On the synthesis of c-n-alkylphenylsubstituted derivatives of benzimidazole Текст научной статьи по специальности «Химические науки»

86

AZeRBAYCAN KIMYA JURNALI № 3 2018

ISSN 2522-1841 (Online) ISSN 0005-2531 (Print)

UDC 547.297.81

ON THE SYNTHESIS OF C-N-ALKYLPHENYLSUBSTITUTED DERIVATIVES OF

BENZIMIDAZOLE

M.A.Rustamov, G.A.Mirzayeva, Sh.M.Eyvazova

Azerbaijan Technical University

mirzayeva [email protected]. ru

Received 08.06.2018

A synthesis of chloroanhydrides of phenyl-, alkylsubstituted dodecacarboxylic acids has been performed and their electrophilic reactions with o-phenylenediamine explored. It is established that during the reaction the cyclic compound, C-alkyl derivatives of benzimidazole were produced with high yield. It as a result of formation of the product determined that mono-carboxyamide compounds transformed into enol form intramolecular cyclization, C-alkyl derivatives. Due to this mono-carboxyamide compounds are obtained with low yield.

Keywords: carboxylic acid, chloroanhydride, carboxyamide, benzimidazole.

Introduction

Benzimidazole derivatives are widely used in chemistry, pharmacy and laquer dye industry. Many scientists focus on the research works carried out in this direction. Considering this we synthesized C-functionally substituted cycloalkane derivatives and studied their properties in our previous works [1-3]. In the present work we the obtaining of new N-alkylphe-nylsubstituted C-derivatives of benzimidazole and research of their properties are reflected. o/7/?o-Phenylenedi amine is acylated with chloroanhydrides of 5-phenyl, alkylphenyldodeca-

carboxylic acids to produce C-N-alkylphenyl derivatives of benzimidazole. 5-phenyl, alkyl-phenyldodecacarboxylic acids were produced by alkylating benzene and its derivatives with S-heptyl-S-valerolactone obtained by the method [4] in Friedel-Crafts reaction using the method [5]. Physical and chemical properties of synthesized acids (Ia-ch) are similar to the literature data [6]. Chloroanhydrides of acids were obtained using the method [7] and reactions with o-phenylenediamine were studied. The reaction proceeds by the following scheme:

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During the reaction carboxyamide (II a- phenyl derivatives (III a-ch) of benzimidazole. ch) compounds are also obtained in small quan- These derivatives (III a-ch) of benzimidazole tities (8-10%) with the main product C-alkyl- are probably obtained due to the intramolecular

ON THE SYNTHESIS OF C-N-ALKYLPHENYLSUBSTITUTED DERIVATIVES

87

cyclization of mono-carboxyamide compounds (II a-ch) by transforming to enol form. Composition and structure of synthesized carboxyamide (II a-ch) and benzimidazole derivatives (III a-ch) were studied by determining their physical and chemical constants and confirmed by the method of IR-spectroscopy and NMR.

Experimental part

Chloroanhydride of 5-phenyldodeca-carboxylic acid (la). 69 g (0.25 mol) of 5-phenyldodecacarboxylic acid and 80 ml of benzene mixture are placed into three-necked flask equipped with a mechanical mixer, reverse cooler, thermometer and drop funnel, then 23.37 g (0.17 mol) of PC13 is added into the mixture using a drop funnel. After PCI3 is added completely the reaction mass is heated for 1.5-2 hours at 70-75°C. Chloroanhydride benzene mixture is separated from yellow deposit by decaptation and distilled in vacuum. Obtained 66.11 g (89.9%) chloroanhydride (I a). 7boii. - 189- 191°C/8 mm Hg, n2D° - 1.4826, df - 0.9745. Ci8H27C10. Calculated MRD -86.689. FoundMRd - 86.248.

Chloroanhydride of 5-(4-methylphe-nyl)dodecacarboxylic acid (I b). Using the above-mentioned technique 66.71 g (86.5%) of chloroanhydride (I b) was obtained by the interaction of 72.50 g (0.25 mol) of 5-(4-methylphe-nyl)dodecacarboxylic acid with 23.37 g (0.17 mol) of phosphorus trichloride in 80 ml of benzene environment. 7b0ii. - 194-196°C/7 mm Hg, n2D° - 1.4835, df - 0.9699. Ci9H29C10. Calculated MRd 91.307. Found MRd - 90.875.

Chloroanhydride of 5-(4-ethylphenyl)-dodecacarboxylic acid (I c). Using the same technique 80.62 g (86.6%) of chloroanhydride (I c) was obtained by the interaction of 76.0 g (0.25 mol) of 5-(4-ethylphenyl)dodecacarboxy-lic acid with 23.37 (0.17 mol) of PC13 in 80 mol of benzene environment. Th0ii-236-239°C, 20 mm Hg, n™-1.4785, df- 0.9536, C20H3iClO. FoundMRd96.182, Calculated MRD -95.925.

Chloroanhydride of 5-(2,5-dimethyl-phenyl)dodecacarboxylic acid (I ch). Using the same technique 69.17 g (85.8%) of chloroa-

nhydride (I ch) was obtained by the interaction of 76.0 g (0.25 mol) of 5-(2,5-dimethylphenyl)-dodecacarboxylic acid with 23.17 (0.17 mol) of PCI3 in 80 mol of benzene environment. 7b0ii.-241- 243°C, 20 mm Hg, n2D° - 1.4796, df-0.9576, C20H31CIO. Found MRD - 95.347. Calculated MR/) - 95.925.

Reaction of chloroanhydride (I a) of 5-phenyldodecacarboxylic acid with o-pheny-lenediamine. 5.4 g (0.05 mol) of o-phenylene-diamine and 70 ml of /»-xylene mixture is placed into a three-necked flask equipped with a reflux condenser, thermometer and mixer and 14.7 g (0.05 mol) of chloroanhydride (I a) is added drop by drop. The temperature of a reaction mass rises up to 40°C when chloroanhydride is added. Then the reaction mass is heated for 2 hours at 75-80°C. After cooling a crystal substance is filtered and separated from a liquid part. When crystal substance is crystallized in a water-alcohol mixture two fractions are obtained. 1) 1.7 g (9.3%) N-(2-aminephenyl)-5-phenyldodecacarboxyamide (II a). rmeit-135-136°C (Et0H-H20). IR spectra (v, sin 1): 3380 (NH2), 3350 (NH), 1650 (-CO-NH), 1600-1500 (C=Car.), 770, 755, 740 (C=Car. 1,2-substituted), 730, 710, 700 (C= Car, mono-sub-stituted). 2) [(4-phenyl)undecyl]-lH-benzimid-azole (Ilia), rmdt.- 71-72°C (Et0H-H20). IR-spectrum (v, sm"1): 3180 (-NH, bonded), 1660 (C=N, valence vibrations of a bond in a cycle), 1600, 1580, 1510, (C=Car.), 730, 710, 700 (C=Car., mono-substituted). Spectrum NMR (8, ppm): 0.88 s (3H, CH3), 1.30 s (2H, CH2), 1.36^-1.84 m (16H, 5CH2), 2.64 s (1H, Ar-CH), 6.70-6.82 m (5H, C6H5), 7.30-7.65 m (4H, C6H4).

Reaction of chloroanhydride of 5-(4-methylphenyl)dodecacarboxylic acid (I b) with o-phenylenediamine. Two substances are obtained by the interaction of 15.32 g (0.05 mol) of chloroanhydride (I b) with 5.4 g (0.05 mol) of o-phenylenediamine in 70 ml of p-xylene environment using the same method: 1) 1.63 g (8.6%) N-(2-aminephenyl)-5-(4-methyl-phenyl)dodecacarboxyamide (II b). 7mdt. -128-129°C (Et0H-H20).

88

M.A.RUSTAMOV et al.

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ON THE SYNTHESIS OF C-N-ALKYLPHENYLSUBSTITUTED DERIVATIVES

89

2) 14.49g (80.5%) 2-[4-(4-methylphenyl)-undecyl]-lH-benzimidazole (II b). Tmsit.-61-62°C (Et0H-H20). IR spectra (v, sin1): 3280 (NH, valence bond), 1690 (C=N-), 600, 540, 500 (C=Car), 860, 830 (C=Car., 1,4-substituted), 775, 770, 700 (C=Car„ 1,2-substituted).

Reaction of chloroanhydride of 5-(4-ethylphenyl)dodecacarboxylic acid (I c) with o-phenylenediamine. Using the same technique two substances are obtained by the reaction of 16.03 g (0.05 mol) of chloroanhydride (I c) with 5.4 g (0.05 mol) of o-phenylenedi amine in 70 ml /»-xylene. 1) 1.52 g (7.8%) N-(2-aminephenyl)-5-(4-ethylphenyl)dodecacarboxyamide (II c). rmeit. -120-121°C (Et0H-H20). IR spectra (v, cm"1): 3380 (NH2), 3350 (-NH), 1670 (-CO-NH), 1600-1480 (C=Car.), 850, 810 (C=Car., 1.4-substi-tuted), 750, 730 (C=Car., 1,2-substituted). 2) 14.75 g (78.9%) 2-[4-(4-ethylphenyl)undecyl]-lH-benz-imidazole (II c). Tmdt- 54-55°C (Et0H-H20). IR spectra (v, sm"1): 3300 (-NH, valence bond), 1680 (C=N-), 600-480 (C=Car.), 860, 840, 810 (C=Car, 1,4-substituted), 770, 750, 710 (CKV, 1,2-substituted).

Reaction of chloroanhydride of 5-(2,5-dimethylphenyl)dodecacarboxylic (II ch). Using the same method two substances are obtained by the interaction of 16.03 g (0.05 mol) of chloroanhydride (I ch) with 5.4 g (0.05 mol) of o-phenylenediamine. 1) 1.99 g (10.2%) N-(2-aminephenyl)-5-(2,5-dimethylpenyl) dodeca-carboxyamide (II c). Tmslt - 123-124°C (Et0H-H20). IR spectra (v, sm"1): 3380 (NH2, free), 3350 (-NH), 1680 (CO-NH), 1600-1500 (C=Car), 870, 860 (C=Car„ 1,2,5-substituted), 750, 710, 700 (C=Car., 1,2-substituted). 2) 15.67 g (83.8%) 2-[4-(2,5-dimethyl-phenyl)undecyl]-lH-benzimidazole (II c). rmeit. - 56-57°C (Et0H-H20). IR spectra (v, cm"1): 3180 (-NH, connected), 1660 valence vibrations of (C=N-) bond in cycle, 1605, 1580 (C=Car), 860-840 (C=Car„ 1,2,5-substituted), 760-700 (C=Car, 1,2-substituted). NMR spectra (5, ppm): 0.935 s

(3H, CH3), 1.30 s (2H, CH2), 1.28 -1.55 m (10H, 5CH2), 1.58-1.62 m (CH, 3CH2), 2.32 s (6H, Ar- (CH3)2), 2.72 s (1H, Ar-CH- ), 6.70-6.80 d (3H, 3ArH), 7.76 s (1H, N-H) absorption bands and signals confirm its structure.

IRspectrum of synthesized substances was recorded on Nicolet 10 spectrometer in suspension state on a thin film or in paraffinic oil.

Spectrum NMR was measured on Bruker 300 spectrometer (operating frequency - 300 MHz), internal standard - hexamethylenedicy-clooxane, chemical shift was measured in a scale 8.

References

1. Rustamov M.A., Eivazova Sh.M. Atcilirovanie o-fenilendiamina khlorangidridami alkil- i fenilza-meshchennykh tciclogeksan(en) karbonovykh kislot // Nauchn. zhurn. "Poisk". Ministerstvo Obra-zovaniia i nauki Kazakhstana. 2009. № 4. S. 10-15.

2. Rustamov M.O.. Veysova N.O.. Abbasov M.F., Eyvazova §.M. Karboksiamid vo heterotsiklik azotiizvi birlosmolorin sintezi haqqinda //A/orb. Kimya Jurnali. 2013. № 1. S. 94-97.

3. Veysova N.O.. Eyvazova §.M., Rustamov M.O. Miixtolif funksionabvazli karboksiamid birlosmolori nin sintezi haqqinda // Kimya problcmlori 2011. № 1. S. 119-122.

4. Abbasov M.F., Alimardanov KH.M., Suleima-nova E.T. Kataliticheskoe okislenie alkil- i tcicloalkilnonanov v laktony // Zhurn. pricl. himii. 1977. T. 20. Vyp. 4. S. 648-655.

5. Rustamov M.A., Ismaiylov A.G., Akhmedov R.Sh., Salmanov V.A., Amirov Sh.A. Tcicloalki-lirovanie benzola mono- i dimetil- zameshchen-nymi 3-tciclogeksenkarbonovymi kislotami i soot-vetstvuiushchimi bitciclicheskimi y- i 5-laktonami //Zhurn. org. himii. 1992. T. 28. № 2. S. 300-305.

6. Mir/oycva G.O.. Nabiyeva R.F., Abbasov M.F., Rustamov MO. Benzol vo onun toromolorinin Fri-del-Krafts reaksiyasi soraitindo 8-heptil-8-valerolak-tonla alkillosdirilmosi // AzTU Elmi osorlor. Fundamental clmlor. 2010. № 1. C. IX (33). S. 123-125.

7. Veigand-Hilgetag. Metody eksperimenta v orga-nicheskoi himii. Ximiia. M.: 1969. S. 231.

AZERBAIJAN CHEMICAL JOURNAL № 3 2018

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СИНТЕЗ БЕНЗИМИДАЗОЛА С С-1Ч-АЛКИЛЗАМЕ1ЦЕННЫМИ ПРОИЗВОДНЫМИ

М.А.Рустамов, Г.А.Мирзоева, Ш.М.Эйвазова

Синтезированы хлорангидриды фенил-, алкилфенилзамещенных додекакарбоновых кислот и изучены их элек-трофильные реакции с о-фенилендиамином. Установлено, что в результате реакции с большим выходом получены циклические производные С-Ы-алкилбензимидазола. Показано, что образование продукта внутримолекулярной циклизации С-Ы-алкилпроизводных связано с переходом моно-карбоксиамидных соединений в ходе реакции в энольную форму. В связи с этим моно-карбоксиамидные соединения получены с низким выходом.

Ключевые слова: карбоновая кислота, хлорангидрид, карбоксиамид, бензимидазол.