Process for the preparation of acylphosphanes

A process for the preparation of compounds of formula (I):

• wherein,
• n is 1,
• m is 1 or 2,
• R1 is a substituent of formula (IIa)
• —C(1)R62—C(2)H(Z)(R7) (IIa)
• wherein,
• (1) and (2) indicate the numeration of the carbon atom, wherein C(1) is bound to the central phosphorous atom depicted in formula (I), and
• Z is a substituent selected from the group consisting of —CN, —NO2, —(CO)H, —(CO)R8, —(CO)OH, —(CO)OR8, —(CO)NH2, —(CO)NH(R8), —(CO)N(R8)2, —(SO2)R8, —(PO)(R8)2, —(PO)(OR8)2, —(PO)(OR8)(R8) or heteroaryl
• R6 and R7 each substituent independently is hydrogen, Z or R8 and
• R8 independently of further substituents R8 which may be present in the substituent of formula (IIa) is alkyl, alkenyl or aryl or two substituents R8 irrespective of whether they are both part of a substituent Z or belong to different substituents selected from Z, R6 and R7 together are alkanediyl or alkenediyl or alternatively, where two substituents —(CO)R8 are present within the substituent of formulae (IIa) are together —O— or —NR4—,
• wherein, the alkyl, alkenyl, aryl, alkanediyl and alkenediyl substituents are
• either not, once, twice or more than twice interrupted by non-successive functional groups selected from the group consisting of:
• —O—, —S—, —SO2—, —SO—, —SO2NR4—, NR4SO2—, —NR4—, —CO—, —O(CO)—, (CO)O—, —O(CO)O—, —NR4(CO)NR4—, NR4(CO)—, —(CO)NR4—, —NR4(CO)O—, —O(CO)NR4—, —Si(R5)2—, —OSi(R5)2—, —OSi(R5)2O—, —Si(R5)2O—,
• and,
• either not, additionally or alternatively either once, twice or more than twice interrupted by bivalent residues selected from the group consisting of heterocyclo-diyl, and aryldiyl,
• and,
• either not, additionally or alternatively either once, twice or more than twice substituted by substituents selected from the group consisting of:
• oxo, hydroxy, halogen, cyano, azido, C6-C14-aryl, C1-C8-alkoxy, C1-C8-alkylthio, —SO3M, —COOM, PO3M2, —PO(N(R5)2)2, PO(OR5)2, —SO2N(R4)2, —N(R4)2, —N(R4)3+An−, —CO2N(R5)2, —COR4, —OCOR4, —NR4(CO)R5, —(CO)OR4, —NR4(CO)N(R4)2, —Si(OR)y(R5)3-y, —OSi(OR)y(R5)3-y with y=1, 2 or 3, or
• or R1 is a substituent of formulae (IIb), (IIc) or (IId)
• —C(1)R62—N(R8)2 (IIb)
• —C(1)R62—NH(R8) (IIc)
• —(C(1)═O)—NHR8 (IId),
• wherein,
• (1) indicates the carbon atom bound to the central phosphorous atom depicted in formula (I), and
• R2 and R3 are independently of each other aryl or heterocyclyl, alkyl or alkenyl,
• wherein, the aforementioned alkyl and alkenyl substituents of R2 and R3 are
• either not, once, twice or more than twice interrupted by non-successive functional groups selected from the group consisting of:
• —O—, —NR4—, —CO—, —OCO—, —O(CO)O—, NR4(CO)—, —NR4(CO)O—, O(CO)NR4—, —NR4(CO)NR4—,
• and,
• either not, additionally or alternatively either once, twice or more than twice interrupted by bivalent residues selected from the group consisting of heterocyclo-diyl, and aryldiyl,
• and
• either not, additionally or alternatively either once, twice or more than twice substituted by substituents selected from the group consisting of:
• oxo, hydroxyl, halogen, cyano, C6-C14-aryl;
• heterocyclyl, C1-C8-alkoxy, C1-C8-alkylthio, —COOM, —SO3M, —PO3M2, —SO2N(R4)2, —NR4SO2R5, —N(R4)2—, —N+(R4)3An−, —CO2N(R4)2, —COR4—, —OCOR5, —O(CO)OR5, NR4(CO)R4, —NR4(CO)OR4, O(CO)N(R4)2, —NR4(CO)N(R4)2,
• wherein, in all formulae where used
• R4 is independently selected from the group consisting of hydrogen, C1-C8-alkyl, C6-C14-aryl, and heterocyclyl or N(R4)2 as a whole is a N-containing heterocycle,
• R5 is independently selected from the group consisting of C1-C8-alkyl, C6-C14-aryl, and heterocyclyl or N(R5)2 as a whole is a N-containing heterocycle,
• M is hydrogen, or 1/q equivalent of an q-valent metal ion or is an ammonium ion or a guanidinium ion or a primary, secondary, tertiary or quarternary organic ammonium ion, and
• An− is 1/p equivalent of a p-valent anion,
• the process comprising at least the step of reacting compounds of formula (III):
• with compounds of formulae (IVa), (IVb), (IVc) or (IVd),
• R62C(1)=C(2)(Z)(R7) (IVa),
• R62C(1)═N+(R8)2An− (IVb),
• R62C(1)═NR8 (IVc),
• R8—NCO (IVd),
• wherein, in formulae (III) and (IVa) to (IVf),
• (1), (2), R2, R3, R6, R7, R8, n, m, An and Z have the same meaning as described for formulae (I) and (IIa) to (IId) above, and
• wherein, in formula (II),
• M2 is hydrogen, or 1/q equivalent of an q-valent metal ion or is an ammonium ion or a heterocycylium cation, a guanidinium ion or a primary, secondary, tertiary or quarternary organic ammonium ion, and
• wherein the reaction if M2 is hydrogen is carried out in the presence of a base.