RU2674448C1 - 3-(3-aminophenyl)-5-(prop-1-en-2-yl)-1,2,4-oxadiazole - Google Patents
3-(3-aminophenyl)-5-(prop-1-en-2-yl)-1,2,4-oxadiazole Download PDFInfo
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- RU2674448C1 RU2674448C1 RU2017124843A RU2017124843A RU2674448C1 RU 2674448 C1 RU2674448 C1 RU 2674448C1 RU 2017124843 A RU2017124843 A RU 2017124843A RU 2017124843 A RU2017124843 A RU 2017124843A RU 2674448 C1 RU2674448 C1 RU 2674448C1
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- oxadiazole
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- chemical industry
- aminophenyl
- polymers
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- CJEZUXFRZSGJGY-UHFFFAOYSA-N 3-(5-prop-1-en-2-yl-1,2,4-oxadiazol-3-yl)aniline Chemical compound CC(=C)c1nc(no1)-c1cccc(N)c1 CJEZUXFRZSGJGY-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 229920000767 polyaniline Polymers 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 7
- 229920000642 polymer Polymers 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- BBVIDBNAYOIXOE-UHFFFAOYSA-N 1,2,4-oxadiazole Chemical group C=1N=CON=1 BBVIDBNAYOIXOE-UHFFFAOYSA-N 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 125000003342 alkenyl group Chemical group 0.000 abstract description 2
- 150000004982 aromatic amines Chemical class 0.000 abstract description 2
- 238000007334 copolymerization reaction Methods 0.000 abstract description 2
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 2
- 239000004020 conductor Substances 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- JPZSWGOXXSZYKG-UHFFFAOYSA-N 3-(3-nitrophenyl)-5-prop-1-en-2-yl-1,2,4-oxadiazole Chemical compound CC(=C)c1nc(no1)-c1cccc(c1)[N+]([O-])=O JPZSWGOXXSZYKG-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- -1 m-lmethylaniline Chemical compound 0.000 description 3
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- ZAIHFKLUPWFUGH-UHFFFAOYSA-N n'-hydroxy-3-nitrobenzenecarboximidamide Chemical compound ON=C(N)C1=CC=CC([N+]([O-])=O)=C1 ZAIHFKLUPWFUGH-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 2
- 238000005917 acylation reaction Methods 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 150000005071 1,2,4-oxadiazoles Chemical class 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VMPITZXILSNTON-UHFFFAOYSA-N o-anisidine Chemical compound COC1=CC=CC=C1N VMPITZXILSNTON-UHFFFAOYSA-N 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
- C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
- C07D271/06—1,2,4-Oxadiazoles; Hydrogenated 1,2,4-oxadiazoles
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
Description
Изобретение относится к области получения новых ароматических аминов, содержащих алкенильный фрагмент и 1,2,4-оксадиазольный цикл, которые могут быть использованы в химической промышленности для получения не писанных ранее полимеров, получаемых окислительной и радикальной полимеризацией, а так же сополимеризацией.The invention relates to the field of production of new aromatic amines containing an alkenyl fragment and a 1,2,4-oxadiazole ring, which can be used in the chemical industry to obtain previously unwritten polymers obtained by oxidative and radical polymerization, as well as copolymerization.
Такие полимеры могут находить использование в химической промышленности в качестве полимеров-проводников, а так же могут быть использованы в производстве жидких кристаллов.Such polymers can be used in the chemical industry as conductive polymers, and can also be used in the production of liquid crystals.
Известны полианилины, полученные на основе анилина, N-метиланилина, м-льметиланилина, о-метоксианилина, однако, данные полимеры, обладая достаточно высокой проводимостью, не проявляют люминесцентных свойств [Stejskal J., Gilbert R.G. Polyaniline. Preparation of a conducting polymer // Pure Appl.Chem., 2002. Vol.74. №5. P. 857-867; Kil-martin P.A., Wright G.A. Photoelectrochemistry and spectroscopy of substituted polyanilines // Synthetic Metals, 1999. Vol.104. P. 145-156].Known polyanilines obtained on the basis of aniline, N-methylaniline, m-lmethylaniline, o-methoxyaniline, however, these polymers, having a sufficiently high conductivity, do not exhibit luminescent properties [Stejskal J., Gilbert R.G. Polyaniline Preparation of a conducting polymer // Pure Appl. Chem., 2002. Vol. 74. No. 5. P. 857-867; Kil-martin P.A., Wright G.A. Photoelectrochemistry and spectroscopy of substituted polyanilines // Synthetic Metals, 1999. Vol. 104. P. 145-156].
Известны поли(1,2,4-оксадиазолы), обладающие люминесцентными свойствами [Chen H.S., Chen Y. Poly(p-phenylenevinylene) Derivatives Containing Electron-Transporting Aromatic Triazole or Oxadiazole Segments // Macromolecules, 2005. Vol. 38. P. 53-60], однако такие полимеры не обладают достаточным уровнем проводимости и не способны проявлять защитные свойства. Таким образом, использование в качестве мономера для полимеризации 3-(3-аминофенил)-5-(проп-1-ен-2-ил)-1,2,4-оксадиазола позволит получить полимер, сочетающий как достоинства полианилинов, так и полиоксадиазолов.Poly (1,2,4-oxadiazoles) having luminescent properties are known [Chen H.S., Chen Y. Poly (p-phenylenevinylene) Derivatives Containing Electron-Transporting Aromatic Triazole or Oxadiazole Segments // Macromolecules, 2005. Vol. 38. P. 53-60], however, such polymers do not have a sufficient level of conductivity and are not able to exhibit protective properties. Thus, the use of 3- (3-aminophenyl) -5- (prop-1-en-2-yl) -1,2,4-oxadiazole as a monomer for polymerization will make it possible to obtain a polymer combining both the advantages of polyanilines and polyoxadiazoles .
Задачей, решаемой настоящим изобретением, является получение 3-(3-аминофенил)-5-(проп-1-ен-2-ил)-1,2,4-оксадиазола как мономера для получения полианилина, содержащего в своем составе кратную связь и 1,2,4-оксадиазольный фрагмент, который позволяет проводить дальнейшую функционализацию полианилинов, с целью расширить область их применения.The problem solved by the present invention is to obtain 3- (3-aminophenyl) -5- (prop-1-en-2-yl) -1,2,4-oxadiazole as a monomer for the production of polyaniline containing a multiple bond and The 1,2,4-oxadiazole moiety, which allows further functionalization of polyanilines, in order to expand the scope of their application.
Заявляется 3-(3-аминофенил)-5-(проп-1 -ен-2-ил)-1,2,4-оксадиазол следующей формулы:3- (3-aminophenyl) -5- (prop-1-en-2-yl) -1,2,4-oxadiazole of the following formula is claimed:
Данное соединение получают реакций ацилирования 3-нитробензамидоксима хлорангидридом метакриловой кислоты и восстановлением полученного 3-(3-нитрофенил)-5-(проп-1-ен-2-ил)-1,2,4-оксадиазола, согласно схеме:This compound is obtained by acylation reactions of 3-nitrobenzamidoxime with methacrylic acid chloride and reduction of the obtained 3- (3-nitrophenyl) -5- (prop-1-en-2-yl) -1,2,4-oxadiazole according to the scheme:
Ацилирование 3-нитробензамидоксима хлорангидридом метакриловой кислоты проводят в пиридине, при комнатной температуре в течение 2 часов, а затем при температуре кипения смеси в течение 4 часов. Восстановление 3-(3-нитрофенил)-5-(проп-1 -ен-2-ил)-1,2,4-оксадиазола проводят безводным хлоридом олова.Acylation of 3-nitrobenzamidoxime with methacrylic acid chloride is carried out in pyridine, at room temperature for 2 hours, and then at the boiling point of the mixture for 4 hours. The reduction of 3- (3-nitrophenyl) -5- (prop-1-en-2-yl) -1,2,4-oxadiazole is carried out with anhydrous tin chloride.
Изобретение иллюстрируется следующими примерами.The invention is illustrated by the following examples.
Пример 1. При интенсивном перемешивании на ледяной бане прибавляли 1,086 г (6 ммоль) хлорангидрида метакриловой кислоты к раствору 0,724 г (4 ммоль) 3-нитробензамидоксима в 15 мл пиридине. После окончания прибавления ледяную баню убирали, и смесь перемешивали 2 ч при комнатной температуре, затем кипятили 4 ч. Смесь осаждали в воду, выпавший осадок отфильтровывали, промывали водой на фильтре. Получают 0,73 г (3 ммоль) 3-(3-нитрофенил)-5-(проп-1-ен-2-ил)-1,2,4-оксадиазола. Выход 79%.Example 1. With vigorous stirring in an ice bath, 1.086 g (6 mmol) of methacrylic acid chloride was added to a solution of 0.724 g (4 mmol) of 3-nitrobenzamidoxime in 15 ml of pyridine. After the addition was completed, the ice bath was removed and the mixture was stirred for 2 hours at room temperature, then boiled for 4 hours. The mixture was precipitated into water, the precipitate formed was filtered off, washed with water on a filter. 0.73 g (3 mmol) of 3- (3-nitrophenyl) -5- (prop-1-en-2-yl) -1,2,4-oxadiazole are obtained. Yield 79%.
Температура плавления 100-102°С.Melting point 100-102 ° C.
Спектр ЯМР 1Н, δ, м.д. (J, Гц): 224 с (3Н, СН3), 5.92 c(H,CH2=С), 6.34 с(H,CH2=C), 7.88 м(Hаром.), 8.44 д (7Hаром, J 8.2), 8.70 с (Наром). 1 H NMR spectrum, δ, ppm (J, Hz): 224 s (3H, CH 3 ), 5.92 s (H, CH 2 = C), 6.34 s (H, CH 2 = C), 7.88 m (H arom .), 8.44 d (7H arom J 8.2), 8.70 s (N arom ).
ИК спектр, см-1: 1654 (C=N),1643 (С=С), 1597 (Аr), 1537, 1350 (NO2), 1268, 1070 (C-O-N).IR spectrum, cm -1 : 1654 (C = N), 1643 (C = C), 1597 (Ar), 1537, 1350 (NO 2 ), 1268, 1070 (CON).
Пример 2. В 15 мл этанола смешивали 0,231 г (1 ммоль) 3-(3-нитрофенил)-5-(проп-1-ен-2-ил)-1,2,4-оксадиазола и 0,948 г (5 ммоль) SnCl2. Реакционную массу кипятили при интенсивном перемешивании 2 ч, охлаждали до комнатной температуры и прибавляли 100 мл 1 М. раствора NaOH. 3-(3-аминофенил)-5-(проп-1-ен-2-ил)-1,2,4-оксадиазол экстрагировали этилацетатом (2×100 мл), экстракт сушили Na2SO4 и при пониженном давлении удаляли растворитель. Остаток перекристаллизовывали из гексана. Получают 0,175 г (0,87 ммоль). Выход 87%.Example 2. In 15 ml of ethanol was mixed 0.231 g (1 mmol) of 3- (3-nitrophenyl) -5- (prop-1-en-2-yl) -1,2,4-oxadiazole and 0.948 g (5 mmol) SnCl 2 . The reaction mass was boiled under vigorous stirring for 2 h, cooled to room temperature and 100 ml of a 1 M NaOH solution was added. 3- (3-aminophenyl) -5- (prop-1-en-2-yl) -1,2,4-oxadiazole was extracted with ethyl acetate (2 × 100 ml), the extract was dried with Na 2 SO 4 and the solvent was removed under reduced pressure . The residue was recrystallized from hexane. Obtain 0.175 g (0.87 mmol). Yield 87%.
Температура плавления 75-76°С.Melting point 75-76 ° C.
Спектр ЯМР 1Н, δ, м.д. (J, Гц): 2.21 с (Н, СН3), 5.42 с (2Н, NH2), 5.85 с (Н,=СН2), 6.25 с (Н,=СН2), 6.74 д (Наром., J 7.1), 7.16 с (2Наром.), 7.28 с (Hаром.). 1 H NMR spectrum, δ, ppm (J, Hz): 2.21 s (H, CH 3 ), 5.42 s (2H, NH 2 ), 5.85 s (H, = CH 2 ), 6.25 s (H, = CH 2 ), 6.74 d (Narom., J 7.1), 7.16 s (2H arom .), 7.28 s (H arom .).
ИК спектр, см-1: 3384, 3326, 1621 (NH2), 1640 (С=С), 1608 (Ar), 1549 (C=N), 1291, 1181 (C-O-N).IR spectrum, cm -1 : 3384, 3326, 1621 (NH 2 ), 1640 (C = C), 1608 (Ar), 1549 (C = N), 1291, 1181 (CON).
Масс спектр (ИЭР), m/z: 202.0978 [М+Н]+. C11H12N3O. Мвыч. 202.0980.Mass spectrum (ESI), m / z: 202.0978 [M + H] + . C 11 H 12 N 3 O. M calc . 202.0980.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU969162A3 (en) * | 1978-01-12 | 1982-10-23 | Шеринг Аг (Фирма) | Process for producing derivatives of 1,2,4-oxadiazole (modification) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU969162A3 (en) * | 1978-01-12 | 1982-10-23 | Шеринг Аг (Фирма) | Process for producing derivatives of 1,2,4-oxadiazole (modification) |
Non-Patent Citations (3)
| Title |
|---|
| База данных REGISTRY [онлайн] * |
| База данных REGISTRY [онлайн] RN 1852272-30-0, 25.01.2016, найдено в STN. * |
| найдено в STN. * |
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