Fluorinated and halogenated phosphinic acids and their active metal derivatives

A method of making (Rf)2PA1A2 comprising:

• (a) admixing RfI with RMgBr or RLi at a temperature below about −40° C. to produce a first mixture;
• (b) stirring the first mixture for between about 2 to about 6 hours at temperature below about −40° C.;
• (c) admixing POCl3 or PSCl3 to the first mixture at a temperature below about −40° C. to produce a second mixture;
• (d) maintaining the second mixture for about 2 to about 4 hours at a temperature between about −40° C. and about −50° C.;
• (e) warming the second mixture to between about 15° C. to about 30° C.;
• (f) optionally, admixing NaSH to the second mixture and refluxing for about 2 hours to about 6 hours to produce a third mixture;
• (g) admixing water or R3OH to the second mixture or the third mixture;
• and
• (h) recovering (Rf)2PA1A2;
• wherein,
• A1 is selected from O and S;
• A2 is selected from —OH, —SH and —OR3;
• Rf can be branched or unbranched, can be linked to form cyclic or extended structures, and is selected from halogenated alkyl, halogenated aryl, halogenated cyclic alkyl, halogenated arylalkyl, halogenated alkylaryl, halogenated polyether, halogenated thioether, halogenated ether thioether, halogenated aklyl amino groups, halogenated alkylene, halogenated silylene, halogenated siloxanes, halogenated silazanes, halogenated olefins, perfluorinated C1-20 alkyl, perfuorinated C1-6 alkyl C1-10 alkyl ethers, n-C8F17, n-C6F13, n-C4F9, n-C2F5, (CF3)2CF(CF2)4, n-C10F21, n-C12F25, (CF3)2CF(CF2)6, and (CF3)2CFO(CF2)2;
• R3 can be branched or unbranched and is selected from C1-15 alkyl, C3-15 aryl, C4-15 alkylaryl and C4-15 arylalkyl;
• and
• R can be branched or unbranched, and is selected from an alkyl, aryl, alkylaryl, arylalkyl, methyl, ethyl, benzyl and phenyl.

A method of making (Rf)(Rf1)PA1A2 comprising:

• (a) admixing RfI with RMgBr or RLi at a temperature below about −40° C. to make a first mixture;
• (b) stirring the first mixture for between about 2 to about 6 hours at temperature below about −40° C.;
• (c) admixing POCl3 or PSCl3 to the first mixture at a temperature below about −40° C. to produce a second mixture;
• (d) maintaining said second mixture for about 2 to about 4 hours at a temperature between about −40° C. and about −50° C.;
• (e) admixing Rf1I with R1MgBr or R1Li in a second container at a temperature below about −40° C. to make a third mixture;
• (f) stirring said third mixture for between about 2 hours and about 6 hours at temperature below about −40° C.;
• (g) admixing the contents of said second container and said first container to make a fourth mixture;
• (h) warming said fourth mixture to between about 15° C. to about 30° C.;
• (i) optionally, admixing NaSH to said fourth mixture and refluxing for about 2 hours to about 6 hours to produce a fifth mixture;
• (j) admixing water or R3OH to said fourth mixture or said fifth mixture;
• and
• (k) recovering (Rf)(Rf1)PA1A2;
• wherein,
• A1 is selected from O and S;
• A2 is selected from —OH, —SH and —OR3;
• Rf and Rf1 can be the same or different, can be branched or unbranched, can be linked to form cyclic or extended structures, and are selected from halogenated alkyl, halogenated aryl, halogenated cyclic alkyl, halogenated arylalkyl, halogenated alkylaryl, halogenated polyether, halogenated thioether, halogenated ether thioether, halogenated aklyl amino groups, halogenated alkylene, halogenated silylene, halogenated siloxanes, halogenated silazanes, halogenated olefins, perfluorinated C1-20 alkyl, perfuorinated C1-6 alkyl C1-10 alkyl ethers, n-C8F17, n-C6F13, n-C4F9, n-C2F5, (CF3)2CF(CF2)4, n-C10F21, n-C12F25, (CF3)2CF(CF2)6, and (CF3)2CFO(CF2)2;
• R3 can be branched or unbranched and is selected from C1-15 alkyl, C3-15 aryl, C4-15 alkylaryl and C4-15 arylalkyl;
• and
• R and R1 can be the same or different, can be branched or unbranched, and are selected from an alkyl, aryl, alkylaryl, arylalkyl, methyl, ethyl, benzyl and phenyl.