Process for the preparation of acylphosphanes

Patent metadata

Field	Value
Publication number	US-10273258-B2
Application number	US-201715603467-A
Country	US
Kind code	B2
Filing date	May 24, 2017
Priority date	Oct 1, 2012
Publication date	Apr 30, 2019
Grant date	Apr 30, 2019

Abstract

The present invention provides a process for the preparation of mono- and bisacylphosphanes based on formula (I):

as well as for their corresponding oxides or sulfides. The present invention further relates to photoinitiators obtainable by said process.

First claim

What is claimed is:

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

wherein,
n is 1,
m is 1 or 2,
R 1 is a substituent of formula (IIa)
—C (1) R 6 2 —C (2) H(Z)(R 7 )  (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, —NO 2 , —(CO)H, —(CO)R 8 , —(CO)OH, —(CO)OR 8 , —(CO)NH 2 , —(CO)NH(R 8 ), —(CO)N(R 8 ) 2 , —(SO 2 )R 8 , —(PO)(R 8 ) 2 , —(PO)(OR 8 ) 2 , —(PO)(OR 8 )(R 8 ) or heteroaryl
R 6 and R 7 each substituent independently is hydrogen, Z or R 8 and
R 8 independently of further substituents R 8 which may be present in the substituent of formula (IIa) is alkyl, alkenyl or aryl or two substituents R 8 irrespective of whether they are both part of a substituent Z or belong to different substituents selected from Z, R 6 and R 7 together are alkanediyl or alkenediyl or alternatively, where two substituents —(CO)R 8 are present within the substituent of formulae (IIa) are together —O— or —NR 4 —,
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—, —SO 2 —, —SO—, —SO 2 NR 4 —, NR 4 SO 2 —, —NR 4 —, —CO—, —O(CO)—, (CO)O—, —O(CO)O—, —NR 4 (CO)NR 4 —, NR 4 (CO)—, —(CO)NR 4 —, —NR 4 (CO)O—, —O(CO)NR 4 —, —Si(R 5 ) 2 —, —OSi(R 5 ) 2 —, —OSi(R 5 ) 2 O—, —Si(R 5 ) 2 O—,
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, C 6 -C 14 -aryl, C 1 -C 8 -alkoxy, C 1 -C 8 -alkylthio, —SO 3 M, —COOM, PO 3 M 2 , —PO(N(R 5 ) 2 ) 2 , PO(OR 5 ) 2 , —SO 2 N(R 4 ) 2 , —N(R 4 ) 2 , —N(R 4 ) 3 + An − , —CO 2 N(R 5 ) 2 , —COR 4 , —OCOR 4 , —NR 4 (CO)R 5 , —(CO)OR 4 , —NR 4 (CO)N(R 4 ) 2 , —Si(OR) y (R 5 ) 3-y , —OSi(OR) y (R 5 ) 3-y with y=1, 2 or 3, or

or R 1 is a substituent of formulae (IIb), (IIc) or (IId)
—C (1) R 6 2 —N(R 8 ) 2   (IIb)

—C (1) R 6 2 —NH(R 8 )  (IIc)

—(C (1) ═O)—NHR 8   (IId),

wherein,
(1) indicates the carbon atom bound to the central phosphorous atom depicted in formula (I), and

R 2 and R 3 are independently of each other aryl or heterocyclyl, alkyl or alkenyl,
wherein, the aforementioned alkyl and alkenyl substituents of R 2 and R 3 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, hydroxyl, halogen, cyano, C 6 -C 14 -aryl; heterocyclyl, C 1 -C 8 -alkoxy, C 1 -C 8 -alkylthio, —COOM, —SO 3 M, —PO 3 M 2 , —SO 2 N(R 4 ) 2 , —NR 4 SO 2 R 5 , —N(R 4 ) 2 —, —N + (R 4 ) 3 An − , —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 ,

wherein, 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,
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,
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),
R 6 2 C (1) =C (2) (Z)(R 7 )  (IVa),

R 6 2 C (1) ═N + (R 8 ) 2 An −   (IVb),

R 6 2 C (1) ═NR 8   (IVc),

R 8 —NCO  (IVd),

wherein, in formulae (III) and (IVa) to (IVf),
(1), (2), R 2 , R 3 , R 6 , R 7 , R 8 , n, m, An and Z have the same meaning as described for formulae (I) and (IIa) to (IId) above, and
wherein, in formula (II),
M 2 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 M 2 is hydrogen is carried out in the presence of a base.

2. The process as recited in claim 1 , wherein
R 8 independently of further substituents R 8 which may be present in the substituent of formulae (IIa) to (IId) is alkyl, alkenyl or aryl or two substituents R 8 irrespective of whether they are both part of a substituent Z or belong to different substituents selected from Z, R 6 and R 7 together are alkanediyl or alkenediyl or alternatively, where two substituents —(CO)R 8 are present within the substituent of formulae (IIa), are together —O— or —NR 4 —,
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—, —SO 2 —, —SO—, —SO 2 NR 4 —, NR 4 SO 2 —, —NR 4 —, —CO—, —O(CO)—, (CO)O—, —O(CO)O—, —NR 4 (CO)NR 4 —, NR 4 (CO)—, —(CO)NR 4 —, —NR 4 (CO)O—, —O(CO)NR 4 —, —Si(R 5 ) 2 —, —OSi(R 5 ) 2 —, —OSi(R 5 ) 2 O—, —Si(R 5 ) 2 O—,
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, C 6 -C 14 -aryl, C 1 -C 8 -alkoxy, C 1 -C 8 -alkylthio, —SO 3 M, —COOM, PO 3 M 2 , —PO(N(R 5 ) 2 ) 2 , PO(OR 5 ) 2 , —SO 2 N(R 4 ) 2 , —N(R 4 ) 2 , —CO 2 N(R 5 ) 2 , —COR 4 , —OCOR 4 , —NR 4 (CO)R 5 , —(CO)OR 4 , —NR 4 (CO)N(R 4 ) 2 , —Si(OR 5 ) y (R 5 ) 3-y , —OSi(OR) y (R 5 ) 3-y , with y=1, 2 or 3.

3. The process as recited in claim 1 , wherein if M 2 is 1/q equivalent of an q-valent metal ion or a quarternary organic ammonium ion or a heterocyclylium cation, an acid is added after the reaction to protonate intermediates.

4. The process as recited in claim 1 , wherein in formulae (IVa) and (I), with R 1 being a substituent of formula (IIa),
m is 1 or 2, and
Z is a substituent selected from the group consisting of —CN, —(CO)R 8 , —(CO)OR 8 , —(CO)N(R 8 ) 2 , —(SO 2 )R 8 , —(PO)(R 8 ) 2 , —(PO)(OR 8 ) 2 , —(PO)(OR 8 )(R 8 ), or 2-pyridyl,
R 6 and R 7 independently of each other are hydrogen, Z or R 8 , and
R 8 independently of further substituents R 8 which may be present in the substituent of formula (IIa) is C 1 -C 4 -alkyl, C 2 -C 4 -alkenyl or C 6 -C 14 -aryl or two substituents R 8 irrespective of whether they are both part of a substituent Z or belong to different substituents select

Assignees

• Eth Zuerich

Inventors

• Gruetzmacher Hansjoerg
• Mueller Georgina

Classifications

• C07F9/53

  Organo-phosphine oxides; Organo-phosphine thioxides · CPC title

• C07F9/50

  Organo-phosphines · CPC title

• C08F218/08

  Vinyl acetate · CPC title

• C08F2/50

  with sensitising agents · CPC title

• C07F9/58

  Pyridine rings · CPC title