Method for producing mono-carboxy-functionalized dialkylphosphinic acids, esters and salts using a vinyl ether and the use thereof

Patent metadata

Field	Value
Publication number	US-8987489-B2
Application number	US-200913132196-A
Country	US
Kind code	B2
Filing date	Oct 6, 2009
Priority date	Dec 4, 2008
Publication date	Mar 24, 2015
Grant date	Mar 24, 2015

Abstract

A method for producing mono-carboxy-functionalized dialkylphosphinic acids, esters and salts using a vinyl ether. The method is characterized by the following steps: a) reacting a phosphinic acid source (I) with olefins (IV) in the presence of a catalyst A to give an alkylphosphonous acid, the salt or the ester (II) thereof, b) reacting the alkylphosphonous acid so obtained, the salt or the ester (II) thereof with a vinyl ether of formula (V) in the presence of a catalyst B to give a mono-functionalized dialkylphosphinic acid derivative (VI) and c) reacting this derivative (VI) with an oxidant or in the presence of a catalyst C to give a mono-carboxy-functionalized dialkylphosphinic acid derivative (III), wherein the catalysts A and C are transition metals and/or transition metal compounds, and the catalyst B is a peroxide-forming compound and/or a peroxo compound and/or an azo compound.

First claim

What is claimed is:

1. A method for producing monocarboxy-functionalized dialkylphosphinic acids, esters or salts thereof comprising the steps of:
a) reacting a phosphinic acid source (I)

with olefins (IV)

in the presence of a catalyst A to form an alkylphosphonous acid, salt or ester (II)

b) reacting the alkylphosponous acid, salt or ester (II) with at least one vinyl ether (V)

in the presence of a catalyst B and a base to form a monofunctionalized dialkylphosphinic acid derivative (VI)

and
c) reacting the monofunctionalized dialkylphosphinic acid derivative (VI) with an oxidizing agent or with an oxidizing agent and water or in the presence of a catalyst C with oxygen and water to form the monocarboxy-functionalized dialkylphosphinic acid derivative (III)

wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 are identical or different and are H, C 1 -C 18 -alkyl, C 6 -C 18 -aryl, C 6 -C 18 -aralkyl, C 6 -C 18 -alkylaryl, CN, CHO, OC(O)CH 2 CN, CH(OH)C 2 H 5 , CH 2 CH(OH)CH 3 , 9-anthracene, 2-pyrrolidone, (CH 2 ) m OH, (CH 2 ) m NH 2 , (CH 2 ) m NCS, (CH 2 ) m NC(S)NH 2 , (CH 2 ) m SH, (CH 2 ) m S-2-thiazoline, (CH 2 ) m SiMe 3 , C(O)R 8 , (CH 2 ) m C(O)R 8 , CH═CHR 8 or CH═CH—C(O)R 8 and wherein R 8 is C 1 -C 8 -alkyl or C 6 -C 18 -aryl and m is an integer from 0 to 10 and X and Y are identical or different and are H, C 1 -C 18 -alkyl, C 6 -C 18 -aryl, C 6 -C 18 -aralkyl, C 6 -C 18 -alkylaryl, (CH 2 ) k OH, CH 2 —CHOH—CH 2 OH, (CH 2 ) k O(CH 2 ) k H, (CH 2 ) k —CH(OH)—(CH 2 ) k H, (CH 2 —CH 2 O) k H, (CH 2 —C[CH 3 ]HO) k H, (CH 2 —C[CH 3 ]HO) k (CH 2 —CH 2 O) k H, (CH 2 —CH 2 O) k (CH 2 —C[CH 3 ]HO)H, (CH 2 —CH 2 O) k -alkyl, (CH 2 —C[CH 3 ]HO) k -alkyl, (CH 2 —C[CH 3 ]HO) k (CH 2 —CH 2 O) k -alkyl, (CH 2 —CH 2 O) k (CH 2 —C[CH 3 ]HO)O-alkyl, (CH 2 ) k —CH═CH(CH 2 ) k H, (CH 2 ) k NH 2 or (CH 2 ) k N[(CH 2 ) k H] 2 , wherein k is an integer from 0 to 10 or wherein X and Y are the same or different and are Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Cu, Ni, Li, Na, K, a protonated nitrogen base or a combination thereof and the catalysts A and C are a transition metal, a transition metal compound, a catalyst system comprising of a transition metal, or a transition metal compound and at least one ligand, and the catalyst B is selected from the group consisting of hydrogen peroxide, sodium peroxide, lithium peroxide, potassium persulfate, sodium persulfate, ammonium persulfate, sodium peroxodisulfate, potassium peroxoborate, peracetic acid, benzoyl peroxide, di-t-butyl peroxide, peroxodisulfuric acid, azodiisobutyronitrile, 2,2″-azobis(2-amidinopropane)dihydrochloride or 2,2′-azobis(N,N-dimethyleneisobutyramidine)dihydrochloride or a combination thereof.

2. The method according to claim 1 wherein the monocarboxy-functionalized dialkylphosphinic acid, its salt or ester (III) obtained after step c) is reacted in a step d) with a metal compound, a protonated nitrogen base or a combination thereof, wherein the metal compound is Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Si, Sr, Mn, Li, Na or K to form the monocarboxy-functionalized dialkylphosphinic acid salts (III) of the metal compound, of the nitrogen base or a combination thereof.

3. The method according to claim 1 wherein the alkylphosphonous acid, salt, or ester (II) obtained after step a), the monofunctionalized dialkylphosphinic acid, salt or ester (VI) obtained after step b) or the monocarboxy-functionalized dialkylphosphinic acid, salt or ester (III) obtained after step c) are esterified with an alkylene oxide or a linear or branched, saturated or unsaturated, monohydric or polyhydric organic alcohol having a carbon chain length of C 1 -C 18 or a combination thereof, and the resulting alkylphosphonous ester (II), monofunctionalized dialkylphosphinic ester (VI), monocarboxy-functionalized dialkylphosphinic ester (III) or a combination thereof are subjected to the further reaction steps b) or c).

4. The method according to claim 1 , wherein C 6 -C 18 -aryl, C 6 -C 18 -aralkyl and C 6 -C 18 -alkylaryl are substituted with SO 3 X 2 , —C(O)CH 3 , OH, CH 2 OH, CH 3 SO 3 X 2 , PO 3 X 2 , NH 2 , NO 2 , OCH 3 , SH, OC(O)CH 3 or a combination thereof.

5. The method according to claim 1 , wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 are identical or different and are H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl or phenyl.

6. The method according to claim 1 , wherein X and Y are identical or different and are H, Ca, Mg, Al, Zn, Ti, Fe, Ce, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, ethylene glycol, propyl butyl glycol, pentyl glycol, hexyl glycol, allyl or glycerol.

7. The method according to claim 1 , wherein the transition metal or the metal in the transition metal compound is selected from first, seventh or eighth transition groups.

8. The method according to claim 1 , wherein the transition metal or the metal in the transition metal compound is rhodium, nickel, palladium, platinum, ruthenium or gold.

9. The method according to claim 1 , wherein the oxidizing agent is potassium permanganate, manganese oxide, chromium trioxide, potassium dichromate, pyridine dichromate, pyridine chlorochromate, Collins reagent, Jones reagent, Corey-Gilman-Ganem reagent, (Dess-Martin)periodinane, o-iodoxybenzoic acid, ruthenium tetroxide, ruthenium dioxide, tetra-n-propyl perruthenate, ruthenium trichloride/sodium periodate, ruthenium dioxide/sodium periodate, chlorine, hypochlorite or peroxo compounds.

10. The method according to claim 1 , wherein the at least one vinyl ether(V) is ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, i-butyl vinyl ether, t-butyl vinyl ether, cyclohexyl vinyl ether, 1-propenyl ether, 1-butenyl ether 1,4-butanediol, ethylene glycol, diethylene glycol, triethylene glycol divinyl ether, di-1-propenyl ether, di-1-butenyl ether or a combination thereof.

Assignees

• Hill Michael
• Dietz Mathias
• Krause Werner
• Sicken Martin
• Clariant Finance Bvi Ltd

Inventors

• Hill Michael
• Dietz Mathias
• Krause Werner
• Sicken Martin

Classifications

• C07F9/301 Primary

  Acyclic saturated acids which can have further substituents on alkyl · CPC title

• C07F9/32

  Esters thereof · CPC title

• C07F9/4816

  Acyclic saturated acids or derivatices which can have further substituents on alkyl · CPC title

• C07F9/30 Primary

  Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids {; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]} · CPC title

• C08K5/5313

  Phosphinic compounds, e.g. R2=P(:O)OR' · CPC title