Phosphorylation process and catalyst
AssigneesPerstorp AB, Polish Academy of Science, Centre of Molecular and Macromolecular Studies
InventorsJan Michalski, Wojciech Dabkowski, Friedrich Cramer
Life of this patent
Estimating the term…
Abstract
A process and use of at least one catalyst for phosphorylation, in particular phosphitylation, of hydroxyl groups, whereby a phosphorous compound is added to a hydroxyfunctional compound having at least one hydroxyl group. The addition yields a phosphorylated product having at least one O—P bond. The catalyst employed in the process is of the general formula (R1)nX(R2)4−n, wherein each R1 independently is hydrogen, at least one hydrocarbyl, amino, halogenated and/or silylated hydrocarbyl group, X is Si, Ge or Sn, each R2 independently is a leavening group and is F, Cl, Br, I or a sulphonate group optionally being halogen substituted and wherein n is 1, 2 or 3.
Claims47
A process for phosphorylation of a hydroxyfunctional compound having one or more hydroxyl group substituents by phosphitylation followed by oxidation comprising addition of a phosphitylation reagent or phosphorous compound to a hydroxyfunctional compound having at least one hydroxyl group which addition yields a product having at least one O—P bond wherein said phosphorylation is performed in the presence of at least one catalyst of general formula (R1)nX(R2)4−n wherein
- i) each R1 independently is
- a) at least one alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloaliknyl, aryl, alkylaryl, alkenylaryl, alkynylaryl, trityl, alkoxy, cycloalkoxy, or aryloxy,
- b) a polymeric moiety selected from the group consisting of organic polymer, copolymer and analogues thereof,
- c) at least one halogenated and/or silylated alkanyl, alkenyl, alkyl, cycloalkanyl, cycloalkenyl, cycloalkynyl, aryl, alkanylaryl, alkenylaryl, alkynylaryl, trityl, alkoxy, cycloalkoxy, aryloxy or amino group, or
- d) a polymeric moiety derived from a compound selected from the group consisting of a halogenated organic polymer, a halogenated organic copolymer, a silylated organic polymer, a silylated organic copolymer, a mixture of silylated and halogenated organic polymers, a mixture of silylated and halogenated organic copolymers, and analogues thereof;
- ii) X is Si;
- iii) each R2 independently is a leaving group and is
- a) F, Cl, Br or I;
- or
- b) a sulphonate group of formula
- wherein R3 is F, Cl, Br, I, alkyl, alkenyl, alkynyl, aryl, arylalkanyl, arylalkenyl, arylalkynyl, haloalkanyl, haloalkenyl, haloalkynyl, haloaryl, haloarylalkanyl, haloarylalkenyl, haloarylalkynyl, arylhaloalkanyl, arylhaloalkenyl, arylhaloalkynyl or a group of formula R4 wherein R4 is selected from the group consisting of CF3, CCl3, CBr3 and CI3, and
- iv) n is 1, 2 or 3.
A catalyst for a process of phosphitylation of general formula (R1)nX(R2)4−n wherein
- i) each R1 independently is
- a) at least one alkanyl, alkenyl, alkynyl, cycloalkl, cycloalkenyl, cycloalkynyl, aryl, alkylaryl, alkenylaryl, alkynylaryl, trityl, alkoxy, cycloalkoxy, or aryloxy,
- b) a polymeric moiety derived from an organic polymer or copolymer,
- c) at least one halogenated and/or silylated alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, alkanylaryl, alkenylaryl, alkynylaryl trityl, alkoxy, cycloalkoxy, or aryloxy,
- d) a polymeric moiety selected from the group consisting of halogenated and silylated organic polymer or copolymers and analogues thereof;
- ii) X is Si;
- iii) each R2 independently is a leaving group and is
- a) F, Cl, Br or I;
- or
- b) a sulphonate group of formula
- wherein R3 is F, Cl, Br, I, alkyl, alkenyl, alkynyl, aryl, arylalkyl, arylalkenyl, arylalkynyl, haloalkanyl, haloalkenyl, haloalkynyl, haloaryl, haloarylalkanyl, haloarylalkenyl, haloarylalkynyl, arylhaloalkanyl, arylhaloalkenyl, arylhaloalkynyl or a group of formula R4, wherein R4 is selected from the group consisting of CF3, CCl3, CBr3 and CI3;
- and
- iv) n is 1, 2 or 3.
Dependencies are inferred from the claim text.