公开(公告)号：US2781410A

公开(公告)日：1957-02-12

申请号：US41544654

申请日：1954-03-10

Applicant: ZIEGLER

Inventor： KARL ZIEGLER ,  GUNTHER WILKE ,  ERHARD HOLZKAMP

IPC: C07C2/30 ,  C07C2/88

CPC classification number: C07C2/30 ,  C07C2/88 ,  C07C2521/02 ,  C07C2523/44 ,  C07C2523/75 ,  C07C2523/755 ,  C07C2531/14 ,  C07C2531/28 ,  Y10S260/25 ,  Y10S585/906 ,  Y10S585/946 ,  Y10S585/951 ,  C07C11/02

公开(公告)号：US2967875A

公开(公告)日：1961-01-10

申请号：US56555456

申请日：1956-02-15

Applicant: ZIEGLER KARL

Inventor： GUNTHER WILKE

IPC: C07F5/06

CPC classification number: C07F5/063

Abstract: Addition products of aluminium hydrocarbons and acetylene or acetylene derivatives are made by reacting an aluminium hydrocarbon of general formula AIR2R1, where R stands for a hydrocarbon radical and R1 for a hydrocarbon radical or hydrogen at temperatures up to 90 DEG C. with acetylene or an acetylene derivative of formula R11-C­C-R111, where R11 stands for a hydrocarbon radical or hydrogen and R111 for a hydrocarbon radical, hydrogen or the group -AIR2 the molar ratio of the alumminium hydrocarbon to the acetylene or acetylene derivative being 1:2, 1:1 or 2:1. On a 1:1 molar basis addition proceeds as follows: (C4H9)2AIH + H.C ­ C.C6H5 --> (C4H9)2 Al-CH = CH-C6H5-iso. On a 2:1 molar basis, using di-isobutyl aluminium hydride and hexine-(1), the addition proceeds If desired the aluminium hydrocarbon used in the second stage can be different from that used in the first. Using aluminium trialkyls and acetylenes (C2H5)2Al-C2H5 + HC ­ CH --> (C2H5)2Al-CH = CH-C2H5. The unsaturated product so obtained will react with a second mol. of acetylene This product may be decomposed with water to give 1,2,3,4-tetraethyl butadiene. A third mol. of acetylene or acetylene derivative may be added to give a trebly unsaturated addition product which gives rise to hexa-substituted benzene by ring closure on formation Thus the trimerization of a large amount of an acetylene with the triple bond in the middle position can be accomplished by a small quantity of dialkyl aluminium hydride. The unsaturated product obtained by adding 1 mol. of aluminium trialkyl to 1 mol. of an acetylene derivative may added to dialkyl aluminium hydrides Further, an acetylene may be added in a 1:1 molar ratio to a dialkyl aluminium hydride and one mol. of aluminium trialkyl added to the product Acetylenes of formula R2Al-C + CR111 (which may be obtained by reacting a dialkyl aluminium chloride with a sodium acetylene) may be added to dialkyl aluminiu hydride or aluminium trialkyl and the unsaturated products so obtained may be added to a second mol. of dialkyl aluminium hydride to obtain a saturated reaction product. Diethyl butinyl aluminium is prepared (Example (10)) by reacting sodium with butine-1 in liquid ammonia, taking up the salt so formed in hexane and adding to the suspension diethyl aluminium monochloride. 1,2,3,4 - Tetraphenyl butadiene is prepared (Example (12)) from 1,2-diphenyl acetylene and di-isobutyl aluminium hydride in a 2:1 molar ratio and decomposing the product with alcohol. Hexaphenyl benzene is prepared (Example (14)) by the trimerization of 1,2-diphenyl acetylene with di-isobutyl aluminium hydride at 140 DEG C. Specifications 713,081, 742,642 and 763,824 are referred to.