Versatile process for the preparation of acylphosphines

Patent metadata

Field	Value
Publication number	US-10889603-B2
Application number	US-201716334668-A
Country	US
Kind code	B2
Filing date	Sep 18, 2017
Priority date	Sep 19, 2016
Publication date	Jan 12, 2021
Grant date	Jan 12, 2021

Abstract

A versatile, highly efficient process for the preparation of acylphosphines such as mono- and bisacylphosphines via reaction of phosphines (PH 3 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.

First claim

The invention claimed is:

1. Compounds of formula (Ia)
[LAF][P(COR 2 ) 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
R 2 is aryl or heterocyclyl alkyl or alkenyl
whereby the aforementioned alkyl and alkenyl substituent R 2 is
either not, once, twice or more than twice interrupted by non-successive functional groups selected from the group consisting of:

—O—, —NR 4 —, —CO—, —OCO—, —O(CO)O—, NR 4 (CO)—, —NR 4 (CO)O—, O(CO)NR 4 —, —NR 4 (CO)NR 4 —,
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, C 6 -C 14 -aryl; heterocyclyl, C 1 -C 8 -alkoxy, C 1 -C 8 -alkylthio, —SO 2 N(R 4 ) 2 , —NR 4 SO 2 R 5 , —N(R 4 ) 2 —, —CO 2 N(R 4 ) 2 , —COR 4 —, OCOR 5 , —O(CO)OR 5 , NR 4 (CO)R 4 , —NR 4 (CO)OR 4 , O(CO)N(R 4 ) 2 , —NR 4 (CO)N(R 4 ) 2 ,

whereby in all formulae where used
R 4 is independently selected from the group consisting of hydrogen, C 1 -C 8 -alkyl, C 6 -C 14 -aryl, and heterocyclyl, or N(R 4 ) 2 as a whole is a N-containing heterocycle, and
R 5 is independently selected from the group consisting of C 1 -C 8 -alkyl, C 6 -C 14 -aryl, and heterocyclyl, or N(R 5 ) 2 as a whole is a N-containing heterocycle,
with the exception of
diphenylboryldipivaloylphosphide and
1-oxa-3-oxonia-5λ 3 -phospha-2-borata-4,6-dimethylcyclohexadiene and 1-oxa-3-oxonia-5λ 3 -phospha-2-borata-4,6-diphenylcyclohexadiene:

with R=methyl or phenyl.

2. Compounds according to claim 1 , wherein
R 2 is C 6 -C 14 -aryl or C 4 -C 13 -heteroaryl.

3. Compounds according to claim 1 , wherein
LAF is dichloroaluminyl (AlCl 2 ) or difluoroboryl (BF 2 ) with q being 1
chloroaluminyl (AlCl) or fluoroboryl (BF) with q being 2 or
aluminum (Al) or boron (B) with q being 3.

4. The following compounds of formula (Ia) according to claim 1 :
dichloroaluminyl-bismesitoylphosphide, difluoroboryl-bismesitoylphosphide, dichloroaluminyl-bisbenzoylphosphide, difluoroboryl-bisbenzoylphosphide, chloroaluminyl-bis(bismesitoylphosphide), chloroaluminyl-bis(bisbenzoylphosphide), chloroboryl-bis(bismesitoylphosphide), chloroboryl-bis(bisbenzoyl-phosphide), aluminium-tris(bismesitoylphosphide), aluminium-tris(bisnaphthoylphosphide) and/or aluminium-tris(bisbenzoylphosphide).

5. Compounds according to claim 1 , wherein LAF is obtainable from a Lewis acid selected from the group consisting of methyl aluminoxane (MAO) and compounds represented by formula (IV)
MR L (r) X (z-r)   (IV)

wherein
z is 2, 3, 4 or 5
r is 0 or an integer of at maximum z
M if z is 2 is an element selected from the group consisting of Sn, Zn, Fe, and Mn
if z is 3 is an element selected from the group consisting of Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Fe, B, Al, Ga, In, and As
if z is 4 is an element selected from the group consisting of V, Ti, Zr, Hf, and Sn
if z is 5 is an element selected from the group consisting of V, P, As, Sb, and Bi
X is independently selected from the group consisting of fluoride, chloride, bromide, iodide, azide, isocyanate, thiocyanate, isothiocyanate, and cyanide
R L represents C 1 -C 18 -alkyl, C 1 -C 18 -haloalkyl, C 1 -C 18 -alkoxy, C 1 -C 18 -haloalkoxy, C 6 -C 14 -aryl, C 7 -C 18 -arylalkyl, C 6 -C 14 -aryloxy, C 7 -C 18 -arylalkoxy, —O(HC═O), —O(C═O)—(C 1 -C 18 -alkyl), —O(C═O)—(C 6 -C 14 -aryl) or —O(C═O)—(C 7 -C 18 -arylalkyl) or
two R L together represent C 4 -C 18 -alkandiyl, C 4 -C 18 -haloalkandiyl, C 4 -C 18 -alkanedioxy, C 4 -C 18 -haloalkanedioxy, C 6 -C 14 -aryldiyl, C 7 -C 18 -arylalkanediyl, C 4 -C 18 -alkanedioxy, C 4 -C 18 -haloalkanedioxy, C 6 -C 14 -aryl)-(C═O)O—, (C 1 -C 18 -alkyl)-(C═O)O—, —O(C═O)—(C 6 -C 14 -aryl)-(C═O)O—, —O(C═O)—(C 7 -C 18 -arylalkyl)-(C═O)O—, or oxo (═O).

6. Compounds according to claim 5 , wherein LAF is a structural unit of formula (IVa)
MR L (rr) X (zz-rr)   (IVa)

wherein
M, X and R L have the same meaning as described for formula (IV)
zz is (z-q) with q being an integer of 1 up to z, wherein z has the same meaning as described for formula (IV) and
rr is 0 or an integer of at maximum zz.

7. A process for the preparation of compounds of formula (I):
[LAF] s [P x (R H ) m (R 1 ) n (COR 2 ) 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,
R H are independently of each other either
hydrogen,
or a residue of formula Si(R 3 ) 3 , wherein the substituents R 3 are independently of each other selected from the group consisting of C 1 -C 18 -alkyl and C 6 -C 14 -aryl

R 1 and R 2 are independently of each other aryl or heterocyclyl, alkyl or alkenyl
whereby the aforementioned alkyl and alkenyl substituents R 1 and/or R 2 are
either not, once, twice or more than twice interrupted by non-successive functional groups selected from the group consisting of:

—O—, —NR 4 —, —CO—, —OCO—, —O(CO)O—, NR 4 (CO)—, —NR 4 (CO)O—, O(CO)NR 4 —, —NR 4 (CO)NR 4 —,
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, C 6 -C 14 -aryl; heterocyclyl, C 1 -C 8 -alkoxy, C 1 -C 8 -alkylthio, —SO 2 N(R 4

Assignees

• Eth Zuerich
• Univ Bristol

Inventors

• Grützmacher Hansjörg
• Pringle Paul Gerard
• Bispinghoff Mark

Classifications

• C07F9/5036 Primary

  Phosphines containing the structure -C(=X)-P or NC-P · CPC title

• C07F9/6596 Primary

  having atoms other than oxygen, sulfur, selenium, tellurium, nitrogen or phosphorus as ring hetero atoms · CPC title