Process for producing phosphonium borate compound, novel phosphonium borate compound, and method of using the same

Abstract

The invention relates to a phosphonium borate compound represented by Formula (I) (hereinafter, the compound (I)). The invention has objects of providing (A) a novel process whereby the compound is produced safely on an industrial scale, by simple reaction operations and in a high yield; (B) a novel compound that is easily handled; and (C) novel use as catalyst. Formula (I): (R 1 )(R 2 )(R 3 )PH.BAr 4   (I) wherein R 1 , R 2 , R 3 and Ar are as defined in the specification. The process (A) includes reacting a phosphine with a) HCl or b) H 2 SO 4 to produce a) a hydrochloride or b) a sulfate; and reacting the salt with a tetraarylborate compound. The compound (B) has for example a secondary or tertiary alkyl group as R 1 and is easily handled in air without special attention. The use (C) is characterized in that the compound (I) is used instead of an unstable phosphine compound of a transition metal complex catalyst for catalyzing C—C bond, C—N bond and C—O bond forming reactions and the compound produces an effect that is equal to that achieved by the transition metal complex catalyst.

1 - 6 . (canceled) 
   
   
       7 . A novel phosphonium borate compound represented by Formula (I):
   (R 1 )(R 2 )(R 3 )PH.BAr 4   (I)   wherein R 1  is a secondary allyl group of 3 to 20 carbon atoms, a tertiary allyl group of 4 to 20 carbon atoms;   R 2  is a hydrogen atom, a primary allyl group of 1 to 20 carbon atoms, a secondary allyl group of 3 to 20 carbon atoms, a tertiary alkyl group of 4 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, or an allyl group of 3 to 20 carbon atoms;   R 3  is a hydrogen atom, a primary allyl group of 1 to 20 carbon atoms, a secondary alkyl group of 3 to 20 carbon atoms, a tertiary alkyl group of 4 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, an aryl group of 6 to 30 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an alkynyl group of 2 to 20 carbon atoms, or an allyl group of 3 to 20 carbon atoms;   R 1 , R 2  and R 3  may be the same or different from one another;   Ar is an aryl group of 6 to 20 carbon atoms;   R 1 , R 2  and R 3  cannot be tert-butyl groups simultaneously and Ar cannot be phenyl group at the same time; and   R 1 , R 2  and R 3  cannot be cyclohexyl groups simultaneously and Ar cannot be phenyl group at the same time.   
   
   
       8 . A novel phosphonium borate compound represented by Formula (I):
   (R 1 )(R 2 )(R 3 )PH.BAr 4   (I)   wherein R 1  is a secondary allyl group of 3 to 20 carbon atoms, a tertiary alkyl group of 4 to 20 carbon atoms, or a cycloalkyl group of 3 to 20 carbon atoms   R 2  is a hydrogen atom, a primary alkyl group of 1 to 20 carbon atoms, a secondary alkyl group of 3 to 20 carbon atoms, a tertiary alkyl group of 4 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, or an allyl group of 3 to 20 carbon atoms;   R 3  is a hydrogen atom, a primary alkyl group of 1 to 20 carbon atoms, a secondary alkyl group of 3 to 20 carbon atoms, a tertiary alkyl group of 4 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an alkynyl group of 2 to 20 carbon atoms, or an allyl group of 3 to 20 carbon atoms;   R 1 , R 2  and R 3  may be the same or different from one another;   Ar is an aryl group of 6 to 20 carbon atoms;   R 1 , R 2  and R 3  cannot be tert-butyl groups simultaneously and Ar cannot be phenyl group at the same time; and   R 1 , R 2  and R 3  cannot be cyclohexyl groups simultaneously and Ar cannot be phenyl group at the same time, which is di-tert-butylmethylphosphonium tetraphenylborate.   
   
   
       9 . A novel phosphonium borate compound represented by Formula (I):
   (R 1 )(R 2 )(R 3 )PH.BAr 4   (I)   wherein R 1  is a secondary alkyl group of 3 to 20 carbon atoms, a tertiary alkyl group of 4 to 20 carbon atoms, or a cycloalkyl group of 3 to 20 carbon atoms;   R 2  is a hydrogen atom, a primary allyl group of 1 to 20 carbon atoms, a secondary alkyl group of 3 to 20 carbon atoms, a tertiary alkyl group of 4 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, or an allyl group of 3 to 20 carbon atoms;   R 3  is a hydrogen atom, a primary allyl group of 1 to 20 carbon atoms, a secondary alkyl group of 3 to 20 carbon atoms, a tertiary alkyl group of 4 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an alkynyl group of 2 to 20 carbon atoms, or an allyl group of 3 to 20 carbon atoms;   R 1 , R 2  and R 3  may be the same or different from one another;   Ar is an aryl group of 6 to 20 carbon atoms;   R 1 , R 2  and R 3  cannot be tert-butyl groups simultaneously and Ar cannot be phenyl group at the same time; and   R 1 , R 2  and R 3  cannot be cyclohexyl groups simultaneously and Ar cannot be phenyl group at the same time, which is tri-tert-butylphosphonium tetra-para-tolylborate.   
   
   
       10 . A novel phosphonium borate compound represented by Formula (I):
   (R 1 )(R 2 )(R 3 )PH.BAr 4   (I)   wherein R 1  is a secondary allyl group of 3 to 20 carbon atoms, a tertiary allyl group of 4 to 20 carbon atoms, or a cycloalkyl group of 3 to 20 carbon atoms;   R 2  is a hydrogen atom, a primary alkyl group of 1 to 20 carbon atoms, a secondary allyl group of 3 to 20 carbon atoms, a tertiary alkyl group of 4 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, or an allyl group of 3 to 20 carbon atoms;   R 3  is a hydrogen atom, a primary allyl group of 1 to 20 carbon atoms, a secondary alkyl group of 3 to 20 carbon atoms, a tertiary alkyl group of 4 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an alkynyl group of 2 to 20 carbon atoms, or an allyl group of 3 to 20 carbon atoms;   R 1 , R 2  and R 3  may be the same or different from one another;   Ar is an alkyl group of 6 to 20 carbon atoms;   R 1 , R 2  and R 3  cannot be tert-butyl groups simultaneously and Ar cannot be phenyl group at the same time; and   R 1 , R 2  and R 3  cannot be cyclohexyl groups simultaneously and Ar cannot be phenyl group at the same time, which is tricyclohexylphosphonium tetra-para-tolylborate.   
   
   
       11 . A novel phosphonium borate compound represented by Formula (I):
   (R 1 )(R 2 )(R 3 )PH.BAr 4   (I)   wherein R 1  is a secondary alkyl group of 3 to 20 carbon atoms, a tertiary allyl group of 4 to 20 carbon atoms, or a cycloalkyl group of 3 to 20 carbon atoms;   R 2  is a hydrogen atom, a primary alkyl group of 1 to 20 carbon atoms, a secondary alkyl group of 3 to 20 carbon atoms, a tertiary allyl group of 4 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, or an allyl group of 3 to 20 carbon atoms;   R 3  is a hydrogen atom, a primary alkyl group of 1 to 20 carbon atoms, a secondary alkyl group of 3 to 20 carbon atoms, a tertiary allyl group of 4 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an alkynyl group of 2 to 20 carbon atoms, or an allyl group of 3 to 20 carbon atoms;   R 1 , R 2  and R 3  may be the same or different from one another;   Ar is an aryl group of 6 to 20 carbon atoms;   R 1 , R 2  and R 3  cannot be tert-butyl groups simultaneously and Ar cannot be phenyl group at the same time; and   R 1 , R 2  and R 3  cannot be cyclohexyl groups simultaneously and Ar cannot be phenyl group at the same time, which is triisopropylphosphonium tetraphenylborate.   
   
   
       12 . A composition comprising a phosphonium borate compound in combination with a transition metal, transition metal salt, transition metal oxide or transition metal complex for use in carbon-carbon bond forming reactions, carbon-nitrogen bond forming reactions and carbon-oxygen bond forming reactions wherein a transition metal complex having a phosphine ligand produces catalytic effects, wherein the phosphonium borate compound in combination with the transition metal, transition metal salt, transition metal oxide or transition metal complex is used in place of the transition metal complex having a phosphine ligand, the phosphonium borate compound being represented by Formula (I):
   (R 1 )(R 2 )(R 3 )PH.BAr 4   (I)   wherein R 1  is a primary allyl group of 1 to 20 carbon atoms, a secondary allyl group of 3 to 20 carbon atoms, a tertiary allyl group of 4 to 20 carbon atoms, or a cycloalkyl group of 3 to 20 carbon atoms;   R 2  is a hydrogen atom, a primary alkyl group of 1 to 20 carbon atoms, a secondary allyl group of 3 to 20 carbon atoms, a tertiary allyl group of 4 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, or an allyl group of 3 to 20 carbon atoms;   R 3  is a hydrogen atom, a primary allyl group of 1 to 20 carbon atoms, a secondary alkyl group of 3 to 20 carbon atoms, a tertiary allyl group of 4 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, an aryl group of 6 to 30 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an alkynyl group of 2 to 20 carbon atoms, or an allyl group of 3 to 20 carbon atoms;   R 1 , R 2  and R 3  may be the same or different from one another; and   Ar is an aryl group of 6 to 20 carbon atoms.   
   
   
       13 . The composition according to  claim 12 , wherein the transition metal is manganese, iron, cobalt, nickel, ruthenium, rhodium, palladium or platinum. 
   
   
       14 . The composition according to  claim 12 , wherein the transition metal salt is a fluoride, chloride, bromide, iodide, sulfate, nitrate, nitrite, carbonate, borate, ammonium salt, sodium salt, potassium salt, acetate, trifluoroacetate, acetylacetone salt, hydride salt, sulfide or cyanide of the transition metal, wherein the transition metal is manganese, iron, cobalt, nickel, ruthenium, rhodium, palladium or platinum. 
   
   
       15 . The composition according to  claim 12 , wherein the transition metal oxide is an oxide of the transition metal as, wherein the transition metal is manganese, iron, cobalt, nickel, ruthenium, rhodium, palladium or platinum. 
   
   
       16 . The composition according to  claim 12 , wherein the transition metal complex is a benzonitrile complex, acetonitrile complex, triphenylphosphine complex, ethylene complex, allyl complex, butadiene complex, cyclopentadiene complex, cyclooctadiene complex, cyclooctatetraene complex, carbonyl complex, dibenzylideneacetone complex, amine complex, ethylenediamine complex, pyridine complex or disiloxane complex of the transition metal, wherein the transition metal is manganese, iron, cobalt, nickel, ruthenium, rhodium, palladium or platinum.