CN1143846C - 2-烷硫基苄腈衍生物的制备方法 - Google Patents
2-烷硫基苄腈衍生物的制备方法 Download PDFInfo
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- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 9
- 125000000171 (C1-C6) haloalkyl group Chemical group 0.000 claims abstract description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000460 chlorine Substances 0.000 claims abstract description 7
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 7
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- 239000012071 phase Substances 0.000 description 1
- PMOIAJVKYNVHQE-UHFFFAOYSA-N phosphanium;bromide Chemical compound [PH4+].[Br-] PMOIAJVKYNVHQE-UHFFFAOYSA-N 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
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- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Saccharide Compounds (AREA)
Abstract
本发明涉及制备式(I)化合物的方法，其中R1代表C1-6烷基；R2代表C1-6卤代烷基、C1-6烷基、C1-6卤代烷氧基、C1-6烷氧基、SOnR5或卤素；R4代表氢、C1-6卤代烷氧基、C1-6烷氧基、SOnR5或卤素；或为含1-3个选自氧、氮和硫的杂原子的5或6-元杂环(可为不饱和的或部分饱和的)，所述杂环可任选地被卤素、C1-6卤代烷基、C1-6烷基、C1-6卤代烷氧基、C1-6烷氧基、SOnR5、硝基或氰基所取代；R5代表C1-6烷基；和n代表0，1或2；该方法包括使式(II)化合物；其中R2和R4的定义同上，R3代表硝基或选自氟、氯和溴的卤原子；与式R1SX反应，其中R1的定义同上，X代表氢或碱金属。
Description
本发明涉及制备某些2-烷硫基取代的苄腈的方法，它可用作，例如制备除草活性化合物的化学中间体。
2-烷硫基取代的苄腈是制备诸如EP 0527036所述的除草剂的农业化学品中的中间体。需要高得率地提供这类化合物，并发展新的方法对2-硝基或2-卤素取代的苄腈进行有效的取代以得到2-烷硫基取代的苄腈。
本发明寻求提供制备2-烷硫基取代的苄腈的高产率方法。
这样，本发明提供了一种制备式(I)2-烷硫基取代的一苄腈衍生物的方法：
其中R1代表C1-6烷基；
R2代表C1-6卤代烷基、C1-6烷基、C1-6卤代烷氧基、C1-6烷氧基、SOnR5或卤素；
R1代表氢、C1-6卤代烷氧基、C1-6烷氧基、SOnR5或卤素；或为含1-3个选自氧、氮和硫的杂原子的5或6-元杂环(可为不饱和的或部分饱和的)，所述杂环可任选地被卤素、C1-6卤代烷基、C1-6烷基、C1-6卤代烷氧基、C1-6烷氧基、SOnR5、硝基或氰基所取代；
R5代表C1-6烷基；和
n代表0，1或2；
该方法包括使下式(II)化合物：
其中R2和R4的定义同上，R3代表硝基或选自氟、氯和溴的卤原子；
与式R1SX反应，其中R1的定义同上，X代表氢或碱金属。
当R4代表杂环时，优选的环包括3-异噁唑基、5-异噁唑基、2-噻唑基、5-噁唑基、2-呋喃基、3-呋喃基、2-噻吩基和3-噻吩基。
R1优选地代表甲基。
R2优选的是三氟甲基。
R3优选的是硝基或氯。
R4优选的是氢。
X优选的是钠、钾或锂原子。
在本发明特别优选的技术方案里，R1代表C1-6烷基(甲基最佳)；
R2代表C1-6卤代烷基(三氟甲基最佳)；
R3代表硝基或选自氟、氯和溴的卤原子(最佳的是硝基或氯)；和
R1代表氢。
通过使式(II)化合物与式R1S-X的化合物反应来制备式(I)化合物的上述反应可用各种溶剂进行，诸如甲苯或二甲苯的芳烃，诸如四氢呋喃、二噁烷或叔丁基甲基醚的醚类；诸如N，N-二甲基甲酰胺的酰胺类；诸如二甲亚砜的砜类；或酮类，如甲乙酮或丙酮。特别优选的溶剂是丙酮，可任选地有水存在。业已发现，用这些条件能使反应以优异的产率进行。
优选的式R1S-X是硫代甲醇钠，它可为无水固体形态或常规的水溶液。
当X是氢时，通常在反应混合物里有碱存在。合适的碱是碱金属或碱土金属碳酸盐、烷醇化物或氢化物如碳酸钠、叔丁醇钾或氢化钠，或诸如1，8-二氮杂双环[5.4.0]十一-7-烯或1，1，3，3-四甲基胍的脒类碱。
反应通常在-20℃到120℃下进行，优选的是约10-60℃，最优选的是约10-40℃。
式(II)苄腈衍生物：式R1S-X烷基硫醇(或其金属盐)的摩尔比通常为约1∶1到约1∶4，优选的是约1∶1到1∶2.5，更优选的是约1∶1到1∶1.2。
任选的是，在相转移催化剂存在下，反应可在由水和在水中溶解度低的另一种溶剂构成的双相***里进行。适用的相转移催化剂的例子包括诸如四丁基氯化铵的铵盐；诸如三丁基十六烷基溴化鏻的鏻盐；诸如六乙基氯化胍或六甲基氯化胍的胍阳离子盐：或诸如18-冠-6的冠醚。与水和相转移催化剂一起使用的合适溶剂包括如甲苯或二甲苯的芳烃，诸如叔丁基甲基醚的醚类，诸如氯苯或二氯甲烷的卤代溶剂，通常与水混合使用。所用的相转移催化剂的用量是2-10摩尔％摩尔(相对于式(II)化合物的摩尔量)。当在这些条件下进行反应时，该反应通常的反应温度为约5-100℃，优选的是约25-70℃。
下列非限制性实施例用于说明本发明。
实施例1
2-甲硫基-4-三氟甲基苄腈的制备
在20-30℃、搅拌下，于3小时里将硫代甲醇钠(366克21％水溶液，1.1M)加到2-硝基-4-三氟甲基苄腈(220.5克，1.0M)在丙酮(340克)的溶液里。继续搅拌1小时，分离出两液相。上层(产物在丙酮里的溶液)保持在20℃下，此时2-甲硫基-4-三氟甲基苄腈结晶(213克)，熔点82℃。得率是97％，产物纯度＞96％。
实施例2
在-15℃下于20分钟里向搅拌着的丙酮(5升)和碳酸钾(592克，4.29M)混合物里加入甲硫醇(278克，5.78M)。在10分钟期间加入2-硝基-4-三氟甲基苄腈(618克，2.86M)在丙酮(500毫升)里的溶液。使混合物搅拌温热到20℃，搅拌23小时，然后在55℃下加热2小时以除去大多数甲硫醇，然后用氮气冲洗4小时。将混合物倒入冰/水，固体过滤出来，洗涤并干燥得到2-甲硫基-4-三氟甲基苄腈(550克)。产品的得率为89％。
实施例3
在30-35℃、搅拌下，于2小时里将硫代甲醇钠(37克，21％水溶液，0.11M)加入2-氯-4-三氟甲基苄腈(20.56克，0.099M)在丙酮(34克)里的溶液。在30-35℃下再搅拌2.5小时，在60℃下搅拌3小时，再加入硫代甲醇钠(3.4克，21％水溶液，0.01M)。使混合物在60℃下保持2小时，冷却，蒸发有机相得到2-甲硫基-4-三氟甲基苄腈(20.3克)。熔点80℃。产品的得率为91％，纯度为97％。
式(II)和式(III)化合物和它们的制备方法是已知的或可通过已知方法制备。上述式(I)化合物和可用来制备的除草活性化合物如文献所述，如欧洲专利公开0418175，0527036或WO/9500476。
Claims (8)
1.一种制备式(I)化合物的方法，
其中R1代表C1-6烷基；
R2代表C1-6卤代烷基或C1-6烷基；
R4是氢；
该方法包括使下式(II)化合物：
其中R2和R4的定义同上，R3代表硝基或选自氟、氯和溴的卤原子；
与式R1SX反应，其中R1的定义同上，X代表氢或碱金属，所述的反应在丙酮溶剂中进行。
2.根据权利要求1所述的方法，其中R2代表C1-6卤代烷基。
3.根据权利要求1或2所述的方法，其中R1代表甲基，R2代表三氟甲基，R4代表氢。
4.根据权利要求1或2所述的方法，其中R3代表硝基或氯。
5.根据权利要求1或2所述的方法，其中X代表钠，钾或锂原子。
6.根据权利要求1所述的方法，其中所述的丙酮中有水存在。
7.根据权利要求1或2所述的方法，其中式(II)化合物：式R1S-X化合物的摩尔比为1∶1到1∶4。
8.根据权利要求7所述的方法，其中式(II)化合物：式R1S-X化合物的摩尔比是1∶1到1∶2.5。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GBGB9714306.9A GB9714306D0 (en) | 1997-07-07 | 1997-07-07 | New processes |
| GB97143069 | 1997-07-07 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1267283A CN1267283A (zh) | 2000-09-20 |
| CN1143846C true CN1143846C (zh) | 2004-03-31 |
Family
ID=10815495
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB988069644A Expired - Lifetime CN1143846C (zh) | 1997-07-07 | 1998-07-03 | 2-烷硫基苄腈衍生物的制备方法 |
Country Status (17)
| Country | Link |
|---|---|
| US (1) | US6506926B1 (zh) |
| EP (1) | EP0994852B1 (zh) |
| JP (1) | JP4172612B2 (zh) |
| KR (1) | KR100573559B1 (zh) |
| CN (1) | CN1143846C (zh) |
| AT (1) | ATE253553T1 (zh) |
| AU (1) | AU756271B2 (zh) |
| BR (1) | BR9810687B1 (zh) |
| CA (1) | CA2295910A1 (zh) |
| DE (1) | DE69819504T2 (zh) |
| GB (1) | GB9714306D0 (zh) |
| HU (1) | HU228842B1 (zh) |
| IL (1) | IL133815A (zh) |
| PL (1) | PL337895A1 (zh) |
| TW (1) | TW528744B (zh) |
| WO (1) | WO1999002490A1 (zh) |
| ZA (1) | ZA985771B (zh) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005121222A1 (en) * | 2004-06-07 | 2005-12-22 | Battelle Memorial Institute | Synthesis of nanoparticles in non-aqueous polymer solutions and product |
| CN107540583A (zh) * | 2017-08-23 | 2018-01-05 | 连云港世杰农化有限公司 | 一种合成2‑甲硫基‑4‑三氟甲基苯甲酸乙酯的方法 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8920519D0 (en) | 1989-09-11 | 1989-10-25 | Rhone Poulenc Ltd | New compositions of matter |
| GB9116834D0 (en) | 1991-08-05 | 1991-09-18 | Rhone Poulenc Agriculture | Compositions of new matter |
| FR2706893B1 (zh) | 1993-06-23 | 1995-08-04 | Rhone Poulenc Agrochimie | |
| CA2151074C (en) * | 1994-07-05 | 2005-08-02 | Hirokazu Kagano | Method for producing 1,2-benzisothiazol-3-ones |
-
1997
- 1997-07-07 GB GBGB9714306.9A patent/GB9714306D0/en active Pending
-
1998
- 1998-07-01 ZA ZA9805771A patent/ZA985771B/xx unknown
- 1998-07-03 IL IL13381598A patent/IL133815A/xx not_active IP Right Cessation
- 1998-07-03 WO PCT/EP1998/004948 patent/WO1999002490A1/en active IP Right Grant
- 1998-07-03 AU AU88636/98A patent/AU756271B2/en not_active Ceased
- 1998-07-03 AT AT98940257T patent/ATE253553T1/de active
- 1998-07-03 EP EP98940257A patent/EP0994852B1/en not_active Expired - Lifetime
- 1998-07-03 US US09/462,177 patent/US6506926B1/en not_active Expired - Lifetime
- 1998-07-03 BR BRPI9810687-2A patent/BR9810687B1/pt not_active IP Right Cessation
- 1998-07-03 HU HU0003321A patent/HU228842B1/hu unknown
- 1998-07-03 TW TW087110790A patent/TW528744B/zh not_active IP Right Cessation
- 1998-07-03 KR KR1020007000045A patent/KR100573559B1/ko not_active IP Right Cessation
- 1998-07-03 DE DE69819504T patent/DE69819504T2/de not_active Expired - Lifetime
- 1998-07-03 CN CNB988069644A patent/CN1143846C/zh not_active Expired - Lifetime
- 1998-07-03 JP JP2000502019A patent/JP4172612B2/ja not_active Expired - Lifetime
- 1998-07-03 CA CA002295910A patent/CA2295910A1/en not_active Abandoned
- 1998-07-03 PL PL98337895A patent/PL337895A1/xx not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| DE69819504D1 (de) | 2003-12-11 |
| KR100573559B1 (ko) | 2006-04-24 |
| AU8863698A (en) | 1999-02-08 |
| ATE253553T1 (de) | 2003-11-15 |
| TW528744B (en) | 2003-04-21 |
| HUP0003321A2 (hu) | 2001-02-28 |
| WO1999002490A1 (en) | 1999-01-21 |
| AU756271B2 (en) | 2003-01-09 |
| CN1267283A (zh) | 2000-09-20 |
| HUP0003321A3 (en) | 2002-02-28 |
| KR20010015546A (ko) | 2001-02-26 |
| CA2295910A1 (en) | 1999-01-21 |
| BR9810687B1 (pt) | 2009-08-11 |
| HU228842B1 (en) | 2013-06-28 |
| IL133815A (en) | 2005-07-25 |
| BR9810687A (pt) | 2000-08-22 |
| US6506926B1 (en) | 2003-01-14 |
| GB9714306D0 (en) | 1997-09-10 |
| EP0994852A1 (en) | 2000-04-26 |
| JP2001509502A (ja) | 2001-07-24 |
| ZA985771B (en) | 2000-01-18 |
| PL337895A1 (en) | 2000-09-11 |
| DE69819504T2 (de) | 2004-11-04 |
| EP0994852B1 (en) | 2003-11-05 |
| IL133815A0 (en) | 2001-04-30 |
| JP4172612B2 (ja) | 2008-10-29 |
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