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US 10,889,603 B2Granted
Versatile process for the preparation of acylphosphines
AssigneesETH Zurich, The University of Bristol
InventorsHansjörg Grützmacher, Paul Gerard Pringle, Mark Bispinghoff
Life of this patent
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Abstract
A versatile, highly efficient process for the preparation of acylphosphines such as mono- and bisacylphosphines via reaction of phosphines (PH3 and higher homologues) or silylated phosphines with acylhalides in the presence of at least one lewis acid. Further a novel acyl phosphines obtainable by the process.
Claims16
Compounds of formula (Ia)
- [LAF][P(COR2)2]q (Ia)
- wherein:
- LAF represents a q-valent Lewis Acid Fragment (LAF) that is a cationic structural unit obtainable by removing q anionic substituents from a Lewis acid,
- q is an integer of 1 to 5, and
- R2 is aryl or heterocyclyl alkyl or alkenyl
- whereby the aforementioned alkyl and alkenyl substituent R2 is
- 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, and
- 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,
- with the exception of
- diphenylboryldipivaloylphosphide and
- 1-oxa-3-oxonia-5λ3-phospha-2-borata-4,6-dimethylcyclohexadiene and 1-oxa-3-oxonia-5λ3-phospha-2-borata-4,6-diphenylcyclohexadiene:
- with R=methyl or phenyl.
18 more elements
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) that is a cationic structural unit obtainable by removing q anionic substituents from a Lewis acid,
- 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.
50 more elements
Dependencies are inferred from the claim text.