Process for Preparing Acylphosphanes and Derivatives Thereof

A process for the preparation of acylphosphanes or bisacylphosphanes of formula I

• wherein
• n and m are each independently of the other 1 or 2;
• R1 if n=1, is unsubstituted linear or branched C1-C18alkyl or C2-C18alkenyl;
• or
• linear or branched C1-C18alkyl or C2-C18alkenyl substituted once or more than once by groups selected from:
• halogen or CN, or
• —OR10, —SR10, —OCO—R10, —COO—R10, —CH═CH—CO—OR10 or
• —C(C1-C4alkyl)═C(C1-C4alkyl)-CO—OR10;
• wherein
• R10 is hydrogen, C1-C18alkyl, or C2-C18alkyl which is interrupted by one or several non-successive —O-atoms, a di, -tri, -tetra- or polyethylene glycol residue, C3-C12-cycloalkyl, tetrahydropyran-2-yl, phenyl-C1-C4-alkylene, phenyl-C1-C4-alkenylene, C1-C6alkyl substituted by halogen or substituted by cyclohexyl or cyclopentyl, or substituted by tetrahydrofuranyl, furanyl, isopropyl-4-methyl-cyclohexyl, C2-C18-alkenyl, unsubstituted phenyl, naphthyl or biphenyl being unsubstituted or phenyl, naphthyl or biphenyl substituted by one to five C1-C8-alkyl, C1-C8-alkoxy, C1-C8-alkylthio and/or halogen;
• or
• R1 is linear or branched C1-C18alkyl or C2-C18alkenyl substituted by —CO—R11;
• wherein
• R11 is C1-C18alkyl, or C2-C18alkyl which is interrupted by one or several non-successive —O-atoms, C3-C12-cycloalkyl, phenyl-C1-C4-alkylene, unsubstituted phenyl, naphthyl or biphenyl being unsubstituted or phenyl, naphthyl or biphenyl substituted by one to five C1-C8-alkyl, C1-C8-alkoxy, C1-C8-alkylthio and/or halogen or
• R1 is linear or branched C1-C18alkyl or C2-C18alkenyl substituted by —CO—(CH)2—CO—C1-C6alkyl, CO—(CH)2—CO-phenyl-, or by CO—(CH)2—COO—C1-C18alkyl;
• or
• R1 is linear or branched C1-C18alkyl or C2-C18alkenyl substituted by —NR12R13, —N(R12)—CO—R10, —N(R12)—CO—OR10, —N(R12)—CO—NR12R13,
• —N(R12)—CO-Hal, —CO—NR12R13, wherein R10 is as defined above and R12 and R13 independently of one another are hydrogen, C1-C18alkyl, C2-C18alkyl which is interrupted by one or several non-successive O atoms, C3-C12-cycloalkyl, C2-C18-alkenyl, phenyl-C1-C4-alkyl, phenyl, naphthyl, pyridyl, the radicals phenyl, naphthyl or pyridyl being unsubstituted or substituted by one to five C1-C8-alkyl, C1-C8-alkoxy, C1-C8-alkylthio and/or halogen;
• or R12 and R13 forms a 5- or 6-membered O-, S- or N-containing heterocyclic ring;
• that may be further annelated by an aliphatic or aromatic ring;
• or —SO2—R10, —SO2—OR10, —SO2—NR12R13, wherein R10, R12 and R13 are as defined above;
• or
• —PO(OC1-C8alkyl)2, or
• —SiR14R15R16, wherein R14, R15 and R16 independently of one another are H, C1-C8alkyl, C2-C8alkenyl, phenyl, C7-C9phenylalkyl, —OC1-C8alkyl, —O—SiR17R18R19, wherein R17, R18 and R19 are independently of each other H, C1-C8alkyl, C2-C8alkenyl, phenyl, C7-C9phenylalkyl, —OC1-C8alkyl;
• or —CH═CH-phenyl or —C(C1-C4alkyl)═C(C1-C4alkyl)-phenyl, phenyl-C1-C4alkyl, phenyl, naphthyl, biphenyl, C5-C12cycloalkyl or a 5- or 6-membered O-, S- or N-containing heterocyclic, ring;
• benzophenonyl, thioxanthonyl;
• or
• R1 is C2-C18alkyl or C2-C18alkenyl which is interrupted by one or several non-successive —O—, —NH—, —NR12— or —S— atoms, and may additionally be substituted once or more than once by groups selected from:
• halogen or CN, or
• —OR10, —SR10, —OCO—R10, —COO—R10 wherein R10 is as defined above;
• or
• —NR12R13, —N(R12)—CO—R10, —N(R12)—CO—OR10, —N(R12)—CO—NR12R13,
• —N(R12)—CO-Hal, —CO—NR12R13, wherein R10 and R12 and R13 are as defined above;
• or
• —SO2—R10, —SO2—OR10, —SO2—NR12R13, wherein R10, R12 and R13 are as defined above;
• or
• —PO(OC1-C8alkyl)2, or
• —SiR14R15R16, wherein R14, R15 and R16 are as defined above;
• or
• phenyl-C1-C4alkyl, phenyl or C5-C12cycloalkyl;
• or
• R1 is C2-C18alkyl or C2-C18alkenyl which is interrupted by —CO—, —COO—, —OCO—, —OCOO—, —CO—N(R12)—, —N(R12)—CO—, —N(R12)—CO—N(R12)—, —N(R12)—COO—, —COO—C1-C18alkylene, —COS—C1-C18alkylene, —SO2—, —SO2—O—, —SO2—N(R12)—, —(CH3)2Si—[OSi(CH3)2]m— with m=1-6, phenyl-C1-C4alkylene, phenylene, naphthylene, biphenylene, C5-C12cycloalkylene or a 5- or 6-membered O-, S- or N-containing heterocyclic ring;
• wherein R12 is as defined above;
• or
• R1 is trimethylsilyl or Hal-(CH3)2Si—[OSi(CH3)2]m— or (CH3)3Si—[OSi(CH3)2]m— with m=1-6;
• or
• R1 is —COOH, —COO—R10, —CO—NR12R13, —CO-vinyl, —CO-phenyl which is unsubstituted or substituted by one or more —CH3, —OCH3, —Cl;
• wherein R10, R12 and R13 are as defined above;
• or
• R1 is phenyl-C1-C4alkyl, phenyl, naphthyl, biphenyl, C5-C12cycloalkyl or a 5- or 6-membered O-, S- or N-containing heterocyclic ring;
• all of the radicals phenyl, naphthyl, biphenyl, C5-C12cycloalkyl or the 5- or 6-membered —O-, S- or N-containing heterocyclic ring being unsubstituted or substituted by one to five halogen, C1-C8alkyl, C1-C8alkylthio, C1-C8alkoxy and/or —NR12R13;
• wherein R12 and R13 are as defined above;
• R1 if n=2, is a divalent radical of the monovalent radical defined above or is
• —CH2—COO-Z-OCO—CH2— wherein
• Q is a single bond, —CH2—, —CR6R7—, —O— or —S—;
• R4 and R5 are each independently of the other hydrogen, C1-C4alkyl or C1-C4alkoxy;
• R6 and R7 are each independently of the other C1-C4alkyl;
• Z is C1-C18 alkylene or a bridge derived from a di, -tri, -tetra- or polyethylene glycol;
• R2 is C1-C18alkyl or C2-C18alkenyl;
• C1-C18alkyl or C2-C18alkenyl substituted once or more than once by halogen;
• or
• —OR10, —OCO—R10, —OCO-Hal, —COO—R10, —CH═CH—CO—OR10—N(R12)—CO—R10, —N(R12)—CO-Hal;
• —C(C1-C4alkyl)═C(C1-C4alkyl)-CO—OR10, —CO—NR12R13, wherein R10, R12 and R13 are as defined above;
• or —CH═CH-phenyl or —C(C1-C4alkyl)═C(C1-C4alkyl)-phenyl;
• C3-C12cycloalkyl, C2-C18alkenyl, phenyl-C1-C4alkyl, phenyl, naphthyl, anthryl. biphenyl or a 5- or 6-membered —O-, S- or N-containing heterocyclic ring, the radicals phenyl, naphthyl, biphenyl or the 5- or 6-membered —O-, S- or N-containing heterocyclic ring being unsubstituted or substituted by one to five halogen, C1-C8alkyl, C1-C8alkoxy and/or C1-C8alkylthio;
• R3 is one of the radicals defined under R1;
• the process comprises the steps
• a) contacting elemental phosphorous [P]∞, P(Hal)3 or other phosphorous compounds in which the formal oxidation state of the phosphorous atom is higher than (−3)
• with a reducing metal optionally in the presence of a catalyst or an activator in a solvent to obtain metal phosphides Me3P or Me′3P2, wherein Me is an alkali metal and Me′ is an earth alkali metal or to obtain metal polyphosphides
• b) optionally adding a proton source, optionally in the presence of a catalyst or an activator to obtain metal dihydrogen phosphides MePH2;
• c) subsequent acylation reaction with m acid halides of formula III or m carboxylic acid esters of formula IV
• or, in case that in formula I m=1, with one carboxylic ester of formula IV followed by one acid halide of formula III or vice versa, wherein R is the residue of an alcohol and R2 is as defined above;
• d) alkylation reaction
• in case of m=2, subsequent reaction with an electrophilic agent R1Hal, R1—OSO2—O—R1, R1—OSO2—R20,
• (R1—O)3PO, H2C═CR23COOR10,
• wherein R1 and R10 are as defined above, R20 is C1-C8-alkyl, C1-C8-perfluoroalkyl, aryl or C1-C4-alkylaryl, R21 is H or C1-C8alkyl;
• R22 is C1-C16alkyl or C2-C16alkenyl substituted once or more than once by halogen —OR10, —NR12R13, —SR10, —OCO—R10, —OCO-Hal, —COO—R10, —N(R12)—CO—R10, —N(R12)—CO—OR10, —N(R12)—CO—NR12R13, —N(R12)—CO-Hal, —CO—NR12R13, —SO2—R10, —SO2—OR10, —SO2—NR12R13, —CH═CH—CO—OR10, —CH═CH-phenyl, —C(C1-C4alkyl)═C(C1-C4alkyl)-CO—OR10 or —C(C1-C4alkyl)═C(C1-C4alkyl)-phenyl, phenyl-C1-C4alkyl, phenyl, naphthyl, biphenyl, C5-C12cycloalkyl or a 5- or 6-membered O-, S- or N-containing heterocyclic ring;
• R23 is H or CH3, and n=1-5 and R10, R12 and R13 is as defined above or other electrophilic agents;
• and in the case of m=1 reaction with an electrophilic agent R1Hal R1—OSO2—O—R1, R1—OSO2—R20,
• (R1—O)3PO, H2C═CR23COOR10,
• wherein R1 and R10;
• R20, R21, R22 and R23 are as defined above or other electrophilic agents followed by the reaction with an electrophilic agent R3Hal or other electrophilic agents such as R3—OSO2—O—R3, R3—OSO2—R20,
• (R3—O)3PO, H2C═CR23COOR10,
• wherein R3 and R10, R20, R21, R22 and R23 are as defined above, or other electrophilic agents to obtain the compounds of formula I.