Method for the production of alkylphosphonic acids, esters, and salts by oxidizing alkylphosphonous acids, and use thereof
View Patent ↗The invention relates to a method for producing monocarboxy-functionalized dialkylphosphinic acids, esters, and salts, characterized in that a) a phosphinic acid source (I) is reacted with olefins (IV) in the presence of a catalyst A to obtain an alkylphosphonous acid, the salt or ester (II) thereof, and b) the obtained alkylphosphonous acid, the salt or ester (II) thereof is reacted with an oxidizing agent or with an oxidizing agent and water or with oxygen and water in the presence of a catalyst B to obtain the alkylphosphonic acid derivative (III), wherein R 1 , R 2 , R 3 , R 4 are identical or different from each other and independently represent, inter alia, H, C 1 -C 18 -alkyl, C 6 -C 18 -aryl, C 6 -C 18 -aralkyl, C 6 -C 18 -alkylaryl, X and Y are identical or different from each other and independently represent 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 protonated nitrogenous base, and catalysts A and B are 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.
1. A method for producing alkylphosphonic acids, esters or salts, 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 alkylphosphonous acid, salt or ester (II) with at least one oxidant or with at least one oxidant and water or in the presence of a catalyst B with oxygen and water to form an alkylphosphonic acid derivative (III)
wherein R 1 , R 2 , R 3 , R 4 are identical or different and are H, methyl, ethyl, n propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl or a combination thereof and X and Y are identical or different and are H, methyl, ethyl, n propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, ethylene glycol, propyl glycol, butyl glycol, pentyl glycol, hexyl glycol, allyl and/or glycerol
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 B are transition metals, transition metal compounds, catalyst systems composed of a transition metal, transition metal compound and at least one ligand or a combination thereof and wherein the oxidizing agents are selected from the group of potassium permanganate, manganese oxide, chromium trioxide, potassium dichromate, pyridine dichromate, pyridine chlorochromate, Collins reagent, Jones reagent, Corey-Gilman-Ganem reagent, (Dess-Martin)periodinane, periodoxybenzoic acid, ruthenium tetroxide, ruthenium dioxide, tetra-n-propyl perruthenate, ruthenium trichloride/sodium periodate, ruthenium dioxide/sodium periodate, chlorine, hypochlorite, peracids, peroxo compounds or a combination thereof and wherein the transition metals and transition metal compounds are rhodium, nickel, palladium, platinum, ruthenium, gold or a combination thereof.
2. The method according to claim 1 wherein the alkylphosphonic acid, its salt or ester (III) obtained after step b) is subsequently reacted in a step c) with metal compounds of Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn a protonated nitrogen base or a combination thereof to form the alkylphosphonic acid salts (III) of these metals, of a nitrogen compound or a combination thereof.
3. The method according to claim 2 wherein the alkylphosphonous acid, salt or ester (II) obtained after step a), the alkylphosphonic acid, salt or ester (III) obtained after step b), the resulting reaction solution thereof or a combination thereof are esterified with an alkylene oxide or an alcohol M-OH, M′-OH or a combination thereof wherein the alcohol of the general formula M-OH comprises linear or branched, saturated and unsaturated, monohydric organic alcohols having a carbon chain length of C1-C18 and the alcohol of the general formula M′ OH comprises linear or branched, saturated and unsaturated polyhydric organic alcohols having a carbon chain length of C1-C18, and the resulting alkylphosphonous ester (II), alkylphosphonic ester (III) or combination thereof are subjected to the further reaction steps b) or c).
4. The method according to claim 1 , wherein X and Y are identical or different and are H, Li, Na, K, Ca, Mg, Al, Zn, Ti or Fe.