Method for the preparation of functionalized cyclosiloxanes

1. A method of preparing a cyclosiloxane of Formula I,

wherein

each R is independently selected from the group consisting of hydrogen and an organic functionality selected from the group consisting of substituted or unsubstituted C 1-28 alkyl, C 2-28 alkenyl, C 2-22 alkynyl, C 3-12 cycloalkyl, C 3-12 cycloalkenyl, C 6-20 aryl, C 3-20 heteroaryl, C 7-9 aralkyl or alkylaryl, C 1-20 heteroalkyl, C 1-20 heterocyclyl with 1 to 5 ring heteroatoms selected from N, O and S, halogen, cyano, nitro, —OR 1 , —C(O)R 1 , —C(O)OR 1 , —OC(O)R 1 , —NR 1 R 2 , —C(O)NR 1 R 2 , —NR 2 C(O)R 1 , and —Si(R 1 ) o (OR 2 ) 3-o ;

R 1 and R 2 are independently selected from the group consisting of hydrogen and C 1-28 alkyl, C 2-28 alkenyl, C 2-22 alkynyl, C 3-12 cycloalkyl, C 3-12 cycloalkenyl, C 6-20 aryl, C 3-20 heteroaryl, with 1 to 5 ring heteroatoms selected from N, O and S, C 7-9 aralkyl or alkylaryl, C 1-20 heteroalkyl, with 1 to 5 heteroatoms selected from N, O, halogen and S, C 1-20 heterocyclyl with 1 to 5 ring heteroatoms selected from N, O and S;

each of m, n1 and n2 is 0 or an integer independently selected from 1 to 10, with m+n1+n2=3 to 10 and provided that not both of n1 and n2 are 0; and

o is 0, 1, 2, or 3;

the method comprising:

reacting (i) a cyclosiloxane of Formula II

wherein m is as defined above and n=n1+n2;

with (ii) a substituted acetylene of Formula III

wherein R is as defined above in the presence of a hydrosilylation catalyst to form the cyclosiloxane of Formula I.

2. The method according to claim 1 , wherein in Formula II m+n=3, 4, 5 or 6.

3. The method according to claim 1 , wherein in Formula II n is 1 and m is 3.

4. The method according to claim 1 , wherein R is selected from the group consisting of H, unsubstituted or substituted phenyl, hydroxyalkyl and R′ being unsubstituted C 1-4 alkyl.

5. The method according to claim 1 , wherein R is selected from the group consisting of H, unsubstituted or substituted phenyl, —(CH 2 ) p —OH, —(CR′OH)—CH 3 , —(CH 2 ) p —COOH and

—COO(CH 2 ) p CH 3 , with p being 0 or an integer from 1 to 10, and R′ being unsubstituted C 1-4 alkyl.

6. The method according to claim 1 , wherein the cyclosiloxane of Formula I is

(i) 2,2,4,4,6,6,8-heptamethyl-8-(1-phenylvinyl)-cyclotetrasiloxane (3B);

(ii) 2,2,4,4,6,6,8-heptamethyl-8-(2-phenylvinyl)-cyclotetrasiloxane (3A);

(iii) ethyl 2-(2,4,4,6,6,8,8-heptamethyl-cyclotetrasiloxan-2-yl)acrylate (4B);

(iv) ethyl 3-(2,4,4,6,6,8,8-heptamethyl-cyclotetrasiloxan-2-yl)prop-2-enoate (4A);

(v) 4-(2,4,4,6,6,8,8-heptamethyl-cyclotetrasiloxan-2-yl)pent-4-en-1-ol (5B);

(vi) 5-(2,4,4,6,6,8,8-heptamethyl-cyclotetrasiloxan-2-yl)pent-4-en-1-o1 (5A);

(vii) 3-(2,4,4,6,6,8,8-heptamethyl-cyclotetrasiloxan-2-yl)-2-methylbut-3-en-2-ol (6B);

(viii) 4-(2,4,4,6,6,8,8-heptamethyl-cyclotetrasiloxan-2-yl)-2-methylbut-3-en-2-ol (6A);

(ix) 4-(2,4,4,6,6,8,8-heptamethyl-cyclotetrasiloxan-2-yl)pent-4-enoic acid (7B);

(x) 5-(2,4,4,6,6,8,8-heptamethyl-cyclotetrasiloxan-2-yl)pent-4-enoic acid (7A);

(xi) 2,2,4,4,6,6,8-heptamethyl-8-(1-(4-(trifluoromethyl)phenyl)vinyl)-cyclotetrasiloxane (8B);

(xii) 2,2,4,4,6,6,8-heptamethyl-8-(2-(4-(trifluoromethyl)phenyl)vinyl)-cyclotetrasiloxane (8A);

(xiii) 2,4,6,8-tetramethyl-2,4,6,8-tetrakis(1-phenylvinyl)-cyclotetrasiloxane (9a);

(xiv) (E/Z)-2,4,6,8-tetramethyl-2,4,6-tris(1-phenylvinyl)-8-styryl-cyclotetrasiloxane (9b);

(xv) 2,4,6,8-tetramethyl-2,6-bis(1-phenylvinyl)-4,8-di((E/Z)-styryl)-cyclotetrasiloxane (9c);

(xvi) 2,4,6,8-tetramethyl-2,4-bis(1-phenylvinyl)-6,8-di((E/Z)-styryl)-cyclotetrasiloxane (9d);

(xvii) 2,4,6,8-tetramethyl-2-(1-phenylvinyl)-4,6,8-tri((E/Z)-styryl)-cyclotetrasiloxane (9e); or

(xviii) 2,4,6,8-tetramethyl-2,4,6,8-tetra((E/Z)-styryl)-cyclotetrasiloxane (9f).

7. The method according to claim 1 , wherein the hydrosilylation catalyst is selected from the group consisting of platinum (Pt)-, rhodium (Rh)- or iridium (Ir)-containing catalysts.

8. The method according to claim 1 , wherein the hydrosilylation catalyst is selected from Pt-containing catalysts of the formula PtL q , wherein q is an integer from 1 to 6 and L is a neutral organic ligand or an inorganic support.

9. The method according to claim 1 , wherein the hydrosilylation catalyst is selected from Pt-containing catalysts of the formula PtL q , wherein q is an integer from 1 to 6 and L is a phosphine or an olefin or an inorganic support selected from at least one of charcoal, silica or alumina.

10. The method of claim 1 , wherein the hydrosilylation catalyst is selected from the group consisting of platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane, tetrakistriphenylphosphine platinum(0), platinum on activated charcoal and platinum on alumina.

11. The method of claim 1 , wherein each R is independently selected from the group consisting of hydrogen and an organic functionality selected from the group consisting of substituted or unsubstituted C 1-28 alkyl, C 2-28 alkenyl, C 2-22 alkynyl, C 3-12 cycloalkyl, C 3-12 cycloalkenyl, C 6-20 aryl, C 7-9 aralkyl or alkylaryl, C 1-20 heteroalkyl with 1 to 5 heteroatoms selected from N, O, halogen and S, C 1-20 heterocyclyl with 1 to 5 ring heteroatoms selected from N, O and S, halogen, cyano, nitro, —OR 1 , —C(O)R 1 , —C(O)OR 1 , —OC(O)R 1 , —NR 1 R 2 , —C(O)NR 1 R 2 , —NR 2 C(O)R 1 , and —Si(R 1 ) o (OR 2 ) 3-o ;

R 1 and R 2 are independently selected from the group consisting of hydrogen and C 1-28 alkyl, C 2-28 alkenyl, C 2-22 alkynyl, C 3-12 cycloalkyl, C 3-12 cycloalkenyl, C 6-20 aryl, C 3-20 heteroaryl with 1 to 5 ring heteroatoms selected from N, O and S, C 7-9 aralkyl or alkylaryl, C 1-20 heteroalkyl with 1 to 5 heteroatoms selected from N, O, halogen and S, C 1-20 heterocyclyl with 1 to 5 ring heteroatoms selected from N, O and S.

12. The method according to claim 1 , wherein:

(i) the reaction is carried out at a temperature in the range of from 30 to 150° C.; and/or

(ii) the reaction time is 1 to 48 hours; and/or

(iii) the concentration of the hydrosilylation catalyst is between about 0.0001 and 1 mol-% based on the total amount of the cyclosiloxane educt(s); and/or

(iv) the reaction is carried out in a suitable organic solvent; and/or

(v) the reaction is carried out under inert atmosphere.