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CHEMICAL PROBLEMS 2018 № 2 (16)
ISSN 2221-8688
191
UDC 547.297.81
STUDY OF ACYLATION REACTION OF AMINES OF VARIOUS STRUCTURES WITH CHLOROANHYDRIDE OF HEXANE ACID
M.A. Rustamov, G.A. Mirzayeva
Azerbaijan Technical University H.Javid Ave. 25, Az 1143 Baku
Received 24.12.2017
Research into the acylation reaction of various amines by chloroanhydride hexane acid showed that the nature and conditions of functional groups in the molecule of amine compounds has a great influence on the reaction direction and reaction yield. Unlike para-phenylenediamine when acylating ortho-phenylenediamine, together with monocarboxyamide formation there is C-alkyl derivative of benzimidazole following the conversion of N-(2-aminophenyl)of pentancarboboxiamide into enolform and intermolecular cyclization.
Keywords: acylation reaction, chloroanhydride hexane acid, o-phenylenediaminein, p-phenylenediamine, monocarboxyamide, intermolecular cyclization
In previous research works [1-5] the acylation reaction of various functionally substituted amines was studied with chloroanhydrides of alicycliccarboxylic acids. It found that in addition to carboxyamide compounds nitrogenous heterocyclic compounds, there are also obtained benzimidazole, benzoxazole, oxadiapezine derivatives. It went to show that synthesized carboxyamide compounds exhibit their inhibitor properties against corrosion [6, 7], stimulator property for plants [8, 9]. The
nature and condition of functional groups in their molecules considerably effect on bioactivity properties of these substances. With that end in view, chloroanhydride of hexane acid was used as a reagent to synthesize new functionally substituted nitrogenous compounds for acylation of amines with varied structures. When acylating chloroanhydride (I) of hexane acid with aromatic ortho- and para-diamines, relevant carboxyamide compounds are obtained. Reaction goes by the following scheme:
h2n
n- H3C-(CH2)4-COCl +
i h2n
p-ksilol, t0 --
- HCl
n- H3C-(CH2)4-CO-NH
ii
h2n
V /
n- H3C-(CH2)4-C
¡O , ■ ■ ! I H-/-N
LH 'I
L.-----I H
—► n-H3C-(CH2)4-C^ H2O 3 2 4 \
iii
As seen from the scheme, due to the reaction of chloroanhydride (I) with ortho-phenylenediamine both carboxyamide, compounds (II) and C-alkyl derivative of benzimidazole (III) are obtained. Generation of the substance (III) is related to
intermolecular cyclization of N-(2-aminephenyl)-pentancarboxyamide compound (II) by converting to enol form.
Unlike ortho-phenylenediamine due to the reaction of chloroanhydride (I) with para-
a
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M.A. RUSTAMOV, G.A. MIRZAYEVA
phenylenediamine, just mono- (IV) and dicarboxyamide (V) compounds are obtained.
p-ksilol, t0
H3C-(CH2)4-COCl + h2n-
+ H3C-(CH2)4-CO-NH-
W
nh2 ■
H3C-(CH2)4-CO-NH^ N
\ /
NH—CO—(CH2)4—CH3
v
As a result of the reaction of Relevant carboxyamide-N-(benzene)-
chloroanhydride (I) para-phenylenedimine at pentancarboxyamide (VI) and N-(pyridin-2-2:1 ratio, the yield of -N,N-(1,4- yl)-pentancarboxyamide (VII) compounds phenylene)dipentancarboxyamide (V) of were synthesized by the interaction of dicarboxyamide compound rose up to 92.8%. chloroanhydride with benzeneamine and
ortho-aminepyridine.
H3C-(CH2)4-COCl + -
H2N-CH2^ \ p-ksilo^ H3C
„co-NHHQ
vi
„ p-ksilol
-»"H3
N—
H3C-(CH2)4-CO-NH—^ \
N—tr
vii
Depending on the nature of functional group in the molecule. Acylation reaction of
groups in the molecule of amine compounds, izobutylamine hexan acid with electrodonor
basicity of amine group changes sharply. Of group in the molecule as substrate with
great interest is the review of acylation chloroanhydride was studied. The reaction
reaction of amine compound with electrodonor goes as follows.
CH3
' p-ksilol
H3C-(CH2)4-COCl + h2n-c-ch3 --»
i CH3
At p-xylene medium when adding chloroanhydride (I) drop by drop on amine compound the temperature of reaction mass roses. Reaction is performed at 55-600C by cooling. Unlike other amine compounds due to the acylation of isobutyl-amine ammonium salt of N-(izobutyl)-hexanecarboxyamide (VIII) is obtained. This causes the growth of basis property of amine group under the positive inductive (+J) effect of methyl groups in the amine molecule and integration of HCl
CH3 I 3
H3C-(CH2)4-CO-NH-C-CH3 HCl CH3
viii
gas emitted during the reaction into amide group.
To obtain acyl derivatives of bipolar amine compounds, we studied the acylation reaction of amine-acetate acid with chloroanhydride (I) of hexane acid.
Since the amine compound contains amine group (NH2) and carboxyl (-COOH) group, the reaction is performed at basis medium, so we controlled the basicity of medium until the reaction was over. The reaction goes as follows.
2
i
STUDY OF ACYLATION REACTION OF AMINES
193
H I
H2N-CH2-COOH + NaOH—► H2N—C—COONa + H3C-(CH2)4—COCl l"HCT
H
—► H2N—(CH2)4—CO—NH—CH2—COONa + HClH3C-(CH2)4—^NH-C^-COOH
O ix
Bioactive property of synthesized 2-(pentancarboxyamide)-acetic acid (IX) and free carboxyl (-COOH) group in the molecule make it possible to use it as a synthon for synthesizing practically useful new class
organic compounds. The composition and structure of synthesized substances and their physical-chemical constants were determined by IR and NMR spectroscopy analysis method.
EXPERIMENTAL PART
Note that IR spectrum of synthesized substances taken in "Nicolet is 10" spectrometer in thin film or paraffinic oil in suspension form.
NMR spectrum is taken in "Bruker 300" spectrometer (operating frequency 300 MHz), internal standard - hexamethyldisiloxane, chemical displacement in scale 5.
Reaction of chloroanhydride (I) of hexane acid with o-phenylenediamine. 60 ml of p-xylene and 10.8 g (0.01 mol) of o-phenylenediamine mixture is placed into three-neck flask provided with a mechanical mixer, thermometer and reverse cooler and 13.45 g (0.01 mol) of chloroanhydride (I) are added to it drop by drop by mixing. When chloroanhydride is added the temperature of reaction mass increased up to 600C. Then the reaction mass is heated at 110-1200C for 50-55 min. After cooling the resultant deposit is filtered and separated from liquid part. Crystalline substance is recrystallized in water-alcohol mixture. Two fractions are obtained: 1) 2.25 g (10.8%) N-(2-aminephenyl)-pentancarboxyamide (II),
Tmelt.193-1940C (EtOH-H2O), in IR-spectrum (v, sm-1): 3280-2900 (NH2, NH), 1740-1620 (CO-NH), 1540-1480 (C = Car), 720-690 (C = Car, 1.2-substituted). 2) 15.55 g (82.7%) 2-pentyl-1H-benzimidazole (III).Tmelt.90-910C (EtOH-H2O). In IR spectrum (v, sm-1): 3250 (-NH, valence connected), 1660 (C = N -), 1580-1480 (C = Car), 1090 (C - N -, valence vibrations), 730, 700 (C = Car., 1.2-substituted), NMR 1H spectrum (5, m.h.): 0.98
s (3H, CH3), 1.32-2.46 m (8H, 4CH2), 5.2 s (1H, NH), 7.30 s (2H, Ar), 7.68 s (2H, Ar.).
Reaction of chloroanhydride (I) of hexane acid with p-phenylenediamine. Two
substances were obtained from the reaction of 6.7 g (0.05 mol) of chloroanhydride (I) with 5.4 g (0.05 mol) of p-phenylenediamine at 60ml p-xylene medium: 1) 6.32 g (41.6%) N,N-(1,40phenylene-dipentacarboxyamide) (V). Tmelt. 196- 197°C (EtOH-H2O). IR spectrum (v, sm-1): 3330-3270 (N - H, trans), 3060-2860 (N - H, sis and trans), 1680, 1620 (- CO - NH, double amide), 1490, 1460 (C = Car), 980-860 (C = Car., 1,4 substituted). 2) 4.76 g (46.2%) N-(4-aminephenyl)-pentancarboxyamide (IV). Tmelt.171-1720C (EtOH-H2O). IR spectrum (v, sm-1): 3450 (NH2, valence vibrations), 1640 (CO - NH), 1560, 1500 (C = Car), 900, 860 (C = Car., 1,4-substituted) absorption bands confirm its structure.
Reaction of chloroanhydride (I) of hexane acid with benzylamine.60 ml of p-xylene and 5.4 ml (0.05 mol) of benzylamine is placed into three-neck flask and mixed with 8 ml (0.05 mol) of chloroanhydride (I). When chloroanhydride is added the temperature of reaction mass rises from 180C to 300C. Then reaction mass is heated at 110-1150C for 45-50 min. After cooling, the resultant white deposit is filtered and separated from liquid part. Obtained: 9.67 g (94.3%) N-(benzyl)-pentancarboxyamide. (VI) Tmelt.179-1800C (benzene). IR spectrum (v, sm-1): 3330 (valence vibrations of N - H bond), 1690 (C = O), 1650 (CO - NH - ), 1600, 1500 (C = Car),
194
M.A. RUSTAMOV, G.A. MIRZAYEVA
759, 700 (C = Car., monosubstituted), NMR 1H spectrum (5 m.h.): 0.97 s (3H, CHs), 1.32-2.45 m (8H, 4CH2), 7.85 (1H, nh), 7.20 s (1H, Pr-H), 8.05 (1H, Pr), 8.4-8.5 d (2H, Pr).
Reaction of chloroanhydride (I) of hexane acid with 2-aminepyridine.The mixture of 9.40 g (0.1 mol) of 2-aminepyridine and 70 ml p-xylene is mixed with 13.45 g (0.1 mol) of chloroanhydride (I) of hexane acid. When chloroanhydride is added, the temperature of reaction mass rises up to 400C. Then reaction mass is heated at 1100C for 45 min. After cooling, the resultant white crystal substance is filtered and separated from liquid part. Obtained: 14.47 g (81.75%) N-(pyridin -2-yl)pentan-carboxyamide (VIII). After recrystallization, it made up (EtOH-№O) Tmelt.97-980C. In IR spectrum (v, sm-1): 3270 (N - H, valence vibrations), 1710 (Co - NH -), 770, 690 (C = Car, monosubstituted) absorption bands confirm its structure.
Reaction of chloroanhdyride (I) of hexane acid with iso-butylamine. Using the
same method, we obtained HCl salt of 15.15 g (88.6%) of N-(isobutyl)-hexanecarboxyamide (VIII) through the reaction of 13.45 g (0.1mol) of chloroanhydride of hexane acid and 7.3 g (0.1mol) of isobutylamine with 60ml p-xylene. Tmelt.2930C (it is decomposed). In IR spectrum (v, sm-1): 3397-3233 (sis-, trans-, linked NH group), 2717-2245 (valence vibrations of ion (NH2), 1712 (C = O), 1625, 1618 (- CO - NH -) absorption bands confirm its composition and structure.
Reaction of chloroanhydride (I) of hexane acid with amineacetic acid. Using the above mentioned method, we obtained 14.16 g (93.8%) of white crystal N-(pentancarboxyamide) of acetic acid (IX) by the reaction of 13.45 g (0.1 mol) of chloroanhydride (I) of hexane acid and 7.5 g (0.1 molamineacetic acid) with 5.2 g (0.13 mol) of NaOH alkali. Tmelt.110-1110C EtOH-H2O.In IR spectrum (v, sm-1): 2980 (- OH), 1710 (C = O), 1650 (- CO - NH -) absorption bands confirm its structure.
REFERENCES
1. Rustamov M.A., Eyvazova Sh.M. Acylation of o-phenylenediamine with chloroanhydrides of alkyl and phenyl substituted chlorohexan(ene) carboxylic acids. Scientific journal "Search", Ministry of Education and Science of Kazakhstan, 2009, no. 4, pp.10-15.
2. Rustamov M.A., Eyvazova Sh.M., Ismayilova S.G. On the reaction of chloroanhydrides of 1,4-dimethylcyclohexene-3-carboxylic acid with di- and monosubstituted monoaromatic amines. Transactions of Azerbaijan Technical University, Fundamental sciences. 2004, vol. 10, no. 2, pp. 26-31.
3. Rustamov M.A., Eyvazova Sh.M., Nabiyeva R.F. Synthesis and study of properties of polyfunctional substituted nitrogenous organic compounds. Kimya Problemleri - Chemical Problems, 2005, no. 4, pp. 101-105. (In Azerbaijan).
4. Rustamov M.A., Eyvazova Sh.M., Veysova N.A. On acylation reaction of toluidines with chloroanhydrides of 1,4-dimethylcyclohex-3-enecarboxylic acid. Journal of Organic Chemistry. 2013, vol. 83, no. 1, pp. 158-160.
5. Rustamov M.A., Veysova N.A., Abbasova M.F., Eyvazova Sh.M. On the synthesis of carboxyamide and heterocyclic nitrogenous organic compounds. Azerbaijan Chemical Journal. 2013, no. 1, pp. 94-97.
6. Eyvazova Sh.M., Veliyeva R.G., Salmanov V.A., Rustamov M.A. Study of corrosion inhibiting properties of new synthesized nitrogenous organic compounds. Azerbaijan Chemical Journal. 2006, no. 1, pp. 210-214.
7. Rustamov M.A., Veysova N.A., Eyvazova Sh.M., Bayramov M.R., Agayeva M.A. N-(1,4-dimethylcyclohex-3-ene carbonyl) benzamide as a corrosion inhibitor of a steel. Patent Azerbaijan, 2016 0035 Decision about publication. 2017.
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8. Rustamov M.A., Veysova N.A., Eyvazova Sh.M., Zamanov P.B., Ismayilova S.H. Potassium salt of 2-(cycl ohex-3 -enecarb oxy ami de) aceti c acid as a growth stimulator for grain -crops and leguminous plants. Patent Azerbaijan I 2016 0051.
9. Rustamov M.A., Eyvazov Sh.M., Afkaribachebac Ahmed Shamuddin, Zamanov P.B., Ismayilova S.H., Gambarova R.F. Growth stimulator of sunflower. Patent Azerbaijan I 2016 0049.
MÜXTBLiF QURULU§L U AMiNLdRiNHEKSAN TUR§USUNUNXLORANHiDRiDiiLB
ASiLLBÇMd REAKSiYASININ TSDQiQi
М.Э. Rüstdmov, G.B. Mirzzyeva
Azdrbaycan Texniki Universiteti AZ1143, H.Cavidpr. 25; e-mail: orqanik_6060@mail. ru
Funksionaldvdzli mono- vd aromatik diaminldrin heksan turçusunun xloranhidridi ild asilld^dirmdkld müvafiq karboksiamid birld^mdldri sintez edilmiçdir. Tddqiqat ndticdsindd müdyydn edilmiçdir ki, amin birld^mdldrin molekulunda olan funksional qruplarin tdbidti vd vdziyydti reaksiyanin getmd istiqamdtind dsasli tdsir göstdrir. Para-fenilendiaminddn fdrqli olaraq orto-fenilendiamini asilld^dirdikdd monokarboksiamid birld^mdsi ild yanaçi, onun enol- formaya keçmdsi vd molekuldaxili tsiklld^mdsi ndticdsindd benzimidazolun C-alkil tördmdsi dd alinir.
Açar sözldr: asilld^dirmd reaksiyasi, heksan turçusunun xloranhidridi, p-fenilendiamin, o-fenilendiamin, monokarboksiamid, molekuldaxili tsiklld^md
ИССЛЕДОВАНИЕ РЕАКЦИИ АЦИЛИРОВАНИЯ АМИНОВ РАЗЛИЧНОГО СТРОЕНИЯ ХЛОРАНГИДРИДАМИ ГЕКСАНОВОЙ КИСЛОТЫ
М.А. Рустамов, Г.А. Мирзоева
Азербайджанский Технический Университет АЗ 1143, г. Баку, пр. Г. Джавида 25, e.mail: orqanik_6060@,mail. ги
В результате исследования реакции ацилирования различных аминов хлорангидридом гексановой кислоты установлено, что на направление реакции и выход продуктов реакции большое влияние оказывает положение и природа функциональных групп, имеющихся в молекуле аминов. В отличие от пара-фенилендиамина, при ацилировании орто-фенилендиамина наряду с образованием орто-фенилендиамина образуется и С-алкил производное бензимидазола в результате перехода N-(2-аминофенил)-пентанкарбоксиамида в енольную форму и внутримолекулярной циклизации. Ключевые слова: реакция ацилирования, хлорангидрид гексановой кислоты, орто-фенилендиамин, пара-фенилендиамин, бензимидазол, внутримолекулярная циклизация
