Catalytic method for obtaining substituted (triorganosilyl)alkynes and their derivatives

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.