SU270718A1 - METHOD OF OBTAINING TETRAFTOR- / g-OXYBENZOIC ACID - Google Patents
METHOD OF OBTAINING TETRAFTOR- / g-OXYBENZOIC ACIDInfo
- Publication number
- SU270718A1 SU270718A1 SU1327739A SU1327739A SU270718A1 SU 270718 A1 SU270718 A1 SU 270718A1 SU 1327739 A SU1327739 A SU 1327739A SU 1327739 A SU1327739 A SU 1327739A SU 270718 A1 SU270718 A1 SU 270718A1
- Authority
- SU
- USSR - Soviet Union
- Prior art keywords
- tetraftor
- obtaining
- oxybenzoic acid
- acid
- hydrolysis
- Prior art date
Links
- 239000002253 acid Substances 0.000 title description 4
- USPWUOFNOTUBAD-UHFFFAOYSA-N 1,2,3,4,5-pentafluoro-6-(trifluoromethyl)benzene Chemical compound FC1=C(F)C(F)=C(C(F)(F)F)C(F)=C1F USPWUOFNOTUBAD-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 4
- -1 fluorine-substituted methylbenzene Chemical class 0.000 claims description 3
- FTLHGQOBAPTEHE-UHFFFAOYSA-N 2,3,5,6-tetrafluoro-4-hydroxybenzoic acid Chemical compound OC(=O)C1=C(F)C(F)=C(O)C(F)=C1F FTLHGQOBAPTEHE-UHFFFAOYSA-N 0.000 claims 1
- 230000003301 hydrolyzing Effects 0.000 claims 1
- 150000005172 methylbenzenes Chemical class 0.000 claims 1
- 239000000243 solution Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L mgso4 Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001588 bifunctional Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000005591 charge neutralization Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000001264 neutralization Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
Description
Изобретение относитс к способу получени тетра-фтор- -оксибензойной кислоты, котора как бифункциональное полифторароматическое соединение может найти применение в качестве мономера дл получени фторсодержащих полимеров, каучуков, пластификаторов, обладающих ценными свойствами: повышенной химической, термической, радиационной стойкостью и негорючестью. Известно получение тетрафтор-и-оксибензойной кислоты гидролизом водным раствором йодистоводородной кислоты тетрафтор-«-этокситрифторметилбензола при кип чении в течение 48 час с выходом 30%. Недостаток способа - низкий выход продукта. Предлагаемый способ позвол ет получить тетрафтор-«-оксибензойную кислоту. Он состоит в том, что октафтортолуол обрабатывают водным раствором калиевой щелочи (берут 20%-ный избыток от стехиометрически необходимого) при температуре 145-150°С в течение 5-6 час. Реакцию осуществл ют в автоклаве под давлением 8-9 атм. Конверси октафтортолуола и выход неочищенного тетрафтор-/г-бензойной кислоты близки к 100%. При гидролизе октафтортолуола более крепкой щелочью конверси заметно уменьщаетс . Так, 30%-ный водный раствор калиевой щелоЗа счет сильного электроноакценторного вли )П1 трифторметильной грунпы получаетс только п-изомер без примеси о- и пг-изомеров, что позвол ет предположить, что образование кислоты происходит через промежуточный гептафтор-л-крезол т . Выход нродукта достигает 80%. Пример. В никелевый автоклав емкостью 150 мл загружают 10,2 г (0,043 г-моль) октафтортолуола (94,9% по ГЖХ), 73 мл 20%-ной КОН (20%-ный избыток), автоклав помещают на встр .хиватель, нагревают до 150°С и выдерживают при этой температуре и непрерывном встр хнвании 5,5 час. Затем автоклав охлаждают до комнатной температуры, вскрывают , извлекают реакционную массу, подкисл ют серной кислотой, экстрагируют эфиром, экстракт сушат сульфатом магни и отгон ют эфир. Получают твердый остаток, сырую кислоту в количестве 8,8 г, которую перекристалмизовывают из бензола и получают 6,9 г (80%) тетрафтор-Л-оксибензойной кислоты, бесцветные иглы; т. пл. 154°С; коэффициент нейтрализации, вычисленный 105, найденный 106,5. В ИК-спектре имеютс полосы поглощени фтор ароматического кольца 1500 и 1650 см, СП-группы 3360 C.U- и СООН-группы 2490- 2720 и 1705 с.и-1. В спектре ЯМР Pia имеютс The invention relates to a process for the preparation of tetrafluoro-β-oxybenzoic acid, which, as a bifunctional polyfluoroaromatic compound, can be used as a monomer for the preparation of fluorine-containing polymers, rubbers, plasticizers with valuable properties: increased chemical, thermal, radiation resistance and incombustibility. It is known to obtain tetrafluoro-and-hydroxybenzoic acid by hydrolysis with an aqueous solution of hydroiodic acid tetrafluoro - “- ethoxytrifluoromethylbenzene at boiling for 48 hours with a yield of 30%. The disadvantage of this method is low product yield. The proposed method allows to obtain tetrafluoro - "- hydroxybenzoic acid. It consists in the fact that octafluorotoluene is treated with an aqueous solution of potassium alkali (take a 20% excess of the stoichiometric required) at a temperature of 145-150 ° C for 5-6 hours. The reaction is carried out in an autoclave under a pressure of 8-9 atm. The conversion of octafluorotoluene and the yield of crude tetrafluoro / g-benzoic acid are close to 100%. In the hydrolysis of octafluorotoluene with a stronger alkali, the conversion is markedly reduced. Thus, a 30% aqueous solution of potassium alkali. Due to the strong electron-accentor effect. P1 of the trifluoromethyl soil, only the p-isomer is obtained without admixing the o- and pg-isomers, which suggests that the formation of acid occurs through the intermediate heptafluoro-l-cresolate. The output of the product reaches 80%. Example. In a nickel autoclave with a capacity of 150 ml, 10.2 g (0.043 g-mol) of octafluorotoluene (94.9% by GLC), 73 ml of 20% KOH (20% excess) are charged, the autoclave is placed on the flasher, heated to 150 ° C and kept at this temperature and continuously embedded for 5.5 hours. Then the autoclave is cooled to room temperature, opened, the reaction mass is removed, acidified with sulfuric acid, extracted with ether, the extract is dried with magnesium sulfate and the ether is distilled off. A solid residue is obtained, a crude acid in the amount of 8.8 g, which is recrystallized from benzene and 6.9 g (80%) of tetrafluoro-L-hydroxybenzoic acid are obtained, colorless needles; m.p. 154 ° C; neutralization ratio, calculated 105, found 106.5. In the IR spectrum, there are absorption bands of fluorine aromatic rings 1500 and 1650 cm, SP groups 3360 C.U- and COOH-groups 2490-2720 and 1705 c.I-1. In the Pia NMR spectrum there are
Наличии только «-изомера. Химические сдвиги относительно СНзР 145,8 и 166,7 м. д. Найдено, %: С 40,10; Н 0,93; F 35,98.Availability only “-isomer. Chemical shifts relative to CH3P 145.8 and 166.7 ppm. Found,%: C 40.10; H 0.93; F 35.98.
C7H2F403.C7H2F403.
Вычислено, %: С 40,00; Н 0,95; F 36,19. Предмет изобретени Calculated,%: C 40.00; H 0.95; F 36.19. Subject invention
Claims (2)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| SU270718A1 true SU270718A1 (en) |
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