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ISSN 2522-1841 (Online) AZERBAIJAN CHEMICAL JOURNAL № 1 2021 ISSN 0005-2531 (Print)
UDC 547.512;535.338
SYNTHESIS OF ETHYL ESTERS OF PHENYL- AND p-PHENYL SUBSTITUTED CYCLOPROPANECARBOXYLIC ACIDS AND THEIR CONVERSION
K.G.Guliyev, A.E.Rzayeva, A.M.Guliyev
Institute of Polymer Materials NAS of Azerbaijan
guliyev.kazim_pm@mail.ru
Received 09.06.2020 Accepted 23.09.2020
The reaction of carboethoxycarbene with styrene and p-substituted styrenes in the conditions of thermocat-alytic decomposition of ethyl diazoacetate has been studied. It has been shown that the substituents in the investigated styrenes have an essential effect on the activity of the double bond with respect to carboethoxycarbene. It has been established as a result of the investigation that the substituents in the para- position of styrene influence essentially on the activity of the double bond with respect to carboethoxycarbene. It has been revealed that carboethoxycarbene is connected to the double bond of styrene and p-styrenes practically without formation of by products. As a result of the reaction, 2-phenyl and 2-p-substituted phenyl-1-ethoxycarbonyl cyclopropane (1-4) as a mixture of cis- and trans- isomers at a ratio of~ (30:70) with the predominant formation of a trans-isomer has been obtained. The composition and structure of the synthesized compounds have been established. It has been revealed that all synthesized cyclopropane-containing compounds show the various biologically active properties. In addition, the compounds 9-12 can be used as a modifier and diluent for epoxy resin ED-20.
Keywords: cyclopropane, p-substituted styrene, carboethoxycarbene, glycidyloxymethylcyclopropane.
doi.org/10.32737/0005-2531-2021-1-11-17
Introduction
Functionally substituted cyclopropanes are one of the leading sections of the organic chemistry, constantly attracting higher interest of researchers. This has been stipulated by both large synthetic and theoretical value of the cyclopropane derivatives and by the fact that they exhibit various biological activity [1-4]. It has been revealed in carrying out of the systematic investigations that the polymers obtained on the basis of cyclopropane derivatives have high photosensitivity [5-9]. The systematic investigations of the reaction of functionally substituted cyclopropanes, study of the composition, structure and properties of these cyclopropane-containing compounds have been presented.
In this work the activity of the double bonds of styrene and para-substituted styrene (p-methyl, p-chloro- and p-nitro styrenes) with respect to carboethoxycarbene has been studied. The reactions of carboethoxycarbene with styrene and p-substituted styrenes were carried out with the use of a twofold excess of styrenes and substituted styrenes under the conditions of thermo-catalytic (CuSO4 anhydrous) decomposition of ethyl diazoacetate.
It has been established as a result of the investigation that the substituents in the paraposition of styrene influence essentially on the activity of the double bond with respect to car-boethoxycarbene. It has been revealed that car-boethoxycarbene is connected to the double bond of styrene and p-styrenes practically without formation of by products. As a result of the reaction 2-phenyl- and 2-p-substituted phenyl-1-ethoxycarbonyl cyclopropane (1-4) as a mixture of cis- and trans-isomers at a ratio of ~(30:70) with the predominant formation of a trans-isomer has been obtained.
In all cases, as expected, the electron-donor substituents increase the reactivity of the double bond, and the electron-acceptor ones decrease it. Indeed, the ethyl ester of fumaric and maleic acids and other side substances in the reaction mixture have been not practically found.
The yields of esters (1-4) largely depend on the reaction conditions and the substituent in the para-position of the styrenes and are on average 65-96%. It was shown that an introduction of a methyl group into phenyl nucleus, i.e. a transition from styrene to p-methylstyrene leads to the expected increase in reactivity.
At restoration of a mixture of isomers of esters 1-4 the corresponding hydroxymethyl substituted phenylcyclopropanes have been obtained. The synthesis of compounds 5-8 was carried out under action of LiAlH4 on 1-4 in boiling diethyl ether converted 82-95% yields to the corresponding carbinols 5-8. The high selectivity of LiAlH4, used as a restoring reagent, allows to carry out the restoration reactions only on the carbonyl group of the initial
ester 1-4, leaving the cyclopropane group unaffected. Consequently, a ratio of stereoisomers at restoration remained practically unchanged, that allows to confirm - the change of configuration of the initial mixture of isomers does not take place.
The synthesis of compounds 9-12 was carried out by interaction reaction of the compounds 5-8 with epichlorohydrin in the present NaOH according to the reaction:
1-4
LiAlH
^ R-C6H4-CH-CH-CH2OH
CH2 5-8
R= H (5), CH3 (6), Cl (7), NO2 (8) R= H (9), CH3 (10), Cl (11), NO2 (12)
A degree of purity of the compounds 1-12 (99.8-99.9%) has been determined by GLC on chromatograph LCM-8 MD. All synthesized compounds 1-12 have been characterized by data of elemental analysis, IR spectra NMR and Figure (1, 2). In the IR spectra of all synthesized compounds there are the absorption bands in the field of 1570-1620 cm-1, 1450-1500 cm-1 and 3000-3030 cm-1 characteristic for valence vibrations of the benzene ring, the bands of low intensity in the field of 1000-1100cm-1, presenting planar deformation vibrations of C-H of the same ring and intensive bands in the field of 690-750 cm-1; characteristic for non-planar deformation vibrations of a three-membered cycle in the field of 3040-3045 cm-1 (C-H valence vibration) and in the field of 1010-1030 cm-1 (vibration of A-cycle itself). In addition, in the IR spectra of the compounds 3, 7, 11, there are the absorption bands at 750-760 cm-1 characteristic for the chlorine atom and bands at 1335 and 1525 cm-1, related to vibrations for NO2 of the compounds 4, 8, 12. It has been revealed that the absorption bands of the benzene and cyclopropane rings are retained in the compounds 9-12 and there are the absorption bands at 875 and
epc+NaOH .
1250 cm- for o fragment.
In the IR spectra of 2-phenylcyclopro-pylcarbinols (5-8) in the pure form, it is seen a
- r-C6H4-CH-CH-CH2OCH2-CH-CH2
CH2 9-12
O
strong absorption in the field of ~1050 cm-1, which is probably characteristic for alcohols CO group. The absorption of alcohols 5-8 is especially appeared as two broad bands: one at 3340 cm-1 and the second, relatively low-intensive at 3560 cm-1. The first is usually referred to the valence vibration of hydroxyl groups included in "polymer complexes". The second - the vibration of OH groups forming the dimer ring. At the solution of carbinols 5-8 are dissolved in CCl4, the band at 3340 cm-1 shifts to ~3360 cm-1, and it is simultaneously appeared a low-intensive band at 3640 cm-1. This fact indicates that at dissolution in CCl4 (~30%) a small number of alcohol molecules is released from hydrogen bond and is in a state of monomers. Indeed, at further dilution of the solution, an intensity of the band at 3640 cm-1 is increased, that corresponds to an increase of a number of monomeric alcohol molecules in the solution. During the study of the spectra of alcohols 5-8 in a dioxane solution (40%), it has been revealed that the absorption band at 3340 cm-1 is shifted toward the waves up to 3500 cm-1.
It has been detected that an increase of dioxane in the solution leads to a decrease of the band intensity at 3500 cm-1 and it is simultaneously appeared a low-intensity band at
3620 cm-1.
Fig. 1. NMR spectra 2-phenyl-1-hydroxymethylcyclopropane.
8 5 8.0 7.5 7.0 65 6.0 5.5 5.0 4 5 40 3.5 3.0 2.5 2.0 1.5 1.0 0.6 ppm
Fig. 2. NMR spectra 2-phenyl-1-ethoxycarbonylcyclopropane.
The band at 3500 cm-1 which can be attributed to the vibration -OH group connected
;>-o-r
to me dimenc ring of type H' . Probably, when the investigated alcohol is dissolved in such a strongly polar solvent as dioxane, a possibility of the formation of a hydrogen bond between dioxane and alcohol molecules, the vibration of hydroxyl group, which in this case appears around 3500 cm-1, cannot be ruled out.
The observed band at 3500 cm-1 in the spectra of a dioxane solution of 2-phenylcyc-lopropylcarbinols (5-8), is probably referred to the vibrations of hydroxyl groups forming hydrogen bonds between alcohol molecules in di-meric complexes and between alcohol molecules in dioxane. The bands at 3620 cm-1, which
appear as a result of some decrease of the concentration of closed dimeric complexes at dilution, probably can be attributed to the vibration of end hydroxyl group of the dimer type
R R o-H—>o-H.
It has been revealed that all synthesized cyclopropane-containing compounds exhibit various biologically active properties. In addition, the compounds 9-12 can be used as a modifier and diluent for epoxy resin ED-20.
Experimental part
The IR spectra have been recorded on an "Agilent Cary 630 FTIR" apparatus in a thin layer. The 1H NMR spectra have been obtained on a Bruker AFR-300 spectrometer in CDCl3, the chemical shifts have been determined rela-
tively tetramethylsilane (TMS). The purity of the synthesized compounds was controlled by methods of GLC and TLC on UV-254 plates, and detected by UV light or iodine vapors.
1. Reaction of carboethoxycarbene with phenyl-substituted styrenes. General method. A mixture of 0.6 mol (62.4 g) of styrene or p-phenyl substituted styrene and 0.2 g of anhydrous copper sulfate as a catalyst was heated to 40-500C and in stirring 0.5 mol of ethyl diazo-acetate was added dropwise (addition rate 1012 g/h). After addition of all of the ethyl diazo-acetate and stopping the isolation of nitrogen, the reaction mixture was cooled to room temperature. The catalyst CuSO4 was filtered off, the filtrate was extracted several times with di-ethyl ether and the resulting reaction mass was combined. Further diethyl ether was distilled and then was distilled in vacuum. At the beginning - an excess of styrene or phenyl substituted styrene, and then - main fraction 1-4.
The IR spectra of the compounds 1-4 contain the absorption bands in the field of 3095-3100, 1030-1035 (vc-h cycle), 2980, 2940, 2880 (vc-h aliph.), 750-760 (vci), 1690, 1720 (vc=o), 1450-1500 cm-1 and 1570-1620 cm-1, 1335 and 1525 cm-1 (NO2) of the compound 4. The bands 690-750 cm-1 are referred, to out-of-planar deformation vibrations of C-H in mono-substituted benzene of the compound 1.
2-phenyl-1-ethoxycarbonylcyclopropane (1). Formula C12H14O2. Yield - 90%, b.p. -68-700C (3 mm Hg), «2° = 1.5125, d420 = 1.08, MRD = 50.713. 1H NMR spectrum, 5, ppm: 6.95 m (5Harom), 1.92 m (1H, CHcycloprop.), 2.56 m (1H, CHcycloprop), 1.65 m (1H, CHcycloprop.), 1.62 m (1H, CH2cydoprop), 3.85 q (2H, CH2), 0.96 t (3H, CH3). Found, %: C 75.20, H 7.91. Calculated, %: C 75.79, H 7.37.
2-p(methylphenyl)-1-ethoxycarbonylcyc-lopropane (2). Formula C13H16O2. Yield - 95%, b.p. - 75-770C (3 mm Hg), «¿0 = 1.500, d420 = 1.06, MRd = 55.331. 1H NMR spectrum, 5, ppm: 7.00 m (4Haran.), 100 s (CH3), 1.93 m
(1H, CHcycloprop.X 2 58 m (1H, CHcycloprop.), 164
m (1H, CH2cycloprop), 1.65 m (1H, CH2cycloprop), 3.92 q (2H, CH2), 1.05 t (3H, CH3). Found, %: C 76.58, H 7.20. Calculated, %: C 76.47, H 7.84.
2-p(chlorophenyl)- 1-ethoxycarbonylcyc-lopropane (3). Formula C12H13O2Cl. Yield -82%, b.p. - 85-870C (3 mm Hg), n™ = 1.5640, d40 = 1.32, MRd = 55.58. 1H NMR spectrum, 5, ppm: 7.10 m (4Harom), 2.08 m (1H, CHcycloprop), 2.55 m (1H, CHcycloprop), 1.71 m (1H,
CH2cycloprop.X 1.65 m (1H, CH2cycloprop.), 4.00 q
(2H, CH2), 1.0 t (3H, CH3). Found, %: C 64.28, H 5.32, Cl 15.75. Calculated, %: C 64.14, H 5.79, Cl 15.81.
2-p(nitrophenyl)- 1-ethoxycarbonylcyc-lopropane (4). Formula C12H13O4N. Yield -65%, b.p. - 140-1420C (3 mm Hg), «20 = 1.5610, d2 = 1.30. 1H NMR spectrum, 5, ppm: 7.50 m (4H^), 2.09 m (1H, CHcycloprop), 2.68 m (1H, CHcycloprop), 1.67 m (1H, CH2cycloprop), 163 m (1 H, CH2cycloprop), 4.13 q (2H, CH2), 1.12 t (3H, CH3). Found, %: C 61.11, H 5.63, N 5.80. Calculated, %: C 61.28, H 5.53, N 5.95.
2. Synthesis of 2-p-phenyl-substituted-1-hydroxymethylyclopropanes. General method. 9.5 g (0.25 g-mol) LiAlH in 200 ml of absolute diethyl ether was placed to a three-necked flask with a capacity of 500 ml, equipped with a mechanical stirrer, a dropping funnel and a reflux condenser and was added 0.25 mol (47.5 g-mol) of ethyl ester of 2-phenylcyclopropane-1-carb-oxylic acid for 2-2.5 hours. With this the temperature of the reaction medium was maintained at 25-350C. After addition the whole initial ester, the stirring was continued for another 30 minutes. Then, the distilled water was added dropwise into the flask, and then - 5% solution of hydrochloric acid. The ether layer was separated; the aqueous layer was extracted with ether (twice in 20 ml). The ether extracts were combined with the ether layer and dried over calcined Na2SO4. After distilling off the sulfuric ether, the reaction products were distilled under vacuum. 6-8 was similarly synthesized.
The IR spectra of the compounds 5-8 contain the absorption bands in the field of 3095-3100 (vc-h cycle.), 2980, 2940, 2880 (vc-h aliph), 2900-3100 cm-1 (OH), 758-770 (vci), 1335 and 1525 cm-1 (NO2).
2-phenyl-1-hydroxymethylcyclopropane (5). Formula C10H12O. Yield - 92%, b.p. - 125-1300C (9 mm Hg), «2° = 15110, d420 = 1.335, MRd = 43.235. 1H NMR spectrum, 5, ppm: 6.92 m (5Harom), 1.93 m (1H, CHcycloprop.), 2.61
m (1H, CHcycloprop.), 1.63 m (1H, CHcycloprop.),
1.65 m (1H, CH2cycloprop), 3.86 s (2H, CH2O),
3.64 s (1H, OH). Found, %: C 81.25, H 8.05. Calculated, %: C 81.08, H 8.10.
2-p(methylphenyl)1-hydroxymethylcyc-lopropane (6). Formula C11H14O. Yield - 93%, b.p. - 130-1370C (9 mm Hg), «2° = 1.5130, d2° = 1.350, MRD = 46.920. 1H NMR spectrum, 5, ppm: 6.95 m (4Harom), 0.95 s (3H, CH3), 1.94 m (1H, CHcycloprop), 2.63 m (1H, CHcycloprop), 166 m (1H, CH2cycloprop.) 1.68m (1H, CH2cycloprop), 3.87 d (2H, CH2O), 3.66 s (1H, OH). Found, %: C 81.59, H 8.83. Calculated, %: C 81.48, H 8.64.
2-p(chlorophenyl)1-hydroxymethylcyc-lopropane (7). Formula C10H11OCl. Yield -94%, b.p. - 135-1420C (9 mm Hg), «2° = 1.5225, d 2° = 1.478, MRD = 48.998. 1H NMR spectrum, 5, ppm: 7.14 m (4Harom), 2.05 m (1H, CHcycloprop.), 2.57 m (1H, CHcycloprop.),
1.66 m (1H, CH2cycloprop), 1.72 m (1H, CH2cycloprop), 3.91 d (2H, CH2O), 3.68 s (1H, OH). Found, %: C 65.20, H 6.75, Cl 19.94. Calculated, %: C 65.75, H 6.03, Cl 19.45.
2-p(nitrophenyl)1-hydroxymethylcyclo-propane (8). Formula C10H11O3N. Yield -93%, b.p. - 131-1490C (2 mm Hg), «2° = 1.5190, d2° = 1.524, MRD = 49.998. 1H NMR spectrum, 5, ppm: 7.55 m (4Harom.) , 2.17
m (1 H, CHcycloprop.), 2.60 m (1 H, CHcycloprop.),
1.65 m (1 H, CH2cycloprop.), 1.69 m (1 H, CH2cycloprop.), 3.98 d (2 H, CH2O), 3.72 s (1 H, OH ). Found, %: C 62.22, H 5.40, N 7.80. Calculated, %: C 62.18, H 5.69, N 7.25.
3. Synthesis of p-substituted 2-phenyl-1-glycidyloxymethylcyclopropane. General method. 14.8 g (0.1 mol) of 2-phenyl-1-hydr-oxymethylcyclopropane in 50 ml of absolute diethyl ether, 0.2 g of hydroquinone and 8 g (0.2 mol) of powdered caustic sodium were placed to a three-necked flask; then with intensive mixing 15.3 g (0.2 mol) of epichlorohydrin
was added. The reaction mixture was stirred for 4 h, the precipitated NaCl was filtered. After this, the diethyl ether was firstly distilled off. The residue was distilled in a vacuum. 10-12 was similarly synthesized.
The IR spectra of the compounds 9-12 contain the absorption bands in the field of 1435-1440 cm-1, 3095-3100 cm-1 (vc-h cycle), 2880 cm-1, 2940 cm-1, 2980 cm-1(vc-H aliph.), 755-770 (vCl), 1365 and 1335 cm-1 (NO2), 875-
1250 cm-1 ( o ).
2-phenyl-1-glyridyloxymethylcyclopro-pane (9). Formula C13H16O2. Yield - 95%, b.p. - 140-1430C (1 mm Hg), «2° = 1.520, df = 1.26, MRd = 54.895. 1H NMR spectrum, 5, ppm: 7.05 m (5Harom.), 1.90 m (1H, CHcycloprop.), 2.57 m (1H, CHcycloprop.), 1.57 m (1H, CH2cycloprop.), 1.60 m (1 H, CH2cycloprop.), 3.50 d (2H, CH2eth), 3.85 d (2H, CH2ether), 2.96 m (1H, CHep), 2.30 d (2H, CH2ep). Found, %: C 76.38, H 7.90. Calculated, %: C 76.47, H 7.84.
2-p(methylphenyl)1-glycidyloxymethyl-cyclopropane (10). Formula C14H18O2. Yield -93%, b.p. - 144-1500C (1 mm mer.c), «2° = 1.5180, d2° = 1.114, MRD = 59.098. 1H NMR spectrum, 5, ppm: 7.10 m (4Harom), 1.10 s (3H, CH3), 1.92 m (1H, CHcycloprop), 2.55 m
(1H, CHcycloprop.X 159 m (1H CH2cycloprop.X 162
m (1H, CH2cycloprop), 3.55 d (2H, CH2eth), 3.90 d (2H, CH2eth), 2.98 m (1H, CHep), 2.35 d (2H, CH2ep). Found, %: C 77.45, H 8.13. Calculated, %: C 77.06, H 8.25.
2-p(chlorophenyl)1-glycidyloxymethyl-cyclopropane (11). Formula C13H15O2Cl. Yield - 96%, b.p. - 144-147°C (1 mm Hg) «2° = 1.5230, d2° = 1.196, MRd = 60.821. 1H NMR spectrum, 5, ppm: 7.16 m (4Hph), 1.87 m
(1H, CHcycloprop.X 2.62 m (1H, CHcycloprop.X 1.58 m (1H, CH2cycloprop ), 1.63 m (1H, CH2cycloprop ),
3.60 d (2H, CH2eth), 4.00 d (2H, CH^.), 3.00 m (1H, CHep), 2.45 d (2H, CH2ep). Found, %: C 65.77, H 6.52, Cl 14.37. Calculated, %: C 65.41, H 6.29, Cl 14.88.
2-p(nitrophenyl)1-glycidyloxymethylcyc-lopropane (12). Formula C13H15O4N. Yield -94%, b.p. - 150-153°C (1 mm Hg),
-"cP
n20 = 1.5250, d420 = 1.228, MRd = 62.007. 1H NMR spectrum, 5, ppm: 7.85 m (4Harom.), 2.15
m (1H, CHcycloprop.), 2.68 m (1H, CHcycloprop.), 1.66 m (1H, CH2cycloprop), 1.71 m (1 H, CH2cycloprop.), 3.70 d (2H, CH2eth.), 4.10 d (2H, CH2eth), 3.08 m (1H, CHep), 2.60 d (2H, CH2ep). Found, %: C 62.11, H 6.78, N 5.89. Calculated, %: C 62.65, H 6.02, N 5.62.
Conclusion
1. The reaction of carboethoxycarbene with styrene and ^-substituted styrenes under the conditions of the thermocatalytic decomposition of ethyl diazoacetate has been studied. It has been revealed that the substituents in the investigated styrenes have an essential effect on the activity of the double bond with respect to carboethoxycarbene.
2. The composition and structure of the synthesized compounds have been established. It has been revealed that all synthesized cyclopropane-containing compounds show the various biologically active properties.
References
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FENiL va ^-FENiL OVOZLi TSiKLOPROPANKARBON TUR§USUNUN ETiL EFiRLORlNiN SiNTEZi
VO CEVRiLMOLaRi
K.Q.Quliyev, A.E.Rzayeva, A.M.Quliyev
Etildiazoasetatin termokatalitik parglanmasi i§tirakinda karboetoksikarbenin stirol va p-xlorstirol ila qar§iliqli tasir reaksiyasi 6yranilmi§dir. A§kar edilmi§dir ki, istifada edilmi§ stirollarda olan avazedicilarin tabiati karboetoksikarbenla reaksiya zamani ikiqat rabitanin aktivliyina ahamiyyatli daracada tasir gostarir. Sintez olunmu§ birla§malarin tarkib va qurulu§u tayin edilmi§dir. Tadqiqatlar naticasinda muayyan edilmi§dir ki, stirola para vaziyyatda birla§mi§ avazlayicilar karboetoksikarbenda olan ikiqat rabitanin aktivliyina ahamiyyatli daracada tasir gostarirlar. A§kar olunmu§dur ki, stirolun va parastirollann ikqat rabitasina karboetoksikarbenin birla§masi praktiki olaraq alava mahsullar alinmadan gedir. Reaksiya, 2-fenil va 2-p-avazli-fenil-1-etoksikarboniltsiklopropan (1-4) birla§malarinin sis- va trans- izormerlari qan§igi §aklinda va ~30:70 nisbatinda, tans izomerin alinmasi ustunluyu ila gedir. Sintez edilmi§ birla§malarin tarkib va qurulu§lan oyranilmi§dir. Malum olmu§dur ki, butun sintez edilmi§ tsiklopropan tarkibli birla§malar muxtalif bioloji aktivliya malikdirlar. Bundan alava, qeyd etmak lazimdir ki, 9-12 birla§malari ED-20 epoksid qatrani ugun modifikator va qatqi maddasi kimi da istifada oluna bilar.
Agar sozlzr: tsiklopropan, p-3V3zli stirol, karboetoksikarben, qlisidiloksimetiltsiklopropan.
СИНТЕЗ ЭТИЛОВЫХ ЭФИРОВ ФЕНИЛ И и-ФЕНИЛЗАМЕЩЕННЫХ ЦИКЛОПРОПАНКАРБОНОВЫХ КИСЛОТ И ИХ ПРЕВРАЩЕНИЯ
К.Г.Гулиев, А.Э.Рзаева, А.М.Гулиев
Изучена реакция карбоэтоксикарбена со стиролом и п-замещенных стиролов в условиях термокаталитического разложения этилдиазоацетата. Показано, что заместители в исследуемых стиролах оказывают существенное влияние на активность двойной связи по отношению к карбоэтоксикарбену. В результате исследования установлено, что заместители в пара положении стирола оказывают существенное влияние на активность двойной связи по отношению карбоэтоксикарбену. Выявлено, что карбоэтоксикарбен присоединяется к двойной связи стирола и п-стиролов практически без образования побочных продуктов. В результате реакции был получен 2-фенил и 2-п-замещенныхфенил-1-этоксикарбонил циклопропан (1-4) в виде смеси цис- и трансизомеров в соотношении ~30:70 с преимущественным образованием транс изомера. Установлены состав и структуры синтезированных соединений. Выявлено, что все синтезированные циклопропансодержащие соединения проявляют различные биологически активные свойства. Кроме этого соединения 9-12 можно использовать в качестве модификатора и разбавителя для эпоксидной смолы ЭД-20.
Ключевые слова: циклопропан, паразамещенный стирол, карбоэтоксикарбена, глицидилоксиметилциклопропан.
