A versatile process for the preparation of acylphosphines

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

• [LAF[s]Px(RH)m(R1)n(COR2)p]q (I)
• wherein
• s is either 0 or, provided that x is 1, m and n are 0 and p is 2, s is 1
• q if s is 0, is 1 and
• if s is 1, is an integer of 1 to 5
• x is an integer of 1 to 15 or 20
• m, n and p are selected such that:
• m is zero or an integer of 1 or more
• n is zero or an integer of 1 or more
• P is an integer of 1 or more
• and one of the following conditions is met:
• If
• x is an integer of 1 to 9
• (m+n+p) is (x+2) where s is 0
• (m+n+p) is (x+1) where s is 1
• x is an integer of 3 to 10
• (m+n+p) is x
• x is an integer of 4 to 12
• (m+n+p) is (x−2)
• x is an integer of 5 to 10 or 13
• (m+n+p) is (x−4)
• x is an integer of 7 to 14
• (n+m+p) is (x−6)
• x is 10, 11 or 15
• (m+n+p) is (x−8)
• x = is 12 or 20
• (m+n+p) is (x−10)
• LAF represents a q-valent Lewis Acid Fragment (LAF),
• RH are independently of each other either
• hydrogen,
• or a residue of formula Si(R3)3, wherein the substituents R3 are independently of each other selected from the group consisting of C1-C18-alkyl and C6-C14-aryl
• R1 and R2 are independently of each other aryl or heterocyclyl, alkyl or alkenyl
• whereby the aforementioned alkyl and alkenyl substituents R1 and/or R2 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, halogen, cyano, C6-C14-aryl;
• heterocyclyl, C1-C8-alkoxy, C1-C8-alkylthio, -SO2N(R4)2, —NR4SO2R5, —N(R4)2—, —CO2N(R4)2, —COR4—, —OCOR5, —O(CO)OR5, NR4(CO)R4, —NR4(CO)OR4, O(CO)N(R4)2, —NR4(CO)N(R4)2,
• whereby 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
• the process comprising at least the step of reacting compounds of formula (II)
• Px(RH)(m+p)(R1)n (II)
• wherein RH, R1, x, and n and the sum of (m+n+p) is as defined above for the sum of (m+n+p) for compounds of formula (I) with s being 0 where x=1
• and the sum of (m+p) is an integer of 1 or more that fits the equation given for the sum of (m+n+p) for compounds of formula (I) with s being 0 where x is 1
• with compounds of formula (III),
• R2COHal (III)
• wherein R2 is as defined above for compounds of formula (I) and
• Hal represents fluoro, chloro, bromo or iodo
• whereby the reaction is carried out in the presence of at least one Lewis acid.