Method for producing dialkylphosphinic acids and esters and salts thereof by means of acrylnitriles and use thereof
View Patent ↗The invention relates to a method for producing mono-carboxyfunctionalized dialkylphosphinic acids and esters and salts thereof, characterized in that a) a phosphinic acid source (I) is reacted with olefins (IV) to yield an alkylphosphonic acid, salt or ester (H) thereof in the presence of a catalyst A, b) the thus obtained alkylphosphonic acid, salt or ester (II) thereof is reacted with compounds of formula (V) to yield mono-functionalized dialkylphosphinic acid derivatives (VI) in the presence of a catalyst B, and c) the thus obtained mono-functionalized dialkylphosphinic acid derivatives (VI) are reacted to yield a mono-carboxyfunctionalized diakylphosphinic acid derivative (III) in the presence of a catalyst C, wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 are the same or different and stand independently of each other, among other things, for H, C 1 -C 18 alkyl, C 6 -C 18 aryl, C 6 -C 18 aralkyl, C 6 -C 18 alkylaryl and X and Y are the same or different and stand independently of each for H, C 1 -C 18 alkyl, C 6 -C 18 aryl, C 6 -C 18 aralkyl, C 6 -C 18 alkylaryl, Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Cu, Ni, Li, Na, K and/or a protonized nitrogen base, and the catalyst A is formed by transition metals and/or transition metal compounds and/or catalyst systems composed of a transition metal and/or a transition metal compound and at least one ligand, and catalyst B is formed by compounds forming peroxides and/or peroxo compounds and/or azo compounds and/or alkali metals and/or alkaline earth metals, alkali hydrides, alkaline earth hydrides and/or alkali alcoholates and alkaline earth alcoholates, and catalyst C is an acid or a base.
1. A method for producing monocarboxy-functionalized dialkylphosphinic acids, esters or salts, comprising the steps of:
a) reacting a phosphinic acid source (I)
with one or more olefins (IV)
in the presence of a catalyst A to form an alkylphosphonous acid, salt or ester (II)
b) reacting the alkylphosphonous acid, salt or ester (II) with one or more acrylonitrile (V)
in the presence of a catalyst B to form a monofunctionalized dialkylphosphinic acid derivative (VI)
and
c) reacting the monofunctionalized dialkylphosphinic acid derivative (VI) in the presence of a catalyst C to form a monocarboxy-functionalized dialkylphosphinic acid derivative (III)
where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 are identical or different and are each independently 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=CH-R 8 or CH=CH-C(O)R 8 and where 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 each independently 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 , where k is an integer from 0 to 10, Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Cu, Ni, Li, Na, K, H, a protonated nitrogen base or a combination thereof and the catalyst A is selected from the group of transition metals, transition metal compounds, catalyst systems composed of a transition metal or transition metal compound and at least one ligand and a combination thereof, and the catalyst B is selected from the group consisting of peroxide-forming compounds, peroxo compounds, azo compounds, comprises alkali hydrides, alkaline earth metal hydrides, alkali alkoxides, alkaline earth metal alkoxides and a combination thereof and the catalyst C is an acid or a base.
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 metal compounds of Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K, a protonated nitrogen base or a combination thereof to form the monocarboxy-functionalized dialkylphosphinic acid salts III of these metals, of a nitrogen compound 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), the monocarboxy-functionalized dialkylphosphinic acid, salt or ester (III) obtained after step c), the reaction solution thereof or a combination thereof are esterified with an alkylene oxide or an alcohol M-OH, M′-OH, and the alkylphosphonous ester (II), monofunctionalized dialkylphosphinic ester (VI) monocarboxy-functionalized dialkylphosphinic ester (III) or combination thereof is subjected to the reaction steps b) or c).
4. The method according to claim 1 , wherein the groups 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 each independently H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl phenyl or a combination thereof.
6. The method according to claim 1 , wherein X and Y are identical or different and are each H, Ca, Mg, Al, Zn, Ti, Fe, Ce, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, ethylene glycol, propyl glycol, butyl glycol, pentyl glycol, hexyl glycol, allyl, glycerol or a combination thereof.
7. The method according to claim 1 , wherein the transition metals, transition metal compounds or a combination thereof are from the seventh and eighth transition groups.
8. The method according to claim 1 , wherein the transition metals transition metal compounds or combination thereof are rhodium, nickel, palladium, platinium or ruthenium.
9. The method according to claim 1 , wherein the catalyst B is hydrogen peroxide, sodium peroxide, lithium peroxide, potassium persulfate, sodium persulfate, ammonium persulfate, sodium peroxodisulfate, potassium peroxoborate, peracetic acid, benzoyl peroxide, di-t-butyl peroxide and/or peroxodisulfuric acid, azobisisobutyronitrile, 2,2′-azobis(2-amidinepropane) dihydrochloride, 2,2′-azobis(N,N′-dimethyleneisobutyramidine) dihydrochloride, lithium, lithium hydride, lithium aluminohydride, methyllithium, butyllithium, t-butyllithium, lithium diisopropylamide, sodium, sodium hydride, sodium borohydride, sodium methoxide, sodium ethoxide, sodium butoxide, potassium methoxide, potassium ethoxide, potassium butoxide or a combination thereof.
10. The method according to claim 1 , wherein the catalyst C is selected from the group consisting of metals, metal hydrides, metal hydroxides, metal alkoxides and mineral acids.
11. The method according to claim 1 , wherein the one or more acrylonitriles (V) areacrylonitrile, methacrylonitrile, ethyl 2-cyanoacrylate, 3-phenylacrylonitrile or 2-methyl-2-butenenitrile.
12. The method according to claim 1 , wherein the alcohol of the general formula M-OH is a linear or branched, saturated or unsaturated, monohydric organic alcohol having a carbon chain length of C 1 -C 18 and the alcohol of the general formula M′-OH is a linear or branched, saturated or unsaturated polyhydric organic alcohol having a carbon chain length of C 1 -C 18 .