Synthesis of bis(ethynylphenyl) compounds

Claim 2

A process for preparing bis(ethynylphenyl) compounds in high yields comprising the steps of diazotizing a dianiline whose structure is ##STR4## where X is a single bond, CO, SO 2 , NC 6 H 5 , S, Si(CH 3 ) 2 , POCH 3 , POC 6 H 5 , (CH 2 ) n , or C(CF n H 3-n ) 2 where n is 0, 1, 2 or 3 to form a dihalogenated diphenyl compound; coupling said diphenyl compound with ethynyltrimethylsilane in the presence of an organopalladium complex and a ligand to yield an end-protected diphenyl compound having acetylenic moieties thereon; and subsequently removing said end-protecting groups from said diphenyl compound by treating said compound with a weak base in an inert atmosphere.

Claim 3

The process of claim 1 wherein an inorganic halide selected from the group consisting of NaI, KI and Cu 2 Br 2 , is employed to form said dihalogenated diphenyl compound, said palladium complex is dichlorobis(triphenylphosphine)palladium[II] or palladium acetate, and said ligand is selected from the group consisting of triphenylphosphine, tris(o-tolyl)phosphine, triphenylarsine, and triphenylstibine.

Claim 4

The process of claim 2 wherein said acid is H 2 SO 4 , said halide is KI, said palladium complex is dichlorobis(triphenylphosphine)palladium[II], said ligand is triphenylphosphine and said weak base is K 2 CO 3 .

Claim 5

An improved process for synthesizing bis(ethynylphenyl) compounds having the structure ##STR5## where X is a single bond, CO, SO 2 , NC 6 H 5 , S, Si(CH 3 ) 2 , POCH 3 , POC 6 H 5 , (CH 2 ) n or C(CF n H 3-n ) 2 , where n is 0, 1, 2, or 3, comprising the steps of: diazotizing a dianiline whose structure is ##STR6## where X is as defined above, by treating said dianiline with NaNO 2 , an organic halide selected from the group consisting of KI, NaI and Cu 2 Br 2 and a strong acid selected from the group consisting of HCl, H 2 SO 4 and HBr to form a dihalo diphenyl intermediate compound; forming a reaction mixture of said dihalo compound with ethynyltrimethylsilane in triethylamine-toluene; warming said reaction mixture in the presence of a catalytic mixture formed from dichlorobis(triphenylphosphine)palladium[II], triphenylphosphine and copper iodide, thereby forming a bis(trimethylsilyl)ethynyl derivative; and desilylating said ethynyl derivative by treating it with a weak base in an ether alcohol solvent, thereby forming the desired diethynyldiphenyl product in high yields.

Claim 6

An improved process for synthesizing bis(ethynylphenyl) compounds having the structure ##STR5## where X is a single bond, CO, SO 2 , NC 6 H 5 , S, Si(CH 3 ) 2 , POCH 3 , POC 6 H 5 , (CH 2 ) n or C(CF n H 3-n ) 2 , where n is 0, 1, 2, or 3, comprising the steps of: diazotizing a dianiline whose structure is ##STR6## where X is as defined above, by treating said dianiline with NaNO 2 , an organic halide selected from the group consisting of KI, NaI and Cu 2 Br 2 and a strong acid selected from the group consisting of HCl, H 2 SO 4 and HBr to form a dihalo diphenyl intermediate compound; forming a reaction mixture of said dihalo compound with ethynyltrimethylsilane in triethylamine-toluene; warming said reaction mixture in the presence of a catalytic mixture formed from dichlorobis(triphenylphosphine)palladium[II], triphenylphosphine and copper iodide, thereby forming a bis(trimethylsilyl)ethynyl derivative; and desilylating said ethynyl derivative by treating it with a weak base in an ether alcohol solvent, thereby forming the desired diethynyldiphenyl product in high yields.

Claim 7

The process of claim 4 wherein X is CH 2 and said weak base K 2 CO 3 .

Claim 8

A process for preparing 4,4'-diethynyldiphenylmethane in high yield comprising the steps of: forming a slurry of 4,4'-diaminodiphenylmethane in concentrated sulfuric acid, adding NaNO 2 to said slurry and mixing said slurry with an aqueous solution of an inorganic halide to form a dihalogenated diphenylmethane; coupling said dihalogenated diphenylmethane with ethynyltrimethylsilane by warming and stirring a mixture of said methane and said silane in the presence of an organopalladium catalytic complex, a ligand and deareated triethylamine and toluene to provide an end-protected diphenylmethane compound having acetylenic moieties as substituents; and subsequently treating said end-protected compound with a weak base in an alcohol-ether solvent to remove said end-protecting groups, thereby yielding 4,4'-diethynyldiphenylmethane.

Claim 9

A process for preparing 4,4'-diethynyldiphenylmethane in high yield comprising the steps of: forming a slurry of 4,4'-diaminodiphenylmethane in concentrated sulfuric acid, adding NaNO 2 to said slurry and mixing said slurry with an aqueous solution of an inorganic halide to form a dihalogenated diphenylmethane; coupling said dihalogenated diphenylmethane with ethynyltrimethylsilane by warming and stirring a mixture of said methane and said silane in the presence of an organopalladium catalytic complex, a ligand and deareated triethylamine and toluene to provide an end-protected diphenylmethane compound having acetylenic moieties as substituents; and subsequently treating said end-protected compound with a weak base in an alcohol-ether solvent to remove said end-protecting groups, thereby yielding 4,4'-diethynyldiphenylmethane.

Claim 10

The process of claim 6 wherein said inorganic halide is KI, said catalytic complex is formed from dichlorobis(triphenylphosphine)palladium[II] and Cu 2 I 2 , said ligand is triphenylphosphine, and said base is K 2 CO 3 .

Claim 11

An improved process for synthesizing bis(ethynylphenyl) compounds whose structures are ##STR7## where X is a single bond, CO, SO 2 , NC 6 H 5 , S, Si(CH 3 ) 2 , POCH 3 , POC 6 H 5 , (CH 2 ) n or C(CF n H 3-n ) 2 where is 0, 1, 2 or 3 comprising the steps of: coupling ethynyltrimethylsilane with a dihalo diphenyl compound whose structure is ##STR8## where X is I or Br and X is as defined above to provide an end-protected diphenyl compound having acetylenic moieties thereon; and subsequently treating said end-protected diphenyl compound with a weak base in an alcoholic solvent.

Claim 12

An improved process for synthesizing bis(ethynylphenyl) compounds whose structures are ##STR7## where X is a single bond, CO, SO 2 , NC 6 H 5 , S, Si(CH 3 ) 2 , POCH 3 , POC 6 H 5 , (CH 2 ) n or C(CF n H 3-n ) 2 where is 0, 1, 2 or 3 comprising the steps of: coupling ethynyltrimethylsilane with a dihalo diphenyl compound whose structure is ##STR8## where X is I or Br and X is as defined above to provide an end-protected diphenyl compound having acetylenic moieties thereon; and subsequently treating said end-protected diphenyl compound with a weak base in an alcoholic solvent.

Claim 13

The process of claim 8 wherein ethynyltrimethylsilane is reacted with said diphenyl compound in the presence of an organopalladium catalyst, a ligand, and an amine solvent.

Claim 14

The process of claim 9 wherein said organopalladium catalyst is dichlorobis(triphenylphosphine)palladium[II].

Claim 15

The process of claim 10 wherein said diphenyl compound is 4,4'-diiododiphenylmethane.