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102 CHEMICAL PROBLEMS 2020 no. 1 (18) ISSN 2221-8688
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UDC 547.32
HALOALKOXYLATION OF 3-ORGANYLOXY-1 -PROPENE S IN DIMETHYLACETYLENECARBINOL MEDIUM
A.R. Ezizbeyli, G.M. Talybov, E.H. Mammadbayli
Y.H. Mammadaliyev institute of Petrochemical Processes Naional Academy of Sciences ofAzerbaijan Khojaly ave. 30, AZ1025, Baku, Azerbaijan e-mail:[email protected], [email protected], [email protected]
Received 08.11.2019
Abstract: Reaction of alkoxyhalogenation 3-organyloxy-1-propenes with N-bromosuccinimide (or iodine) in dimethylacetylenecarbinol medium proceeds regioselectively according to NMR spectra. It proceeds at a low temperatureg cooling the reaction mixture with ordinary ice. The main reaction products, diethers - 3-bromo (iodine) -1,2-propanediol, are formed in high yields. it founded that the alkoxyhalogenation of allyl ethers with propinol proceeds regioselectively with fixation of the halogen atom to the peripheral carbon atom of C=C bond. The yields of bromine-containing products are higher than those for iodine analogues. Iodine-containing products boil at a higher temperature than bromine analogues. In the reaction products, substances with the replacement of the halogen atom with unsaturated alcohol are not observed. The reaction was monitored by means of thin layer chromatography. Similar synthesized compounds are used as biologically active compounds. Keywords: alkoxyhalogenation, C3-unsaturated alcohols, P-halogenethers, FT-IR spectra, 1H NMR spectra
DOI: 10.32737/2221-8688-2020-1-102-105
Introduction
Alkoxyhalogenation of alkenes [1,2] halogenethers which are used in the synthesis with C3-unsaturated alcohols is a common of heterocyclic compounds [4-6] and method for the synthesis of unsaturated P- biologically active preparations [3-9].
Experimental
The reaction was carried out at low same process in the temperature range (-5 ^ 10 temperature (-5^0 °C) in order to prevent 0C) was observed yield reduction (I-VI) by tarring process. Upon implementation the about half.
(I-VI)
We found that the alkoxyhalogenation of allyl ethers with propinol proceeds regioselectively with fixation of the halogen atom to the peripheral carbon atom of C=C
bond. Regioselectivity of reactions (according to the Markovnikov rule) is confirmed by 1H NMR spectral data of compounds (I-VI) which says that the presence of doublet signals of
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A.R. EZIZBEYLI et al.
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protons in methylene groups bonded to a halogen atom due to spin-spin interaction with methine protons in the region of 3.28 dd (1H, J = 10.3, 5.8 Hz CH2I), 3.41 dd. (1H, J = 10.3, 5.8 Hz CH2I) for CH2I and 3.38 dd (1H, J=10.5, 5.7 Hz CH2Br) and 3.42 dd. (1H, J=10.5, 5.7 Hz CH2I), for CH2Br respectively.
In the FT-IR spectra of synthesized compounds (I-VI), absorption bands are observed in the region of 1150-1085 cm1 due to asymmetric stretching vibrations of the C-O-C bond. The bands in the regions of 3333-
3267 cm-1 and 2140-2100 cm-1 are characteristic for stretching vibrations of monosubstituted acetylenes.
The synthesized compounds are readily soluble in organic solvents and stable when stored under normal conditions.
This method allows to synthesize 3-halo-1,2-propanediol diethers in 60-70% yield. The composition and structure of the obtained compounds are established on the basis of FT-IR and 1H NMR spectral data.
Results an
FT-IR spectra of compounds were measured on Specord-75 instruments in the microlayer and using KBr disks. 1H NMR spectra of substances in the solution CDCh recorded on «Bruker SF-400" (300.134 MHz) device, an internal standard HMDS.
3-[(1-Bromo-3-propyloxypropan-2-yl)oxy]-3-methylbut-1-in (I). It was gradually added with 44 g of N-bromosuccinimide (NBS) to a cooled equimolar mixture of 25 g allylpropyl ether and 14 g propargyl alcohol with stirring, so that a temperature of the reaction mixture could not exceed 0 oC. The stirring was carried out for a period 5 hours at a room temperature. The succinimide formed was filtered off, and the mixture was alkalized by solution of 15 g of sodium hydroxide in 100 ml of water, then extracted with ether and dried with CaCl2. Following ether removal, the resudio was distilled by means of vacuum distillation method. Allocated 41.15 g (70 %) of compound (I) T. boil. 65-66 °C (2 mmHg art.) d420 1.2728, ^1.4924. MRd 53.63,
calcd. 52,95. FT-IR spectra (v/sm-1): 620 (C-Br), 1100 (C-O-C), 2100 and 3300 (C=CH). 1H NMR (5, ppm.,CDCl3): 0.75 t (3H, CH3, J=7.5 Hz), 1.08 s (6H, 2CH3) 1.21 k (2H, CH2, J=7.5 Hz), 2.48 s (1H, CH), 3.21 m (4H, CH2OCH2), 3.38 dd (1H, CH2Br, J=10.5, 5.7 Hz), 3.42 dd (1H, CH2Br, J=10.5, 5.7 Hz), 3.85 m (1H, CH). Found %: C 50.22, H 7.30, Br 30.38. CnH19BrO2. Calculated,%: C 50.20, H 7.28, Br 30.36. Similarly based on:
-allylcyclohexyl ether, propargyl alcohol and NBS was obtained 3-Bromo-2-[(2-metylbut-3-in-2-yl)oxy] propyl} cyclohexane
discussion
(II) by yield of 65%, T.boil.80-82°C (2 mm Hg art.), d|01.2763, ^1.5060. MRd 64.06,
calcd. 64.68. FT-IR spectra (v/sm-1): 628 (C-Br), 1140 (C-O-C), 2100 and 3300 (C=CH). 1H NMR (5, ppm.,CDCl3): 0.782-1.24 m, (11H, 1.09 s, (6H, 2CH3) protons of the cycle), 2.48 s (1H=CH), 3.39 dd (1H, C^Br, J=10.5, 5.7 Hz), 3.42 dd (1H, C^Br, J=10.5, 5.7 Hz), 3.83 m (1H, CH). Found %: C 55.47, H 7.67, Br 26.37. C14H23BrO2. HMDS. calculated,%: C 55.45, H 7.65, Br 26.35.
- allylphenyl ether, propargyl alcohol and NBS 3-Bromo-2- [(2-methylbut-3-yn-2-yl)oxy]propyl}benzene (III) obtained by yield of 68.5 %, T.boil. 99-100 °C d420 1.2894, nD
1.5256. MRd 64.04,. calculated,%: 63.52. Found %: C 56.60, H 5.79, Br 26.91. C14H17BrO2. HMDS. calculated,%: C 56.58, H 5.77, Br 26.89.
3 - [(1-Iodo-3-propoxypropan-2-yl) oxy] -3-methylbut-1-in (IV). It was added 26 g (0.12 mol) of HgO to a cooled (-5 - 0 °C) and intensively stirred mixture of 14 g (0.25 mol) of propargyl alcohol and 25 g (0.25 mol) of allyl propyl ether ,then 63.45 g (0.25 mol) of finely crushed crystal of iodine (1 g each). The stirring was carried out for a period 3-4 hours at a room temperature, the mixture was filtered, the filtrate washed by Na2S2O3 solution and extracted with ether. The extract is dried using CaCh. Ether was removed in a rotary evaporator, and the residue was recrystallized. Received 47.9 g (68%) of substance (IV), melt.point 52-53 ° C (from heptane). FT-IR spectra (v/sm-1): 550 (c-I), 1100 (C-O-C) 2100 and 3300 (C=CH). 1H NMR (5, ppm.,CDCl3): 0.75 t. (3H, CH3),
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HALOALKOXYLATION OF 3-ORGANYLOXY-1 -PROPENE S
1.11s (6H, 2CH3), 1.24 m. (2H, CH2), 2.43 s. (1H, =CH), 3.21-3.43 m. (4H, CH2OCH2), 3.28 dd. (1 H, CH2I, J=10.5, 5.7 Hz), 3.41 dd. (1H, CH2I, J=10.5 5.7 Hz), 3.85 m. (1H, CH), Found %: C 42.62, H 6.19, I 40.93. C11H19IO2. HMDS. calculated, %: C 42.60, H 6.17, I 40.91.
Similarly based on:
- allyl ether of cyclohexanol, propargyl alcohol and crystalline iodine was obtained {3-Iodo-2- [(2-methylbut-3-yn-2-yl)oxy]propyl}cyclohexane (V) by yeald of 57.6%, melt.point 60-61 0C (from heptane) ). FT-IR spectra (v/sm-1): 560 (C-I), 1100 (C-O-C), 2100 and 3330 (C=CH). 1H NMR (5, m.d.,CDCl3): 1.08 (6H, 2CH3) m. (10H, C6H10), 2.45 t.(1H, =CH), 3.28 dd. (1H, CH2I, J=10.5 5.7 Hz), 3.45 d (2H, 2CHO), 3.65 m.
(2H 2CHO), Found %: C 48.03, H 6.64, I 36.25, C14H23IO2. HMDS. calculated,%: C 48.01, H 6.62, I 36.23.
- allyl ether of phenol, propargyl alcohol and crystalline iodine was obtained 3-Iodo-2 -[(2-methylbut-3-yn-2-yl) oxy] propyl} benzene (VI) by yeald of 67.2%, t. boil. 115 0C (2 mmHg art.), d|01.4502, ^2D0 1.5450.,
MRd 68.93, calculated 68.93 FT-IR spectra (v/sm-1): 560 (C-I), 1100 (C-O-C), 2100 and 3330 (C=CH), 1515, 1620, 3060, 3080 (C6H5). 1H NMR (5, ppm, CDCh): (5, m.d.,CDCl3): 2.5 t.(1H, =CH, J=2.4Hz), 3.41 d. (2H, 2 CH2O), 3.28 dd. (1H, CH2I, J=10.5 5.7 Hz), 7.15 m. (5H, C6H5). Found %: C 48.87, H 5.02, I 36.89, C14H17IO2. HMDS. calculated,%: C 48.85, H 4.98, I 36.87.
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3-ORQANÍLOKSÍ-1-PROPENLdRÍNDÍMETÍLASETÍLENKARBÍNOL MÜHÍTÍNDO HALOGENALKOKSÍDL3$DÍRÍLM3SÍ
A.R. Ozizbdyli, G.M. Talibov, E.H. Mzmmzdbzyli
AMEA akam. Y.H. Mammadaliyev ad. Neft-Kimya Prosesbri institutu AZ 1025, Baki §., Xocali pr. 30 e-mail:ezizbeyli83@mail. ru, ahmed_adna@rambler. ru, eldar_mamedbeyli@mail. ru
NMR spektrlarin naticalarina göra dimetilasetilenkarbinolda N-bromsuksinimid (va ya kristal yod) ila 3-orqaniloksi-1-propenlarin alkoksihalogenla§masi ikiqat rabita üzra regioselektiv gedir. Reaksiya a§agi temperaturda adi buzla soyudularaq aparilir. Osas reaksiya mahsullari 3-brom(yod)-1,2-propandiol diefirlari yüksak giximla alinir. Müayyan edilib ki, allil efirlarinin propinolla alkoksihalogenla§ma reaksiyasi halogen atomunun С=С rabitasina regioselektiv birla§masi ila hayata kegir. Bromsaxlayan birla§malarin mahsuldarligi yodsaxlayan analoqlarindan daha yüksakdir. Yod tarkibli mahsullar bromlu analoqlarindan daha yüksak temperaturda qaynayir. Reaksiya mahsullarinda halogen atomu doymami§ spirtla avaz olunmur. Reaksiya nazik layli xromatoqrafiya vasitasila mü§ahida edilir. Bu tip birla§malar üzvi kimyada va bioloji aktiv birla§malar kimi istifada olunur.
Agar sözlzr: alkoksihalogenla§ma, allil efirlari, propinol, regioselektivlik, dimetilasetilenkarbinol
ГАЛОГЕНАЛКОКСИЛИРОВАНИЕ 3-ОРГАНИЛОКСИ-1-ПРОПЕНОВ В СРЕДЕ ДИМЕТИЛАЦЕТИЛЕНКАРБИНОЛА
А.Р. Азизбейли, Г.М. Талибов, Э.Г. Мамедбейли
Институт нефтехимических процессов им. акад. Ю.Г. Мамедалиева AZ1025, г. Баку пр. Ходжалы, 30 e-mail:ezizbeyli83@mail. ru, ahmed_adna@rambler. ru, eldar_mamedbeyli@mail. ru
Алкоксигалогенирование 3-органилокси-1-пропенов N-бромсукцинимидом (или кристаллическим иодом) в среде диметилацетиленкарбинола по данными ЯМР спектров протекает региоселективно по двойной связи. Реакцию проводят при низкой температуре, охлаждая реакционную смесь обычным льдом. Основные продукты реакции - диэфиры-3-бром(иод)-1,2-пропандиола образуются с высокими выходами. Установлено, что алкоксигалогенирование аллиловых эфиров пропинолом протекает региоселективно с фиксацией атома галогена у периферийного атома углерода связи С=С. Выходы бромсодержащих продуктов выше их иоданалогов. Иодсодержащие продукты кипят более высокой температуре, чем их броманалоги. В продуктах реакции не наблюдаются вещества с заменой атома галогена непредельным спиртом. За ходом реакции следили с помощью тонкослойной хроматографии. Синтезированные соединения используются в качестве биологически активных соединений.
Ключевые слова: aлкоксигалогенирование, пропинол, диэфиры 3-бром(иод)-1,2-пропандиола, диметилацетиленкарбинол
