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AZ9RBAYCAN KIMYA JURNALI № 3 2017
43
UDC 547. 36.37.1'13.345 SYNTHESIS AND PROPERTIES OF 2-SUBSTITUTED 1,4-ENYNE CHLOROHYDRINS
A.M.Garamanov, M.Sh.Gurbanov, A.F.Guliyeva, S.N.Allakhverdiyeva
Institute of Polymer Materials, NAS of Azerbaijan ipoma@science.az Received 08.12.2016
By interaction of 2-substituted 1,4-enyne alcohols with 1-chloro-2,3-epoxy propane in the presence of boron trifluoride etherate there have been synthesized 2-substituted 1,4-enyne chlorohydrin by dehydrochlorination of which epoxy-1,4-enynes and epoxy-1,3,4-triens have been prepared. The addition reaction of the methyl diethyl silane to epoxy-1,4-enynes leads to the formation of mixture of silicoorganic epoxy-1,4-dienes.
Keywords: 5-methyl hexen-5-yn-2-ol-1, 2,6-dimethyl hepten-6-in-3-ol-2, 1-chloro-2,3-epoxy propane, boron trifluoride etherate, dehydrochlorination, epoxy-1,4-enyne, epoxy-1,3,4-trien, hydrosilylation.
We have synthesized the unconjugated 1,4-enyne chlorohydrins and studied their de-hydrochlorination reaction in the presence of potassium hydroxide [1-4]. But, 2-substituted unconjugated 1,4-enyne chlorohydrins have not been investigated in detail. Although, the syntheses of 2-substituted 1,4-enynes and investigation of their properties is of considerable theoretical and practical interest and deserves a comprehensive study.
The aim of this work is synthesis of 2-substituted 1,4-enyne chlorohydrin on the basis of 5-methyl hexen-5-yn-2-ol-1 I (Figure 1) and 2,6-dimethyl hepten-6-yn-3-ol-2 II and study of their dehydrochlorination in the presence of KOH in a medium of diethyl ether.
With this aim we have synthesized 2-substituted 1,4-enyne chlorohydrin by interaction of alcohols I and II with 1-chloro-2,3-epoxy propane in the presence of boron trifluoride etherate:
/O\
ROH + ClCH2CH _CH2-► ROCH2CH(OH)CH2Cl
I, II III, IV
R=CH2=C(CH3)CH2C^CCH2- I, III; R= CH2=C(CH3)CH2^=C(CH3)2_ II, IV.
Fig.1. Spectrum NMR 1H of 5-methyl hexen-5-yn-2-ol-1 I.
In the NMR 1H-spectrum of chlorohydrin III (Figure 2) a narrow singlet (b) at 1.80 ppm corresponds to the protons of the methyl group connected with double bond.
Fig.2. Spectrum NMR 1Н of 1-(5-methyl hexen-5-yn-2-yloxi)-3 -chloropropanol-2 III.
The broadened singlet (c) at 2.90 ppm has been referred to the protons of the methylene group. A multiplet (e, g, h) at 3.50 ppm is referred to the methylene protons connected with chlorine and oxygen atoms and also to the proton of OH group. A quintet (J=5 Hz) f) at 3.95 ppm corresponds to the proton -CH group connected with oxygen atom. With constant J= 2 Hz the signal at 4.20 ppm of the protons of the methylene group located between multiple bond and oxygen atom has been splitted to triplet (d). The multiplets (a) at 4.90 and 4.75 ppm correspond to the signals of absorption of CH2= group.
Their dehydrochlorination in the presence of КОH in a medium of the diethyl ether proceeds in two directions with formation of epoxy-1,4-enynes V, VI (at temperature 4-60C for 2 h) and epoxy-1,3,4-triens VII, VIII (at temperature 34-360C for 7 h):
III, IV +
KOH
/O\
CH2=C(CH3)CH2C = CCR2OCH2CH _ CH2
V, VI
/O\
CH2=C(CH3)CH=C=CHCR2OCH2CH _ CH2 VII, VIII
R= H V, VII; R= CH3 VI, VIII.
j.-------l
5 4 3 2 8, м.д.
Fig.3. Spectrum NMR 1Н of 1-(5-methyl hexen-5-yn-2-yloxi)-2.3-epoxypropane V.
In the spectrum NMR 1H of epoxy-1,4-enyne V (Figure 3) an intensive singlet (e) at 1.80 ppm corresponds to signal of the protons of CH3 group. Two geminate protons (g) of the oxirane ring with SSI J= 5 Hz are observed at 2.50 and 2.65 ppm. At 3.00 ppm the proton f) of OCH group as a multiplet is detected. The degenerated multiplet (c) with chemical shift at 2.90 ppm absorbs the protons of -CH2 group located between multiple bonds. These protons have a far spin enyne bond with protons (d) of OCH2 group at 4.05 ppm, as a result the signals of the last ones have been splitted to triplet (J=3 Hz). The protons (e) of OCH2 group are detected at 3.4 (d.d) and 3.65 ppm(d.d) (J=12 Hz, 5 Hz, 4 Hz). The protons (a) of =CH2 groups are observed at 4.80 and 4.95 ppm as multiplet. In the IR spectrum of the individual, on data TLC [Rf 0.60 (benzene:ether - 5:1)] of epoxy-1,4-enyne V the availability of epoxide
group has been detected in the field of 3065 and 1255 cm-1. There are also the absorption bands in the field 3090, 1640 cm1 and 2250 cm-1, characteristic CH2=C and C=C groups. In the field of 1940-1970 cm-1, characteristic for bond C=C=C were absent. In the IR-spectrum of the individual [Rf 0.62 (benzene:ether - 5:1)] of epoxy-1,3,4-triene VII there are the absorption bands in the field of 1970 cm-1, characteristic for C=C=C group. The frequencies in the field of 2190-2260 cm-1, characteristic for valence vibrations of bond C=C were absent.
The interactions of V and VI with methyl diethyl silane in the presence of the platinum-hydrochloric acid lead to the formation of mixture of the silicon-containing epoxy-1,4-dienes, i.e. the reaction proceeds on triple bond with formation of P- and y-isomers (relatively oxygen atom):
- CH2=C(CH3)CH2CH=C[Si(C2H5)2CH3]CR2OX
HSi(C2H5)2CH3
V, VI + -1 IX, X
1-► CH2=C(CH3)CH2C[Si(C2H5)2CH3]=CHCR2OX
/ O\ / O\ X1, XI1
R= H, X= _CH2CH _ CH2 IX, XI; _CH2CH _ CH2 X, XII.
With the aim of establishment of structure of the prepared products of reaction (R=H), they were investigated with physical and chemical methods. So, an absence of a-oxide ring in molecules of mixture of isomers, a purity of which has been determined by a method of TLC [Rf 0.72 and 0.80 (benzene:ether - 5:1)], has been confirmed by availability of the absorption bands 3065 cm-1in the IR spectrum, inherent to vibrations of methylene group of the epoxide ring. There is an intensive absorption band in the field of 1250 cm-1, characteristic for symmetric deformation vibrations Si-C. The availability of 1,4-diene system of bonds has been detected in the field of 1610 and 1640 cm-1. In the spectrum the bands in the field of 1940-1970 and 21902260 cm-1, characteristic for C=C=C and C=C bonds are absent.
It has been established that the epoxy-1,4-enynes (V, VI) were more reactive compounds in the hydrosilylation reactions than the isomer
epoxy-1,3,4-triens (VII, VIII). So, the attempts to carry out the hydrosilylation of the epoxy-1,3,4-trienes VII, VIII in the presence of chloro-platinic acid in a medium of benzene at temperature 81-830C for 18 h have been finished unsuccessfully - the initial components in invariable form returned from the experience. With solvent the reaction proceeds with difficulty in several directions.
Experimental
The IR spectra were taken on spectrometer "UR-20" [5]. The spectra NMR 1H have been registered on spectrometer "Tesla BS-487" (80 MHz) HMDS as internal standard, solvent - CCl4 [6]. The purity of the synthesized compounds was controlled by means TLC on chromatogram "LKHM-8 MD-5" and TLC (plates Silufol UV-250 in the various systems of solvents, developer - iodine vapors).
5-Methyl hexen-5-yn-2-ol-1, prepared by
the method [7], has the following constants: b.p. 85-860C (1.6 kPa), n 2°-1.4762, d2° - 0.9290.
2,6-Dimethyl hepten-6-yn-3-ol-2, prepared by the method [7], has the following constants: b.p. - 82-830C (1.6 kPa), n 2° -1.4620, d 2° - 0.8830.
1-Chlor-2,3-epoxy propane has the
at temperature 34-360C. After treatment and rundown of the solvent by distillation in vacuum there was isolated 6.32 g of the compound VII. B.p. - 84-850C (0.067 kPa), n2- 1.5055, df - 0.9815. MRd - 50.26, calc. -48.61. Yield - 76.14%. Found, %: C 72.33, H 8.45. C10H14O2. Calculated, %: C 72.26, H 8.49. It has been analogously prepared the epoxy-
following constants: b.p. - 7 С (101.325 kPa), 1,3,4-trien VIII. B.p. - 80-810С (0.067 kPa), n2 -1.4382, d20 - 1.1800 [8]. „20 , ^c ^20 nn,,-0 г4П ,
-1.4382, d 2° - 1.1800 [8].
18.51 g (0.2 mol) of 1-chloro-2,3-epoxy-propane was added to 55.08 g (0.5 mol) I containing 0.2 of boron trifluoride etherate in mixing and cooling (0-50C). The reaction mixture was stirred for 5 h at temperature 250C. By distillation in vacuum it was isolated 26.35 g of the compound (III). B.p. - 114-1150C (0.067 kPa), n2° - 1.4900, d2° - 1.0787. MRd - 54.32, calc. - 54.44. Yield - 65%. Found, %: C 59.12 , H 7.35, Cl 17.41, C10H15O2CL Calculated, %: C 59.26, H 7.46, Cl 17.49. There has been analogously prepared the compound IV from 27.64 g 2,6-dimethyl hepten-5-yn-3-ol-1 (II) and 11.1 g 1-chloro-2,3-epoxypropane. B.p. - 112-1130C (0.067 kPa), n2° - 1.4780, d2° - 1.0272. MRd -63.59, calc. - (53.74. Yield - 66.02%. Found, %: C 62.53, H 8.36, Cl 15.29. C12H19O2Cl. Calculated, %: C 62.47, H 8.30, Cl 15.36.
16.8 g (0.3 mol) of the powdered KOH was added to 20.27 g (0.1 mol) of solution of the compound III in 50 ml ether in mixing and cooling (4-60C). The reaction mass was stirred at temperature 4-60C. After usual treatment and rundown of the solvent by distillation in vacuum it was isolated 12.63 g of the compound V. B.p. - 94-950C (0.067 kPa), n 2° - 1.4805, d 2° -0.9860. MRd - 47.94, calc. - 47.81. Yield -76%. Found, %: C 72.19, H 8.54. C10H14O2. calculated, %: C 72.26, H 8.49. There has been analogously prepared the compound VI. B.p. -87-880C (0.067 kPa), n 2° - 1.4660, d 2° -0.9520. MRd- 56.60, calc.- 57.11. Yield - 75%. Found, %: C 74.31, H 9.37. C12H18O2. Calculated, %: C 74.19, H 9.34.
10.13 g (0.05 mol) of the compound III in 10 ml ether was added to 8.4 g (0.15 mol) of the powdered KOH. There was stirred more 7 h
n20 - 1.4948, d20 - 0.9478. MRd - 59.75, calc. - 57.91. Yield - 79.38%. Found, %: С 74.11, Н 9.42. C12H18Ü2. Calculated, %: С 74.19, Н 9.34.
4.08 g (0.04 mol) of the methyldi-ethylsilane was added to 6.64 g (0.04 mol) of the compound V in the presence of 0.05 ml 0.1 N H2PtCl66H2Ü in the absolute isopropyl ether in boiling in a medium of 25 ml benzene. Then it was boiled more 18 h. After rundown of the solvent by distillation in vacuum it was isolated 6.66 g mixture of the isomers IX, XI. B.p. -126-1270С (0.067 kPa), n 20 - 1.4770, d 2° -0.9298. MRd - 81.60, calc. - 81.44. Yield -62%. Found, %: С 67.25, H 10.44, Si 28.90 C15H28O2SL Calculated, %: C 67.10, H 10.52, Si 28.86. There have been analogously prepared the mixtures of isomers X, XII. B.p. - 125-1260С (0.067 kPa), n2° - 1.4790, d2° - 0.9285. MRD -90.57, calc. - 90.70. Yield - 65.00%. Found, %: С 68.95, H 10.81, Si 9.40. C15H28Ü2SL Calculated, %: С 68.86, Н 10.88, Si 9.47.
References
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3. Qaramanov Э.М., Allahverdiyeva S.N., Hasanova S.S., Quliyeva A.F. 2-Metilhepten-6-in-3-ol-2 asa-sinda eninlarin sintezi //Akad.S.C.Mehdiyevin 100 illik yubil. hasr olunmu§ Resp. elmi konf. Baki. 2-3 dekabr 2014. I cild. S. 141-143.
4. Qaramanov O.M.,.Valiyev M.H, Allahverdiyeva S.N., Hasanova S.S., Quliyeva A.F. 2-Metilhep-ten-6-in-3-ol-2 asasinda eninlarin sintezi //Azarb. kimya. jurn. 2014. № 4. S. 41-46.
5. Беллами Л. Новые данные по ИК-спектрам сложных молекул. М.: Мир, 1971. 186 с.
6. Гордон А., Форд Р. Спутник химика. М.: Мир, 1976. 541 с.
7. Малиновский М.С., Хмель М.П. Баранов Н.Н., Кривошеева Н.Г. Синтез и исследование аце-
тиленовых спиртоокисей //Укр. хим. журн. 1975. Т. 41. № 10. C. 1064-1067. 8. Перельман В.И. Краткий справочник химика. М.: Химия, 1964. 620 с.
2-ЭVЭZLi XLORHiDRlNLЭRlNiN SiNTEZi VЭ XASSЭLЭRl
Э.M.Qaramanov, М.§^игЬапоу, А^.ОиНуеуа, S.N.AUahverdiyeva
2-Эvэzli 1,4-еп1п 8рМэпп1п, Ьог-3-Аиопй efiratшln ф^ак1 Пэ, 1-xlor-2,3-epoksipropanla qar§lhqh tэsirindэn 2-эуэ7И еп1п x1orhidrin1эri sintez edilmi§dir, hansllaпn ki, dehidroxlorla§dmlmasmdan epoksi-1,4-enin1эr уэ epoksi-1,3,4-trien1эr а1шт1§&1\ MeШdieШsilamn epoksi-1,4-eпiп1эrэ bir1э§mэsi silisiumиzvi epoksi-1,4-dieп1эr qan§lglшn этэ-1эgэ1mэsinэ gэtirir.
Адаг sдzlэr: 5-metilheksen-5-in-2-ol-1, 2,6-dmetilhepten-6-in-3-ol-2, 1-xlor-2,3-epoksipropan, bor-3-flйoridin еАтй, dehidroxlorla§dlrma, epoksi-1,4-enin, epoksi-1,3,4-trien, hidrosilШэ§mэ.
СИНТЕЗ И СВОЙСТВА 2-ЗАМЕЩЕННЫХ 1,4-ЕНИНОВЫХ ХЛОРГИДРИНОВ
А.М.Гараманов, М.Ш.Гурбанов, А.Ф.Гулиева, С.Н.Аллахвердиева
Взаимодействием 2-замещенных 1,4-ениновых спиртов с 1-хлор-2,3-эпоксипропаном в присутствии эфирата трехфтористого бора синтезированы 2-замещенные 1,4-ениновые хлоргидрины, дегидрохлорированием которых получены эпокси-1,4-енины и эпокси-1,3,4-триены. Реакция присоединения метилдиэтилсилана к эпокси-1,4-енинам приводит к образованию смеси кремнийорганическим эпокси-1,4-диенам.
Ключевые слова: 5-метилгексен-5-ин-2-ол-1, 2,6-диметилгептен-6-ин-3-ол-2, 1-хлор-2,3эпоксипропан, эфират трехфтористого бора, дегидрохлорирование, эпокси-1,4-енин, эпокси-1,3,4-триен, гидросилилирование.
