# US 9,518,069 B2 · Catalytic method for obtaining substituted (triorganosilyl)alkynes and their derivatives

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- Number: US 9,518,069 B2
- Document ID: US9518069B2
- Status: Granted
- Kind: B2
- Application number: 14/796,370
- Filed: 2015-07-10
- Published: 2015-12-17
- Granted: 2016-12-13
- Earliest claimed: 2010-12-30
- Assignees: Adam Mickiewicz University
- Applicants: Adam Mickiewicz University
- Inventors: Ireneusz Kownacki; Bogdan Marciniec; Beata Dudziec; Agnieszka Kownacka; Mariusz Majchrzak; Mateusz Szulc; Bartosz Orwat
- Web page: https://patentgrep.com/patent/US9518069B2

## CPC

- C07F 7/0827: {Syntheses with formation of a Si-C bond}
- C07F 7/0805: {comprising only Si, C or H atoms}
- C07F 7/081: {comprising at least one atom selected from the elements N, O, halogen, S, Se or Te}
- C07F 7/0838: {Compounds with one or more Si-O-Si sequences (compounds with a ring containing only alternating Si and O atoms, i.e. cyclosilanes C07F7/21)}
- C07F 7/0876: {Reactions involving the formation of bonds to a Si atom of a Si-O-Si sequence other than a bond of the Si-O-Si linkage}
- C07F 7/0896: {Compounds with a Si-H linkage}
- C07F 7/10: containing nitrogen {having a Si-N linkage}
- C07F 7/1804: {Compounds having Si-O-C linkages (Si-O-acyl linkages C07F7/1896)}
- C07F 7/1876: {by reactions involving the formation of Si-C linkages}
- C07F 7/188: {by reactions involving the formation of Si-O linkages}
- C07F 7/1892: {by reactions not provided for in C07F7/1876 - C07F7/1888}
- C07F 13/00: Compounds containing elements of Groups 7 or 17 of the Periodic Table
- C07F 17/02: of metals of Groups 8, 9 or 10 of the Periodic Table
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)

## Abstract

New (triorganosilyl)alkynes and their derivatives having general formula R1—C≡C—Z are provided along with methods for the preparation of (triorganosilyl)alkynes and their derivatives having the general formula R1—C≡C—Z. The methods may include silylative coupling of terminal alkynes with halogenotriorganosilanes in the presence of an iridium catalyst and a tertiary amine.

## Claims

### Claim 1

A method to obtain (triorganosilyl)alkynes having the general formula 1, in which
R1—C≡C—Z (1)
R1 denotes —SiR2R3R4
where R2R3R4 are equal or different and denote
a C1-5 alkyl,
a phenyl, aryl, containing from 1 to 5 alkyl substitutes containing C1-4,
a siloxy group having the formula 7,
in which R9 are equal or different and denote a C1-3 alkyl, an aryl or alkylaryl, containing from 1 to 5 C1-4 alkyl substitutes
so that none of the R2R3R4 substitutes has a heteroaryl or a heteroaryl derivative,
Z denotes a group having the formula 2,
-E-C≡C—R1 (2)
in which:
R1 denotes the same as stated above
E denotes phenylene or a group having the formula 3,
in which:
R5, R6, R7, R8 denote a C1-5 alkyl group or a phenyl or siloxy group having the general formula 7, in which R9 denotes the same as stated above,
n takes the value 0 or 50
o takes the value 0 or 1
Y denotes O, the group —(CH2)m— where m=1-16, —NR10—, where the group R10 denotes H, a C1-5 alkyl, an aryl containing from 1 to 5 C1-4 alkyl substitutes or alkoxy substitutes having C1-4 alkyl radicals, an arylalkyl where the alkyl chain contains C1-4, a silyl group having the general formula 8, in which:
the substitutes R11 are equal or different and denote a C1-3 alkyl, an aryl containing from 1 to 5 alkyl substitutes containing C1-4, a siloxy group having the general formula 7
where R9 denotes the same as stated above, however the group R10 is not a heteroaryl or a heteroaryl derivative,
so that:
if n denotes 0, then R4 and R5 are equal to each other or different,
if n=1 and o=1 and Y denotes —(CH2)m— or O or NR10, then R5, R6, R7 and R8 are equal to one another; or the pairs R5 and R7, R6 and R8, R5 and R6, R7 and R8 are equal to one another but different from another pair,
if n=1 and o=0, then it is possible that R5, R6, R7 and R8 are equal to one another;
or the pairs R5 and R7, R6 and R8 are equal but different from the other pair,
if Y═O and n=2-50, then R4, R5, R6 and R7 are equal to one another,
wherein it consists in reacting a suitable terminal alkyne having the general formula 9,
H—C≡C—Z (9)
in which Z denotes the same as stated above,
and a suitable halogenotriorganosilane having the general formula 10, in which
X—R1 (10)
X denotes Cl, Br, I,
R1 denotes the same as stated above,
in the presence of an iridium catalyst having the general formula 4,
[{Ir(μ-Cl)(L)}2], (4)
in which L denotes (CO)2 or cis,cis-1,5-cyclooctadiene (cod),
and a tertiary amine having the general formula 5 in which
NA1A2A3 (5)
A1A2A3 are equal or different and denote a C1-5 alkyl, a C5-7 cycloalkyl, an aryl, an arylalkyl where the alkyl chain contains C1-4, an alkylaryl where the alkyl chain contains C1-4, so that none of the substitutes is a heteroaryl or a heteroaryl derivative.

### Claim 2 (depends on 1)

A method as claimed in claim 1 wherein the iridium complex used is [{Ir(μ-Cl)(CO)2}2].

### Claim 3 (depends on 1)

A method as claimed in claim 1 wherein the iridium complex is used in an amount in the range from 0.01 to 4 mol % relative to the functional terminal alkyne group.

### Claim 4 (depends on 3)

A method as claimed in claim 3 wherein the iridium complex is used in an amount in the range from 1 to 2 mol % relative to the functional terminal alkyne group.

### Claim 5 (depends on 1)

A method as claimed in claim 1, wherein the amine having the formula 5 is used in an amount not smaller than that equivalent to the sum of a stoichiometric amount of the hydrogen halide formed and a 2.2-fold excess relative to the iridium ion in the complex used.

### Claim 6

A method to obtain (triorganosilyl)alkynes having the general formula 1,
R1—C≡C—Z (1)
in which
R1 denotes —SiR2R3R4 where R2R3R4 are equal or different and denote
a C1-5 alkyl, a C5-7 cycloalkyl,
a phenyl, aryl, containing from 1 to 5 alkyl substitutes containing C1-4,
a siloxy group having the formula 7,
in which R9 are equal or different and denote a C1-3 alkyl, an aryl or alkylaryl, containing from 1 to 5 alkyl substitutes containing C1-4,
so that none of the R2R3R4 substitutes has a heteroaryl or a heteroaryl derivative,
Z denotes:
a silyl group having the general formula 8 in which R11 denotes the same as stated above, a siloxy group having the general formula 7 in which R9 denotes the same as stated above
a ferrocenyl group,
a C1-5 alkyl,
a C5-7 cycloalkyl,
—CH2NR12 in which R1 denotes the same as stated above
an arene with the fused aromatic ring number in the range from 2 to 6,
a group having the general formula 11,
in which:
y takes the values 0 or 1, and w takes the values from 0 to 2
—R12 denotes a C1-5 alkylene group, a C5-7 cycloalkylene group,
R13, R14, R15, R16, R17 are equal or different and denote a hydrogen atom, a C1-4 alkyl chain, a halogen, an alkoxy group where the alkyl radical contains C1-3, —OH, or —OR1 in which R1 denotes the same as stated above,
so that when:
w=1 and y=1, then R13, R14, R15, R16, R17 are equal or different and denote a hydrogen atom, a C1-4 alkyl chain, a halogen, an alkoxy group in which the alkyl radical contains C1-3,
y=0 and w takes a value from 0 to 2, then R13, R14, R15, R16, R17 denote the same as stated above and, moreover, at least one of the substitutes R13, R14, R15, R16, R17 denotes phenyl, aryl with the exception of heteroaryls, —OH or —OR1, in which R1 denotes the same as stated above,
wherein it consists in reacting a suitable terminal alkyne having the general formula 9,
H—C≡C—Z (9)
in which Z denotes the same as stated above,
and a suitable halogenotriorganosilane having the general formula 10, in which
X—R1 (10)
X denotes Cl, Br, I,
R1 denotes the same as stated above,
in the presence of an iridium catalyst having the general formula 4,
[{Ir(μ-Cl)(L)}2], (4)
in which L denotes (CO)2 or cis,cis-1,5-cyclooctadiene (cod),
and a tertiary amine having the general formula 5 in which
NA1A2A3 (5)
A1A2A3 are equal or different and denote a C1-5 alkyl, a C5-7 cycloalkyl, an aryl, an arylalkyl where the alkyl chain contains C1-4, an alkylaryl where the alkyl chain contains C1-4, so that none of the substitutes is a heteroaryl or a heteroaryl derivative.

### Claim 7 (depends on 6)

A method as claimed in claim 6 wherein the iridium complex used is [{Ir(μ-Cl)(CO)2}2].

### Claim 8 (depends on 6)

A method as claimed in claim 6 wherein the iridium complex is used in an amount in the range from 0.01 to 4 mol % relative to the functional terminal alkyne group.

### Claim 9 (depends on 8)

A method as claimed in claim 8 wherein the iridium complex is used in an amount in the range from 0.5 to 1 mol % relative to the functional terminal alkyne group.

### Claim 10 (depends on 8)

A method as claimed in claim 8 wherein, in the synthesis of the compounds containing an amine substitute, the iridium complex is used in an amount in the range from 0.5 to 2 mol % relative to the functional terminal alkyne group.

### Claim 11 (depends on 6)

A method as claimed in claim 6, wherein the amine having the formula 5 is used in an amount not smaller than that equivalent to the sum of a stoichiometric amount of the hydrogen halide formed and a 2.2-fold excess relative to the iridium ion in the complex used.