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THE HYDROSILYLATION OF 3-(HEXEN-5-IN-2-ILOXY) PROPIONITRILE A.M.Garamanov, M.Sh.Gurbanov, D.G.Abdullaev, N.Kh.Husiev, S.N.Allakhverdieva
Institute of Polymer Materials, NAS of Azerbaijan ipoma@science. az Received 03.07.2017
The addition reaction of triorganosilanes to 3-(hexen-5-in-2-iloxy) propionitryle in the presence of acetylacetonate dicarbonyl rhodium catalyst proceeds on triple bonds in two directions obtaining of P(52-65%)- and y(35-48%)-isomers mixture (relatively oxygen atom) and with advantage of p-yield.
Keywords: 3-(hexen-5-in-2-iloxy) propionitrile, triorganosilanes, acetylacetonate dicarbonyl rhodium, hydrosilylation, fS-isomer, y-isomer.
Catalytic hydrosilylation reaction in the presence of hexene-5-in-2-ol-1 [1] and its acetate [2] acetylacetonate dicarbonyl rhodium [(acac)Rh(CO)2] has been studied. Hydrosilylation reactions of 3-(hexen-5-in-2-iloxy)pro-pionitrile (HPN) (Figure 1) in the presence of shown catalyst has been carried out and their
condensation reactions with polychlorinecyclo-pentadienes have been studied.
As expected HPN addition reactions of trioorganosilanes proceed on triple bonds and reaction occurs with the formation of P- and y-isomer mixture in two directions [3]:
CH2=CHCH2C = CCH2OCH2CH2CN
+ RRSiH
»► CH2=CHCH2CH=CCH2OCH2CH2CN RRJSi
(I, III, V, VII, IX, XI)
CH2=CHCH2C=CHCH2OCH2CH2CN RR'Si
2 (II, IV, VI, VIII, X, XII) R=CH3, R'=C2H5 (I, II), n-C3H7 (III, IV), _(CH2)4_ (V, VI), C6H5 (VII, VIII); R=R'=C2H5 (IX, X), C2H5O (XI, XII) .
In (VII, VIII) IR spectrum of mixture (Figure 2) Si-C=CH (1610), C=N (2260) and CH2=CH (1630, 3025 and 3080 cm-1) fragments absorption lines exist. With TLC and NMR 1H spectroscopy methods it was defined that the synthesized nitriles consist of mixture of two substances (I, II) (Figure 3) protons of CH2O group were found in 4.12 (s) and 4.06 (d) ppm (I:II=60:40) CH2=CH fragment of nitrile mixture in I, II NMR 1H spectrum in 4.75-6.00 ppm area that consists of seven group absorption lines belong to protons (compared with =CH (b) group the last CH2= (a) was found in stronger area), Si-C=CH (d) group proton correspond 5.40-6.00 area. Methylene protons of CH2-C= (c) is situated in 2.70-3.00 ppm range. OCH2 (f group protons were found out singlet in 4.2 ppm and doublet in 4.06 ppm triplets in 2.52 and 3.56 ppm belongs to (.1=6 Hz) CH2CH2C=N group protons. (C2H5)2Si
group protons have multyplet signals in 0.30-1.05 ppm area (CH3Si group protons were found out as singlet in CDCl3 0.024 and 0.044 ppm [3]).
Corresponding to [4, 5] methods with the preparative chromatographic column (length 800 mm, diameter 21 mm, 1 g subs for 200 g adsorbent, adsorbent - Al2O3, eluent - benzene:ether -5:1, additive - iodine) XI and XII isomers were separated and their composition and structure confirmed by modern research methods. For example, in XI NMR 1H spectrum of 3-(2-tri-etoxysilylhexadiene-2,5-iloxy) propionitrile all signals of proton fragments were found out (Figure 4). In the spectrum of 3-(3-triethoxysilyl-hexadiene-2,5-iloxy) propionitrile protons of CH2O group are observed in 4.10 doublet form (J=6 Hz). All chemical replacements are characteristic for all kind of protons of researched compounds.
Fig. 1. IR spectrum of 3-(hexene-5-in-2-iloxy)propionitrile.
Fig. 2. IR spectrum of 3-(2-metyldiphenilsililhexadiene-2,5-iloxy propionitrile (VII) and 3-(3-methyldiphenilsililhexadiene-2,5-iloxy) propionitrile VIII mixtures.
Fig. 3. NMR 1H spectrum of 3-(2-methyldiethylhexadiene-2,5-iloxy) propionitrile (I) and 3-(2-methyldiethylhexadiene-2,5-iloxy) propionitrile II mixtures.
(a) (b) (c) (d) (f) (g) (h)
ch2 = chch2ch=c-ch2och2ch2cn
(e^Si(OC2h5)3 / (e)
(f)
1
(a)
(b) (Ф
Ла^mJ^V^J
(> > 4 3 2 I о 5, ppm
Figure 4. NMR 1H spectrum of 3-(2-triethoxysililhexadiene-2,5-iloxy) propionitrile (XI).
Figure 5. NMR 1H spectrum of 3-(2-methyldi-w-propylsililhexadiene-2,5-iloxy) propionitrile (III) and 3-(3-methyldi-w-propylsililhexadiene-2,5-iloxy) propionitrile (IV) mixtures (was obtained in the presence of H2PtCl66H2O catalyst).
62
As a result of experiments it was defined that the most efficient catalyst for this reaction is (acac)Rh(CO)2, as it gives opportunity to realize the reaction in short time, in soft condition without solvent and with high yield. But, the amount of y-isomer in isomer mixture increases and sometimes it is 48%. For comparison we can mention the ratio of nitrile synthesized in benzene in the presence of H2PtCl66H2O is like this III:IV=74:26 (Figure 5).
It was defined that merging yield of triorganosilanes to HPN depends on character of radicals merged to silica atom and decreases in alkoxysilane anhydride case. Thus, methyl tetra-methylenesilane reaction with HPN proceeds exothermically and the yield is 82%. High reactivity of methyltetramethylenesilane can be ex-
plained only with steric efficiency in silica atom molecule. In alkoxysilaneanhydride case low yield can be explained with the position of ethoxy group in space. Low yield (58%) is connected with disproportion reaction of triethoxy-silane that is not reactive in hydrosilylation.
Isomer mixture enter diene synthesis reaction with (I, II) hexachlorine- and 5,5-di-methoxytetrachlorocyclopentadiene in m-xylene condition at 125-1300C temperature, with the formation of polychlorine containing bicyclic silica organic nitriles (XI, XII)-(XIII, XIV) by double bond at the end of molecules. The shown adducts, also methyldiethylenesilane are obtained by mutual influence of polychlorine bicyclic nitriles [6]:
Cl Cl
Cl
H
X
X^L _ Cl
X
CHCH?C=| = CCH2OCH2CH2CN Cl
SX CH CH3Si(C2H5)2
Cl
X=Cl (XIII, XIV); OCH3 (XV, XVI)
H
CH2C=| = CCH2OCH2CH2CN
CH3Si(C2H5)2 XIII, XIV, XV, XVI
Absorption lines of obtained adducts in IR spectrum CH2=CH (3000-3100 cm-1) and C=C (2190-2260 cm-1) are not found out. Valence vibrations of C=C (2190-2260 cm"1) and C=N (2220-2260 cm"1) are found out almost in the same area. Absence of C=C bonds in that area is proved by being valence vibration line which is characteristic to Si-C=CH group in IR spectrum 1610 cm-1 of (I, II) isomers mixture.
Experimental part
The IR spectra were taken on spectrometer "UR-20" [7]. The spectra NMR 1H have been registered on spectrometer "Tesla BS-487" (80 MHz) as internal standard, solvent - CCl4 [8]. The purity of synthesized compounds was controlled by means TLC (plates Silufol UV-254, eluent - benzene:ether = 3:1, developer -
iodine vapors).
HPN, prepared by the method [6], has the following constants: b.p. 99-1000C (0.067 kPa), n2° - 1.4720, df - 0.9732. Yield - 90%.
Interaction of HPN with methyldi-ethylsilane. 4.1 g (0.04 mol) methyldiethyl-silane in presence of 0.007 g (acac)Rh(CO)2 is added to 6 g (0.04 mol) HPN with drops and mixing reaction mixture is mixed at 70-800C temperature for 3 hours. With extracting in vacuum 7.7 g isomer mixture (I, II) are separated. (III, IV-XI, XII) isomer mixture are obtained by analogical method. Constants and analysis of synthesized substances are given in the table.
Reaction of (I, II) isomer mixture with hexachlorocyclopentadiene. 25 g (0.01 mol) (I, II) and 2.1 g (0.01 mol) hexachlorcyclopen-tadiene mixture in the presence of 0.01g hydroquinone are mixed at 125-1300C tempe-
rature in 10 ml m-xylene condition for 25 hours. Then, reaction mixture is cooled, solvent and preliminary components that did not enter reaction are extracted in vacuum. By column (column length - 250 mm, diameter - 21 mm, adsorbent - Al2O3, eluent benzene:ether =5:1, developer - iodine vapors) chromatography method 4.02 g (87.20%) adduct mixture (XIII, XIV) cleaned from preliminary substances are obtained. By analogical method from condensation reaction of (I, II) isomer mixture with 5,5-di-methoxy-tetrachlorinecyclopentadiene (XV, XVI) adduct mixture were obtained.
Constants and analysis of synthesized compounds
Mutual synthesis. 0.51 g (0.005 mol) boiling in 10 ml benzene methyldiethylsilane in the presence of 0.2 ml 0.1 N solution in H2PtCl66H2O isopropyl alcohol is added to 2.11 g (0.005 mol) 1,2,3,4,7.7-hexachlorine-5 - [4-(2-si a-noethoxy)butin-2-il])bicyclo[2.2.1 ]hepten-2 reaction mixture is boiled another 18 hours. After extracting benzene 1.66 g (63.36%) (XIII, XIV) are obtained by colonnade chromatography method. By analogical method from 2.1 g (0.005 mol) 1,2,3,4-tetrachlorine-7,7-dmethoxy-5-[4-(2-sianoethoxy)butin-2-il]bicyclo[2.2.1] hepten-2 and 0.51 g (0.005 mol) methyldiethylesilane 1.76 g (64.00%) (XV, XVI) are obtained.
No of compaunds o O o 20 "d J 20 d4 Yield, % MRd Rf Brutto-formule Found/Calculated, % IR spectrum, cm 1
found calculated C H N Si
I, II 121-122 1.4760 0.9299 76.54 76.25 77.05 0.66 0.55 C14H25ONSi 66.81 66.87 9.85 10.02 5.66 5.57 11.27 11.17 1250 (Si-C), 1610 (SiC=CH), 2260 (C=N), 3080 (CH2=CH)
III, IV 130-132 1.4735 0.9118 68.33 86.08 86.55 0.72 0.60 C16H29ONSi 68.85 68.76 10.33 10.46 4.87 5.01 9.94 10.05 1255 (Si-C), 1610 (SiC=CH), 2260 (C=N), 3085 (CH2=CH)
V, VI 125-126 1.4978 0.9546 82.50 76.56 76.16 0.65 0.54 C14H23ONSi 67.49 67.42 9.22 9.29 5.51 5.62 11.33 11.26 1250 (Si-C), 1610 (SiC=CH), 2260 (C=N), 3080 (CH2=CH)
VII, VIII 209-212 1.5630 1.0500 80.00 107.50 107.67 0.78 0.66 C22H25ONSi 75.92 76.03 7.29 7.25 3.98 4.03 8.15 8.08 1260 (Si-C), 1610 (SiC=CH), 2260 (C=N), 3085 (CH2=CH
IX, X 131-133 1.4794 0.9200 72.25 81.80 81.56 0.70 0.59 C15H27ONSi 67.89 67.87 10.18 10.25 5.35 5.28 10.67 10.58 1255 (Si-C), 1610 (SiC=CH), 2260 (C=N), 3090 (CH2=CH)
XI, XII 139-141 1.4552 1.0090 57.90 84.32 84.20 0.73 0.60 C15H27O4NSi 57.64 57.47 8.61 8.68 4.38 4.47 9.03 8.96 1250 (Si-C), 1610 (SiC=CH), 2260 (C=N), 3080 (CH2=CH)
XIII, XIV 212 decomp 1.5190 1.2780 87.20 124.49 124.96 0.90 0.78 C19H25ONCl6Si 43.65 43.53 4.88 4.81 2.74 2.67 5.27 5.36 1255 (Si-C), 1610 (C=C), 2260 (C=N), 790 (C-Cl)
XV, XVI 209 decopm 1.5086 1.2022 85.60 127.80 128.10 0.88 0.76 C21H31O3NCl4Si 49.07 48.94 6.15 6.06 2.57 2.72 5.39 5.45 1255 (Si-C), 1610 (C=C), 2260 (C=N), 785 (C-Cl)
References
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3-(HEKSEN-5-iN-2-iLOKSi)PROPiONiTRiLiN HiDROSiLiLLO^MOSi
O.M.Qaramanov, M.§.Qurbanov, D.Q.Abdullayev, N.X.Hüsiyev, S.N.Allahverdiyeva
3-(Heksen-5-in-2-iloksi)propionitrila asetilasetonatdikarbonilrodium katalizatorunun i§tiraki ila triorqanosilanlann birla§ma reaksiyasi, ügqat rabita üzra, lakin iki istiqamatda ß(52-65%)- уэ у (35-48%)-izomerlar (oksigen atomuna nazaran) qan§igimn alinmasi va ß-mahsulun giximimn üstünlüyü ila ba§ verir.
Agar sözlar: 3-(heksen-5-in-2-iloksi)propionitril, triorqanosilanlar, asetilasetonatdikarbonilrodium, hidrosiUÜ3§m3, ß-izomer, y-izomer.
ГИДРОСИЛИЛИРОВАНИЕ 3-(ГЕКСЕН-5-ИН-2-ИЛОКСИ)ПРОПИОНИТРИЛА
А.М.Гараманов, М.Ш.Гурбанов, Д.Г.Абдуллаев, Н.Х.Гусиев, С.Н.Аллахвердиева
Реакция присоединения триорганосиланов к 3-(гексен-5-ин-2-илокси)пропионитрилу в присутствии катализатора ацетилацетонатдикарбонила родия протекает по тройной связи, но в двух направлениях с образованием смеси ß(35—48%)- и у(52-65%)-изомеров (относительно атома кислорода) с преимущественным выходом ß-продукта.
Ключевые слова: 3-(гексен-5-ин-2-илокси)пропионитрил, триорганосиланы, ацетилацетонатдикарбонил родия, гидросилилирование, ß-изомер, у-изомер.
