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CHEMICAL PROBLEMS 2019 no. 1 (17) ISSN 2221-8688
93
UDC 547.729
ON DIOXOLANATION REACTION OF CYCLOHEX-3-ENE-1-CARBALDEHYDES WITH 1,2-DIOLS AND PROPERTIES OF PREPARED
PRODUCTS
A.Kh. Kerimov, A.T. Orudzheva, Kh.A. Mamedova
Institute of Polymer Materials of Azerbaijan National Academy of Sciences 124, S. Vurgun str., AZ 5004, Sumgait, Azerbaijan; e-mail: [email protected]
Received 21.06.2018
Generalized results of the analysis of synthesis reaction of cyclic acetals of 1,3-dioxolane series by condensation of cyclohex-3-ene-1-carbaldehydes with 1,2-propanediol and its 3-chloro-, 3-chloroalkoxy derivatives, as well as their epoxidation, bromination, dichlorocarbenylation on C=C bond of cycle and dienophilic activity were presented. The influence of the nature of substituents on relative reactivity of reacting components and efficiency of the prepared products as the ED-20-based active diluent of the polymer composition has been considered.
Keywords: five-membered heterocycles with vicinal dioxagroups, reaction rate, relative reactivity, mechanism of dioxolanation reaction Doi.org/10.32737/2221-8688-2019-1-93-99
The reaction of vicinal diols with carbonyl addends is an accessible method of synthesis of five-membered heterocycles with vicinal dioxogroups - 1,3-dioxolanes [1-3]. The cyclic acetals of 1,3-dioxolane series are applied as plasticizers [4], modifiers [5], solvents of cellulose esters [6], metal corrosion inhibitors [7] and substances intensifying oil extraction [8] etc. In addition, they are of the utmost interest as perspective monomers for polymerization processes [9]; intermediate compounds in the synthesis of biologically active and pharmaceutical preparations [10]. It should be noted that an additional interest to this class of compounds stimulated an opening of anti-HIV activity of some preparations prepared on the basis of substances containing 1,3-dioxolane cycle [11, 12]. However, there are very few reports in the literature devoted to the synthesis of 1,3-dioxolanes from aldehydes having unsaturated carbocyclic substituents in line with the cyclohexene structure while
current works have often sporadic nature [13, 14]. Consequently, the involvement of 1,3-dioxolane derivatives, cyclohex-3-ene-1-carbaldehydes, on the one hand, and functionally substituted 1,2-propanediol derivatives, on the other hand, not only allows expanding their assortment but also puts forward an important task - establishment of the relative reactivity of the reacting components depending on the electronic and spatial factors stipulated by their substituents.
The work provides the generalized information on the analysis of synthesis of 2,4-disubstituted 1,3-dioxolanes by interaction of cyclohex-3-ene-1-carbaldehyde (I), its 4-methyl- (II), 6-methyl- (Ill) and 4,6-dimethyl derivatives (IV) with 1,2-propane diol (V) and its 3-chloro- (VI), 3-(2-chloroethoxy)- (VII), 3-(1,3-dichloropropoxy)derivatives (VIII) in the presence of ion-exchange resin KU-2 (H+ -form) as appears from the scheme below:
(Scheme 1)
R=Ri=H (I); R=CH3, Ri=H (II); R=H, Ri=CH3 (III); R=Ri=CH3 (IV). R2=H (V); Cl (VI); CICH2CH2O (VII); (ClCH2)CHO (VIII).
R=R1=R2=H (IX); R=CH3, R1=R2=H (x). R2=Cl: R=R1=H (XI); R=CH3, R1=H (XII); R=H, Ri=CH3 (XIII); R= R1 =CH3 (XIV).
R2= ClCH2CH2O: R=R1=H (XV); R=CH3, R1=H (XVI); R=H, R1=CH3 (XVII); R=R1=CH3 (XVIII).
R2= (ClCH2)2CHO: R=R1=H (XIX); R =CH3, R1=H (XX); R=H, R1=CH3 (XXI); R=R1=CH3 (XXII).
The reaction course was controlled by means of GLC method- by fixation of concentration change in the base product over time [15]. The method of internal standard [15] was used for quantitative calculation of the conversion of initial components into the base product. On chromatograms the components of reaction mixture [as an example of synthesis of compound (XI)], are placed according to their retention time in the following sequence: toluene (solvent), cyclohex-3-ene-1-carbaldehyde, 3-chloro-1,2-propanediol, dimethyl phthalate (standard) and 2-(3 -cyclohexenyl)-4-chloromethyl-1,3-dioxolane. According to GLC analysis, each of the synthesized 2,4-disubstituted compounds (IX-XXII) is a mixture of cis- and trans-isomers with ratio of 55-45 %. We failed to isolate the separate isomers from their mixture; however, the PMR-spectroscopy data reaffirm the availability of these isomers notable for the arrangement of substituents on either sides of the five-membered rigid heterocycle [16].
With the aim of examining the nature of substituents of initial diols on their relative reactivity in the reaction with aldehyde (I) it was introduced diol (V) (taken as a standard) and its above-listed chloro- and chloroalkoxy derivatives (VI-VIII). It was established that in the optimal conditions [17] an initial rate (Wo-104) of the formation reaction of dioxolane (XI) from diol (VI) is 5.60 ± 0.48
mol/(l.s.) (calculations were carried out by least-squares method [18]) and more than two times exceeds the same index of the formation reaction of dioxolane (IX) from diol (V) [2.75 ± 0.22 mol/(l.s.)] which is apparently a logical consequence of the influence of the inductive effect of the electron-acceptor substituent (Cl) coupled with field effect [19]. Since the chlorine atom and primary OH group in a diol molecule (VI) are at peripheral atoms of unsaturated chain (consisting of three carbon atoms), and transfer of the inductive effect in such saturated systems is rapidly fading [see [19] p. 31-37], the observed effective transfer of the latter can be realized only with the participation of the field effect, i.e. according to the Newman projection formulas, (91-) beveled conformer (20) is energetically more advantageous out of three possible odd conformations of diol (VI) (91, 9 , 95).
A geometry of the latter one favors the formation of the hydrogen bond between chlorine atom and hydrogen atom of primary OH group of diol (VI), which apparently facilitates not only approach of nucleophile (VI) to substrate (I), but also elimination of water molecule from protonated hemiacetal (A) (scheme 2).
However, when introducing more voluminous electron-acceptor substituents (OCH2CH2O) or [(ClCH2)2CHO] in the
methyl group of diol (V), an initial rate (Wo-104) of the
formation reaction of compounds (XV, XIX) from diols (VII, VIII) and aldehydes (I) is 3.95 ± 0.32 and 2.65 ± 0.19 mol/(l.s.), respectively. Note that the generalization of the obtained data of
the initial rates of the interaction reaction of 1,2-propanediol and its above-listed chloro-, chloroalkoxy derivatives (VI -VIII) with the same aldehyde (I) [ 2.75, 5.60, 3.95 and 2.60 mol/(l.s.)] respectively shows that as the volume of substituents introduced in methyl group of diol (V) rises, the reaction rate subsequently runs low and in a case of diol (VIII) it comes short of the same index in the formation reaction of dioxolane (IX) from diol
(V). Consequently, in case of the possibility of electron and spatial factors' influence on relative reactivity of the initial diols, the latter is decisive [see [19]. p. 37].
When generalizing the kinetic data obtained, it is possible to conclude that the analyzed reaction is reversible and described by kinetic equation of the second order [18]. Based on these determinations and given the that the mechanism of dioxolanation with regard to aldehydes of cyclohexene series with 1,2-diols has not thoroughly been in the literature and using the conformation of the semi-armchair of the cyclohexene ring (see [20], p. 456), we assume that the reaction proceeds according to the scheme described below (with reference to literature [21]:
RCH(OH)CH2OH/H
CHO
> __ V
■\ZCH
Yh Hi
+H+
( A)
H2O+
-H2O
cH \
1+ hT
P1 H
(B)
R
+
H
R
Since the initial stage of the reaction formation mechanism of acetals of 1,3-dioxolane series (realized by interaction of aldehydes with 1,2-diols) is identical to the mechanism of the acyclic acetals preparation reaction [21], the subject of discussion in this case can be only the cyclization process of intermediate (or so-called resonance hybride (RH)) (scheme 2) with formation of the basic product (B), i.e. according to the proposed mechanism (scheme 2) the protonated hemiacetal (A) losing water molecule (with participation of an electron pair in the neighboring oxygen atom) is converted into "RH". Then, there is an apparent attack of carbocation in "RH" with lone-electron pair of carbon atom of "OH" group and as a result a bond "O-H" is weakened and after a proton is
(Scheme 2)
torn away the cycle formation is over (scheme 2).
Relatively alternative variants of cyclization "RH" are presented in the work [21]. It should be noted that the implementation of cyclization with conversion of "RH" in enol ether is impeded due to
3
unlikelihood of proton's tearing away from sp of the hybridized carbon atom of carbocycle in these conditions. Consequently, the implementation of cyclization through enol ether would lead to extremely low yields of the corresponding basic product which is contrary to the experimental data [22-25]. The incapacity of cyclization by means of formation of intermediate with endo-carbon-oxygen double bond was convincingly proved in the work [21], based on Baldwin rule for ring closure [26].
The supposed reaction mechanismamino- (XLVIII-L), alkoxy a^KOKCH- (LI, LII), (scheme 2) is in accordance with experimentalpropylthiogroup (LIII) which allows to expand data that makes it possible to explain thethe assortment of functionally substituted five-influence of the electron and steric factorsmembered heterocycles with vicinal caused by an appropriate substituent on relativedioxagroups.
reactivity of the initial diols. The above-mentioned characteristic
Owing to the fact that the aldehyde groupchemical conversions of the synthesized in the conformation of the semi-armchair ofcompounds (IX-XXII) determining their cyclohex-3-ene-1-carbaldehyde and its above-synthetic possibilities in the generalized form are listed methyl substituted homologs (II-IV) has apresented in scheme 3. The synthesized 2,4-real equatorial orientation (see [20] p. 456), andi substituted 1,3-dioxolanes (IX-XXII) and attack of its protonated intermediate byproducts of their conversion (XXIII-LIII) are corresponding nucleophile (V-VIII) is essentiallyodourless, transparent liquids. They are insoluble facilitated and consequently, an availability ofi n water, well dissolved in organic solvents the methyl group in position 4C, 6C of carbocycle(acetone, ether, ethanol, etc). The physical-has no effect on its reactivity. chemical constants, as well as data of elemental
It revealed that an oxidation of theanalysis and spectral indices of the synthesized compounds (IX-XXII) by 50 % aqueous solutioncompounds (IX-XXII) and products of their of peroxyacetc acid leads to the correspondingconversion (XXIII-LIII) were offered in the epoxy-derivatives (XXIII-XXXVI) (scheme 3)work [22] and following publications [1, 3, 4, 17, with good yields while an example of22-25]. Owing to the fact that the creation of conjunctive bromination andpolymer composition materials with high
dichlorocyclopropanation of the compounds (IX,operational properties based on industrial XI, XV h XIX) makes it possible to synthesizeepoxide resins is topical, especially as it becomes their corresponding trans-dibromo- (XXXVII-increasingly important with the growth of XL) and gemdichloromethylene derivativestechnological progress, as exemplified by some (XLI-XLIV). Further, as an example ofrepresentatives among the synthesized condensation of the compounds (XI, XV andcompounds (XLV-XLVII). It revealed the XIX) with hexachlorcyclopentadiene it found thepossibility of their application as an active possibility of their application as dienophilediluent (modifier) hardened by polyethylene which allows to synthesize the polychlorine-polyamine (PEPA) of epoxy diane composition containing derivatives of 1,3-dioxolanes withbased on the industrial epoxy diane resin ED-20. norbornene fragment (XLV-XLVII). It showedThe description of experiment and physical-by the example of the compound (XI) that themechanical characteristics of the prepared chlorine atom in the chloromethyl side-chain ofcomposition materials were presented in the 1,3-dioxolanes of cyclohexene series is notablepublication [4]. for high mobility and easily substituted for
1. Kerimov A.Kh., Mamedova Kh.A., Orudzheva A.T. Synthesis, properties and application of functionally substituted cyclic acetals of 1,3-dioxolane ring. ANAS, IPM investigations (Scientific works) Sumgait 2014, pp.189-195.
2. Zumach Gerhard, Kuehle Enqelbert, Behrenz
Wolfqand. Acaricidal, funqicidal and
insecticidal 0-(1,3-dioxolan-2-yi)phenyl N-
[(trihalomethyl)thio] -N-methylcarbamates.
Pat. USA. 2113454, 1972.
REFERENCES
3. Kerimov A.Kh., Babaev M.G., Mishiev D.E. The Synthesis and study of the properties of cyclic acetals on the base of trichlorethanal. Russian Journal of Organic Chemistry. 1987, vol. 28, no. 6. pp. 1194-1198.
4. Kerimov A.Kh., Orudzheva A.T. New modifers of epoxide resins containing polychlorosubstituted norbornene frame. Poly Plastic, 2013, no. 3. pp. 17-19.
5. Babaev M.G., Kerimov A.Kh., Khalilov Kh.D., Mishiev D.E. 2-Trichloromethyl-4-(P,
P-dichloropropoxy)methyl-1,3-dioxolane as plasticizer-modifier of epoxy diane resin. A.s. 1099576 (USSR). B.R. 1984. № 23.
6. Lebedev N.N. The chemistry and technology of main organic and petrochemical synthesis. Moscow: Khimiya Publ., 1975, 734 p.
7. Terequlova G.G., Rolnik L.Z., Zlotskiy S.S., Rakhmankulov D.L., Silishev N.N., Sokolova T.A., Khazinov R.Kh. The synthesis, properties and application of ethers of 4-hydroxymethyl-1,3-dioxolane. The Russian Journal Of Applied Chemistry. 1989, vol. 62, no. 7, pp. 1620-1624.
8. A.s. 281461 (USSR). The methods of preparation of phosphonemethyl 1,3-dioxolanes. Trafimov B.A., Atavin A.S., Gavrilova G.M.. B.R. 1973, no. 25.
9. Okaoda M., Mita K. Sumitomo H. Polymerizability of methyl 1,3-dioxolanes. Makromolecular Chemistry and Physics. 1975, vol. 176, no. 4, pp. 859-872.
10. Heterocyclic compounds. Edited by Elderphylda. R.M. 1961, vol. 5, 602 p.
11. Bredikhin A. A., Novikova V. G., Bredikhina Z. A. The determination of configuration of 2,4-disubstituted 1,3-dioxolanes by X-ray structural analyses and magnetic resonance. Russian Journal of General Chemistry. 1998, vol. 68, no. 11, pp. 1842-1846.
12. Donna M., Huryn, and Masami Okabe. ALDS-driven nucleoside chemistry. Chemical Reviews. 1992, vol. 92 (8), pp. 1745-1768.
13. Movsumzadeh M.M., Shabanov A.L., Kazimov A.S., Agaev F.Kh. Epoxidation of A 3-tetrahydrobenzoic aldehyde.. Proceedings of the Azerbaijan National Academy of Sciences, chemical series. 1969, vol. 25, no. 10, pp. 27-30.
14. The qettinq of acetals by 3-(1,3-dimetil-3-cycloheksenil) propanol. Pat.55-87733 Japan.1980.
15. Olishanova K.M., Potapova M.A., Morozova N.M. Practical work on chomotographical analysis. Moscow: V. Sh. Publ., 1970, 307 p.
16. Kerimov A.Kh. The syntheses of unsaturated derivatives of 1,3-dioxalanes and study of their properties. Russian Journal of General Chemistry. 2004, vol. 74, no. 2, pp. 287-292.
17. Babayev M.G., Kerimov A.Kh., Mishiev D.E. Kinetic of regularities of formation reactions of 2-styrene-4-chloromethyl-1,3-dioxolane. VINITI 1985. B.R. № 6895-85.
18. Leydler K. Dzh. The kinetics of organic reactions. Moscow: Mir Publ., 1966, 346 p.
19. Sayks P. The reaction mechanizms in organic chemistry. Moscow: Khimiya Publ.,1991, 448 p.
20. Potapov V.M. Stereochemistry. Moscow: Khimiya Publ., 1976, 695 p.
21. Reddy C.P., Singh S.M. and Ralaji Rao. Some thoughts on the mechanism of acetal formation and related reactions : extension of Baldwins rules for ring closure. Tetrahedron Lett. 1981, vol. 22, рр. 973-976.
22. Kerimov A.Kh., Babayev M.G., Mishiev D.E. Synthesis of derivatives of 1,3-dioxolanes from 1-formylcyclohexene and study of their properties. Russian Journal of Organic Chemistry. 1985, vol. 21, no. 3, pp. 645-648.
23. Kerimov A.Kh., Babaev M.G., Alieva E.S., Mishiev D.E. Synthesis of derivatives of 1,3-dioxolane on the basis of 3-cyclohexene-
1-carbaldehyde and bicyclo[2,2,1]hept-5-en-
2-carbaldehyde and study of their properties. Russian Journal of General Chemistry. 1991, vol. 61, no. 10. pp. 2328-2332.
24. Kerimov A.Kh. The syntheses of derivatives of 1,3- dioxolanes on the basis of carbocyclic aldehide and study of their properties. Russian Journal of Organic Chemistry. 1991, vol. 37, no. 1. pp. 144-147.
25. Kerimov A.Kh. The syntheses of chlorine-containing derivatives of 1,3-dioxolane from 4-cyclohexenecarbaldehyde and study of their properties. Russian Journal of General Chemistry. 2003, vol. 73, no. 1, pp. 139-142.
26. Baldwin J.E. Rules for Rinq closure. Journal Chemical Communication. 1976, p. 743.
TSIKLOHEKS-3-EN-1-KARBALDEHIDLORIN 1,2-DIOLLAR ILd DIOKSOLANLA§MASI REAKSiYASI Yd ALINAN BiRLd§MdLdRINXASSSLdRIHAQQINDA
B.X. Kzrimov, A.T. Orucova, X.A. Mzmmzdova
AMEA Polimer Materiallari institutu AZ5004 Sumqayit, S.Vurgun kug., 124; e-mail: [email protected]
Tsikloheks-3-en-1-karbaldehidlarin 1,2-propandiol va onun 3-xlor-, 3-xloralkoksi toramalari ila kondensla§masi reaksiyasi asasinda 1,3-dioksolan sirasi tsiklik asetallarin sintezi, onlarin epoksidla§ma, bromla§ma, dixlorkarbenilla§ma va dienofil faalliginin muayyan edilmasi istiqamatinda aparilmi§ tadqiqatlarin umumila§dirilmi§ tahlili verilmi§ va elaca da qar§iliqli tasirda olan komponentlarin avazlayicilarinin tabiatinin onlarin nisbi reaksiya qabilliyatina tasiri ara§dirilmi§dir. Hamginin alinan birla§malarin ED-20 qatrani asasinda hazirlanan polimer kompozisiyalarinin faal durula§diricisi kimi effektliyinin oyranilmasi va alda edilan naticalar §arh edilmi§dir.
Agar sozlar: visinal dioksoqrup saxlayan be§uzvlu heterotsikllar, reaksiya surati, nisbi reaksiya qabiliyati, dioksolanla§ma reaksiyasinin mexanizmi.
О РЕАКЦИИ ДИОКСОЛАНИРОВАНИЯ ЦИКЛОГЕКС-3-ЕН-1-КАРБАЛЬДЕГИДОВ С 1,2-ДИОЛАМИ И СВОЙСТВАХ ПОЛУЧЕННЫХ ПРОДУКТОВ
А.Х. Керимов, А.Т.Оруджева, Х.А. Мамедова
Институт полимерных материалов Национальной АН Азербайджана AZ 5004 Сумгайыт, ул С. Вургуна, 124; e-mail: [email protected]
Приведены обобщенные результаты исследования реакции синтеза циклических ацеталей 1,3-диоксоланового ряда конденсацией циклогекс-3-ен-1-карбальдегидов с 1,2-пропандиолом и его 3-хлор-, 3-хлоралкоксипроизводными, а также их эпоксидирование, бромирование,
дихлоркарбенилирование по С=С связи цикла и диенофильной активности. Рассмотрено влияние природы заместителей на относительную реакционную способность реагирующих компонентов и эффективность полученных продуктов в качестве активного разбавителя полимерной композиции на основе ЭД-20.
Ключевые слова: пятичленные гетероциклы с вицинальными диоксогруппами, скорость реакции, относительная реакционная способность, механизм реакции диоксоланирования.
