的仲醇溶液:环醇,2-十二烷醇,4-苯基-2-丁醇,聚丙二醇,OH改性的天然脂肪酸和OH改性的天然酯流体非气相中的脂肪酸B)使所述相与游离氨和均相催化剂相互作用。在由液相和气相组成的两相系统中,在20至50 bar的过高压力和80-220°C的温度下进行工艺步骤B),其中液相体积与气相体积的体积比在工艺步骤B中,其摩尔比大于或等于0.25,和/或在步骤B)中以仲醇中的羟基计的氨气的摩尔比至少为5:1。如果需要,方法包括步骤C):分离在步骤B)形成的伯胺。所用的均相催化剂是至少一种选自钌,,铑,铱,钯和铂的元素的贵金属的配位化合物的催化剂。在步骤A)中使用的醇具有至少两个仲羟基,并且优选选自2-十二烷醇,环十二烷醇,4-苯基-2-丁醇,异山梨醇,异甘露糖苷,异锌矿,聚丙二醇,甘露醇,山梨醇,半乳糖醇和烷基糖苷。优选地,在步骤B)中,使用液氨,并且所使用的均相催化剂为至少一种夹钳催化剂。优选的均相催化剂是羰基氯氢化物[4,5-(二异丙基膦基甲基ac啶子基)钌(II)]。 ;并防止形成副产物。; 8 cl,1 dwg,1 tbl,9 ex

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