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Process for the preparation of tertiary amines from nitriles and primary animas.

机译:由腈和一级苯胺制备叔胺的方法。

摘要

A process for preparing at least one tertiary amine product having the formula wherein R is a C1-C12 substituent selected from the group consisting of linear aliphatic, cycloaliphatic, and heterocyclic or branched; wherein R '' is a C1-C12 substituent selected from the group consisting of linear aliphatic, cycloaliphatic, and heterocyclic or branched; wherein A is selected from the group consisting of hydrogen, cyano, amide, aliphatic, cycloaliphatic, aromatic, heterocyclic, alkoxy, aryloxy, hydroxy, alkylamino, dialkylamino, arylamino, diarylamino, haloaryl, fluorinated alkyl, and linear silyl or branched ; wherein A '' is selected from the group consisting of hydrogen, amino, amide, aliphatic, cycloaliphatic, aromatic, heterocyclic, alkoxy, aryloxy, hydroxy, alkylamino, dialkylamino, arylamino, diarylamino, haloaryl, fluorinated alkyl, and linear silyl or branched; said process comprising contacting at least one primary amine having the general formula H2N it comprises - R '' - A '' (III) wherein R '' is a substituent C1-C12 selected from the group consisting of aliphatic, cycloaliphatic or linear or branched heterocyclic; and wherein A '' is selected from the group consisting of hydrogen, amino, amide, aliphatic radicals, cycloaliphatic, aromatic, heterocyclic, alkoxy, aryloxy, hydroxy, alkylamino, dialkylamino, arylamino, diarylamino, haloaryl, fluorinated alkyl, and silyl linear or branched; with at least one nitrile having the general formula A - R - CN (II) wherein R is a C1-C12 substituent selected from the group consisting of linear aliphatic, cycloaliphatic, and heterocyclic or branched; and wherein A is selected from the group consisting of hydrogen, cyano, amide, aliphatic radicals, cycloaliphatic, aromatic, heterocyclic, alkoxy, aryloxy, hydroxy, alkylamino, dialkylamino, arylamino, diarylamino, haloaryl, fluorinated alkyl, and linear silyl or branched; with the proviso that when A is H or linear or branched aliphatic, and R is linear or branched aliphatic, said nitrile is a C2-C7 nitrile; in the presence of hydrogen gas and a catalyst at a temperature of 50 to 200 and a pressure of from 689.475 to 10342.135 kPa, and wherein the ratio of nitrile to amine is greater than 1: 1; and wherein the catalyst comprises at least two metal elements; wherein the first metal element is palladium, and the at least one second metal element is selected from iridium, rhodium, platinum and ruthenium.
机译:制备至少一种具有下式的叔胺产物的方法:其中R是选自直链脂族,脂环族和杂环或支链的C1-C12取代基;其中R''是选自直链脂族,脂环族和杂环或支链的C1-C12取代基;其中A选自氢,氰基,酰胺,脂族,脂环族,芳族,杂环,烷氧基,芳氧基,羟基,烷基氨基,二烷基氨基,芳基氨基,二芳基氨基,卤代芳基,氟化烷基和直链甲硅烷基或支链的基团;其中A''选自氢,氨基,酰胺,脂族,脂环族,芳族,杂环,烷氧基,芳氧基,羟基,烷基氨基,二烷基氨基,芳基氨基,二芳基氨基,卤代芳基,氟化烷基和直链甲硅烷基或支链的组;所述方法包括使至少一种通式为H 2 N的伯胺接触,所述伯胺包括:-R” -A”(III),其中R”是选自脂族,脂环族或直链或支链的取代基C1-C12杂环其中A''选自氢,氨基,酰胺,脂族基团,脂环族,芳族,杂环,烷氧基,芳氧基,羟基,烷基氨基,二烷基氨基,芳基氨基,二芳基氨基,卤代芳基,氟化烷基和线性或甲基的甲硅烷基分支至少一个具有通式A-R-CN(II)的腈,其中R是选自直链脂族,脂环族和杂环或支链的C1-C12取代基;其中A选自氢,氰基,酰胺,脂族基团,脂环族,芳族,杂环,烷氧基,芳氧基,羟基,烷基氨基,二烷基氨基,芳基氨基,二芳基氨基,卤代芳基,氟化烷基和直链甲硅烷基或支链的基团;前提是当A为H或直链或支链脂族基,R为直链或支链脂族基时,所述腈为C2-C7腈;在氢气和催化剂的存在下,温度为50至200,压力为689.475至10342.135 kPa,其中腈与胺之比大于1:1;并且其中所述催化剂包含至少两种金属元素;其中第一金属元素是钯,并且至少一个第二金属元素选自铱,铑,铂和钌。

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