Method for Producing Aromatic and Heteroaromatic Carboxylic Acids, Carboxylic Acid Esters and Carboxylic Acid Amides
申请人:Challand Nina
公开号:US20110172456A1
公开(公告)日:2011-07-14
Process for the preparation of aromatic and heteroaromatic carboxylic acids, carboxylic acid esters and carboxamides by the reaction of aromatic or heteroaromatic halides R—X
n
, in which n=integer from 1 to 6, R=substituted or unsubstituted and aromatic or heteroaromatic radical and X=chlorine, bromine or iodine atom, with carbon monoxide and water, ammonia, alcohols or amines in the presence of bases and zero-valent or divalent palladium compounds and bidentate diphosphanes or complexes of zero-valent or divalent palladium with bidentate diphosphanes, in which use is made of bidentate diphosphanes
(R
1
—)(R
2
—)P—Y—P(—R
3
)(—R
4
)
in which R
1
to R
4
=unsubstituted aryl radicals or aryl radicals substituted with at least one radical exhibiting a positive resonance effect or a positive inductive effect, or unsubstituted or substituted cycloalkyl radicals, and Y=hydrocarbon group with a total of 2 to 20 carbon atoms, in which at least one of the carbon atoms carries only one or no hydrogen atom as substituent; except for the reaction of 4-bromo-3-difluoromethyl-1-methylpyrazole with 2-(3,4,5-trifluorophenyl)aniline and carbon monoxide to give N-[2-(3,4,5-trifluorophenyl)phenyl]-3-difluoromethyl-1-methylpyrazole-4-carboxamide.
用芳香或杂芳卤代烃R—Xn(其中n=1到6的整数,R=取代或未取代的芳香或杂芳基团,X=氯、溴或碘原子)与一氧化碳和水、氨、醇或胺在碱存在下,以及零价或二价钯化合物和双膦或零价或二价钯与双膦的配合物反应,制备芳香和杂芳羧酸、羧酸酯和羧酰胺的方法的过程,其中使用双膦(R1—)(R2—)P—Y—P(—R3)(—R4),其中R1到R4=未取代芳基基团或带有至少一个正共振效应或正归纳效应的基团的取代芳基基团,或未取代或取代的环烷基基团,Y=含有2到20个碳原子的碳氢基团,其中至少一个碳原子只携带一个或没有氢原子作为取代基;但不包括4-溴-3-二氟甲基-1-甲基吡唑与2-(3,4,5-三氟苯基)苯胺和一氧化碳反应形成N-[2-(3,4,5-三氟苯基)苯基]-3-二氟甲基-1-甲基吡唑-4-羧酰胺。