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41
https://doi.org/10.29013/ESR-19-9.10-72-76
Shirinova Shams Radjab, posrdoktoral student of Petrochemistry and chemical engineering department, Sumgait State University, Republic of Azerbaijan
Mustafayev Musa Musa, candidate of chemical sciences, associate professor Head of department Chemistry and methods of its teaching, Sumgait State University Republic of Azerbaijan Aghayev Akbar Ali, Ph.D., in Chemistry, professor Head of Petrochemistry and chemical engineering department, Sumgait State University, Republic of Azerbaijan E-mail: [email protected]
INVESTIGATION OF ADDITION REACTION OF DIALKYL(ARYL) SILANES TO P-CYANOETHYL ETHER OF DIMETHYLACETYLENE CARBINOL IN THE PRESENCE OF PLATINUM HYDROCHLORIC ACID
Abstract. The addition reaction of dialkyl(aryl)silanes to ^-cyanoethyl ether of dimethylacety-lene carbinol in the presence of platinum hydrochloric acid has been investigated. It has been established that the reaction proceeds easily and exothermally leading to the corresponding unsaturated organic-silicon mono- and dinitriles. The structure and composition of the prepared nitriles has been established with use of the modern physical-chemical methods of analysis and methods of counter synthesis.
Keywords: addition, ^-cyanoethyl ether of dimethylacetylene carbinol, platinum hydrochloric acid, exothermally, mixtures of isomers, unsaturated, organic-silicon, mono- and dinitriles.
It has been known that a direction of the catalytic hydrosilylation reaction ofunsaturated hydrocarbons and their functional derivatives depends both on composition and structure of substrate and reagent and on nature of using catalyst and catalytic systems. For ex., the nitrogen-containing catalysts and catalytic systems containing metal chlorides favor formation of only ^-adduct, whereas the catalysts on the basis of nickel and rhodium lead to a-adduct (1-5).
With the aim of synthesis and study of properties of the organic-silicon compounds containing high-
polar and reactive nitrile group in molecule, we have in detail studied the addition reaction of dialkyl(aryl) silanes to ^-cyanoethyl ether of dimethylacetylene carbinol in the presence of catalyst of platinum hydrochloric acid.
It has been established in this case that the studied reaction in contrast to 2-cyanobicyclo[2.2.l] hept-5-ene and ^-cyanoethyl ether of allyl alcohol proceeds easily and exothermally leading to the corresponding unsaturated organic-silicon nitriles:
+
HoSiRR1
H2PtCl6
-Si"
-si=X
O^^-^^N (1)
R
R=CH3, R1=C6H5 (I), C3H7 (II), hso-c3h7 (III), C4H9 (IV), CH2C6H5 (V), CH2CH2C6H5(VI), CH2CH2CH2C6H5(VII); R=R1=C2H5 (VIII). (1) The structure and composition of unsaturated organic-silicon mononitriles prepared on reaction (l) has been established with use of the modern physical-chemical methods of analysis of GLC, IR- and NMR-spectroscopy and in some cases by a method of counter synthesis. So, for ex., in the IR-spectrum of mononitrile VIII, a purity of which on data of GLC was 99.6% in the field of C-H valence (2800 -3000cm 1, prism LiF) and deformation (1300-1500 cm-1, prism NaCl) there are a peak of average intensity 2250 cm-1, indicating to availability of N=C-group and a peak 2105 cm-1, characterizing a bond Si-H (6). Maximum of absorption at 1610 cm-1 corresponds to the valence vibrations of -CH=CH- group of fragment Si-CH=CH-. A displacement of this maximum in 1610 cm-1 to the side of low frequences in comparison with two-substituted ethylene of type X-C=C-Y (1680-1640 cm-1), apparently, is the result procrastination of n-electrons of -CH=CH- bond to vacant 3d-orbital of silicon atom in this fragment. Such interaction is referred to dn-pn type and can be shown by means of resonance structures presented below (7):
peared in the field of strong areas of PMR-spectrum and have a center at S = 0.8 ppm. The adjusted triplets of two terminal CH3 groups of the same substituents are appeared at S = 1.10 ppm. Two triplets with S = 2.68 ppm and S = 3.70 ppm are the signals of -CH2CN and -O-CH2-C-CN groups with viccinal mutual SSIC=7.0 Hz. The adjusted overlapping proton signals of -O-CH2-C=C groups ofboth isomer (A) and (B) are appeared as the unresolved multiplet at S = 4.11 ppm. The broadened proton signal Si-H has S = 4.75 ppm. In the field of weak areas of this spectrum the broadened singlet of -C=CH2 group of isomer (A) with S = 5.62 ppm and multiplet of -CH=CH-group in isomer (B) with S = 6.10 ppm are appeared.
All this unambiguously indicates that the investigated compound VIII consists of a mixture of two structural isomers (A) and (B): R
N
'Si I
R
(A)-gem isomer
~Si' I
R
N
(B)-trans isomer
R = C2H5.
X= -CH=CH-.
However, a complexity of these spectral data does not allow to judge unambiguously the order of addition of dialkyl(aryl)silanes to the investigated unsaturated nitrile. Therefore, we have also studied the PMR spectra of the reaction products (1).
Badly resolved signals of two Si-CH2- groups of ethyl substituents of organic-silicon nitrile VIII are ap-
Judging on integral intensity of protons in double bonds and chromatographic (GLC) analysis data, a ratio of isomers is A: B =1: 3, respectively.
The formation of a mixture of these isomers is confirmed by the fact that the isomer (B) prepared by counter synthesis by reduction of 1-diethyl-chlorosilyl-3-methyl-3-(21-cyanoethoxy)-1-butyne knowingly structure with LiAlH4 and on reaction (1) had the same yield time at their chromatography:
R
Si ^
O^-^N
+ LiAlH
4
R
(2)
R1
R = R1 = C2H5 (VIII).
Thus, the hydrosilylation reaction of ^-cyanoethyl ether of dimethylacetylene carbinol with dialkyl(aryl)silanes in the conditions accepted by us lead to the mixture of isomeric unsaturated organic-silicon nitriles (A) and (B) with predominance of the latter ones.
N.
It should be noted that in all cases at reaction (1) there are also formed the unsaturated organic-silicon dinitriles - products on both Si-H bonds, the isolation of which didn't carry out due to high boiling point. However, in use of diethylsilane as a hydrosi-lylating agent, we were able to isolate and characterize the corresponding organic-silicon dinitrile:
N
R = R1 = C2H5 (IX).
Experimental
The purity of the synthesized compounds was controlled by gas-liquid chromatography (GLC) on apparatus "Khrom-3".
The IR-spectra ofthin layer of the substances were taken on apparatus "Specord-75" or on two-beam infrared spectrophotometer UR-20 in the field of 600-2400 cm-1 (prism NaCl) and 2400-3600 cm-1 (prism LiF).
The initial ^-cyanoethyl ether of dimethylacetylene carbinol has been prepared by cyanoethylation of dimethylacetylene carbinol with acrylonitrile in the presence of concentrated KOH solution on known proceduree (8). B.p. 125-126 °C (25 mm merc.c.), nD20 1.4460, d420 0.9932. Yield - 62.5%.
Dialkyl(aryl)silanes have been prepared by interaction of the corresponding alkyl(aryl)dichlorosi-lanes with LiAlH in a medium of absolute ether.
4
Synthesis of 1-dialkyl(aryl)silyl-3-meth-yl-3-(21-cyanoethoxy)-1-butenes
1-dialkyl(aryl)silyl-3-methyl-3-(21-cyanoethoxy)-1-butenes have been synthesized by addition of the corresponding dialkyl(aryl)silanes to ^-cyanoethyl ether of dimethylacetylene carbinol in the presence of 0.1 ml of 0.1 n. solution of platinum
hydrochloric acid in isopropyl alcohol in a medium of anhydrous benzene.
1-Methylphenylsilyl-3-methyl-3-(21-cyasnoe-thoxy)butene-1 (I). The reaction was carried out in a round-bottom flask equipped with reflux condenser. The mixture consisting of 24.4 g(0.2 mol) of methyl phenyl silane, 13.7 g (0.1 mol) of ^-cyanoethyl ether of dimethylacetylene carbinol, 50 ml of dry benzene and 0.1 ml of the catalyst was boiled for 48 h. After distillation of the solvent and easily-boiling components, 16.1 g of unsaturated organic-silicon nitrile I, which after repeated distillation had: B.p. 158-159 °C (0.5 mm merc.c.), nD20 1.4966, d420 0.9625. Yield: 62.2%. Found: C 69.27, 69.56; H 8.27, 8.35; Si 10.68, 10.75%; MRD78.81. C15H21SiNO. Calculated: C 69.45; H 8.16; Si 10.82%; JMRD79.32 was isolated from residue by vacuum distillation. The purity of the prepared product on data of chromatographic analysis was 99.8%. The residue in a quantity 5.4 g was viscous undistillable liquid.
IR-spectrum I (v, cm-1): 725 (4.1), 840 (4.3), 885 (4.1), 940 (0.9), 1000 (3.1), 1078 (2.6), 1120 (3.9), 1225 (2.6), 1255 (4.8), 1330 (0.9), 1360 (1.2), 1425 (2.7), 1485 (1.9), 1620 (2.6), 2130 (3.9), 2258 (2.5), 2880 (3.6), 2970 (3.4), 3060 (2.1). Rf = 0.67.
The following unsaturated organic-silicon nitrile have been prepared similarly:
1-Methylpropyl silyl-3-methyl-3-(21-cyanoe-thoxy)butene-1 (II). B.p. 120-121 °C (0.5 mm merc.c.), nD20 1.4545, d420 0.8969. Yield: 25%. Found: C63.86, 64.07; H 10.36, 10.44; Si 12.21, 12.35%; MRd68.11. C12H23SiNO. Calculated: C63.94; H 10.28; Si 12.416%; MRD68.31.
1 -Methylisopropyl silyl-3 -methyl-3 -(21-cy-anoethoxy)butene-1 (III). B.p. 122-123 °C (0.5 mm merc.c.), nD20 1.4551, d420 0.8952. Yield: 18%. Found: C63.71, 63.89; H 10.17, 10.38; Si 12.24, 12.51%; MRd68.33. C12H23SiNO. Calculated: C63.94; H 10.28; Si 12.46%; MRD68.31.
1-1 -Methylbutyl silyl-3-me thyl-3-(21-cya-noethoxy)butene-1 (IV). B.p.134-135 °C (0.5 mm merc.c.), nD20 1.4590, d420 0.897. Yield: 22%. Found: C65.09, 65.18; H 10.68, 10.75; Si 11.55, 11.67%; MRd72.98. C13H25SiNO. Calculated: C65.21; H 10.53; Si 11.72)%%; MR^.31.
1-1-Methylbenzyl silyl-3-methyl-3-(2*-cya-noethoxy)butene-1 (V). B.p. 162-163 °C (0.5 mm merc.c.), nD20 1.4932, d420 0.9511. Yield: 51%. Found: C70.14, 70.37; H 8.333, 8.52; Si 10.22, 10.31%; MRd83.58. C16H23SiNO. Calculated: C70.28; H 8.48; Si 10.27%; MR^.13.
1-Methyl(21-phenylethyl)silyl-3-meth-yl-3-(2'-cyanoethoxy)butene-1 (VI). B.p. 170171 °C (0.5 mm merc.c.), nD20 1.4921, d420 0.9466. Yield: 50%. Found: C 69.87, 69.96; H 8.82, 8.95; Si 9.59, 9.71%; MRd88.10. C17H25SiNO. Calculated: C 71.03; H 8.76; Di 9.77%; mrD88.37.
1-Methyl(31-phenylpropyl)silyl-3-meth-yl-3-(2'-cyanoethoxy)butene-1 (VII). B.p.178-179 °C (0.5 mm merc.c.), nD20 1.4908, d420 0.9421. Yield: 49%. Found: C 71.54,71.67; H 8.96, 9.12; Si 9.13, 9.22%; MRd92.65. C18H27SiNO. Calculated: C 71.71; H 9.03; Di 9.32%; mrD93.00.
1-Diethyl silyl-3-methyl- 3-(21- cyanoethoxy) butene-1 (VIII). B.p.121-122 °C (0.5 mm merc.c.), nD20 1.4584, d420 0.8999. Yield: 22%. Found: C 64.08, 64.13; H 10.32, 10.37; Si 12.33, 12.41%; MRd68.40.
C12H23SiNO. Calculated: C 63.94; H 10.28; Si 12.4-6%; MRd68.52.
Counter synthesis of 1-diethyl silyl-3-meth-yl-3-(21-cyanoethoxy-1 (VIII)
The reaction was carried out in a flask equipped with a reflux condenser, dropping funnel and a mechanical stirrer. The calculated quantity of lithium tetrahydroaluminate in the ether was slowly poured to the mixture of 13.0 g (0.05 mol) of freshly distilled 1-diethylchlorosilyl-3-methyl-3-(21-cyanoethoxy) butene-1 prepared by a method (9) and 80 ml of absolute ether with intensive stirring and cooling at a temperature of+5 °C. After pouring the solution of lithium tetrahydroaluminate, the flask contents was stirred for another 8 hours at room temperature and left for the night.
The next day, the reaction mixture was treated with acidified water, the organic layer was separated from water layer and the last one three times was extracted with ether. The ether extracts and organic layer were combined together and dried over calcined MgSO4 for one day.
After distillation of the solvent and easily-boiling components from residue by vacuum distillation it has been isolated 9.1 g of crude VIII, which after redistillation had: B.p. 120-121 °C (0.5 mm merc.c.), nD20 1.4591, d420 0.8995. Found: C63.78, 63.97; H 10.36, 10.43; Si 12.27, 12.39%. C12H23SiNO. Calculated: C63.94; H 10.28; Si 12.46%.
The IR-spectrum of VIII prepared by counter synthesis (v, cm-1): 705 (3.6), 820 (3.7), 1025 (2.4), 1120 (3.8), 1230 (2.4), 1360 (1.8), 1420 (2.8), 1465 (1.9), 1625 (2.8), 2115 (4.2), 2260 (2.7), 2885 (3.5), 2920 (3.2), 2980 (2.2), 3060 (2.1).
2,8-Dimethyl-2,8-di(21 - cyanoethoxy)-5,5-diethyl-5-silanonadiene-3,6 (IX). 27.4 g (0.2 mol) of freshly distilled (3-cyanoethyl ether of dimethyl-acetylene carbinol and 0.2 ml of a solution of platinum hydrochloric acid was placed in a three-necked flask, equipped with reflux condenser, dropping funnel and mechanical mixer and then with stirring and heating 8.9 g (0.1 mol) of diethylsilane was
gradually added. The mixture heating continued for 72 h. After distillation of unreacted components and mononitrile VIII, from the residue was isolated 19.2 g of 2,8-dimethyl-2,8-di(21-cyanoethoxy)-5,5-diethyl-5-silanonadiene-3,6 (IX) by vacuum distillation. B.p. 196-197 °C (0.5 mm merc.c.), nD20 1.4718, d420 0.9546. Yield: 52.9%. Found: C 66.11, 66.23; H 9.53, 9.62; Si 7.59, 7.66%; MRD106.26.
C20H34SiN2O2. Calculated: C 66.25; H 9.45; Si 7.75%>; mrd106.48.
IR-spectrum 2,8-dimethyl-2,8-di(21-
cyanoethoxy)-5,5-diethyl-5-silanonadiene-3,6 (IX) (v, cm-1): 740 (3.6), 790 (0.9), 840 (4.1),1010 (2.7), 1110 (2.8), 1245 (4.2), 1330 (1.2), 1360 (2.3), 1415 (2.8), 1470 (1.9), 1620 (2.8), 2260 (2.8), 2885 (3.6), 2915 (3.4), 2960 (2.1).
References:
1. Pukhnarevich V. B., Lukeevich E. Ya., Kopylova L. I., Voronkov M. G. Perspectives of hydrosilylation. Riga. Zinatne, 1992.- 383 p.
2. Kaverin V. V., Salimgareeva I. M., Yuryev V. P. Use of Ni-containing catalytic system in the hydrosilylation reactions of functional olefins // ZhOKh, 1978.- V. 48.- No. 1.- P. 122-125.
3. Tarverdiyev Sh. A. Hydrosilylation ofunsaturated nitriles //Azerbaijan Chemical Journal, Baku, 1998.-No. 1.- P. 52-56.
4. Tarverdiyev Sh. A., Bayramov G. K., Mustafayev M. M. Epoxy- and cyan-containing organosilicon monomers // Materials of Scientific Conference dedicated to the centenary of the corr.member ofAzerbaijan National Academy of Sciences G. Kh. Efendiyev. - Baku, 2007.- P. 364-365.
5. Kirilin A. D., Belova L. O., Lega A. V., Pobedimsky D. G. The development of improved thechnology for synthesis of silicon monomers with functional groups - starting materials for preparation of effective gas separation membranes // Workshop-Symposium "Membranes for Medicine and Environmental Chemistry".- M., 2003.- P. 25-27.
6. Kazitsyna L. A., Kupletskaya N. B. Application of UV-, IR- and NMR-spectroscopy in organic chemistry.- M.: Vysshaya shkola, 1971.- 264 p.
7. Roberts J., Kaserio M. Bases of organic chemistry.- P. 1.- M.: Mir, 1968.- 592 p.
8. Terentyev A. P., Kost A. N. Reactions and methods of investigations of organic compounds.- M.: Khi-miya, 1952.- 605 p.
9. Sadikh-zade S. I., Sultanov R. A., Khalilova E. M. // Azerbaijan Chemical Journal,- Baku, 1964.-No. 1.- P. 57-61.
