CN1157284A - 制备2-氯-5-氯甲基噻唑的方法 - Google Patents
制备2-氯-5-氯甲基噻唑的方法 Download PDFInfo
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- CN1157284A CN1157284A CN96117934A CN96117934A CN1157284A CN 1157284 A CN1157284 A CN 1157284A CN 96117934 A CN96117934 A CN 96117934A CN 96117934 A CN96117934 A CN 96117934A CN 1157284 A CN1157284 A CN 1157284A
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- 238000000034 method Methods 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- AIKDVHPBLPODIO-UHFFFAOYSA-N 3-chloro-5-(chloromethyl)-2H-1,3-thiazole Chemical compound ClCC1=CN(Cl)CS1 AIKDVHPBLPODIO-UHFFFAOYSA-N 0.000 title 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 claims description 2
- VRMUIVKEHJSADG-UHFFFAOYSA-N 2-chloro-5-(chloromethyl)-1,3-thiazole Chemical compound ClCC1=CN=C(Cl)S1 VRMUIVKEHJSADG-UHFFFAOYSA-N 0.000 abstract description 2
- 239000012320 chlorinating reagent Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 13
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- ZOJBYZNEUISWFT-UHFFFAOYSA-N allyl isothiocyanate Chemical compound C=CCN=C=S ZOJBYZNEUISWFT-UHFFFAOYSA-N 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 229960001701 chloroform Drugs 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
- C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Thiazole And Isothizaole Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及通过使5-亚甲基-1，3-塞唑啉-2-硫酮与氯化剂反应来制备2-氯-5-氯甲基塞唑的新方法。
Description
本发明涉及制备2-氯-5-氯甲基噻唑的新方法。
人们知道，如果使式(A)异硫氰酸烯丙酯(烯丙基芥子油)与氯化剂按照下式反应，则可以制得2-氯-5-氯甲基噻唑：(参见EP-A0260560)。
人们还知道，如果使式(B)异硫氰酸烯丙酯与氯化剂按照下式反应，则可以制得2-氯-5-氯甲基噻唑：
X＝离去基团(参见EP-A0446913)。
然而，这些方法要使用大量过量的氯化剂，必须在高度稀释的体系中工作，而且必须对反应温度精确观察，这是不利的。
此外，反应过程中生成的稳定中间体必须用附加的反应步骤转化为所需的终产品，该反应是放热反应。这便需要额外的费用来监控，当该反应以工业规模进行时尤其如此。
业已发现，如果使式(II)的5-亚甲基-1，3-噻唑烷-2-硫酮可选地在稀释剂存在下与氯化剂反应，则可以良好的产率和高纯度获得式(I)的2-氯-5-氯甲基噻唑；式(I)和(II)如下：
式中，R1代表氢或基团R2-CO-，其中R2代表烷基或可选地取代的苯基。
令人惊讶的是，按照本发明的方法能够以良好的产率和高纯度获得式(I)的2-氯-5-氯甲基噻唑，尽管从先有技术人们必然可以预期到在如此温和的氯化条件下，＞N-CS基团将不能脱硫(参见例如Org.Synthesis 51，139(1971))。人们也预期不到在氯化的过程中二硫代氨基甲酸酯仍然能保留下来(参见例如Houben Weyl，Methoden derorganischen Chemie，vol.5/3，p.648(1962))。
因此，本发明的反应具有能简单而迅速地实施的优点，甚至不需要纯化步骤也可获得高的粗产率。
此外，不出现稳定中间体，彻底地免除了后续的散热反应步骤。
例如，使用5-亚甲基-1，3-噻唑烷-2-硫酮作原材料，以元素氯为氯化剂，则本发明方法的反应过程可用下述反应方程式表示：
式(II)是在本发明的方法中用作原材料的5-亚甲基-1，3-噻唑烷-2-硫酮的一般性描述。在式(II)中，R1优选代表氢或基团R2-CO-，其中R2优选代表直链或支链C1-C4烷基，例如特别是甲基、乙基或异丙基；并且代表苯基或被相同或不同的取代基例如甲基、乙基、氟、氯、硝基和氰基一取代或二取代的苯基。
式(II)的5-亚甲基-1，3-噻唑烷-2-硫酮原则上是已知的(参见LiebigsAnn.Chem.1985，58 ff.)。
适宜的氯化剂是元素氯和在反应条件下能够给出氯的化合物，例如磺酰氯或碳酰氯。
本发明的方法最好在稀释剂的存在下进行。
适宜的稀释剂是常规的有机溶剂。它们优选包括氯化的脂族和芳族烃，例如二氯甲烷、三氯甲烷、三氯乙烯、四氯乙烯和四氯化碳以及氯苯或二氯苯。
在实施本发明的方法时，反应温度可以在较宽的范围内改变。通常在-80℃至150℃之间的温度下、优选在-30℃至80℃温度下进行。
反应和后处理的实施是以一般的常规方法进行的(参见制备实施例)。
如果在本发明中用溴化剂代替相应的氯化剂，则得到式(III)的2-溴-5-溴甲基噻唑：
式(III)的2-溴-5-溴甲基噻唑是已知的(参见EP-A0376279)。
用本发明方法制备的式(I)2-氯-5-氯甲基噻唑可以在生物活性化合物例如杀昆虫剂的制备中用作中间体(参见例如EP-A0192060)。
制备实施例实施例1
在-10℃下，将氯气流通入20克(0.15mol)5-亚甲基-1，3-噻唑烷-2-硫酮在200ml氯仿中的悬浮液中。过一会儿得到清澈溶液，随着产物的沉淀变浑浊。不再吸收氯后，立即将混合物于-10℃搅拌10分钟，升温至20℃，用水将反应混合物洗涤数次。然后，真空除去溶剂。
得到26.9克黄色液态粗产品，GC纯度为87％，对应的理论收率为92.8％。
可以用硅胶色谱将粗产品进一步纯化(洗脱剂体系：氯仿/乙酸乙酯(4∶1))。
获得10.6克(GC纯度＞99％)熔点为32℃的2-氯-5-氯甲基噻唑。实施例2
在0℃下，将氯气流通入2.6克(0.015mol)3-乙酰基-5-亚甲基-1，3-噻唑烷-2-硫酮在50ml氯仿中的溶液中。然后将混合物于20℃搅拌20分钟，用水将溶液洗涤两次。用硫酸镁干燥后，将有机相浓缩。
得到2.4克黄色油状粗产品，根据GC分析，它含有41％所需的2-氯-5-氯甲基-1，3-噻唑。
Claims (1)
1.制备式(I)的2-氯-5-氯甲基噻唑的方法，其特征在于使式(II)的5-亚甲基-1，3-噻唑啉-2-硫酮可选地在稀释剂存在下与氯化剂反应；式(I)和(II)如下：
式中，R1代表氢或基团R2-CO-，其中R2代表烷基或可选地取代的苯基。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19548417A DE19548417A1 (de) | 1995-12-22 | 1995-12-22 | Verfahren zur Herstellung von 2-Chlor-5-chlormethylthiazol |
| DE19548417.7 | 1995-12-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1157284A true CN1157284A (zh) | 1997-08-20 |
Family
ID=7781198
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96117934A Pending CN1157284A (zh) | 1995-12-22 | 1996-12-20 | 制备2-氯-5-氯甲基噻唑的方法 |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US5679796A (zh) |
| EP (1) | EP0780384A3 (zh) |
| JP (1) | JPH09176140A (zh) |
| KR (1) | KR970042530A (zh) |
| CN (1) | CN1157284A (zh) |
| DE (1) | DE19548417A1 (zh) |
| TW (1) | TW323277B (zh) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU1193597A (en) * | 1995-12-21 | 1997-07-17 | Ciba-Geigy Ag | Process for the preparation of 2-chloro-5-chloromethyl-thiazole |
| DE19908447A1 (de) | 1999-02-26 | 2000-08-31 | Bayer Ag | Verfahren zur Herstellung von 2-Chlor-5-chlormethylthiazol |
| ES2194783T3 (es) | 1999-11-15 | 2003-12-01 | Dsm Fine Chem Austria Gmbh | Procedimiento para la obtencion de 2-cloro-5-clorome-til-1,3-tiazol. |
| AT409760B (de) * | 1999-11-15 | 2002-11-25 | Dsm Fine Chem Austria Gmbh | Verfahren zur herstellung von 2-chlor-5-chlormethyl-1,3-thiazol |
| WO2002012209A1 (de) * | 2000-08-10 | 2002-02-14 | Bayer Cropscience Ag | Verfahren zur reinigung von 2-chlor-5-chlormethylthiazol |
| DE102006015467A1 (de) | 2006-03-31 | 2007-10-04 | Bayer Cropscience Ag | Substituierte Enaminocarbonylverbindungen |
| DE102006015456A1 (de) | 2006-03-31 | 2007-10-04 | Bayer Cropscience Ag | Bicyclische Enamino(thio)carbonylverbindungen |
| DE102006033572A1 (de) | 2006-07-20 | 2008-01-24 | Bayer Cropscience Ag | N'-Cyano-N-halogenalkyl-imidamid Derivate |
| KR100844860B1 (ko) * | 2006-09-28 | 2008-07-09 | 일진중공업 주식회사 | 조류터빈용 커플링 장치 |
| EP2039678A1 (de) | 2007-09-18 | 2009-03-25 | Bayer CropScience AG | Verfahren zum Herstellen von 4-Aminobut-2-enoliden |
| EP2107058A1 (de) | 2008-03-31 | 2009-10-07 | Bayer CropScience AG | Substituierte Enaminothiocarbonylverbindungen |
| EP2264008A1 (de) | 2009-06-18 | 2010-12-22 | Bayer CropScience AG | Substituierte Enaminocarbonylverbindungen |
| DK2638010T3 (en) | 2010-11-12 | 2015-04-13 | Bayer Ip Gmbh | PROCEDURE FOR PREPARING 2,2-DIFLUORETHYLAMINE DERIVATIVES FROM N- (2,2-DIFLUORETHYL) PROP-2-EN-1-AMINE |
| BR112013028895A2 (pt) | 2011-05-10 | 2016-08-09 | Bayer Ip Gmbh | (tio)carbonilamidinas bicíclicas |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54109969A (en) * | 1978-02-14 | 1979-08-29 | Shionogi & Co Ltd | Novel method of preparing thiazole derivative |
| DE3631538A1 (de) * | 1986-09-17 | 1988-03-24 | Bayer Ag | Verfahren zur herstellung von 2-chlor-5-chlormethylthiazol |
| US5180833A (en) * | 1990-03-16 | 1993-01-19 | Takeda Chemical Industries, Ltd. | Process for the preparation of chlorothiazole derivatives |
| HRP921128B1 (en) * | 1991-10-30 | 1998-10-31 | Sandor Garaczy | Novel process for the preparation of 4-methyl-5(2-chloroethyl)-thiazole and analogues thereof |
| JPH11512407A (ja) * | 1995-09-11 | 1999-10-26 | ノバルティス アクチェンゲゼルシャフト | ２−クロロ−５−クロロメチル−チアゾール化合物を調製するための方法 |
-
1995
- 1995-12-22 DE DE19548417A patent/DE19548417A1/de not_active Withdrawn
-
1996
- 1996-12-10 EP EP96119776A patent/EP0780384A3/de not_active Withdrawn
- 1996-12-13 US US08/764,952 patent/US5679796A/en not_active Expired - Lifetime
- 1996-12-16 TW TW085115494A patent/TW323277B/zh active
- 1996-12-17 JP JP8353342A patent/JPH09176140A/ja active Pending
- 1996-12-18 KR KR1019960067303A patent/KR970042530A/ko not_active Application Discontinuation
- 1996-12-20 CN CN96117934A patent/CN1157284A/zh active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP0780384A2 (de) | 1997-06-25 |
| US5679796A (en) | 1997-10-21 |
| JPH09176140A (ja) | 1997-07-08 |
| DE19548417A1 (de) | 1997-06-26 |
| KR970042530A (ko) | 1997-07-24 |
| EP0780384A3 (de) | 1997-07-09 |
| TW323277B (zh) | 1997-12-21 |
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