DUDZIEC, Beata (os. Jana III Sobieskiego 2/41, Poznan, PL-60-688, PL)
SZUBERT, Karol (ul.Swarzedzka 9, Kicin, Czerwonak, PL-62-004, PL)
WALKOWIAK, Jedrzej (os. Stefana Batorego 21/16, Poznan, PL-60-687, PL)
MARCINIEC, Bogdan (Wilkonskich 13, Poznan, PL-62-020, PL)
DUDZIEC, Beata (os. Jana III Sobieskiego 2/41, Poznan, PL-60-688, PL)
SZUBERT, Karol (ul.Swarzedzka 9, Kicin, Czerwonak, PL-62-004, PL)
WALKOWIAK, Jedrzej (os. Stefana Batorego 21/16, Poznan, PL-60-687, PL)
Claims
1. New silylsubstituted 1,2-alkynes of general formula I 5 in which R 1 stands for a trialkoxysilyl group, phenyldimethylsilyl group, dimethyl(trimethylsiloxy)silyl group or methylbis(trimethylsiloxy)silyl group; while R 2 stands for alkyl, trialkylsilyl group, 1- trimethylsiloxycycloalkyl group, cycloalkyl group, tertbutyl group, 1-trimethylsiloxyalkyl group, tertbutyldimethylsilyl group or 1-alkoxyalkyl group.
2. The synthesis of silylsubstituted 1,2-alkynes of general formula 1, in which R 1 stands for a trialkoxysilyl group, phenyldimethylsilyl group, dimethyl(trimethylsiloxy)silyl group or methylbis(trimethylsiloxy)silyl group, while R 2 stands for an alkyl group, tertbutyl group, cycloalkyl group, 1-trimethylsiloxycycloalkyl group, phenyldimethylsilyl group, trialkylsilyl group with all alkyl substituents the same, tertbutyldimethylsilyl group, 1- trimethylsiloxyalkyl group or 1-alkoxyalkyl group, in which process a relevant alkene of general formula 2, with R 1 specified as above is subjected to silylative coupling with a terminal alkyne of general formula 3, with R 2 specified as above, in the presence of a catalyst of general formula 4 with R 3 standing for a cyclohexyl group or isopropyl group; the reaction is conducted in temperatures from the range 100-130°C, possibly in an organic solvent, preferably a hydrocarbon or aromatic solvent, preferably in toluene, in a neutral gas atmosphere.
3. The method of synthesis of silylsubstituted 1,2-alkynes of general formula 1, in which R 1 stands for a trialkoxylsilyl group, phenyldimethylsilyl group dimethyl(trimethylsiloxy)silyl group or methylbis(trimethylsiloxy)silyl group, while R 2 stands for alkyl, tertbutyl, cycloalkyl, 1-trimethylsiloxycycloalkyl group, phenyldimethylsilyl group, trialkylsilyl group, tertbutyldimethylsilyl group, 1- trimethylsiloxalkyl group or 1-alkoxyalkyl group, in which process a relevant alkene of general formula 2 with R 1 specified as above is subjected to silylative coupling with a terminal alkyne of general formula 3 with R 2 specified as above, in the presence of a catalyst of general formula 5, with R 3 standing for a cyclohexyl or isopropyl group; the reaction is conducted in temperatures from the range 100- 13 O 0 C, possibly in an organic solvent, preferably a hydrocarbon or aromatic solvent, preferably in toluene, in a neutral gas atmosphere. 4. The method of synthesis of silylsubstituted 1 ,2-alkynes of general formula 1 , in which R 1 stands for a trialkoxylsilyl group, phenyldimethylsilyl group dimethyl(trimethylsiloxy)silyl group or methylbis(trimethylsiloxy)silyl group, while R 2 stands for alkyl, tertbutyl, cycloalkyl, 1-trimethylsiloxycycloalkyl group, phenyldimethylsilyl group, trialkylsilyl group, tertbutyldimethylsilyl group, 1- trimethylsiloxyalkyl group or 1-alkoxyakyl group, in which process a relevant alkene of general formula 2 with R 1 specified as above is subjected to silylative coupling with a terminal alkyne of general formula 3, with R 2 specified as above in the presence of iόdotris(triphenylphosphine)rhodium (I) of formula 6 as a catalyst; the reaction is conducted in temperatures from the range 100-130 0 C, possibly in an organic solvent, preferably a hydrocarbon or aromatic solvent, preferably in toluene, in a neutral gas atmosphere. 5. The method of synthesis of silylsubstituted 1 ,2-alkynes of general formula 1 , in which R 1 stands for a trialkoxylsilyl group, phenyldimethylsilyl group, dimethyl(trimethylsiloxy)silyl group or methylbis(trimethylsiloxy)silyl group , while R stands for alkyl, tertbutyl, cycloalkyl, 1-trimethylsiloxycycloalkyl group, phenyldimethylsilyl group, trialkylsilyl group, tertbutyldimethylsilyl group, 1- trimethylsiloxyalkyl group or 1-alkoxyalkyl group, in which process a relevant alkene of general formula 2, with R specified as above, is subjected to silylative coupling with a terminal alkyne of general formula 3, with R 2 specified as above, in the presence of di-μ- iodobis(l,5-cyclooctadiene)dirhodium (I) of formula 7 as a catalyst; the reaction is conducted in temperatures from the range 100-130°C, possibly in an organic solvent, preferably in a hydrocarbon or aromatic solvent, preferably in toluene, in a neutral gas atmosphere.
6. The method of synthesis of silylsubstituted 1 ,2-alkynes of general formula 1, in which R 1 stands for a trialkoxysilyl group, phenyldimethylsilyl group, dimethyl(trimethylsiloxy)silyl group or metylbis(trimethylsiloxy)silyl group, while R stands for alkyl, tertbutyl, cycloalkyl, a 1-trimethylsiloxycckloalkyl group, phenyldimethylsilyl group, trialkylsilyl group, tertbutyldimethylsilyl group, 1- trimethylsiloxyalkyl group or 1-alkoxyalkyl group, in which process a relevant alkene of general formula 2 with R 1 specified as above is subjected to silylative coupling with a terminal alkyne of general formula 3, with R 2 specified as above, in the presence of dodecacarbonyltriruthenium (0) of formula 8 as a catalyst; the reaction is conducted in temperatures from the range 100-130 0 C, possibly in an organic solvent, preferably a hydrocarbon or aromatic solvent, preferably in toluene, in a neutral gas atmosphere. |
New silylsubstituted 1,2-alkynes and synthesis of silylsubstituted 1,2-alkynes
The subject of the invention are new silylsubstituted 1,2-alkynes of the general formula 1 and a new way of synthesis of new and already known silylsubstituted 1,2-alkynes of the general formula 1.
A few methods of synthesis of silylsubstituted 1,2 -alkynes have been hitherto proposed and used.
The most often used is the reaction of chlorosubstituted silanes with lithium- or magnesium substituted alkynes (Baba, T.; Kato, A.; Takahanashi, H.; Toriyama, F.; Handa, H.; Ono, Y.; Sugisawa, H. J Catal. 1998, 176, 488-494; Brandsma, L.; Verkruijsse, H.D. Synthesis, 1999, 1727-1728), also in the presents of palladium complexes (Yang, L.-M; Huang, L.-F.; Lull, T.-Y. Org. Lett. 2004, 6, 1461-1463). Another very popular method of synthesis of silylsubstituted 1,2 —alkynes is the Sonogashira reaction of silylsubstituted terminal alkynes with alkyl or aryl halides the presence of palladium complexes in triethylamine (Sonogashira, K.; Tohda, Y.; Hagihara, N. Tetrahedron Lett. 1975, 4467; Takahashi, S.; Kuroyama, Y.; Sonogashira, K.; Hagihara, N. Synthesis, 1980, 627; Uenishi, J.; Matsui, K. Tetrahedron Lett. 2001, 42, 4353-4355). The direct methods of synthesis of silylsubstituted 1,2-alkynes include: direct silylation of terminal alkynes with aminosilanes in the presence of zinc halides in 1,4-dioxane (Anreev, A. A.; Konshin, V. V.; Komarov, N.V.; Rubin, M.; Brouwer, Ch.; Gevorgyan, V. Org. Lett. 2004, 6, 421-424), and direct silylation of terminal alkynes with chlorosilanes in the presence of zinc dust or zinc complexes (Sugita, H.; Hatanaka, Y.; Hiyama, T. Tetrahedron Lett. 1995, 36, 2769-2772; Jiang, H.; Zhu, S. Tetrahedron Lett. 2005, 46, 517-519). Another method of synthesis of silylsubstituted 1,2 -alkynes is the reaction of terminal silylsubstituted alkynes with disulfides in the presence of rhodium complexes in acetone (Arisawa, M.; Fujimoto, K.; Morinaka, S.; Yamaguchi, M. J. Am. Chem. Soc. 2005, 127, 12226-12227). The relevant
compounds can be also obtained by modification of silylsubstituted 1,2-alkynes by metathesis over a molybdenum catalyst (Fϋrstner, A.; Mathes, Ch. Org. Lett. 2001, 3, 221- 223), or over palladium catalysts with addition of copper or silver halides (Chen, L.; Li, Ch.- J. Tetrahedron Lett. 2004, 45, 2771-277 r 4; Halbes, U.; Pale, P. Tetrahedron Lett. 2002, 43, 2039-2042) or in addition of phosphines (Trost, B.M.; Mclntosh, M.C. Tetrahedron Lett. 1997, 38, 3207-3210; Trost, B.M.; Sorum, M.T.; Chan, Ch.; Harms, A.E.; Rϋhter, G. J. Am. Chem. Soc. 1997, 119, 698-708), or in the presence of ruthenium catalysts (Yi, Ch.S.; Liu, N. Organometallics 1998, 17, 3158-3160) or cesium fluorides and crown ethers (Lukevics, E.; Rubia, K.; Abele, E.; Fleisher, M.; Arsenyan, P.; Grϊnberga, S.; Popelis, J. J. Organomet. Chem. 2001, 634, 69-73). They also have been synthesized by dehydrogenating silylation of terminal alkynes with silanes in the presence of iridium complexes (Fernandez, MJ.; Oro, AJ. J. MoI. Catal. 1988, 45, 7-15; Esteruelas, M.A.; Nϋrnberg, O.; Olivan, M.; Oro, L.A. Organometallics 1993, 12, 3264-3272; Shimizu, R.; Fuchikami, T. Tetrahedron Lett. 2000, 41, 907-910 ) or ytterbium complexes (Takaki, K.; Kurioka, M.; Kamata, T.; Takehira, K.; Makioka, Y.; Fujiwara, Y. J. Org Chem. 1998, 63, 9265-9269) or lithium or barium compounds (Ishikawa, J.; Itoh, M. J. Catal. 1999, 185, 454-461; Itoh, M.; Kobayashi, M.; Ishikawa, J. Organometallics 1997, 16, 3068-3070). The silylsubstituted 1,2 -alkynes have been also synthesized by thermal desulfinylation of 2-trialkylsilylvinylsulfoxides (Nakamura, S.; Kusuda, A.; Kawamura, K. Toru, T. J. Org. Chem. 2002, 67, 640-647). The silylsubstituted 1,2-alkynes obtained by the above-mentioned methods of synthesis contain considerable amounts of side products, which decreases the yield of the pure target product.
The subject of invention are new silylsubstituted 1,2-alkynes of the general formula 1 and a new way of synthesis of new and already known silylsubstituted 1 ,2-alkynes of the general formula 1.
The subject matter of the invention are new, hitherto unknown silylsubstituted 1,2- alkynes of general formula 1, in which R 1 stands for trialkoxysilyl group, dimethyl(trimethylsiloxy)silyl group, phenyldimethylsilyl group, methylbis(trimethylsiloxy)silyl group; R 2 stands for alkyl, trialkylsilyl group with all alkyl substituents the same, 1-trimethylsiloxycycloalkyl group, cycloalkyl group, tertbutyl group, 1-trimethylsiloxyalkyl group, tertbutyldirnethylsilyl group or 1-alkoxyalkyl group. Silylsubstituted 1,2-alkynes of general formula 1, in which R 1 stands for a trialkoxysilyl group while R 2 stands for a trialkylsilyl group with all alkyl substituents the same or
tertbutyl group and silylsubstituted 1,2-alkynes of general formula 1 in which R 1 stands for a phenyldimethylsilyl group while R 2 stands for a cycloalkyl, phenyldimethylsilyl or tertbutyl group are the known compounds.
The subject matter of the invention is a new way of synthesis of new and already known silylsubstituted 1,2-alkynes of general formula 1, in which R 1 stands for a trialkoxysilyl group, methylbis(trirnethylsiloxy)silyl group, dimethyl(trimethylsiloxy)silyl group or phenyldimethylsilyl group, while R 2 stands for alkyl, tertbutyl, cycloalkyl, trialkylsilyl group with all alkyl substituents the same, 1-trimethylsiloxy cycloalkyl group, phenyldimethylsilyl group, tertbutyldimethylsilyl group, 1-trimetylsiloxyalkyl group or 1- alkoxyalkyl group, in which an alkene of general formula 2, with R 1 specified above is subjected to silylative coupling with a terminal alkynes of the general formula 3, with R specified above, in the presence of a catalyst.
According to the invention the reaction is conducted in temperatures from the range 100-130°C, possibly in the presence of a solvent, in particular hydrocarbon or aromatic solvent, preferably toluene, in a neutral gas atmosphere.
In the first version of the synthesis method proposed in the invention the catalyst is the compound of general formula 4 in which R 3 stands for a cyclohexyl or isopropyl group. .
In the second version of the synthesis method proposed in the invention the catalyst is the compound of general formula 5, with R 3 as specified above. In the third version of the synthesis method proposed in the invention the catalyst is iodotris(triphenylphosphine)rhodium (I) of formula 6.
In the fourth version of the synthesis method proposed in the invention the catalyst is di- di-μ-iodobis(l,5-cyclooctadiene)dirhodium (I) of formula 7.
In the fifth version of the synthesis method proposed in the invention the catalyst is jest dodecacarbonyltrimthenium (0) of formula 8.
In contrast to the hitherto proposed solutions, the method of synthesis according to the invention permits obtaining silylsubstituted 1,2-alkynes of general formula 1, with R 1 , R 2 , as specified above, in high yields in a single-step process and with a considerable reduction of formation of side products relative to their formation in the majority of the hitherto known processes. Another advantage of the method of synthesis proposed in the invention is the use of a low amount of ruthenium complex 0.01 - 2% molar ratio. Silylsubstituted alkynes have a number of applications in organic synthesis (Kawanami, Y.; Katsuki, T.; Yamaguchi, M. Tetrahedron Lett 1983, 24, 5131-5132; Greene, T.W.; Wuts, P.G.M. Protective Groups in Organic Synthesis, Wiley, New York,
1999; Saeeng, R.; Sirion, U.; Sahakitpichan, P.; Isobe, M. Tetrahedron Lett. 2003, 44, 6211- 6215; Anderson, J.C.; Munday, R.H.. J. Org. Chem. 2004, 69, 8971-8974; Lettan II, R.B.; Scheidt, K.A. Org. Lett. 2005, 7, 3227-3230). They are used in different processes as e.g. in metathesis of alkynes (Fϋrstner, A.; Mathes, Ch. Org. Lett. 2001, 3, 221-223; Brizius, G.; Bunz, U.H.F. Org. Lett. 2002, 4, 2829-2831), or in synthesis of compounds being potential insecticides (Palmer, CJ.; Casida, J.E. J. Agric. Food Chem. 1989, 37, 213-316; Palmer, C.J.; Smith, I.H.; Moss, M.D.V.; Casida, J.E. J. Agric. Food Chem. 1990, 38, 1091-1093; Palmer, CJ.; Cole, L.M; Smith, I.H.; Moss, M.D.V.; Casida, J.E. J. Agric. Food Chem. 1991, 39, 1335-1341).
The invention is illustrated by the few examples given below. The structure of the new silylsubstituted 1,2-alkynes has been confirmed by GC-MS and NMR spectroscopy. Example I In a reactor equipped with a reflux and a stirrer, in argon atmosphere, a portion of 0.07g of carbonylchlorohydridobis(tricyclohexylphosphine)ruthenium (II) was placed, to which 14mL of toluene, 3.5mL of dimethylphenylvinylsilane and 1.7mL triethylsilylethyne were subsequently added. The reaction mixture was heated for 24 hours at 120°C. The catalysts were removed from the raw product on a chromatographic column filled with silica and then the product was distilled. The compound obtained was l-dimethylphenylsilyl-2- (triethylsilyl)ethyne in the yield of 94% of the pure product and 100% yield of the raw product.
Results of the GCMS analysis: m/z (%): 274 (23) [M + ], 259 (34), 246 (100), 218 (89), 189 (68), 159 (12), 145 (13), 135 (34), 105 (36), 91 (10), 58 (14), 53 (18) Spectroscopic characterization of the product: 1 H NMR (CDCl 3 ) δ (ppm): 0.42 (s,CH 3 SiC≡); 0.63-0.68 (tr, CH 3 CH 2 SiC=); 1.00-1.05 (qu, CH 3 CH 2 SiC=); 7.39-7.40 (m, C 6 H 5 SiC=)
13 C NMR (CDCl 3 ) δ (ppm): -0.68 (CH 3 SiC=); 4.49 (CH 3 CH 2 SiC=); 7.44 (CH 3 CH 2 SiC=); 113.57, 112.81 (C≡C); 127.79-137.11 (C 6 H 5 SiC=) 29 Si NMR (CDCl 3 ) δ (ppm): -20.07; -19.10 Example II
As in example I, 4.OmL of dimethylphenylvinylsilane were reacted with 1.8mL of tertbutyldimethylsilylethyne in the presence of 10.2mL of toluene and 0.07g of carbonylchloiOhydridobis(tricyclohexylphosphine)ruthenium (II). The compound obtained was l-dimethylphenylsilyl-2-(tertbutyldimethylsilyl)ethyne in the yield of 70% of the pure product and 77% yield of the raw product.
Results of GCMS analysis: m/z (%): 274 (47) [M + ], 259 (74), 218 (100), 157 (39), 135 (46),
105 (11), 74 (69), 53 (16)
Spectroscopic characterisation of the product:
1 H NMR (CDCl 3 ) δ (ppm): 0.16 (s, CH 3 ((CH 3 ) 3 C)SiC≡); 0.43 (s, CH 3 (C 6 H 5 )SiC=); 0.98 (s, CH 3 ((CH 3 ) 3 C)SiC≡); 7.37-7.68 (m, C 6 H 5 SiC=)
13 C NMR (CDCl 3 ) δ (ppm): -4.54 (CH 3 ((CH 3 ) 3 C)SiC≡); -0.59 (CH 3 (C 6 H 5 )SiC=); 16.62
(CH 3 ((CH 3 ) 3 C)SiC≡); 26.13 (CH 3 ((CH 3 ) 3 C)SiC≡); 112.07, 114.40 (C≡C); 127.07-136.91
(C 6 H 5 SiC=)
29 Si NMR (CDCl 3 ) δ (ppm): -20.06; -5.95 Example III
As in example I, 8.8mL of dimethylphenylvinylsilane were reacted with 1.2mL of 3,3 - dimethyl- 1-butyne in the presence of 0.07 g of carbonylchlorohydridobis(tricyclohexylphosphine)ruthenium (II) and 9.3mL of toluene. The compound obtained was 3,3-dimethyl-l-(dimethylphenylsilyl)-l-butyne in the yield of 90% of the pure product and 100% yield of the raw product.
Results of GCMS analysis: m/z (%): 216 (21) [M + ], 201 (100), 185 (5), 159 (33), 135 (6),
105 (9)
Spectroscopic characterization of the product:
1 H NMR (CDCl 3 ) δ (ppm): 0.36 (s, (CH 3 ) 2 Si); 1.25 (s, (CH 3 ) 3 C); 7.37-7.68 (m, C 6 H 5 SiC=) 13 C NMR (CDCl 3 ) δ (ppm): -0.59 (CH 3 (C 6 H 5 )SiC=); 16.62 (CH 3 ((CH 3 ) 3 C)SiC≡); 29.01
((CHs) 3 C); 30.82 ((CHs) 3 C); 112.07, 88.40 (C≡C); 127.07-136.91 (C 6 H 5 SiC=)
Example IV
As in example 1, 3.8mL of dimethylphenylvinylsilane were reacted with 0.9mL ethynylcyclohexane in the presence of 0.07g of iodotris(triphenylphosphine)rhodium (I) at 100°C. The compound obtained was (dimethylphenylsilylethynyl)cyclohexane in the yield of
65% of the pure product and 100% yield of the raw product.
Results of GCMS analysis: m/z (%): 227 (100) [M + -CH 3 ], 163 (12), 145 (31), 121 (8), 105
(10), 78 (7), 53 (7)
Spectroscopic characterization of the product: 1 H NMR (CDCl 3 ) δ (ppm): 0.38 (s, CH 3 Si); 1.2-2.4 (m, C 6 H n ); 7.33-7.68 (m, C 5 H 5 )
13 C NMR (CDCl 3 ) δ (ppm): 0.3 (CH 3 Si); 24.8-32.6 (C 6 H 11 ); 81.6, 113.7 (C=C); 127.6-137.8
(C 5 H 5 )
29 Si NMR (CDCl 3 ) δ (ppm): -20.02
Example V
As in example I 7.9mL dimethylphenylvinylsilane were reacted with 0.95mL 1-heptyne in the presence of 0.07g carbonylchlorohydridobis(tricyclohexylphosphine)ruthenium (II) and
5.55mL of toluene . The compound obtained was l-(dimethylphenylsily I)- 1-heptyne in the yield of 95% of the pure product and 100% yield of the raw product. 5 Results of the GCMS analysis m/z (%): 215 (100) [M + - CH 3 ], 174 (28), 159 (21), 145 (25),
135 (14), 121 (30), 105 (14), 53 (10)
Spectroscopic characterization of the product:
1 HNMR (CDCl 3 ) δ (ppm): 0.09 (s, CH 3 Si); 0.33-2.30 (m, C 5 H 11 ); 7.36-7.66 (m, C 5 H 5 )
13 C NMR (CDCl 3 ) δ (ppm): -0.4 (CH 3 Si); 14.0-31.1 (C 5 H 11 ); 82.1, 109.6 (C≡C); 127.6-137.7 10 (C 5 H 5 )
29 Si NMR (CDCl 3 ) δ (ppm): -20.09
Example VI
As in example 1, 4.38mL of dimethylphenylvinylsilane were reacted with 0.62mL of ethynylcyclohexane in the presence of 4.64mL of toluene and 0.07g of 15 carbonylchlorohydridobis(tricyclohexylphosphine)ruthenium (II). The compound obtained was (dimethylphenylsilylethynyl)cyclohexane in the yield of 60% of pure product and 67% of raw product. The product characteristic is as in example IV.
Example VII
As in example I, 5.65mL of dimethylphenylvinylsilane were reacted with 1.85mL of 20 triethylsilylethyne in the presence of 0.07g di-μ-iodobis(l,5-cyclooctadiene)dirhodium (I) at
130°C. The compound obtained was l-dimethylphenylsilyl-2-(triethylsilyl)ethyne in the yield of 70% of pure product and 90% of raw product. The product characteristic is as in example I.
Example VIII • " As in example I 5.65mL dimethylphenylvinylsilane were reacted with 1.38mL dimethylphenylsilylethyne in the presence of argon 0.07g di-μ-iodobis(l,5- cyclooctadiene)dirhodium (I) at 130°C. The compound obtained was 1,2- bis(dimethylphenylsilyl)ethyne in the yield of 80% of the pure product and 100% of raw product. 30 Results of the GCMS analysis m/z (%): 294 (9) [M + ], 279 (100) [M + - CH 3 ], 263 (2), 219
(10), 159 (4), 135 (13), 105 (10), 91 (5), 73 (3), 53 (5)
Spectroscopic characterization of the product:
1
H NMR (CDCl 3
) δ (ppm): 0.37
13 C NMR (CDCl 3 ) δ (ppm): -0.68 (CH 3 SiC=); 113.81 (C≡C); 127.80-136.80 (C 6 H 5 SiCs)
35
Example IX
As in example 1 3.76mL dimethylphenylvinylsilane were reacted with 0.92mL dimethylphenylsilylethyne in the presence of 0.07g iodotris(triphenylphosphine)rhodium (I) at 100°C. The compound obtained was l,2-bis(dimethylphenylsilyl)ethyne in the yield of 60% of the pure product and 100% of raw product. The product characteristic is as in example VIII.
Example X
As in example I 5.65mL dimethylphenylvinylsilane were reacted with 1.35mL 1-heptyne in the presence of 0.07g di-μ-iodobis(l,5-cyclooctadiene)dirhodiurn (I) at 130°C. The compound obtained was 1-dimethylphenylsilyl- 1-heptyne in the yield of 65% of the pure product and 80% of raw product. The product characteristic is as in example V.
Example XI
As in example I 5.65mL dimethylphenylvinylsilane were reacted with 1.33mL ethynylcyclohexane in the presence of 0.07g di-μ-iodobis(l,5-cyclooctadiene)dirhodium (I) at 130°C. The compound obtained was (dimethylphenylsilylethynyl)cyclohexane in the yield of 60% of the pure product and 100% of raw product. The product characteristic is as in example IV.
Example XII
As in example I 5.65mL dimethylphenylvinylsilane were reacted with 2.32mL triisopropylsilylethyne in the presence of 0.07g di-μ-iodobis(l,5-cyclooctadiene)dirhodium
(I) at 130°C. The compound obtained was l-triisopropylsilyl-2-(dimethylphenylsilyl)ethyne in the yield of 95% of the pure product and 100% of raw product.
Results of the GCMS analysis m/z (%):301 (21) [M + - CH 3 ], 273 (100), 246 (22), 232 (50),
203 (8), 157 (28), 135 (29), 105 (8), 91 (3), 73 (14) Spectroscopic characterization of the product:
1 HNMR (CDCl 3 ) δ (ppm): 0.40 (s,CH 3 SiC≡); 1.06-1.2 (m, (CH 3 ) 2 CH); 7.37-7.40 (m,
C 6 H 5 SiC≡)
13 C NMR (CDCl 3 ) δ (ppm): -2.16 (CH 3 Si); -0.68 (CH 3 SiC=); 11.24 ((CH 3 ) 2 CHSi); 18.70
((CHs) 2 CHSi); 110.1, 113.81 (OC); 127.80-136.80 (C 6 H 5 SiC=) Example XIII
As in example I 4.45mL dimethylphenylvinylsilane were reacted with 1.46mL triethylsilylethyne in the presence of 10.42mL dichloromethane, and 0.07g diacetonitrilecarbonylhydridobis(tricyclohexylphosphine)ruth enium (II) tetrafluoroborate at
100°C. The compound obtained was l-dimethylphenylsilyl-2-(triethylsilyl)ethyne in the yield of 40% of the pure product and 43% of raw product. The product characteristic is as in
example I.
Example XIV
As in example I 3.44mL dimethylphenylvinylsilane were reacted with 1.47mL triethylsilylethyne in the presence of 0.07g dodecacarbonyltriruthenium (0) and 11.5mL of 5 toluene at 120°C. The compound obtained was l-dimethylphenylsilyl-2-(triethylsilyl)ethyne in the yield of 10% of the pure product and 20% of raw product. The product characteristic is as in example I.
Example XV
In a reactor equipped with a reflux and a stirrer, in argon atmosphere, a portion of 0.07g of 10 carbonylchlorohydridobis(tricyclohexylphosphine)ruthenium (II) was placed, to which
11.9mL of toluene, 5.5mL of dimethylphenylvinylsilane and 1.9mL 1-ethynyl-l-
(trimethylsiloxy)cyclohexane were subsequently added. The reaction mixture was heated for
24 hours at 11O 0 C. The catalyst was removed from the raw product on a chromatographic column filled with silica modified with 15% wt. Et 3 N and then the product was distilled. The 15 compound obtained was 1 -dimethylphenylsilylethynyl- 1 -(trimethylsiloxy)cyclohexane in the yield of 88% of the pure product and 93% of raw product.
Results of the GCMS analysis m/z (%): 315 (47) [M + - CH 3 ], 287 (44), 242 (12), 196 (15),
171 (100), 159 (14), 147 (42), 133 (38), 73 (22), 45 (22)
Spectroscopic characterization of the product: 20 1 U NMR (CDCl 3 ) δ (ppm): 0.18 (S 5 CH 3 SiO); 0.42 (s, CH 3 (C 6 H 5 )SiC=); 1.55-1.91 (m,
(C 6 Hi 0 )O); 7.37-7.66 (m, (C 6 H 5 )SiC≡)
13 C NMR (CDCl 3 ) δ (ppm): -0.85 (CH 3 (C 6 H 5 )SiC=); 2.08 (CH 3 SiO); 21.39-70.26
((C 6 Hi 0 )O); 87.49, 111.96 (OC); 127.81-137.13 ((C 6 H 5 )SiC≡)
29 Si NMR (CDCl 3 ) δ (ppm): -19.38; 16.00 25 Example XVI
As in example XV 3.8mL dimethylphenylvinylsilane were reacted with 1.4mL 1-ethynyl-l-
(trimethylsiloxy)cyclohexane in the presence of 0.07g iodotris(triphenylphosphine)rhodium
(I) at 100°C. The compound obtained was 1 -dimethylphenylsilylethynyl- 1-
(trimethylsiloxy)cyclohexane in the yield of 78% of the pure product and 100% of raw ^ 0 product. The product characteristic is as in example XVIII .
Example XVII
As in example XV 5.3mL dimethylphenylvinylsilane were reacted with 2.8mL 1-ethynyl-l-
(trimethylsiloxy)cyclohexane in the presence of 0.07 g carbonylchlorohydridobis(triisopropylphosphine)ruthenium (II) and 20.7mL of toluene , at ^ 5 100°C. The compound obtained was 1 -dimethylphenylsilylethynyl- 1-
(trimethylsiloxy)cyclohexane in the yield of 89% of the pure product and 93% of raw product. The product characteristic is as in example XV .
Example XVIII
As in example XV 5.26mL dimethylphenylvinylsilane were reacted with 1.35mL 3-methyl- 5 3-ethoxy-l-pentyne in the presence of 12.69mL of toluene and 0.07g carbonylchlorohydridobis(tricyclohexylphosphine)ruthenium (II) at 120 0 C. The compound obtained was 3-methyl-3-ethoxy-l-(dimethylphenylsilyl)-l-pentyne in the yield of 50% of the pure product and 63% of raw product.
Results of the GCMS analysis m/z (%): 245 (5) [M + - CH 3 ], 231 (100), 187 (10), 159 (18), 10 145 (12), 125 (37), 83 (12), 75 (19)
Spectroscopic characterization of the product:
1 H NMR (CDCl 3 ) δ (ppm):0.40 (s, CH 3 Si); 0.97-1.02 (tr, CH 3 CH 2 C); 1.18-1.22 (tr,
CH 3 CH 2 O); 1.41 (s, CH 3 C); 1.69-1.74 (qu, CH 3 CH 2 C); 3.59-3.63 (qu, CH 3 CH 2 O); 7.36-7.65
(m, C 5 H 5 Si) 15 13 C NMR (CDCl 3 ) δ (ppm): -0.52,1.15 (CH 3 Si); 8.78 (CH 3 CH 2 C); 15.90 (CH 3 CH 2 O); 25.84
(CH 3 C); 34.29 (CH 3 CH 2 C); 59.29 (CH 3 CH 2 O); 73.86 (CH 3 C); 86.78, 109.52 (OC); 127.71-
137.19 (C 5 H 5 Si)
29 SiNMR (CDCl 3 ) δ (ppm): -19.10
Example XIX z 90 υ As in example XV 7.OmL dimethylphenylvinylsilane were reacted with 2.3mL 3-methyl-3- trimethylsiloxy-1-pentyne in the presence of 9.96mL of toluene and 0.07g carbonylchlorohydridobis(tricyclohexylphosphine)ruthenium (II) at 120 0 C. The compound obtained was 3-methyl-3-trimethylsiloxy-l-(dimethylphenylsilyl)-l-pentyne in the yield of
90% of the pure product and 92% of raw product. 25 Results of the GCMS analysis m/z (%): 289 (14) [M + - CH 3 ], 275 (10O) 5 145 (8), 135 (18),
133 (33), 73 (17)
Spectroscopic characterization of the product:
1 H NMR (CDCl 3 ) δ (ppm):0.09 (s, CH 3 SiO); 0.18 (s, CH 3 PhSi); 0.98-1.01 (tr, CH 3 CH 2 );
1.46 (s, CH 3 C); 1.64-1.69 (m, CH 3 CH 2 ); 7.37-7.65 (m, C 5 H 5 Si) 30 13 C NMR (CDCl 3 ) δ (ppm): 1.16 (CH 3 Si); 2.04 (CH 3 SiO); 9.16 (CH 3 CH 2 ); 30.80 (CH 3 C);
37.9 (CH 3 CH 2 ); 70.24 (CH 3 C); 86.33, 111.78 (OC); 127.72-136.913 (C 5 H 5 Si)
29 Si NMR (CDCl 3 ) δ (ppm): -19.15; 16.18
Example XX
As in example XV 11.76mL dimethyl(trimethylsiloxy)vinylsilane were reacted with 2.3mL 5
3-methyl-3-trimethylsiloxy-l-pentyne in the presence of 5.24mL of toluene and 0.07g carbonylchlorohydridobis(tricyclohexylphosphine)ruthenium (II) (9.65xlO '5 mol) at 120°C.
The compound obtained was 3-methyl-3-trimethylsiloxy-l-(dimethyl(trimethylsiloxy)silyl )-
1-pentyne in the yield of 85% of the pure product and 90% of raw product. 5 Results of the GCMS analysis m/z (%): 301 (26) [M + - CH 3 ], 287 (100), 221 (14), 147 (32),
73 (22)
Spectroscopic characterization of the product:
1 H NMR (CDCl 3 ) δ (ppm):0.11 (CH 3 Si); 0.18-0.20 (s, CH 3 SiO); 0.95-0.99 (tr, CH 3 CH 2 );
1.41 (s, CH 3 C); 1.60-1.64 (m, CH 3 CH 2 ) 10 13 C NMR (CDCl 3 ) δ (ppm): 1.16 (CH 3 Si); 1.9-2.3 (CH 3 SiO); 9.09 (CH 3 CH 2 ); 30.64 (CH 3 C);
37.8 (CH 3 CH 2 ); 70.05 (CH 3 C); 88.31, 108.55 (C≡C)
29 Si NMR (CDCl 3 ) δ (ppm): -16.74; 12.49; 16.02
Example XXI
As in example XV 8.55mL dimethyl(trimethylsiloxy)vinylsilane were reacted with 1.76mL 15 l-ethynyl-l-(trimethylsiloxy)cyclohexane in the presence of 8.96mL of toluene and 0.07g carbonylchlorohydridobis(tricyclohexylphosphine)ruthenium (II) at 120° C. The compound obtained was l-dimethyl(trimethylsiloxy)silylethynyl-l-(trimethylsiloxy)c yclohexane in the yield of 90% of the pure product and 100% of raw product.
Results of the GCMS analysis m/z (%): 328 (100) [M + -CH 3 ], 314 (31), 300 (97), 222 (80), 0 108 (18), 195 (8), 171 (19), 147 (38), 74 (55), 45 (21)
Spectroscopic characterization of the product:
1 H NMR (CDCl 3 ) δ (ppm): 0.09-0.19 (s, CH 3 SiO, CH 3 Si ); 1.21-2.12 (m, (C 6 Hi 0 )O);
13 C NMR (CDCl 3 ) δ (ppm): 1.70 (CH 3 Si); 2.07 (CH 3 SiO); 23.07-70.03 ((C 6 Hi 0 )O); 89.20,
108.66 (C≡C) 5 Example XXII
As in example XV 14.34mL methylbis(trimethylsiloxy)vinylsilane were reacted with
1.76mL l-ethynyl-l-(trimethylsiloxy)cyclohexane in the presence of 2.9mL of toluene and
0.07g carbonylchlorohydridobis(tricyclohexylphosphine)ruthenium (II) at 12O 0 C. The compound obtained was l-methylbis(trimethylsiloxy)silylethynyl-l- 0 (trimethylsiloxy)cyclohexane in the yield of 91% of the pure product and 100% of raw product.
Results of the GCMS analysis m/z (%): 401 (73) [M + -CH 3 ], 388 (14), 374 (47), 222 (100),
172 (15), 74 (24)
Spectroscopic characterization of the product:
1 H NMR (CDCl 3 ) δ (ppm): 0.07-0.19 (s, CH 3 SiO, CH 3 Si ); 1.25-1.86 (m, (C 6 Hi 0 )O);
13 C NMR (CDCl 3 ) δ (ppm): 1.03 (CH 3 Si); 2.07 (CH 3 SiO); 23.02-77.42 ((C 6 Hi 0 )O); 88.26,
106.47 (C≡C)
Example XXIII As in example XV 5.65mL dimethylphenylvinylsilane were reacted with 1.89mL 1-ethynyl- l-(trimethylsiloxy)cyclohexane in the presence of 0.07g di-μ-iodobis(l,5- cyclooctadiene)dirhodium (I) at 130°C. The compound obtained was 1- dimethylρhenylsilylethynyl-l-(trimethylsiloxy)cyclohexane in the yield of 95% of the pure product and 100% of raw product. The product characteristic is as in example XV . Example XXIV
As in example XV 5.65mL dimethylphenylvinylsilane were reacted with 2.48mL 3-methyl-
3-trimethylsiloxy-l-pentyne in the presence of 0.07g di-μ-iodobis(l,5- cyclooctadiene)dirhodium (I) at 130 0 C. The compound obtained was 3-methyl-3- trimethylsiloxy-l-(dimethylphenylsilyl)-l-pentyne in the yield of 90% of the pure product and 95% of raw product. The product characteristic is as in example XIX.
Example XXV
As in example XV 3.76mL dimethylphenylvinylsilane were reacted with 1.65mL 3-methyl-
3-trimethylsiloxy-l-pentyne in the presence of 0.07g iodotris(triphenylphosphine)rhodiurn
(I) at 100°C. The compound obtained was 3-methyl-3-trimethylsiloxy-l- (dimethylphenylsilyl)- 1 -pentyne in the yield of 50% of the pure product and 65% of raw product. The product characteristic is as in example XIX.
Example XXVI
As in example XV 6.5mL triethoxyvinylsilane were reacted with 1.89mL 1-ethynyl-l-
(trimethylsiloxy)cyclohexane in the presence of 0.07g di-μ-iodobis(l,5- cyclooctadiene)dirhodium (I) at 13O 0 C. The compound obtained was 1-triethoxysilylethynyl- l-(trimethylsiloxy)cyclohexane in the yield of 95% of the pure product and 100% of raw product. Results of GCMS analysis: [M + ] (m/z) = 358
Spectroscopic characterization of the product:
1 H NMR (CDCl 3 ) δ (ppm): 0.2 (s,CH 3 Si0C≡); 1.22-1.27 (tr, CH 3 CH 2 OSi); 1.49-2.59 (m, (C 6 H 10 )-); 3.86-3.89 (qu, CH 3 CH 2 OSi)
13 C NMR (CDCl 3 ) δ (ppm): 2.14 (CH 3 SiOO); 18.13 (CH 3 CH 2 OSi); 58.96 (CH 3 CH 2 OSi);
23.14-70,09 ({C 6 H 10 }-≡); 81.24, 109.30 (C≡C)
Example XXVII
As in example XV 9.23mL methylbis(trimethylsiloxy)vinylsilane were reacted with 1.89mL
l-ethynyl-l-(trimethylsiloxy)cyclohexane in the presence of 0.07g di-μ-iodobis(l,5- cyclooctadiene)dirhodium (I) at 13O 0 C. The compound obtained was 1- methylbis(trimethylsiloxy)silylethynyl-l-(trimethylsiloxy)cy clohexane in the yield of 80% of the pure product and 100% of raw product. The product characteristic is as in example XXII
Example XXVIII
As in example XV 10.1 mL triethoxyvinylsilane were reacted with 1.7 mL triethylsilylethyne in the presence of 7.5mL of toluene and 0.07g carbonylchlorohydridobis(tricyclohexylphosphine)ruthenium (II) at 110°C. The compound obtained was l-triethoxysilyl-2-(triethylsilyl)ethyne in the yield of 65% of the pure product and 90% of raw product. Results of the GCMS analysis m/z = 302 Spectroscopic characterization of the product: 1 H NMR (CDCl 3 ) δ (ppm): 0.55-0.57 (qu, CH 3 CH 2 SiC=); 0.94-0.98 (tr, CH 3 CH 2 SiC=); 1.15-1.19 (tr, CH 3 CH 2 OSiC=); 3.73-3.78 (qu, CH 3 CH 2 OSiC=)
13 C NMR (CDCl 3 ) δ (ppm): 3.25 (CH 3 CH 2 SiC=); 7.53 (CH 3 CH 2 SiC=); 18.57
(CH 3 CH 2 OSiC=); 58.13 (CH 3 CH 2 OSiC=); 84,86, 106,15 (C≡C)
Example XXIX
As in example XV 20.2 mL triethoxyvinylsilane were reacted with 1.2 mL 3,3 -dimethyl- 1- butyne in the presence of 6.3mL of toluene and 0.07g carbonylchlorohydridobis(tricyclohexylphosphine)ruthenium (II) at 100°C. The compound obtained was 3, 3 -dimethyl- l-(triethoxysilyl)-l -butyne in the yield of 85% of the pure product and 93% of raw product. Results of the GCMS analysis m/z = 244 Spectroscopic characterization of the product:
1 H NMR (CDCl 3 ) δ (ppm): 3.86 (q, CH 3 CH 2 OSi); 1.26-1.24 (m, CH 3 CH 2 OSi, (CH 3 )C) 13 C NMR (CDCl 3 ) δ (ppm): 18.2 (CH 3 CH 2 OSi); 30.8 ((CH 3 )C, CH 3 CH 2 OSi); 59.1 (CH 3 CH 2 OSi); 73.8, 115,9 (C≡C) Example XXX As in example XV 8.1 mL triethoxyvinylsilane were reacted with 1.9 mL 1-ethynyl-l- (trimethylsiloxy)cyclohexane in the presence of 9.3mL of toluene and 0.07g carbonylchlorohydridobis(tricyclohexylphosphine)ruthenium (II) at 110 0 C. The compound obtained was l-triethoxysilylethynyl-l-(trimethylsiloxy)cyclohexane in the yield of 92% of the pure product and 100% of raw product. The product characteristic is as in example XXVI
Example XXXI
As in example XV 8.5 mL triethoxyvinylsilane were reacted with 1.6 mL 1-ethynyl-l- (trimethylsiloxy)cyclohexane in the presence of 0.07g diacetonitrilecarbonylhydridobis(tricyclohexylphosphine)ruth enium (II) tetrafhioroborate at 120° C. The compound obtained was l-triethoxysilylethynyl-l-(trimethylsiloxy)cyclohexane in the yield of 95% of the pure product and 100% of raw product. The product characteristic is as in example XXVI Example XXXII As in example XV 11.8mL triethoxyvinylsilane were reacted with 2.2mL 1-ethynyl-l- (trimethylsiloxy)cyclohexane in the presence of 0.07g diacetonitrilecarbonylhydridobis(triisopropylphosphine)ruthe nium (II) tetrafluoroborate at 120°C. The compound obtained was l-triethoxysilylethynyl-l-(trimethylsiloxy)cyclohexane in the yield of 92% of the pure product and 98% of raw product. The product characteristic is as in example XXVI
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