Process for the preparation of acylphosphanes

Patent metadata

Field	Value
Publication number	US-9701700-B2
Application number	US-201314432212-A
Country	US
Kind code	B2
Filing date	Sep 30, 2013
Priority date	Oct 1, 2012
Publication date	Jul 11, 2017
Grant date	Jul 11, 2017

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 an integer from 2 to 6
m is 1 or 2,
R 1 is a substituent of formula (IIe)
R*[C (2) HR 9 —C (1) (R 9 ) 2 —] n   (IIe)

wherein, in formula (IIe),

R* is
a n-valent substituent selected from the group consisting of heteroaryl-n-yl and R 10 (-Het-(C═O)—) n , wherein Het independently is either O or NR 4 and R 10 is alkane-n-yl, alkene-n-yl or aryl-n-yl and wherein the carbonyl carbons are bound to the C (2) carbon atoms,
wherein, the aforementioned alkane-n-yl and alkene-n-yl substituents of R 10 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—, —O(CO)—, —(CO)O—, NR 4 (CO)—, —(CO)NR 4 —,
and,
either not, additionally or alternatively either once, twice or more than twice interrupted by aryldiyl,

and,
either not, additionally or alternatively either once, twice or more than twice substituted by substituents selected from the group consisting of:
hydroxy, C 1 -C 8 -alkoxy, —COOM, —N(R 4 ) 2 , —CO 2 N(R 5 ) 2 , —COR 4 , —OCOR 4 , —NR 4 (CO)R 5 , —(CO)OR 4 ,

(1) and (2) indicate the numeration of the carbon atom, wherein each of the n C (1) carbon atoms is bonded to the central phosphorous atom depicted in formula (I) via the bond “-” shown on the right side of the bracket, and
R 9 independently of each other are hydrogen, alkyl, alkenyl or aryl or two substituents R 9 irrespective of whether they are both bound to C (2) or not are together alkanediyl or alkenediyl, wherein, the aforementioned alkyl, alkenyl, alkane-n-yl and alkene-n-yl substituents of R 9 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 5 ) y (R 5 ) 3-y , —OSi(OR 5 ) y (R 5 ) 3-y with y=1, 2 or 3,

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,
wherein “aryl” denotes carbocyclic aromatic substituents, the carbocyclic, aromatic substituents being unsubstituted, or being substituted by up to five identical or different substituents per cycle,

the process comprising at least the step of reacting compounds of formula (III)

with compounds of formula (IVe),
R*[R 9 C (2) ═C (1) (R 9 ) 2 ] n   (IVe),

wherein, in formula (IVe),
(1), (2), R 2 , R 3 , R 9 , R*, n and m have the same meaning as described for formulae (I) and (IIe) 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 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 or an aqueous reference system is added after the reaction to protonate intermediates.

3. The process as recited in claim 1 , wherein, in compounds of formulae (I) and (III),
m is 1 or 2, and
R 2 is C 6 -C 14 -aryl or heterocyclyl, or
is C 1 -C 18 -alkyl or C 2 -C 18 -alkenyl,

wherein, the aforementioned substituents C 1 -C 18 -alkyl or C 2 -C 18 -alkenyl of 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 —, —N + (R 4 ) 2 An − -, —CO—, NR 4 (CO)—, —NR 4 (CO)O—, (CO)NR 4 —,
and which is not, additionally or alternatively either once, twice or more than twice substituted by substituents selected from the group consisting of:
halogen, cyano, C 6 -C 14 -aryl; heterocyclyl, C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, C 1 -C 8 -alkylthio, C 2 -C 8 -alkenyl, C 4 -C 15 -arylalkyl, —COOM, SO 2 N(R 3 ) 2 —, N(R 4 ) 2 —, —N + (R 4 ) 3 An − , —CO 2 N(R 4 ) 2 ,
wherein,
R 4 is independently selected from the group consisting hydrogen, C 1 -C 8 -alkyl, C 6 -C 14 -aryl, C 7 -C 15 -arylalkyl and heterocyclyl or N(R 4 ) 2 as a whole is a N-containing heterocycle or N + (R 4 ) 2 An − and N + (R 4 ) 3 An − as a whole is or contains a cationic N-containing heterocycle with a counteranion,
R 5 is independently selected from the group consisting C 1 -C 8 -alkyl, C 6 -C 14 -aryl, C 7 -C 15 -arylalkyl and heterocyclyl or N(R 5 ) 2 as a whole is a N-containing heterocycle or N + (R 5 ) 2 An − and N + (R 5 ) 3 An − as a whole is or contains a cationic N-containing heterocycle with a counteranion,
M is hydrogen, lithium, sodium, potassium, one half equivalent of calcium, zinc or iron (II), or one third equivalent of aluminium (III) or is an ammonium ion or a primary, secondary, tertiary or quarternary organic ammonium ion, and
An − is 1/p equivalent of an p-valent anion.

4. The process as recited in claim 1 , wherein,
m is 2, and
R 2 is C 6 -C 14 -aryl.

5. The process as recited in claim 1 , wherein the process is carried out in water.

6

Assignees

• ETH Zürich
• 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