CC BY
17
42
AZ9RBAYCAN KIMYA JURNALI № 2 2016
UDC 547.512. + 057
SYNTHESIS OF Aerne-DICHLOROSUBSTITUTED CYCLOPROPANES BY DICHLOROCYCLOPROPANATION OF LIQUID PYROLYSIS PRODUCTS
OF THE OIL HYDROCARBONS
R.Z.Shahnazarli, K.G.Guliyev, N.Ya.Ishenko, A.M.Aliyeva, B.A.Mamedov, D.R.Nurullayeva, J.I.Fattayeva, A.M.Guliyev
Institute of Polymer Materials NAS of Azerbaijan
[email protected]; [email protected]
Received 06.01.2016
Under the conditions of interphase catalysis the dihlorcyclopropanation of fraction C5 of liquid pyrolysis products of the oil hydrocarbons was carried out and heme-dichlorosubstituted vinyl cyclopropanes and tetrachlorobicyclopropyls have been synthesized. The optimal conditions of preparation of these compounds have been found. The possibility of carrying out the dichlorocyclopropanation reaction of non-fractionated liquid pyrolysis products has been revealed and it has been shown that in this case, along with mono- and bis-adducts, the addition products of dichlorocarbene to alkenes being a part of pyro-condensate are formed.
Keywords: chlorinated cyclopropanes, interphase catalysis, dichlorocarbene, pyrocondensate, unsaturated hydrocarbons.
Introduction
The liquid pyrolysis products (LPP) of the oil hydrocarbons are used as the initial raw material for preparation of the oil-polymer resins. The petroleum polymer resins serve as effective and accessible substitutes of the vegetable oils, natural resins, plasticizers, deficit monomer raw material [1, 2].
Up to present the problem of rational use of LPP has not been solved yet due to availability of the unsaturated compounds (piperilene, isoprene, cyclopentadiene, etc.) in the composition of LPP. There have been made numerous attempts with the aim of removal of unsaturated compounds from the system and their conversion into valuable products [3, 4].
It was known that the addition reaction of dihalocarbenes to olefins and dienes smoothly proceeds in the presence of catalyst of interphase transfer and leads to the formation of di-halosubstituted cyclopropanes [5-7]. Depending on reaction conditions, in the reaction of dihalocarbenes with dienes there are formed the mono- or diadducts. Using excess quantity of carbene source the tetrahalogen substituted bis-adducts are prepared [7, 8]. The unconjugated dienes are slightly differed on activity from cy-cloalkenes and the alicyclic dienes are more reactive than alkenes. The double bond in conju-
gated dienes is more active than in heme-dichlorocyclopropyl alkenes due to influence of heme-dichlorine groups or steric factor. heme-Dichlorocyclopropanes are of great interest as semiproducts in the organic synthesis of various reagents and biopreparations, as additions to polymers, fuels, oils, etc. [9].
In this connection the regularities and addition reaction products of dichlorocarbene to unsaturated compounds of fraction C5, extracted from LPP of the oil hydrocarbons have been investigated.
Experimental
The spectral investigations were carried out on IR-spectrophotometer "Specord-80-IR" in the field of prisms KBr as the thin films.
The spectra were registered on
spectrometer BS-787-B (80 MHz) of firm "Tes-la" in various solvents. As an internal standard there was used hexamethyldisiloxane. The chemical shifts of proton signals have been presented in ppm in a scale 5.
The isomer composition and purity of the initial and prepared compounds were investigated by a method of gas-liquid chromatog-raphy (GLC). For GLC-analysis the chromatograph of mark "^eT-100" was used.
SYNTHESIS OF feme-DICHLOROSUBSTITUTED CYCLOPROPANES BY 43
Methodology of synthesis of heme-di-chlorocyclopropyl alkenes. 6.5 g of fraction C5, 42 g of chloroform and 0.23 g (0.001 mol.) of interphase catalyst - triethylbenzyl ammonium chloride (TEBAC) was placed to three-necked round-bottomed flask, equipped with mechanical mixer, dropping funnel, reflux condenser and water bath for cooling. In intensive mixing and cooling to reaction mixture 320 g of 50%-s solution of NaOH was dropped for 1 h. After this, the reaction mass was stirred for a further 1 hour at 100C temperature. On the end of the reaction the mixture was washed with water to neutral medium. The lower organic layer was separated, dried with fresh-calcined magnesium sulfate, filtered and after distillation of chloroform the reaction mixture was subjected to the distillation at atmosphere pressure.
Synthesis of tetrachlorosubstituted bi-cyclopropyls at 6.5 g of fraction C5, 84 g of chloroform and 1 g (0.004 mol.) of interphase catalyst TEBAC, as well synthesis of interaction of light pyrolisis resin with dichlorcar-bene at 84 g of chloroform and 1 g (0.004 mol.) TEBAC were performed by the methods for synthesis of ^ewe-dichloropropyl alkenes.
Results and discussion
The dichlorocarbene reaction with fraction C5 of LPP containing the mixture of various quantities of diene hydrocarbons in the conditions of interphase catalyst has been studied. The dichlorocarbene prepared by alkali hydrolysis of chloroform was used in this reaction. In a case of dienes of unsymmetric structure it is possible a formation of mixtures of the structural isomers in various ratios:
R1 R I I
CH=C
R1 R2 I R CH=C
\
C
r3
C=CH
:CCl2
-2
N _ /Cl
/C\ ZC>Cl
R3 CH2
R1 I
CH
R2 I
C
+
/\ Cl Cl
C=CH
/3
R
2
3
For carrying out the dichlorocyclopropa-nation reaction there were taken: chloroform, 50%-s solution of sodium hydroxide, interphase catalyst - TEBAC. The obtained results showed that with use of equimolar quantities of diene and chloroform it is advantageously formed monoadduct and small quantity of diadduct. A quantity of diadduct grows with increase of ratio of chloroform to diene, and in larger excess of dichlorocarbene only diadduct is formed in the reaction medium [10, 11].
The optimum conditions of carrying out the reaction (duration, quantity of catalyst, temperature) have been selected on the basis of li-
terary data [10]. 0.4 mol. of chloroform, 0.4 mol. of NaOH (50%-s) and 0.001 mol. of interphase catalyst TEBAC was introduced into 0.1 mol. of unsaturated compound as a mixture (fraction C5). The reaction mixture was vigorously stirred at room temperature for 2 h. In these conditions already in 2 hours the corresponding ^ewe-dichlorosubstituted vinylcyclo-propanes with high yield have been prepared. In continuation of the reaction it is formed a product of complete addition on both double bonds, and for 4-5 h the initial dienes are completely converted into tetrachlorbicyclopropyls:
R1 R
I R
CH=C.
\
I
R3
,C=CH
:CCl2
■2
R1 R2
I I
CH-Cv
C /\
Cl Cl
:CCl9
/3
R
C=CH
2
3
R1 R2 Cl Cl
I I \/
CH~C\
c-CH2
/\ L
Cl Cl
R3
By GLC-analysis the composition of these fractions has been established and revealed that each of these fractions consists of mixture of heme-dichlorovinylcyclopropanes and mixture of tetrachlorobicyclopropyls in various ratios.
In Table 1 the results of GLC-analysis are presented. It follows from Table that at ratio CHCl3:diene = 4:1 there are basically formed the monoadducts, and at ratio CHCl3:diene = 8:1 (or in increase of reaction duration) - ¿/'s-adducts.
Table 1. Composition and content of adducts on data
of GLC-analysis
Composition and content of reaction products, %
mono-adduct èw-adduct
Isolated и и n -at и и n -ta
fraction S <u § ä S <u § ä
a ■Й a ■Й
o rn & o rn &
ft Sy c ft y c
Fraction 1 17.6 18.0 14.0 1.0 2.0 1.0
Fraction 2 0.5 1.0 1.5 28.0 32.0 14.0
In the individual form these adducts have been isolated by rectification on column. It has been firstly isolated the fraction with b.p.. to 1600C, consisting of heme-dichloro-cyclopropanes and then fraction with b.p. 80-950C/10 mm merc.c., containing only tetra-chloroderivatives.
By rectification of the reaction products the fractions containing as mono-, as well as ¿/'s-adducts have been isolated. In the IR-spectrum of fractions isolated in the range of temperatures 120-1600C there are characteristic absorption bands at 1640, 2900 and 750 cm-1, referring to vinyl group, CH2-fragments and chlorine atoms, correspondingly. The absorption bands at 1030-1045 cm- characterize the skeleton vibrations of three-membered cycle.
In the spectra NMR1H of fractions there are 4 groups of signals characterizing an availability of protons of double bond, cyclopropane ring, methyl groups of double bond and three-membered cycle (Table 2).
Table 2. Data of spectra NMR:H of fraction of monoadducts la-le
Adduct number Chemical shifts of protons (5, ppm)
Structural formula CH2— C\ >C=CH- -CH-C< V ✓C CHo \ / 2 я CH3-CH=CH- CH3-CH-CH- 3 V
1 CHo CH CH CHo 2 У2 Cl Cl 5.30 m (2Н) 5.65 m (1Н) 2.95 m (1Н) 1.55 m (2Н) - -
CH3
2 CH CH C CH 2 У 2 Cl Cl 5.16 m (2Н) 5.80 m (1Н) - 1.36 m (2Н) - 1.4 с (3Н)
CH3
3 CH2 C CH CH2 я Cl Cl 4.6 d (2Н) - 2.8 m (1Н) 1.55 m (2Н) 1.72 d (3Н) -
4 CH3—CH= CH_ CH_CH2 3 Y Cl Cl - 4.55 qu (2Н) 2.80 m (1Н) 1.45 m (2Н) 1.2 d (3Н) -
5 CH2= CH— CH CH CH3 я Cl Cl 5.35 m (2Н) 5.70 m (1Н) 2.25 m (1Н) 1.45 m (1Н) - 1.45 qu (3Н)
CH3 CHt 1 M 3
6 CH2=C—C-CH2 У Cl Cl 4.3 qu (2Н) - - 1.4 d (2Н) 1.95 d (3Н) 1.45 (3Н)
SYNTHESIS OF heme-DICHLOROSUBSTITUTED CYCLOPROPANES BY 45
Table 3. Data of spectra NMR1H of ¿is-adducts
Adduct number Structural formula Chemical shifts of protons (5, ppm)
CH2^T< >^ch CH3 ^
1 Cl Cl /\ Cl Cl 1.3 m (2H) 1.5 m (2H) 1.8 m (2H) -
2 Cl Cl 0.9 m (2H) subst. 1.0 m (2H) unsubst. 1.3-2.0 t (1H) 1.2 s (3H)
3 CH Cl Cl H Cl Cl 1.3-1.4 d (2H) subst. 1.4-1.5 m (1H) unsubst. 1.6-1.9 m (2H) 1.3 m (3H)
4 Hv ¿^¿H ¿ICI CH^; H Cl Cl 1.6 qu (4H) - 1.3 t (6H)
In the same Table for comparison, the data of NMR1H of monoadducts of butadiene-1,3 and its 2,3-dimethylsubstituted derivative are also presented. These results indicate that the composition of fractions contains only hewe-dichlorosubs-tituted vinylcyclopropanes (adducts 1-5) forming from mixture of cis- and trarns-piperilenes and isoprene. The monoadduct prepared from cyclo-pentadiene as a result of cyclopropylallyl rear-rangemeent is converted into chlorobenzene.
An increase in ratio of chloroform:diene in 6-fold leads to that the both double bonds of diene are subjected to the dichlorocarbenylation and as a result only tetrachlorsubstituted bicy-clopropyls are formed. In the IR-spectra of isolated fraction the signals of methyl, methylene and methine groups (v, 2900 cm-1), chlorine atoms (v, 750 cm-1) and skeleton vibrations of three-memberd cycle (v, 1040 cm-1) are observed. In the spectra NMR1H of this fraction there are 3 groups of signals: protons of CH2-cycle, CH-cycle and CH3-cycle. These data and results of spectra NMR1H of ¿is-adducts of bu-tadiene-1,3 and its 2,3-dimethylsubstituted derivative are presented in Table 3.
The calculated values of chlorine content in isoprene or piperilene are 47% for monoadduct and 60% - for ¿¿s-adduct, which is agreed with data obtained by experimental way.
Conclusions
Under conditions of interphase catalysis the dichlorocyclopropanation of fraction C5 of liquid pyrolysis products of the oil hydrocarbons has been carried out and both monoadducts - hewe-dichlorosubstituted vinylcyclopropanes and ¿¿s-adducts - tetrachlorosubstituted dicyclopropanes have been synthesized. The conditions of formation of both mono- and ¿¿s-adducts have been found out. In case of addition of carbene to dienes of unsymmetric structure a low regioselectivity of addition, which leads to parallel formation of two possible structural isomers is observed.
It has been shown that in case of use of ratio CHCl3:diene = 4:1 for 2 h the formation of only hewe-dichlorovinylcyclopropane is observed and at ratio CHCl3:diene = 8:1 the forming hewe-dichlorocyclopropanes are converted into ¿¿s-adducts - tetrachlorobicyclopropyls.
The possibility of carrying out the dichlo-rocyclopropanation reaction of non-fractionated liquid pyrolysis products has been revealed and it has been shown that in this case, along with mono- and ¿¿s-adducts, the addition products of dichlorocarbene to alkenes being a part of pyro-condensate are formed.
The work has been executed at financial support of SOCAR on grant Science Development Foundation (project № 24).
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NEFT karbohídrogenlorInín pírolízínín maye mohsullarinin
DÍXLORTSÍKLOPROPANLA§MASI YOLU ÍLO Aem-DiXLOROVOZLi TSiKLOPROPANLARIN SiNTEZi
R.Z.§ahn3zarli, K.Q.Quliyev, N.Y.i^enko, A.M.0liyeva, B.O.Mammadov, D.R.Nurullayeva,
C.I.Fattayeva, A.M.Quliyev
Fazalararasi kataliz §araitinda neft karbohidrogenlarinin pirolizinin maye mahsullarinin C5 fraksiyasinin dixlortsik-lopropanla§ma reaksiyasi hayata kegirilmi§, hem-dixloravazli viniltsiklopropanlar va tetraxlorbitsiklopropanlar sintez edilmi§dir. Bu birla§malarin optimal alinma §araitlari tapilmi§dir. Pirolizin fraksiyalara aynlmai§ maye mahsullarinin dixlortsiklopropanla§masi reaksiyasinin haata kegirilmasinin imkanlari müayyan edilmi§va göstarilmi§dir ki, bu halda mono- va bis- adduktlarla yana§i, dixlorkarbenin pirokondensatin tarkibinda olan alkenlara birla§ma mahsullari da alinir.
Agar sözlar: xlor3V3zli tsiklopropanlar, fazalararasi kataliz, dixlorkarben, pirokondensat, doymami§ karbohidrogenbr.
СИНТЕЗ гем-ДИХЛОРЗАМЕЩЕННЫХ ЦИКЛОПРОПАНОВ ПУТЕМ ДИХЛОРЦИКЛОПРОПАНИРОВАНИЯ ЖИДКИХ ПРОДУКТОВ ПИРОЛИЗА НЕФТЯНЫХ УГЛЕВОДОРОДОВ
Р.З.Шахназарли, К.Г.Гулиев, Н.Я.Ищенко, A.M-Алиева, Б.А.Мамедов, Д.Р.Нуруллаева,
Дж.И.Фаттаева, А.М.Гулиев
В условиях межфазного катализа осуществлено дихлорциклопропанирование фракции С5 жидких продуктов пиролиза нефтяных углеводородов и синтезированы гем-дихлорзамещенные винилциклопропаны и тетрахлор-бициклопропилы. Найдены оптимальные условия получения этих соединений. Выявлена возможность осуществления реакции дихлорциклопропанирования нефракционированных жидких продуктов пиролиза и показано, что в этом случае наряду с моно- и бис-аддуктами образуются и продукты присоединения дихлоркарбена к алкенам, входящим в состав пироконденсата.
Ключевые слова: хлорзамещенные циклопропаны, межфазный катализ, дихлоркарбен, пироконденсат, непредельные углеводороды.
