SU328082A1 - METHOD FOR PRODUCING METHYL (BISCHLOROMETHYL-4-ALKYLPHENYL) CARBONATES - Google Patents
METHOD FOR PRODUCING METHYL (BISCHLOROMETHYL-4-ALKYLPHENYL) CARBONATESInfo
- Publication number
- SU328082A1 SU328082A1 SU1454586A SU1454586A SU328082A1 SU 328082 A1 SU328082 A1 SU 328082A1 SU 1454586 A SU1454586 A SU 1454586A SU 1454586 A SU1454586 A SU 1454586A SU 328082 A1 SU328082 A1 SU 328082A1
- Authority
- SU
- USSR - Soviet Union
- Prior art keywords
- bischloromethyl
- alkylphenyl
- carbonates
- methyl
- producing methyl
- Prior art date
Links
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 title description 2
- 238000004519 manufacturing process Methods 0.000 title description 2
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical class [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 title 1
- 238000000034 method Methods 0.000 description 7
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 4
- HKYGSMOFSFOEIP-UHFFFAOYSA-N dichloro(dichloromethoxy)methane Chemical compound ClC(Cl)OC(Cl)Cl HKYGSMOFSFOEIP-UHFFFAOYSA-N 0.000 description 4
- -1 monochloromethyl Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 125000005911 methyl carbonate group Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 2
- 238000004452 microanalysis Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- HJPOKQICBCJGHE-UHFFFAOYSA-J [C+4].[Cl-].[Cl-].[Cl-].[Cl-] Chemical compound [C+4].[Cl-].[Cl-].[Cl-].[Cl-] HJPOKQICBCJGHE-UHFFFAOYSA-J 0.000 description 1
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 1
- 150000005224 alkoxybenzenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 238000007265 chloromethylation reaction Methods 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- GQKZBCPTCWJTAS-UHFFFAOYSA-N methoxymethylbenzene Chemical class COCC1=CC=CC=C1 GQKZBCPTCWJTAS-UHFFFAOYSA-N 0.000 description 1
- FLSOKBQNISCLMI-UHFFFAOYSA-N methyl (4-methylphenyl) carbonate Chemical compound COC(=O)OC1=CC=C(C)C=C1 FLSOKBQNISCLMI-UHFFFAOYSA-N 0.000 description 1
- XMJHPCRAQCTCFT-UHFFFAOYSA-N methyl chloroformate Chemical compound COC(Cl)=O XMJHPCRAQCTCFT-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- NRZWYNLTFLDQQX-UHFFFAOYSA-N p-tert-Amylphenol Chemical class CCC(C)(C)C1=CC=C(O)C=C1 NRZWYNLTFLDQQX-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Description
Изобретение касаетс .получени д)етил (бисхлорметил-4-алкилфенил) карбонатов, на основе которых можно получать бисфункциональные серу- н азотсодержащие производные , представл ющие большой интерес как веHiecTBa , обладаюнхие физиологической активностью .The invention relates to the preparation of e) ethyl (bischloromethyl-4-alkylphenyl) carbonates, on the basis of which it is possible to obtain bis-functional sulfur-nitrogen-containing derivatives, which are of great interest as heHiecTBa, possessing physiological activity.
Известны способы бисхлорметилировани фенола, крезолов, анизола, алкоксибензолов и некоторых метоксиметилбензолов действием формальдегида н его нолимеров в концентрированной НС1 В присутствии НзРО4 и без катализаторов . Однако при проведении этих способов ВО многих случа х нар ду с бисхлорметилпроизводными образуетс значительное количество монохлорметилпроизводных. Выходы нродуктов бисхлорметилировани не превышают 42-75%.There are known methods for bis-chloromethylation of phenol, cresols, anisole, alkoxybenzenes and some methoxymethylbenzenes by the action of formaldehyde and its polymers in concentrated HC1 In the presence of H3PO4 and without catalysts. However, when carrying out these methods in many cases, along with bischloromethyl derivatives, a significant amount of monochloromethyl derivatives is formed. The yields of bischloromethylation products do not exceed 42-75%.
Целью изобретени вл етс разработка способа получени бисхлорметилнроизводныхThe aim of the invention is to develop a process for the preparation of bis-chloromethyl derivatives
метилкарбоиатоп 4-алкнлфенолов с высокими выходами.methylcarboxyop 4-alknophenol with high yields.
Предлагаетс способ получени метил-(бнсхлорметил-4-алкнлфенил )«арбонатов действием бнсхлорметилового эфира на метилкарбонаты 4-алкнлфенолов в четыреххлорнстом углероде в присутствии п тихлористой сурьмы В качестве катализатора при температуре до 10°С В зависимости от величины алкильногоA method is proposed for producing methyl- (benchloromethyl-4-alkylphenyl) "arbonates by action of benchloromethyl ester on methylcarbonates of 4-alkylphenols in tetrachloride carbon in the presence of antimony pentachloride as a catalyst at a temperature of up to 10 ° C, depending on the value of alkyl
радикала в метнлкарбонатах 4-алкилфенолов.radical in methylcarbonates 4-alkylphenols.
Продолжительность синтеза 3-4 час. ВыходThe duration of the synthesis is 3-4 hours. Output
метил-(бнсхлорметил -4- алкилфенил)карбонатов составл ет 78-84%.methyl- (benchloromethyl-4-alkylphenyl) carbonates is 78-84%.
Предлагаемым методом ироведеио бисхлорметилирование метнлкарбоиатов /г-крезола. 4-изонропил-, 4-вго/ -бутил-, 4-грег-бутил- и 4-трет-амилфенолов. Полученные бисхлорметильные производные выдел ли вакуумной перегонкой и первкристаллизовывали из лед нойThe proposed method irovedeio bischloromethylation of metncarboate / g-cresol. 4-isonropyl-, 4-vg / -butyl-, 4-greg-butyl- and 4-tert-amylphenols. The resulting bis chloromethyl derivatives were isolated by vacuum distillation and crystallized from ice
уксусной кислоты. Данные о полученных метил- (бнсхлорметил -4- алкилфенил)карбонатах приведены в таблице.acetic acid. Data on the obtained methyl- (benchloromethyl-4-alkylphenyl) carbonates are given in the table.
Метилкарбонаты 4-алкилфенолов получают по известной методике из фенол тов и метилхлорформиата .Methylcarbonates of 4-alkylphenols are prepared according to a known procedure from phenols and methyl chloroformate.
В четырехгорлую колбу с мешалкой, внутренним термометром и хлоркальциевой трубкой помещают исходный метилкарбонат 4-алкилфенола, бисхлорметиловый эфир и ecu в качестве растворител , вз тые в мол рном соотношении 1 : 2, 7 ; 1. Смесь охлаждают на лед ной бане и к ней медленно добавл ют 1 г моль SbCls при энергичном перемешивании в течение 3-4 час, выдержива заданную температуру. По окончании реакционную смесь выливают в лед ную воду, органический слой отдел ют, многократно промывают водой и после высушивани над безводным Na2SO4 перегон ют в вакууме.In a four-necked flask with a stirrer, an internal thermometer and a calcium chloride tube, the starting 4-alkylphenol methyl carbonate, bischloromethyl ether and ecu are placed as a solvent, taken in a molar ratio of 1: 2, 7; 1. The mixture is cooled in an ice bath and 1 g of SbCls is slowly added to it with vigorous stirring for 3-4 hours, maintaining the desired temperature. At the end, the reaction mixture was poured into ice water, the organic layer was separated, washed several times with water, and after drying over anhydrous Na2SO4, it was distilled in vacuo.
Пример 1. В смесь 8,3 г метил-/г-крезилкарбоната , 10 мл CCU и 12 мл бисхлорметилового эфира медленно при энергичном перемешивании добавл ют 6 мл SbCls. Температура реакции пе должна первышать 3°С, продолжительность 3 час.Example 1. In a mixture of 8.3 g of methyl- / g-cresyl carbonate, 10 ml of CCU and 12 ml of bischloromethyl ether, 6 ml of SbCls was slowly added with vigorous stirring. The reaction temperature ne should exceed 3 ° С, the duration is 3 hours.
После обработки и перегонки в вакууме получают 10,8 г (82%) метил-(бисхлорметил-4метилфенил ) карбоната. Чистота-продукта подтверждаетс данными микроанализа.After treatment and distillation in vacuo, 10.8 g (82%) of methyl- (bischloromethyl-4-methylphenyl) carbonate are obtained. The purity of the product is confirmed by microanalysis data.
Пример 2. В смесь 10,4 г метилкарбоната 4-т/9ет-бутилфенола, 10 Л1Л CCU и 12 мл бисхлорметилового эфира добавл ют 6 Л1Л SbCU. Температура реакции 5-7°С, продолжительность 4 час.Example 2. To a mixture of 10.4 g of 4-t / 9-t-butylphenol methyl carbonate, 10 L1L CCU and 12 ml of bischloromethyl ether was added 6 L1L SbCU. The reaction temperature is 5-7 ° C, the duration is 4 hours.
Получают 12,8 г (84%) метил-(бисхлорметил-4-г/7ег-бутилфенил ) карбоната. Чистота продукта подтверждаетс данными микроанализа .12.8 g (84%) of methyl- (bischloromethyl-4-g / 7g-butylphenyl) carbonate are obtained. The purity of the product is confirmed by microanalysis data.
Предмет изобретени Subject invention
Способ получени метил-(бисхлорметил-4алкилфенил ) карбонатов, отличающийс тем,A method for producing methyl- (bischloromethyl-4-alkylphenyl) carbonates, characterized in
что метил-п-крезилкарбонат подвергают взаимодействию с бисхлорметиловым эфиром в присутствии п тихлористой сурьмы в среде органического растворител , например четыреххлористого углерода, при температуре неthat methyl p-cresyl carbonate is reacted with bischloromethyl ether in the presence of antimony pentachloride in an environment of an organic solvent, for example carbon tetrachloride, at a temperature not
выше 10°С с носледуюш,им выделением целевого продукта известными приемами.above 10 ° C with nesledyushush, the selection of the target product by known methods.
Publications (1)
| Publication Number | Publication Date |
|---|---|
| SU328082A1 true SU328082A1 (en) |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5082964A (en) * | 1984-02-01 | 1992-01-21 | Lehigh University | Selective acetylcholinesterase inhibitors and methods of making and using same |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5082964A (en) * | 1984-02-01 | 1992-01-21 | Lehigh University | Selective acetylcholinesterase inhibitors and methods of making and using same |
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