# US 9,518,070 B2 · Use of cyclohexa-2,5-dien-1-yl-silanes as precursors for gaseous hydrosilanes

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- Number: US 9,518,070 B2
- Document ID: US9518070B2
- Status: Granted
- Kind: B2
- Application number: 15/021,222
- Filed: 2014-09-04
- Published: 2016-08-04
- Granted: 2016-12-13
- Earliest claimed: 2013-09-10
- Assignees: Technische Universitaet Berlin
- Applicants: Technische UniversitäT Berlin
- Inventors: Martin Oestreich; Antoine Simonneau
- Web page: https://patentgrep.com/patent/US9518070B2

## CPC

- C07F 7/0827: {Syntheses with formation of a Si-C bond}
- C07B 63/02: by treatment giving rise to a chemical modification
- C07F 7/0805: {comprising only Si, C or H atoms}
- C07F 7/083: {Syntheses without formation of a Si-C bond}
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- C07B: GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR (preparation of carboxylic acid esters by telomerisation C07C67/47; telomerisation C08F)

## Abstract

A method of making hydrosilanes having a formula R1R2R3SiH by reacting a compound having formula I: in solution using a strong Lewis acid. This way, e.g., alkenes or carbonyl compounds can be hydrosilylated in good yields using the cyclohexa-2,5-dien-1-yl-silanes of general formula I as transfer hydrosilylating agents in the presence of a strong Lewis acid as catalyst with concomitant formation of an arene solvent.

## Claims

### Claim 1

A method for making hydrosilanes having formula R1R2R3SiH (Ia), by reacting a compound having formula I with a Lewis acid of general formulae II or IIa:
wherein
R1 and R2 represent independently from each other C1-C3-alkyl or C1-C3-alkoxy,
R3 represent independently from R1 and R2 H, C1-C3-alkyl, C1-C3-alkoxy or aryl and
R4 and R5 represent independently from each other H, C1-C3-alkyl or R1R2R3Si with R1 to R3 as defined above,
R is methyl or ethyl,
m+n=5, m=0 to 5 and n=0 to 5,
with concomitant formation of an arene solvent.

### Claim 2 (depends on 1)

The method of claim 1, wherein alkenes of general formula III
react in solution with the hydrosilanes of general formula Ia
R1R2R3SiH (Ia),
with R1 to R3 as above,
to form silanes of general formula IV
with R1 to R3 as above.

### Claim 3 (depends on 1)

The method of claim 1 wherein carbonyl compounds of general formula V
react in solution with the formed hydrosilanes of general formula Ia
R1R2R3SiH (Ia),
wherein R1 to R3 have the above meaning,
to form silanes of general formula VI
with R1 to R3 as above.

### Claim 4 (depends on 1)

The method of claim 1, wherein R1, R2 and R3 in formula I are equal to each other representing methyl, ethyl, i-propyl, methoxy or ethoxy.

### Claim 5 (depends on 1)

The method of claim 1, wherein R1 and R2 in formula I are equal to each other representing methyl, ethyl, methoxy or ethoxy, and R3 represents H or aryl.

### Claim 6 (depends on 1)

The method of claim 1 wherein m in general formula II is 5 and n is 0.

### Claim 7 (depends on 1)

The method of claim 1, wherein the reaction is conducted in a solvent at ambient temperature, preferably an arene solvent or a halogenated solvent.

### Claim 8 (depends on 1)

The method of claim 1 wherein the reaction is conducted in a solvent at 70-120° C., preferably in an arene solvent or a halogenated solvent.

### Claim 9 (depends on 1)

The method of claim 1, wherein the alkenes which are hydrosilylated are alkenes of general formula IIIa
wherein
R6 represents H, C4-C20-alkyl, C4-C20-cycloalkyl or aryl,
R7 represents H, C1-C10-alky, C4-C10-cycloalkyl or aryl,
or R6 and R7 form together a cycloalkane ring,
and
R8 represents H, methyl, ethyl, —CH2Hal or phenyl.

### Claim 10 (depends on 1)

The method of claim 1, wherein R6 and R7 represent H and R8 represents a —CH2Hal group, preferably —CH2Cl.

### Claim 11 (depends on 1)

The method of claim 1, wherein the alkenes which are hydrosilylated are alkenes of general formula III b
wherein
a) in case that both rings A and B are present,
n is 1 or 2,
R9 represents H, C1-C20-alkyl or C4-C20-cycloalkyl,
R10 represents H or halogen;
and
b) in case that ring B is not present,
in the cyclic alkene of ring A n is 1-4 and R9 represents H or methyl.

### Claim 12 (depends on 1)

The method of claim 1, wherein the alkene which is hydrosilylated is norbornene (III c).

### Claim 13 (depends on 1)

The method of claim 1, wherein the carbonyl compounds which are hydrosilylated are compounds of general formula Va
wherein
R represents C1-C20 alkyl or aryl,
R′ represents H, C1-C20 alkyl or aryl or
R and R′ form together a C3-C20 cycloalkane ring.

### Claim 14

A method comprising reacting cyclohexa-2,5-dien-1-yl-silanes of general formula (I)
wherein
R1 and R2 represent independently from each other C1-C3-alkyl or C1-C3-alkoxy,
R3 represent independently from R1 and R2 H, C1-C3-alkyl, C1-C3-alkoxy or aryl and
R4 and R5 represent independently from each other H, C1-C3-alkyl or R1R2R3Si with R1 to R3 as defined above,
and a Lewis acid of general formula II or IIa
B(C6FmHn)3 (II)
wherein m+n=5, m=0 to 5 and n=0 to 5,
BF3.O(R)2 (IIa)
wherein R is methyl or ethyl,
for hydrosilylation of alkenes and carbonyl compounds under concomitant formation of an arene solvent.