New (triorganosilyl)alkynes and their derivatives and a new catalytic method for obtaining new and conventional substituted (triorganosilyl)alkynes and their derivatives

A method to obtain new and conventional (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 C1-5alkyl,
• 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. 3.

A method to obtain new and conventional (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 R1 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, R5, 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, —NH2, —OH, —OR1 or NR12 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, R17denote 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, —NH2, —OH, —OR1 or NR12, 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.