Method of producing ethynyl aromatic compounds

The process of producing ethynyl aromatic compounds from the group consisting of the classes represented by structural formulas (1), (2) and (3) which follow:

• (1) ##STR13## in which R is selected from the group H, alkyl and phenyl, (2) ##STR14## (3) ##STR15## in which R.sub.1 and R.sub.2 are selected from the group H and alkyl and n is 1, 2, 3 or 4,
• and which comprises four steps:
• A. chloracetylating a compound selected from the classes represented by the structural formulas (4), (5) and (6) which follow:
• (4) ##STR16## in which R has the same significance as in Formula (1), (5) ##STR17## (6) ##STR18## in which R.sub.1, R.sub.2 and n have the same significance as in Formula (3),
• B. reducing each carbonyl group in the reaction product of step A to a hydroxyl group;
• C. converting each hydroxyl group in the reaction product of step B to an easily eliminatable group, and
• (D) converting the reaction product of step C to a compound within a class represented by structural formulas (1), (2) and (3) by eliminating chlorine and the easily eliminatable groups under basic conditions.

The process of preparing 4,4'-diethynyldiphenyl methane which comprises the following four steps:

• A. preparing 4,4'-di(2-chloroacetyl)-diphenyl methane by a Friedel-Crafts reaction of diphenyl methane with chloroacetyl chloride as the chloroacetylating agent and recrystallizing the reaction product to purify it,
• B. preparing 4,4'-di(1-hydroxy-2-chloroethyl)-diphenyl methane from the purified reaction product of step A by reacting it with sodium borohydride and crystallizing the reaction product,
• C. preparing 4,4'-di(1-methane sulfonoxy-2-chloroethyl)-diphenyl methane by reacting the reaction product of step B with methane sulfonyl chloride in the presence of a suitable solvent, and
• D. converting the product prepared in step C to 4,4'-diethynyldiphenyl methane with sodium methoxide in a suitable solvent.

The process of preparing 1,2-(4,4'-diethynyldiphenyl)ethane which comprises:

• A. reacting bibenzyl with chloroacetyl chloride in the presence of a Friedel-Crafts catalyst in a suitable solvent to produce 1,2-[4,4'-(2-chloroacetyl)-diphenyl]ethane,
• B. reacting the product of step A with sodium borohydride in a suitable solvent to produce 1,2-[4,4'-di(1-hydroxy-2-chloroethyl)-diphenyl]ethane,
• C. reacting the product of step B with methane sulfonyl chloride in the presence of a suitable solvent to produce 1,2-[4,4'-di(1-methane sulfonoxy-2-chloroethyl)-diphenyl]ethane, and
• D. Reacting the product of step C with sodium methoxide in a suitable solvent and neutralizing the solution to produce 1,2-[4,4'diethynyldiphenyl]ethane.

The process of producing 1,1-(4,4'-diethynyldiphenyl)ethane which comprises:

• A. reacting 1,1-diphenylethane with chloroacetyl chloride in the presence of a Friedel-Crafts catalyst in a suitable solvent to produce 1,1-[4,4'di(2-chloroacetyl)-diphenyl]ethane,
• B. Reacting the product of step A with sodium borohydride in a suitable solvent to produce 1,1-[4,4'-di(1-hydroxy-2-chloroethyl)-diphenyl]ethane,
• C. Reacting the product of step B with methane sulfonyl chloride to produce 1,1-[4,4'-Di(1-methane sulfonoxy-2-chloroethyl)-diphenyl]ethane, and
• D. Reacting the product of step C with sodium methoxide in a suitable solvent and neutralizing the solution to produce 1,1-(4,4'-diethynyldiphenyl)ethane.

The process of producing tris(4-ethynylphenyl)methane which comprises:

• A. Reacting triphenylmethane with chloroacetyl chloride to produce tris[4-(2-chloroacetyl)-phenyl]methane,
• B. Reacting the product of step A with sodium borohydride in a suitable solvent to produce tris[4-(1-hydroxy-2-chloroethyl)-phenyl]methane,
• C. Reacting the product of step B with methane sulfonyl chloride in a suitable solvent to produce tris[4-(1-methane solfonoxy-2-chloroethyl)-phenyl]methane, and
• D. Reacting the product of step C with sodium methoxide in a suitable solvent and neutralizing the solution to produce tris(4-ethynylphenyl)methane.

The process of producing 4-ethynyl toluene which comprises:

• A. reacting toluene with chloroacetyl chloride in the presence of a Friedel-Crafts catalyst in a suitable solvent to produce 4-(2-chloroacetyl)toluene,
• B. Reacting the product of step A with sodium borohydride in a suitable solvent to produce 4-(1-hydroxy-2-chloroethyl)toluene,
• C. Reacting the product of step B with methane sulfonyl chloride in a suitable solvent to produce 4-(1-methane sulfonoxy-2-chloroethyl)toluene, and
• D. Reacting the product of step C with sodium methoxide in a suitable solvent and neutralizing the solution to produce 4-ethynyl toluene.

The proess of producing 2,2'-(4,4'-diethynyldiphenyl)propane which comprises:

• A. reacting 2,2-diphenyl propane in the presence of a Friedel-Crafts catalyst in a suitable solvent with chloroacetyl chloride to produce 2.2-[4.4'-di(2-chloroacetyl)-diphenyl]propane,
• B. reacting the product of step A with sodium borohydride in a suitable solvent to produce 2,2'-[4.4'-di(1-hydroxy-2-chloroethyl)-diphenyl]propane,
• C. reacting the product of step B with methane sulfonyl chloride in a suitable solvent to produe 2,2'-[4,4'-di(1methane sulfonoxy-2-chloroethyl)-diphenyl]propane, and
• D. Reacting the product of step C with sodium methoxide in a suitable solvent and neutralizing the solution to produce 2,2'-(4,4'-diethynyldiphenyl)propane.

The process of producing 4-ethynylbiphenyl which comprises:

• A. reacting biphenyl in the presence of a Friedel-Crafts catalyst in a suitable solvent with chloroacetyl chloride to produce 4-(2-chloroacetyl)-biphenyl,
• B. reacting the product of step A with sodium borohydride in a suitable solvent to produce 4-(1-hydroxy-2-chloroethyl)-biphenyl,
• C. reacting the product of step B with methane sulfonyl chloride in a suitable solvent to produce 4-(1-methane sulfonoxy-2-chloroethyl)-biphenyl, and
• D. reacting the product of step C with sodium ethoxide in a suitable solvent and neutralizing the solution to produce 4-ethynylbiphenyl.

The process of preparing 4,4'-diethynyldiphenyl membrane which comprises the following four steps:

• A. preparing 4,4'-di(2-chloroacetyl)-diphenyl methane by a Friedel-Crafts reaction of diphenyl methane with chloroacetyl chloride as the chloracetylating agent and recrstallizing the reaction product to purify it,
• B. preparing 4,4'-di(1-hydroxy-2-chloroethyl)-diphenyl methane from the purified reaction product of step A by reacting it with sodium borohydride and crystallizing the reaction product,
• C. preparing 4,4'-di(methane sulfonoxy-2-chloroethyl)-diphenyl methane by reacting the reaction product of step B with methane sulfonyl chloride in a solvent comprising dimethylformamide and di-t-butyl hydroquinone, and
• D. converting the product prepared in step C to 4,4'-diethynyldiphenyl methane with sodium methoxide in a solvent comprising dimethyl sulfoxide and di-t-butyl hydroquinone.