SU345676A1 - METHOD OF OBTAINING ALKENTHIOLS - Google Patents
METHOD OF OBTAINING ALKENTHIOLSInfo
- Publication number
- SU345676A1 SU345676A1 SU1264875A SU1264875A SU345676A1 SU 345676 A1 SU345676 A1 SU 345676A1 SU 1264875 A SU1264875 A SU 1264875A SU 1264875 A SU1264875 A SU 1264875A SU 345676 A1 SU345676 A1 SU 345676A1
- Authority
- SU
- USSR - Soviet Union
- Prior art keywords
- alkenthiols
- atoms
- acid catalyst
- target products
- group
- Prior art date
Links
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 239000003377 acid catalyst Substances 0.000 claims description 3
- 125000004432 carbon atoms Chemical group C* 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 125000004429 atoms Chemical group 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims 1
- 125000001246 bromo group Chemical group Br* 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 150000007970 thio esters Chemical class 0.000 claims 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- -1 aryl radicals Chemical class 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 240000001340 Gmelina philippensis Species 0.000 description 1
- 229920004449 Halon® Polymers 0.000 description 1
- WCYWZMWISLQXQU-UHFFFAOYSA-N Methyl radical Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 description 1
- DPLVEEXVKBWGHE-UHFFFAOYSA-N Potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N Sodium sulfide Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- UMGDCJDMYOKAJW-UHFFFAOYSA-N Thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 1
- 235000015450 Tilia cordata Nutrition 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 230000002378 acidificating Effects 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 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
- 238000000605 extraction Methods 0.000 description 1
- 230000000855 fungicidal Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000000749 insecticidal Effects 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L na2so4 Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000010992 reflux Methods 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
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
Description
Изобретение относитс к способу получени алкентиолов, замещенных атомами галогсиа, например хлора или брома, алкильными или арильными радикалами. Указанные соединени примен ют при получении тиосоединений, а также в качестве инсектицидов и фунгицидов .This invention relates to a process for the preparation of alkentiols substituted by halo atoms, for example chlorine or bromine, by alkyl or aryl radicals. These compounds are used in the preparation of thio compounds, as well as insecticides and fungicides.
Известные методы получени алкеитиолов, в частности галоидалкеитилов, взаимодействием галоидалкена с кислым сульфидом кали или натри , а также реакцией галоидалкенов с тиомочевииой и иоследующим разложением получениой соли щелочью характеризуютс невысоким выходом целевого продукта.The known methods for the preparation of alkeiols, in particular haloalkyl, by the interaction of a haloalkene with acidic potassium or sodium sulphide, as well as the reaction of haloalkenes with thiourea and the subsequent decomposition with alkali, are characterized by low yield of the desired product.
Применение предлагаемого способа позвол ет в значительной степени новысить выход известиых галоидалкентиолов, а также получать р д не известных ранее галоидзамещениых алкентиолов.The application of the proposed method makes it possible to significantly increase the yield of lime haloalkentiols, as well as to obtain a number of previously unknown halogen-substituted alkentyols.
Предлагаемый способ получени алкентнолов заключаетс в том, что сложный алкентиоили алкендитиоэфир, например галоидалкеитиоацетат , подвергают взаимодействию с алифатическим иасыщенным спиртом при нагревании , преимущественно при температуре кипени спирта, к присутствии кислотного катализатора . В результате реакции образуетс галоидалкентнол , который носле отгонкп спирта извлекают иодход щнм растворителем.The proposed method for the preparation of alkenthols is that the alkentio or alkydithio ester, for example, haloalkitythioacetate, is reacted with an aliphatic and saturated alcohol when heated, preferably at the boiling point of the alcohol, to the presence of an acid catalyst. As a result of the reaction, a haloalkenol is formed, which, when distilling off the alcohol, is extracted with the solvent input.
ИсходнЕзп алкентиоэфир может иметь в качестве заместителей в алкеннльном остатке кроме атомов галонда алкильный радикал с 1-6 атомами углерода или арильный радикал . Остаток тиокислоты может быть как алифатическим, насыщенным, так и ненасыщенньт , ациклическим илп циклическим, но преимущественно метильным радикалом.The base alkentio ether may have, as substituents in the alkenele residue, in addition to halon atoms, an alkyl radical with 1-6 carbon atoms or an aryl radical. The thioacid residue can be either aliphatic, saturated, or unsaturated, acyclic or cyclic, but predominantly methyl radical.
В качестве алифатических насыщенных спнртов примен ют сиирты, содержащие в радикале 1-30 атомов углерода, преимущественно 1-4. Дл осуществлени способа используют избыток сппрта от 2 до 50 моль, главным образом от 5 до 20 мо.гь на 1 моль тиоэфира.Syryths containing 1-30 carbon atoms, preferably 1-4 in the radical, are used as aliphatic saturated sprints. For carrying out the process, an excess of sulphate from 2 to 50 mol, mainly from 5 to 20 mol per 1 mol of thioether, is used.
Реакцию ведут в ирнсутствнн безводной неорганической кислоты, иаиример хлористоводородиой , вз той в количестве 0,5-5%, преимущественно 1-3% от веса реакционной смеси.The reaction is carried out in anhydrous inorganic acid, and hydrochloride, taken in an amount of 0.5-5%, preferably 1-3% by weight of the reaction mixture.
Пример 1. Хлор-2-пропен-2-тиол.Example 1. Chlorine-2-propen-2-thiol.
В растворе 500 мл метанола (12,5 моль In a solution of 500 ml of methanol (12.5 mol
СП.ОИ), содержащем 2% ИС1, нагревают доSP.OI), containing 2% IS1, is heated to
тем реакционную смесь обрабатывзЕОт эфиром и эфирный слой после нромывки водой и сушки над безводным сульфатом натри перегон ют . В остатке получают 87 г (80%) тиола CH2 CC1CH2SH, т. кип. 70°С/150 мм рт. ст.,the reaction mixture is treated with ether and the ether layer after distillation with water and drying over anhydrous sodium sulfate is distilled. The residue gives 87 g (80%) of the thiol CH2 CC1CH2SH, t. Bale. 70 ° C / 150 mmHg Art.,
2020
1,507.1.507
ИК-спектр: v (ел-), 2980, 2950, 2580, 1640, 1420, 1390, 1250, 1220, ИЗО, 900, 730, 680, 630. Найдено, %: С 32,87; Н 4,57.IR spectrum: v (el), 2980, 2950, 2580, 1640, 1420, 1390, 1250, 1220, FROM, 900, 730, 680, 630. Found:%: 32.87; H 4.57.
CsHsSCl. Вычислено, 7о: С 33,2; Н 4,6.CsHsSCl. Calculated 7o: C 33.2; H 4.6.
Пример 2. Дихлор-3,3-пропеп-2-тиол.Example 2. Dichloro-3,3-propane-2-thiol.
64 г тиоацетил-1-дихлор-3,3-пронена-2 нагревают с обратным холодильником в течение 3 час в растворе 160 мл метанола с 2% НС1. Затем смесь охлаждают н обрабатывают хлороформом , а полученный раствор промывают водой и сушат. После отгонки хлороформа оставшийс продукт перегон ют в вакууме. Получают 36 г (72%) тиола, т. кип. 62С/28 мм рт. ст., п 1,508.64 g of thioacetyl-1-dichloro-3,3-prone-2 is heated under reflux for 3 hours in a solution of 160 ml of methanol with 2% HCl. The mixture is then cooled and treated with chloroform, and the resulting solution is washed with water and dried. After distilling off the chloroform, the remaining product is distilled under vacuum. Receive 36 g (72%) of thiol, t. Kip. 62C / 28 mmHg Art., p 1,508.
ИК-спектор: v (еж-) 3060, 3000, 2960, 2560, 1630, 1435, 1290, 1240, 1190, 1070, 1030, 990, 890, 840, 780, 690, 600.IR Spector: v (hedgehog) 3060, 3000, 2960, 2560, 1630, 1435, 1290, 1240, 1190, 1070, 1030, 990, 890, 840, 780, 690, 600.
Найдено, %: С 25,76; Н 3,01; S 21,82; С1 49,96.Found,%: C 25.76; H 3.01; S 21.82; C1 49.96.
СзН4С128.SzN4S128.
4 four
Вычислено, 7о: Calculated 7o:
Н 2,8; S 22,37; С 25,87; С1 49,65.H 2.8; S 22.37; C, 25.87; C1 49.65.
Если предварительно перед экстракцией целевого продукта хлороформом отогнать больШую часть метанола, то выход повышаетс до 83%.If prior to the extraction of the target product with chloroform, if most of the methanol is distilled off, the yield rises to 83%.
Предмет изобретени Subject invention
Claims (3)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| SU345676A1 true SU345676A1 (en) |
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