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AZERBAIJAN CHEMICAL JOURNAL № 2 2019
UDC 547.36.37.345
CATALYTIC HYDROSILYLATION OF 5-METHYLHEXENE-5-YN-2-OL-1 A.M.Garamanov, N.Kh.Gusiev, D.G.Abdullaev, O.B.Abdiev, M.Sh.Gurbanov, S.A.Rzaeva
Institute of Polymer Materials, NAS of Azerbaijan [email protected] Received 02.07.2018
The addition of trialkylsilanes to 5-methylhexene-5-yn-2-ol-1 in the presence of H2PtCl66H2O proceeds via a triple bond, but with an advantageous yield (80-90%) of the p-isomer (relatively oxygen atom). The reaction of organosilicon 1,4-diene alcohol with 1-chloro-2,3-epoxypropane, boric acid and acrylonitrile produced corresponding chlorohydrin, tris-borate and nitrile.
Keywords: 5-methylhexene-5-yn-2-ol-1, trialkylsilane, benzene, hydrosilylation, 1-chloro-2,3-epoxypro-pane, boric acid, acrylonitrile.
https://doi.org/10.32737/0005-2531-2019-2-62-66
The shortage of oil and the possibility of producing acetylene not only from natural gas and coal, but in the future, even from carbonate minerals, makes it possible to consider the further development of new methods for the production of organic compounds on the basis of acetylene an important and urgent task. In light of the above, unsaturated organosilicon compounds with various functional groups obtained on basis of acetylenic compounds acquire undeniable value. The extremely high reactivity of functional groups with respect to various reagents will make it possible to easily carry out number of transformations leading to a new class of organosilicon compounds with useful properties for practice [1].
With the aim of synthesizing organosilicon 1,4-diene alcohols and studying their properties, we investigated the catalytic hydrosilylation of 5-methylhexene-5-yn-2-ol-1 (Figure 1) in benzene in the presence 0.1 N solution of H2PtCl6 6H2O in isopropyl alcohol
at a molar ratio of 1:1 reacting components. It has been established that the reaction proceeds via a triple bond.
Fig. 1. Spectrum NMR 1H of 5-methylhexene-5-yn-2-ol-1.
In this case, it could be expected the formation of two isomeric products (relatively oxygen atom) [2, 3] to the scheme:
H
CH2=C(CH3)-CH2-C =C-CH2-OH + RR'2SiH — CH2=C(CH3)-CH2-C=C-CH2-OH
RR'2Si
IP,y"IVP,y
R=CH3, R'=C2H5 (Ip y ), «-C3H7 (IIp y ), -(CH2)4- (IIIp,); R=R'=C2H (IVp,y)
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It has been established according to TLC and GLC data that the alcohols prepared organosilicon alcohols consist of two substances [ratio of isomers - P:y=(80-92):(8-20)]. With the aid of a chromatographic column (length 800 mm, diameter 21 mm, 1 gram of substance 200 grams of adsorbent, adsorbent -Al2O3, eluent - benzene:ether=5:1), the main product of the reaction - P-isomer has been isolated [4, 5]. In the IR spectrum (Figure 2), chromatographically individual according to TLC, compound (IIp) (b.p. - 114-1160C/0.135 kPa, n™ - 1.4740, df - 0.8833), the availability of a 1,4-diene bond system has been detected in the field of 1625 and 1650 cm-1,
characteristic for bonds of the Si-C=CH and CH2=C groups.
There are no bonds in the spectrum in the 1940-1970 and 2190-2260 cm"1 regions, which are characteristic for the C=C=C and C=C bonds. In the NMR 1H spectrum (Figure 3), chromatographically of individual compound (Ip) (b.p. - 960C/0.135 kPa, n™ - 1.4766, df -
0.8843), the proton signal of the Si-C=CH group was detected as a broadened triplet at 5.75 ppm. Consequently, the trialkylsilyl radical is attached to the P-carbon atom (relatively oxygen atom). The spectrum also contains signals from other fragments.
3400 3000 2600 2200 1900 1500 1100
Fig. 2. Spectrum IR of 5-methyl-2-methyldipropylsilylhexadiene-2,5-ol-1 (IIp).
(a) (c) (d) (g) (h) CH2=y-CH2-CH=y-CH2-OIl
H3c CH3Si(C2H5)2
(b)
(d)
......
Xw KJL-•■..A.,i..I ' 6 5
M
_......A.
(e) 0
(0
4
3 2
0
^ 8, ppm
Fig. 3. Spectrum NMR 1H of 5-methyl-2-methyldiethylsilylhexadiene-2,5-ol-1 (Ip).
The reaction of the compound Ip with opening of the oxirane ring to form a silicon 1-chloro-2,3-epoxypropane in the presence of containing chlorohydrin (V). boron trifluoride etherate proceeds with the
(Ip) + ClCH2CH-CH2-► CH2=C(CH3)CH2CH=C[CH3(C2H5)2Si]CH2OCH2CH(OH)CH2Cl .
V
It turned out that the silicon-containing alcohol (Ip) reacts with boric acid to form tris-borate (VI):
(Ip) + H3BO3
B + 3H2O .
3
CH2=C(CH3)CH2CH=C[CH3(C2H5)2Si]CH2O VI
The reaction of compound (Ip) with acrylonitrile leads to the formation of nitrile (VII):
(Ip) + CH2=CHCN"
CH2=C(CH3)CH2CH=C[CH3(C2H5)2Si]CH2OCH2CH2CN .
VII
The antibacterial properties of compounds V and VI have been studied in a wide range of microorganisms using the emulsion-contact method [6]. As test cultures used Gram-positive (staphylococcus, intestinal shelf), Gram-negative (blue-bacillus), bacteria of the genus Serratia and yeast-like fungi of the genus Candida. The greatest effect is found in tris-borate VI, in which complete absence of growth is observed after 30, 40, 60 minutes at a dilution of 1:4 and after 20 minutes at a dilution of 1:3, and when using conventional antimicrobial agents in the same dilution there is a continuous growth of microorganisms.
Experimental part
IR spectra are recorded on a spectrometer "UR-20" (prisms NaCl and LiF) [7]. NMR 1H was obtained on a spectrometer "Tesla BS-487" (80 MHz, internal standard - hexamethyl-disiloxane, solvent - CCl4) and on a spectrometer "Bruker WM-250" (250 MHz, internal standard -tetramethylsilane, solvent - CDCl3) [8]. The purity of the synthesized compounds was controlled by gas-liquid chromatography on a "HXM-8 Mfl,-5" and by thin-layer chromatography (plates Silufol UV-254 in various solvent systems, developer - iodine vapor).
5-Methylhexene-5-yn-2-ol-1, prepared by the method [9], has the following constants: b.p. -
85-860C/1.6 kPa, < - 1.4762, df - 0.9290.
The physical constants of trialkylsilanes correspond to the literature data [10, 11].
Reaction of methyldiethysilane with 5-methylhexene-5-yn-2-ol-1. 10.2 g (0.1 mol) of methyldietylsilane was added to 11 g (0.1 mol) of 5-methylhexene-5-yn-2-ol-1 in the presence of 0.2 ml 0.1 N solution of ^PtCU^O in absolute isopropyl alcohol while boiling in benzene. Then they boiled for another 18 hours. After distilling off the solvent by distillation in vacuum, 11.5 g of mixture isomers (Ip,Y) was isolated. B.p. - 95-960C/0.136 KPa, n2° -
I.4772, df - 0.8850. MRd - 67.65, MRD/calc. -67.69. Yield - 54.3%. Found, %: C 67.91, H
II.44, Si 13.18. C12H24OSL Calculated, %: C 67.86, H 11.39, Si 13.22.
The mixtures of isomers were prepared in a similar way.
(np,Y). B.p. - 115-1160C/0.136 KPa, n™ -
I.4746, d2°- 0.8842. MRD - 76.56, MRD/calc. -76.29. Yield - 48%. Found, %: C 69.99, H
II.82, Si 11.60. C14H28OSL Calculated, %: C 69.93, H 11.74, Si 11.68.
(mp,Y). B.p. - 97-980C/0.136 KPa, n2° -
1.5032, d2° - 0.9522. MRD - 65.34, MRD/calc. -
65.80. Yield - 58.1%. Found, %: C 68.60, H
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10.63, Si 13.27. C12H22OSi. Calculated, %: C 68.51, H 10.54, Si 13.35.
(IVp,y). B.p. - 1070C/0.136 KPa, nf -
I.4805, df - 0.8898. MRd - 72.37, MR^/calc. -72.20. Yield - 52.1%. Found, %: C 68.88, H
II.63, Si 12.47. C13H26OSL Calculated, %: C 68.96, H 11.57, Si 12.40.
Interaction of compound (Ip) with 1-chloro-2,3-epoxypropane. To 10.5 g (0.05 mol) of compound Ip, containing 0.2 ml of boron trifluoride etherate, 2.3 g (0.025 mol) of 1-chloro-2,3-epoxy propane were added with stirring and cooling (0-5)0C. The reaction mixture was stirred at 250C for 5 hours. By distillation in vacuum, 5 g of compound V were isolated. B.p. - 145-1460C/0.136 KPa, nf -
1.4850, df - 0.9940. MRd - 87.92, MR^/calc. -88.19. Yield - 65.6%. Found, %: C 59.13, H 10.66, Cl 11.57, Si 9.17. C15H29O2ClSi. Calculated, %: C 59.08, H 9.59, Cl 11.63, Si 9.21.
Reaction of compound (Ip) with boric acid. To 10.6 g (0.05 mol) of compound Ip in 30 ml of benzene was boiled with 0.9 g (0.015 mol) of boric acid for 8 hours: the evolved water was continuously removed as an azeotrope. After distilling off the benzene, 7.3 g compound VI was isolated by distillation under vacuum. B.p. - 230-2310C/0.136 KPa, nf -
I.4900, df - 0.9945. Yield - 75.8%. Found,
%: C 67.40, H 10.28, B 10.88, Si 13.07. C36H66 BOsSis. Calculated, %: C 67.33, H 10.36, B
II.00, Si 13.12.
Condensation of compound (Ip) with acrylonitrile. By mixing to 10.6 g (0.05 mol) of compound Ip containing 1 ml of a 40% aqueous solution of potassium hydroxide, 2.7 g (0.05 mol) of acrylonitrile was added at 250C. The next day, it was stirred for an additional 3 hours at 200C, and then reaction mass was washed by water, it was extracted with ether and dried with magnesium sulfate. After distilling off the solvent, 11.1 g of compound VII isolated by distillation under vacuum. B.p. - 136-1380C/0. 136 KPa, nf - 1.4760, df - 0.9215. MRD -81.24, MRD/calc. - 79.18. Yield - 90%. Found,
%: C 67.93, H 10.18, N 5.34, Si 10.50. C15H27ONSL Calculated, %: C 67.87, H 10.25, N 5.28, Si 10.58.
Conclusion
1. It has been established that triorganosi-lanes, regardless of the size of the alkyl radicals bound to the silicon atom, are attached to 5-methylhexene-5-yn-2-ol-l exclusively via the C=C bond the formation of mixture of isomers of the p- and y-products, with the predominance of p-isomer.
2. Silicon-containing chlorohydrin (V) and tris-borate (VI) have been shown to have strong antimicrobial activity.
References
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2. Garamanov A.M., Gulieva A.F., Gurbanov M.Sh., Allakhverdieva S.N. Synthesis and properties of 2-substituted 1,4-enyne chlorohydrins. Azerb. Chem. Journ. 2017. No 3. P. 43-47.
3. Garamanov A.M., Gusiev N.Kh., Abdullaev D.G., Allakhverdieva S.N., Balaeva Kh.M., Rzaeva S.A. Gidrosililirovanie metalliletinilkarbinola i ego funktcionalnozameshchennykh proizvodnykh. "Funrsional monomerlar va xususi xassali polimer materiallar: problemlar, perspektivlar va praktiki baxi§lar" movzusunda beynalxalq konfrans. 15-16 noyabr 2017-ci il. Sumqayit - 2017. S. 68-69.
4. Cherkezishvili K.I., Gverdtciteli I.M., Taktakish-vili M.O. Gidrosililirovanie tretichnykh p-spirtov trietilsilanom. Zhurn. obshch. himii. 1975. T. 45. № 8. S. 1802-1807.
5. Cherkezishvili K.I., Kublashvili R.I., Gverdtciteli I.M. Gidrosililirovanie atcetilenovykh a-glikolei v prisutstvii katalizatora SPEIERA. Zhurn. obshch. himii. 1971. T. 41. № 9. S. 2051-2055.
6. A.s. 1147007 SSSR. (Ne podlezhit opublikovaniiu).
7. Bellami L. Novye dannye po IK-spektram slozh-nykh molekul. M.: Mir, 1971. 186 s.
8. Gordon A., Ford R. Sputneyk himika. M.: Mir, 1976. 541 s.
9. Malinovskii M.S., KHmel M.P., Baranov N.N., Krivosheeva N.G. Sintez i issledovanie atcetilenovykh spirtookisei. Ukr. him. zhurn. 1975. T. 41. № 10. S.1064-1067.
10. Andrianov K.A. Metody elementoorganicheskoi himii. Kremnii. M.: Nauka, 1968. 699 s.
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5-METÍLHEKSEN-5-ÍN-2-OL-1-ÍN KATALÍTÍK HÍDROSÍLÍLLa§MaSÍ
0.M.Qaramanov, N.X.Hüsiyev, D.Q.Abdullayev, O.B.Abdiyev, M.§.Qurbanov, S.O.Rzayeva
Trialkilsilanlann 5-metilheksen-5-in-2-ol-1-a birla§ma reaksiyalan H2PtCl66H2O katalizatorunun i§tiraki ib ügqat rabita üzra, lakin p-izomerin (oksigen atomuna nazaran) üstün giximi (80-92%) ila ba§ verir. Silisiumüzvi 1,4-dien spirtini 1-xlor-2,3-epoksipropan, borat tur§usu va akriilonitrilla qar§iliqli tasirindan uygun xlorhidrin, tris-borat va nitril alinmüjdir.
Agar sozlar: 5-metilheksen-5-in-2-ol-1, trialkilsilan, benzol, hidrosüiÜ3§m3, 1-xlor-2,3-epoksipropan, borat tur§usu, akrilonitril.
КАТАЛИТИЧЕСКОЕ ГИДРОСИЛИЛИРОВАНИЕ 5-МЕТИЛГЕКСЕН-5-ИН-2-ОЛ-1-А
А.М.Гараманов, Н.Х.Гусиев, Д.Г.Абдуллаев, О.Б.Абдиев, М.Ш.Гурбанов, С.А.Рзаева
Реакция присоединения триалкилсиланов к 5-метилгексен-5-ин-2-ол-1-у в присутствии катализатора H2PtCl66H2O протекает по тройной связи, но с преимущественным выходом (80-92%) p-изомера (относительно атома кислорода). Взаимодействием кремнийорганического 1,4-диенового спирта с 1-хлор-2,3-эпоксипропаном, борной кислотой и акрилонитрилом получены соответствующие хлоргидрин, трис-борат и нитрил.
Ключевые слова: 5-метилгексен-5-ин-2-ол-1, триалкилсилан, бензол, гидросилилирование, 1-хлор-2,3-эпокси-пропан, борная кислота, акрилонитрил.
АЗЕРБАЙДЖАНСКИЙ ХИМИЧЕСКИЙ ЖУРНАЛ № 2 2019
