PROCESS FOR SYNTHESIS OF ORGANOSILICON COMPOUNDS FROM HALOSILANES
A process for synthesis of an organosilicon compound is provided herein. Also, novel organosilicon compounds prepared by the present process is provided herein. The process comprises the reaction of a halosilane with an organofunctional alkyl halide in the presence of a metal catalyst, a promoter, and an optional co-catalyst. The process provides an efficient synthetic route to produce organosilicon compounds. The process also allows synthesis of organosilicon compounds with a plurality of different functional groups.
1 . A process for synthesis of an organosilicon compound of the formula (1),
the process comprising reacting (i) a halosilane of the formula (2)
with (ii) p moles of an organofunctional alkyl halide of the formula (3)
in the presence of (iii) a non-magnesium metal, and (iv) a promoter:
where R 1 is an organofunctional group;
R 2 is H or a C 1 -C 20 alkyl;
R 3 is H or a C 1 -C 20 alkyl;
R 4 is a C 1 -C 20 alkyl;
X 1 is F, Cl, Br, or I;
X 2 is F, Cl, Br, or I;
m is an integer in the range of 1-10;
n is an integer in the range of 1-4; and
p is an integer in the range of 1-4 with the proviso that p is ≤ n.
2 . The process of claim 1 , wherein R 1 is independently selected from a C1-C20 alkyl, -CR 5 =CR 6 2 , -C≡CR 7 , —CN, -C(O)R 8 , —OC(O)R 9 , -C(O)OR 10 , -SR 11 , —S(O) 2 R 12 , -NR 13 2 , C(O)NR 14 2 , -OC(O)-CR 15 =R 16 2 , —CF 3 , -(CR 17 2 )n-CF 3 , —NCO, -CS-OR 18 , -CSSR 19 , -NR 20 C(O)-CR 21 =CR 22 2 a C6-C20 aryl, an aralkyl, or an alkaryl, where R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 18 , R 19 , R 20 , R 21 , and R 22 are each independently H, a C1-C20 alkyl, a C3-C20 cycloalkyl, a C6-C30 aryl, an aralkyl, or an alkaryl, and R 17 is H, a C1-C10 alkyl, or F.
3 . The process of claim 1 , wherein the non- magnesium metal is selected from an alkali metal, an alkaline earth metal, a transition metal, a post transition metal, a metalloid, a lanthanide, an actinide, or a combination of two or more thereof.
4 . The process of claim 3 , wherein the non-magnesium metal is selected from Li, Na, K, Rb, Cs, Be, Ca, Sr, Ba, Fe, Co, Ni, Cu, Zn, B, Sb, Te, La, Ce, Sm, or a combination of two or more thereof.
5 . The process of claim 4 , wherein the non-magnesium metal is Zn.
6 . The process of claim 1 , wherein molar ratio of the non-magnesium metal to the organofunctional alkyl halide in a range of 0.5: 1 to 1:5.
7 . The process of claim 1 , wherein the promoter is a phosphorous containing compound, a sulfur containing compound, or a combination of two or more thereof.
8 . The process of claim 1 , wherein the promoter is selected from a phosphine oxide, a phosphate, a phosphite, a phosphine, a phosphoramide, or a combination of two or more thereof.
9 . The process of claim 8 , wherein the phosphine oxide is of the formula R 20 3 P=O or formula (R 21 2 N) 3 P=O where each R 20 is independently a C 4 -C 20 alkyl, a C 3 -C 20 cyclic alkyl, an aralkyl, or an alkaryl, where each R 21 is independently selected from a C 1 -C 10 alkyl and a C 3 -C 20 cyclic alkyl.
10 . The process of any of claims 9 , wherein the promoter is tributyl phosphine oxide (TBPO), trioctylphosphine oxide (TOPO), hexamethylphosphoramide (HMPA), trimorpholinophosphine Oxide or Tripyrrolidinophosphine Oxide, or a combination thereof.
11 . The process of claim 1 further comprising a catalyst.
12 . The process of claim 11 , wherein the catalyst is a metal salt selected from of a metal halide, a metal acetate, a metal ester, a metal amide, a metal triflate, a metal borate, a metal nitrate, or a combination of two or more thereof.
13 . The process of claim 12 , wherein the metal salt comprises a metal selected from an alkali metal, an alkaline earth metal except magnesium, a transition metal, a post transition metal, a metalloid, a lanthanide, an actinide, or a combination of two or more thereof.
14 . The process of claim 12 , wherein the catalyst is a metal halide.
15 . The process of claim 1 , wherein the catalyst is a metal iodide.
16 . The process of claim 11 , wherein X 2 is Cl.
17 . The process of claim 1 , wherein the halosilane is reacted with the alkyl halide at a temperature in the range of, from about 10° C. to about 200° C.
18 . A process of claim 1 , wherein the organosilicon compound has at least two non-identical organofunctional groups.
19 . The process of claim 18 , the process comprising:
(i) reacting a halosilane of the formula (X 1 ) n -Si(R 4 ) 4-n with p moles of a first organofunctional alkyl halide of the formula [(R 1 )-(C(R 2 )(R 3 )) m] -X 2 to produce a first organosilicon compound of the formula [(R 1 )-(C(R 2 )(R 3 )) m ] p -Si(R 4 ) 4-n (X1) n-p ; and
(ii) reacting the first organosilicon compound of the formula [(R 1 )-(C(R 2 )(R 3 )) m ] p -Si(R 4 ) 4-n (X 1 ) n-p with p′ moles of a second organofunctional alkyl halide of the formula [(R 1′ )-(C(R 2′ )(R 3′ )) m′ ]-X 2′ to produce a second organosilicon compound of the formula ([(R 1 )-(C(R 2 )(R 3 )) m ] p )([(R 1′ )-(C(R 2′ )(R 3′ )) m′ ] p′ )(-Si(R 4 ) 4-n (X 1 ) n-p-p′
where R 1 and R 1′ are each independently an organofunctional group;
R 2 and R 2′ are each independently H or a C1-C20 alkyl;
R 3 and R 3′ are each independently H or a C1-C20 alkyl;
R 4 is a C1-C20 alkyl;
X 1 is F, Cl, Br, or I;
X 2 and X 2′ are each independently F, Cl, Br, or I;
m and m′ are each independently 1-10;
n is 1-4;
p is 1-4 with the proviso that p is ≤ n;
where R 1′ is different from R 1 ; R 2′ is the same or different than R 2 ; R 3′ is the same or different from R 3 , m′ is the same or different from m, p′ is ≤ (n-p).
20 . The process of claim 19 , wherein the process is a one-pot process.
21 . The process of claim 19 , wherein the first organosilicon compound and the second organosilicon compound are obtained with a selectivity of more than 99%.
22 . A compound of formula (1) : [(R 1 )-(C(R 2 )(R 3 )) m ] p -Si(R 4 ) 4-n (X 1 ) n-p (1)
where R 1 is an organofunctional group;
R 2 is H or a C 1 -C 20 alkyl;
R 3 is H or a C 1 -C 20 alkyl;
R 4 is a C 1 -C 20 alkyl;
X 1 is F, Cl, Br, or I;
m is an integer in the range of 1-10;
n is an integer in the range of 1-4; and
p is an integer in the range of 1-4 with the proviso that p is ≤ n.
23 . The compound of claim 22 , wherein m is an integer in the range of 3 to 10 and/or wherein p is an integer in the range of 2 to 4.
24 . The compound of claim 22 , wherein R 1 is independently selected from a C 1 -C 20 alkyl, -CR 5 =CR 6 2 , -C≡CR 7 , —CN, -C(O)R 8 , -OC(O)R 9 , C(O)OR 10 , -SR 11 , -S(O) 2 R 12 , -NR 13 2 , -C(O)NR 14 2 , -OC(O)-CR 15 =R 16 2 , —CF 3 , -(CR 17 2 )n-CF 3 ,—NCO, -CS-OR 18 , -CSSR 19 , -NR 20 C(O)-CR 21 =CR 22 2 a C 6 -C 20 aryl, an aralkyl, or an alkaryl, where R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15, R 16 , R 18 , R 19 , R 20 , R 21 , and R 22 are each independently H, a C 1 -C 20 alkyl, a C 3 -C 20 cycloalkyl, a C 6 -C 30 aryl, an aralkyl, or an alkaryl, and R 17 is H, a C 1 -C 10 alkyl, or F.
25 . The compound of claim 22 , wherein R 1 is independently selected from a -C≡CR 7 , -C(O)R 8 , -C(O)OR 10 , -SR 11 , -CS-OR 18 , -CSSR 19 , -NR 20 C(O)-CR 21 =CR 22 2 a C 6 -C 20 aralkyl, or an alkaryl, where R 7 , R 8 , R 10 , R 11 , R 18 , R 19 , R 20 , R 21 , and R 22 are each independently H, a C 1 -C 20 alkyl, a C 3 -C 20 cycloalkyl, a C 6 -C 30 aryl, an aralkyl, or an alkaryl, and R 17 is H, a C 1 -C 10 alkyl, or F.
26 . The compound of claim 22 , wherein X 1 is Cl.