CN1705632A - 农药合成中间体的新颖制备方法 - Google Patents
农药合成中间体的新颖制备方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000575 pesticide Substances 0.000 title description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- ODGIMMLDVSWADK-UHFFFAOYSA-N 4-trifluoromethylaniline Chemical compound NC1=CC=C(C(F)(F)F)C=C1 ODGIMMLDVSWADK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 239000003880 polar aprotic solvent Substances 0.000 claims abstract description 5
- 125000005843 halogen group Chemical group 0.000 claims abstract description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Substances ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 12
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 8
- 239000000376 reactant Substances 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- IPGPMDGVMCYODH-UHFFFAOYSA-N n-chloro-4-(trifluoromethyl)aniline Chemical class FC(F)(F)C1=CC=C(NCl)C=C1 IPGPMDGVMCYODH-UHFFFAOYSA-N 0.000 claims description 3
- 239000012429 reaction media Substances 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical group ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 239000003849 aromatic solvent Substances 0.000 claims description 2
- MVPPADPHJFYWMZ-IDEBNGHGSA-N chlorobenzene Chemical group Cl[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 MVPPADPHJFYWMZ-IDEBNGHGSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- ITNMAZSPBLRJLU-UHFFFAOYSA-N 2,6-dichloro-4-(trifluoromethyl)aniline Chemical compound NC1=C(Cl)C=C(C(F)(F)F)C=C1Cl ITNMAZSPBLRJLU-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000008048 phenylpyrazoles Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 1
- ZOCSXAVNDGMNBV-UHFFFAOYSA-N 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazole-3-carbonitrile Chemical compound NC1=C(S(=O)C(F)(F)F)C(C#N)=NN1C1=C(Cl)C=C(C(F)(F)F)C=C1Cl ZOCSXAVNDGMNBV-UHFFFAOYSA-N 0.000 description 1
- OEDUIFSDODUDRK-UHFFFAOYSA-N 5-phenyl-1h-pyrazole Chemical compound N1N=CC=C1C1=CC=CC=C1 OEDUIFSDODUDRK-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000005899 Fipronil Substances 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- MMCPOSDMTGQNKG-UHFFFAOYSA-N anilinium chloride Chemical compound Cl.NC1=CC=CC=C1 MMCPOSDMTGQNKG-UHFFFAOYSA-N 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229940013764 fipronil Drugs 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- CZGDYZDUMJDQSD-UHFFFAOYSA-N hydron;4-(trifluoromethyl)aniline;chloride Chemical compound Cl.NC1=CC=C(C(F)(F)F)C=C1 CZGDYZDUMJDQSD-UHFFFAOYSA-N 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- -1 pyrazolines compound Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
- C07C209/74—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by halogenation, hydrohalogenation, dehalogenation, or dehydrohalogenation
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
- A01N33/02—Amines; Quaternary ammonium compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
- C07C211/45—Monoamines
- C07C211/46—Aniline
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- Chemical Kinetics & Catalysis (AREA)
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- Engineering & Computer Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
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- Agronomy & Crop Science (AREA)
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Abstract
由式(II)所示的对三氟甲基苯胺与卤素X2的反应制备式(I)所示化合物的制备方法，式(I)中，X表示卤原子。对三氟甲基苯胺与卤素这两种化合物在100－300℃的温度下同时加入极性非质子溶剂中，卤素与化合物(II)的摩尔比为1.9－2.5。
Description
本发明涉及由对三氟甲基苯胺制备2，6-二卤代-对三氟甲基苯胺的新方法。
为了开发2，6-二卤代-对三氟甲基苯胺的制备方法，已作过大量的研究。专利申请WO00/35851提供了一种在130-350℃的温度和优选的极性溶剂中由三卤代-对三氟甲基苯制备2，6-二卤代-对三氟甲基苯胺的方法。用对三氟甲基苯胺制备2，6-二卤代-对三氟甲基苯胺没有出现在该专利申请中。
专利申请FR2810665和WO 01/64623揭示了一种在氢氟酸介质中氯化苯胺前体制备2，6-二氯代-对三氟甲基苯胺的方法。该前体化合物是三氟甲基苯氨基甲酰氟。没有提到使用氢氟酸以外的溶剂。
然而，这些方法会形成缩聚物或重的多氯化物之类的杂质。这些杂质使得2，6-二卤代-对三氟甲基苯胺不经预先的提纯步骤不能继续用于制备苯基吡唑类杀虫剂化合物。当按工业规模制备2，6-二氯代-对三氟甲基苯胺时，特别是用于制备苯基吡唑类杀虫剂时，这种提纯步骤是一个大缺点。
现在令人惊奇地发现，本发明的2，6-二卤代-对三氟甲基苯胺的制备方法能生产足够纯的化合物，可以直接用于继续苯基吡唑类杀虫剂化合物的生产方法。
因此，本发明的主题是式(I)表示的化合物的制备方法，
式中，X表示卤原子，
该方法通过式(II)所示的对三氟甲基苯胺与卤素X2的反应进行，
这两种化合物在100-300℃的温度下同时加入极性非质子溶剂中，卤素与化合物(II)的摩尔比为1.9-2.5。
在本发明的上下文中，X表示卤原子。X可以是氯原子、溴原子、碘原子或氟原子。
用本发明方法制备的式(I)化合物优选是2，6-二氯代-对三氟甲基苯胺。这种化合物特别适用于合成芬普尼(fipronil)，一种苯基吡唑类杀虫剂化合物。
制备本发明式(I)化合物时所用的溶剂是极性非质子溶剂。优选的极性非质子溶剂是氯苯之类的氯化芳族溶剂或二氯乙烷之类的氯化脂族溶剂。特别优选地将氯苯选作溶剂。
在制备本发明的2，6-二氯代-对三氟甲基苯胺时，卤素/化合物(II)摩尔比选择为1.9-2.5，优选为2-2.05。
本发明反应介质的温度选择为100-300℃，优选为100-130℃，特别优选为105-115℃。
特别优选的是，本发明的方法用于制备2，6-二氯代-对三氟甲基苯胺，即通过在105-115℃的温度下把对三氟甲基苯胺和Cl2同时加入氯苯中，Cl2与对-三氟甲基苯胺的摩尔比为1.85-2.05。
本发明的方法可以按本领域中熟练技术人员已知的通用技术进行。因此，本发明的方法在装有搅拌器和顶上装有回流冷凝器的夹套式反应器中进行。上述回流冷凝器维持在低于或等于-10℃的温度。反应所需的卤素通过***的浸入管在搅拌条件下通入。所用的搅拌器较好能提供反应物的最佳微混合。这可以用叶片式搅拌器或本领域中熟练技术人员已知的其它类型的搅拌器实现。
在本发明的反应中，产生气态的盐酸。这种氯化氢气体一般被氢氧化钠阱吸收。当对三氟甲基苯胺与盐酸接触时，瞬时反应形成对三氟甲基苯胺盐酸盐。为了避免阻塞，优选用浸入管将对三氟甲基苯胺加入到反应器中。
在加入反应物时，有时观察到形成泡沫的明显倾向。这种倾向一般可以通过降低加入反应物的流速加以避免。不过，为了避免泡沫的积聚，这种泡沫应被液体吸收。因此，一种方案一般是提高搅拌速度。
用本发明的方法制得的产物(2，6-二卤代-对三氟甲基苯胺)具有足够的纯度，可以直接用于合成苯基吡唑类杀虫剂化合物。一般认为，为了能用于继续制备方法，该产物的纯度应至少为96％。
所得的2，6-二卤代-对三氟甲基苯胺也可以分离，特别是为了储存，通过本领域中熟练技术人员已知的技术蒸馏掉溶剂。
如下化合物的制备实施例用于说明本发明的目的，而不应视为对本发明的限制。
98％2，6-二氯代-对三氟甲基苯胺的制备
将12140千克纯的氯苯加入到一个已充满氮气的20立方米夹套式反应器中。然后通过加热夹套把溶剂(solvent heel)加热至110℃。
然后以792千克/小时的流速向该反应器中加入对三氟甲基苯胺的70％氯苯溶液，同时以488千克/小时的流速加入Cl2，历时6小时30分钟。通过冷却夹套将温度维持在110℃。
加料完成后，立即监测对三氟甲基苯胺或其一氯衍生物的残余量。如果仍残留其中之一化合物，宜调节氯气量，以消耗残余的产物。
反应结束时，逐渐增加反应器的真空度，通过蒸馏柱蒸馏掉氯苯。除去溶剂后，将2，6-二氯代-对三氟甲基苯胺冷却到60℃，然后把反应器中的物料全部转移到储存槽中。
分析按上述方法制得的产物。下表中所示的结果相应于一年内所得产物的分析结果平均值。
| 2，6-二氯代-对三氟甲基苯胺化验(无溶剂) | 对三氟甲基苯胺化验(无溶剂) | 一氯代-对三氟甲基苯胺化验(无溶剂) |
| 98.1％ | 0.05％ | 0.09％ |
这些结果表明，用本发明方法制得的2，6-二氯代-对三氟甲基苯胺的纯度大于98％，反应产率很好，因为仅残留0.05％的反应物(对三氟甲基苯胺)，且只有0.09％一氯代-对三氟甲基苯胺没有转化为2，6-二氯代-对三氟甲基苯胺。
Claims (10)
1.式(I)化合物的制备方法：
式中X表示卤原子，该方法通过式(II)所示的对三氟甲基苯胺与卤素X2的反应进行，
对三氟甲基苯胺与卤素这两种化合物在100-300℃的温度下同时加入极性非质子溶剂中，卤素与化合物(II)的摩尔比为1.9-2.5。
2.如权利要求1所述的方法，其特征在于式(I)表示的化合物是2，6-二氯-对三氟甲基苯胺。
3.如权利要求1或2所述的方法，其特征在于所用溶剂是氯化脂族溶剂。
4.如权利要求3所述的方法，其特征在于所用的溶剂是二氯乙烷。
5.如权利要求1或2所述的方法，其特征在于所用的溶剂是氯化芳族溶剂。
6.如权利要求5所述的方法，其特征在于所用的溶剂是氯苯。
7.如权利要求1-6中任一项所述的方法，其特征在于以2-2.05的卤素/化合物(II)摩尔比加入反应物。
8.如权利要求1-7中任一项所述的方法，其特征在于反应介质的温度选择为100-130℃。
9.如权利要求8所述的方法，其特征在于反应介质的温度选择为105-115℃。
10.如权利要求2所述的方法，其特征在于在氯气/化合物(II)摩尔比为1.85-2.05和温度为105-115℃的条件下将反应物加入到氯苯中。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0213392A FR2846325B1 (fr) | 2002-10-25 | 2002-10-25 | Nouveau procede de preparation d'un intermediaire de synthese de pesticide |
| FR0213392 | 2002-10-25 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1705632A true CN1705632A (zh) | 2005-12-07 |
| CN100519510C CN100519510C (zh) | 2009-07-29 |
Family
ID=32088287
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2003801019166A Expired - Lifetime CN100519510C (zh) | 2002-10-25 | 2003-10-24 | 农药合成中间体的制备方法 |
Country Status (23)
| Country | Link |
|---|---|
| US (1) | US7553993B2 (zh) |
| EP (1) | EP1558560B1 (zh) |
| JP (1) | JP4511359B2 (zh) |
| KR (1) | KR20050055780A (zh) |
| CN (1) | CN100519510C (zh) |
| AT (1) | ATE419230T1 (zh) |
| AU (1) | AU2003288184B2 (zh) |
| BR (1) | BR0315671B1 (zh) |
| CA (1) | CA2503188A1 (zh) |
| DE (1) | DE60325631D1 (zh) |
| DK (1) | DK1558560T3 (zh) |
| EA (1) | EA008062B1 (zh) |
| ES (1) | ES2316840T3 (zh) |
| FR (1) | FR2846325B1 (zh) |
| IL (1) | IL168096A (zh) |
| MX (1) | MXPA05004234A (zh) |
| PL (1) | PL207084B1 (zh) |
| PT (1) | PT1558560E (zh) |
| SI (1) | SI1558560T1 (zh) |
| TW (1) | TWI295154B (zh) |
| UA (1) | UA79998C2 (zh) |
| WO (1) | WO2004037766A2 (zh) |
| ZA (1) | ZA200504203B (zh) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103408437A (zh) * | 2013-08-30 | 2013-11-27 | 江苏丰华化学工业有限公司 | 一种制备2,6-二氯-4-三氟甲基苯胺的方法 |
| CN103910639A (zh) * | 2014-03-13 | 2014-07-09 | 凯美泰克（天津）化工科技有限公司 | 一种制备2,6-二氯-4-三氟甲基苯胺的方法 |
| CN104072379A (zh) * | 2014-06-10 | 2014-10-01 | 台州海辰药业有限公司 | 一种2,6-二氯-4-三氟甲基苯胺的制备方法 |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2846325B1 (fr) * | 2002-10-25 | 2006-09-08 | Bayer Cropscience Sa | Nouveau procede de preparation d'un intermediaire de synthese de pesticide |
| US7846399B2 (en) * | 2004-03-23 | 2010-12-07 | W.R. Grace & Co.-Conn. | System and process for injecting catalyst and/or additives into a fluidized catalytic cracking unit |
| US9725409B2 (en) * | 2013-10-10 | 2017-08-08 | Bayer Cropscience Aktiengesellschaft | Process for preparing 4[[(benzoyl)amino]sulphonyl]benzoyl chlorides and preparation of acylsulphamoylbenzamides |
| WO2015125155A1 (en) | 2014-02-19 | 2015-08-27 | Srf Limited | Process for the preparation of 2,6-dihalo-para-trifluoromethyl- anilines as intermediates of pyrazoles |
| TWI699351B (zh) * | 2015-04-08 | 2020-07-21 | 德商拜耳作物科學公司 | 製備醯基胺磺醯苯甲醯胺之方法 |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0034402B1 (en) * | 1980-02-05 | 1984-08-29 | Imperial Chemical Industries Plc | Method of preparing fluorine-substituted diphenyl ether derivatives and fluorine-substituted halogeno benzene derivatives for use therein |
| FR2787445B1 (fr) * | 1998-12-17 | 2001-01-19 | Rhone Poulenc Agrochimie | Procede de preparation de para-trifluoromethylanilines polyhalogenees |
| FR2805809B1 (fr) * | 2000-03-01 | 2003-08-08 | Rhodia Chimie Sa | Chloration d'une aniline en ortho dans un milieu fluorhydrique |
| FR2810665A1 (fr) * | 2000-06-21 | 2001-12-28 | Rhodia Chimie Sa | Chloration en ortho d'un fluorure de n-arylcarbamoyle dans un milieu fluorhydrique |
| FR2846325B1 (fr) * | 2002-10-25 | 2006-09-08 | Bayer Cropscience Sa | Nouveau procede de preparation d'un intermediaire de synthese de pesticide |
-
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103408437A (zh) * | 2013-08-30 | 2013-11-27 | 江苏丰华化学工业有限公司 | 一种制备2,6-二氯-4-三氟甲基苯胺的方法 |
| CN103910639A (zh) * | 2014-03-13 | 2014-07-09 | 凯美泰克（天津）化工科技有限公司 | 一种制备2,6-二氯-4-三氟甲基苯胺的方法 |
| CN104072379A (zh) * | 2014-06-10 | 2014-10-01 | 台州海辰药业有限公司 | 一种2,6-二氯-4-三氟甲基苯胺的制备方法 |
| CN104072379B (zh) * | 2014-06-10 | 2018-03-20 | 台州海辰药业有限公司 | 一种2,6‑二氯‑4‑三氟甲基苯胺的制备方法 |
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