SU355139A1 - METHOD OF OBTAINING DIFTOROALKYLBENZENES - Google Patents
METHOD OF OBTAINING DIFTOROALKYLBENZENESInfo
- Publication number
- SU355139A1 SU355139A1 SU1604493A SU1604493A SU355139A1 SU 355139 A1 SU355139 A1 SU 355139A1 SU 1604493 A SU1604493 A SU 1604493A SU 1604493 A SU1604493 A SU 1604493A SU 355139 A1 SU355139 A1 SU 355139A1
- Authority
- SU
- USSR - Soviet Union
- Prior art keywords
- obtaining
- diftoroalkylbenzenes
- difluoro
- oxide
- naf
- Prior art date
Links
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Inorganic materials [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 4
- 235000013024 sodium fluoride Nutrition 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N oxane Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- GQOQTUOLCZOXSN-UHFFFAOYSA-N (1,2-difluoro-2-phenylethyl)benzene Chemical compound C=1C=CC=CC=1C(F)C(F)C1=CC=CC=C1 GQOQTUOLCZOXSN-UHFFFAOYSA-N 0.000 description 2
- FBXNRKRVSUNNEF-UHFFFAOYSA-N 1-(2,2-difluoroethyl)-4-nitrobenzene Chemical class [O-][N+](=O)C1=CC=C(CC(F)F)C=C1 FBXNRKRVSUNNEF-UHFFFAOYSA-N 0.000 description 2
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 2
- QHMQWEPBXSHHLH-UHFFFAOYSA-N Sulfur tetrafluoride Chemical compound FS(F)(F)F QHMQWEPBXSHHLH-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012025 fluorinating agent Substances 0.000 description 2
- 239000008079 hexane Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene dichloride Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- SVQHPJKYUJYLJD-UHFFFAOYSA-N 2,2-difluoroethylbenzene Chemical compound FC(F)CC1=CC=CC=C1 SVQHPJKYUJYLJD-UHFFFAOYSA-N 0.000 description 1
- YKIUTLHCSNCTDZ-UHFFFAOYSA-N 2-(4-nitrophenyl)oxirane Chemical compound C1=CC([N+](=O)[O-])=CC=C1C1OC1 YKIUTLHCSNCTDZ-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 229920000591 gum Polymers 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing Effects 0.000 description 1
Description
Изо6ретеМ|Ие относитс к способу получени дифторалкилбензолов, которые Я|Вл ютс промежуточным ,и соединени ми дл синтеза мономеров , компонентов красителей, физиологически активных веш,еств.Iorete | Ie relates to a process for the production of difluoroalkylbenzenes, which I | Intermediates, and compounds for the synthesis of monomers, components of dyes, physiologically active substances.
Известно получение 1,1-дифтор-2-фенилэтана путем фторировани стирола арилйоддифторидом .It is known to obtain 1,1-difluoro-2-phenylethane by fluorination of styrene with aryl iodo difluoride.
Основным недостатком указанного метода вл етс труднодоступность арилйоддифтоРида .The main disadvantage of this method is the inaccessibility of aryl iododifluoroRide.
С целью использовани более доступного фторирующего агента моло- И диарилзамещепные окиси этилена фторируют с помощью 5р4 в автоклаве предпочтительно при 20- .In order to use a more accessible fluorinating agent, the young and diaryl-substituted ethylene oxides are fluorinated with a 5p4 in an autoclave, preferably at 20-.
Целевой продукт выдел ют известнымИ способами .The desired product is isolated by known methods.
При взаимодействии окисей стирола и rt-нит.ростирола образуютс 1,1-дифтор-2-фенил- и 1,1-дифтор-2-п-нитрофенилэтаны соответственно:1,1-Difluoro-2-phenyl and 1,1-difluoro-2-p-nitrophenylethanes are formed by the interaction of styrene and rt-nit.rostyrol oxides, respectively:
- ХСбНчСН.СНГо - XSbNchSN.SGO
ристого натри (NaF). Во всех случа х выдел ют только соединени формул I и И, причем более высокий выход и меньшее смолообразование наблюдаетс при добавлении NaF.sodium salt (NaF). In all cases, only the compounds of the formulas I and I were isolated, with a higher yield and a lower gum formation when NaF was added.
Окись стирола реагирует с SF4 уже при 20°С, а окись г-нитростирола требует нагревани до 50-85°С.Styrene oxide reacts with SF4 already at 20 ° C, and g-nitrostyrene oxide requires heating to 50-85 ° C.
При взаимодействии окиси г/оанс-стильбена (диарилзамещенна симметрична окись этилена ) с SF4 образуетс вицинальный продукт- 1,2-дифенил-1,2-дифторэтан, аналогичный продукту присоединени двух атомов фтора к стильбену:The interaction of g / oans-stilbene oxide (diaryl-substituted symmetric ethylene oxide) with SF4 forms a vicinal product, 1,2-diphenyl-1,2-difluoroethane, similar to the product of the addition of two fluorine atoms to stilbene:
SFSF
« бНзСН-СНС.“BNzSN-SNS.
Нз--CfiHsGHFCHFCeHrMMNz - CfiHsGHFCHFCeHrMM
/ /
Строение полученных фторидов подтверждаетс химическим анализом и спектрами ЯМР F19 и ПМР.The structure of the fluorides obtained is confirmed by chemical analysis and F19 and HMR NMR spectra.
Пример 1. 1,1-Дифтор-2-п-нитрофенилэтан .Example 1. 1,1-Difluoro-2-p-nitrophenyl ethane.
3,3 г окиси 4-нитростирола и 4,6 г четырехфтористой серы выдерживают 3 час в автоклаве при 85°С. Затем к реакционной смеси, растворенной в эфире, добавл ют NaF. Через 2 час iNaF отфильтровывают, эфир отгон ют и продукт реакции извлекают гор чим гексаном.3.3 g of 4-nitrostyrene oxide and 4.6 g of sulfur tetrafluoride are kept in an autoclave for 3 hours at 85 ° C. NaF is then added to the reaction mixture, dissolved in ether. After 2 hours, the iNaF was filtered off, the ether was distilled off and the reaction product was extracted with hot hexane.
Выход 1,78 г (47%), т. пл. 55°С. Найдено, %: F 20,25; 20,26. СвНуРгЫОг. Вычислено, %: F 20,30.The output of 1.78 g (47%), so pl. 55 ° C. Found,%: F 20.25; 20.26. SvNurGyOg. Calculated,%: F 20.30.
Пример 2. 1,2-Дифтор-1,2-дифенилэтан.Example 2. 1,2-Difluoro-1,2-diphenyl ethane.
0,98 г окиси гранс-стильбена, 0,4 г NaF, 10 мл безводного метиленхлорида и 6 г четырехфтористой серы нагревают 5 час в автоклаве при 50°С. Содержимое выдерживают над iNaF, выпавшие кристаллы после отделени iNaF « отгонки растворител отфильтровывают и кристаллизуют. Выход 0,62 г (57%), т. пл. 102°С (гексан).0.98 g of granules-stilbene oxide, 0.4 g of NaF, 10 ml of anhydrous methylene chloride and 6 g of sulfur tetrafluoride are heated for 5 hours in an autoclave at 50 ° C. The contents were incubated over iNaF, the precipitated crystals after separation of the iNaF " distillation of the solvent were filtered and crystallized. The output of 0.62 g (57%), so pl. 102 ° C (hexane).
Найдено, %; F 17, 20; 17, 38.Found,%; F 17, 20; 17, 38.
Ci4Hl2F2.Ci4Hl2F2.
Вычислено, %: F 17,41.Calculated,%: F 17.41.
Предмет изобретени Subject invention
1.Способ получени дифторалк«лбензолов, отличающийс тем, что,, с .целью использовани болеедоступного фторирующего агента, моно- и диарилзамещенные окиси этилена обрабатывают SF4 в автоклаве с последующим выделением целевого продукта известным методом.1. A method of obtaining difluoroalkenzenes, characterized in that, in order to use a more readily available fluorinating agent, mono- and diaryl-substituted ethylene oxides are treated with SF4 in an autoclave, followed by isolation of the target product by a known method.
2.Способ ПО п. 1, отличающийс тем, что процесс провод т при 20-150°С.2. Method according to claim 1, characterized in that the process is carried out at 20-150 ° C.
Publications (1)
| Publication Number | Publication Date |
|---|---|
| SU355139A1 true SU355139A1 (en) |
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