CN1142483A - α-氯烷芳酮的制备方法 - Google Patents
α-氯烷芳酮的制备方法 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title description 2
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 5
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 3
- 125000004104 aryloxy group Chemical group 0.000 claims abstract description 3
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 3
- 150000002367 halogens Chemical class 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 9
- -1 Alkyl ketone Chemical class 0.000 claims description 7
- 150000002191 fatty alcohols Chemical class 0.000 claims description 4
- 125000002252 acyl group Chemical group 0.000 claims 1
- 125000003368 amide group Chemical group 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 abstract description 2
- 125000004423 acyloxy group Chemical group 0.000 abstract description 2
- 125000004442 acylamino group Chemical group 0.000 abstract 1
- 150000004983 alkyl aryl ketones Chemical class 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- CVMOPKROILOZFI-UHFFFAOYSA-N O=S(=O)=Cl Chemical compound O=S(=O)=Cl CVMOPKROILOZFI-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229950005499 carbon tetrachloride Drugs 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Substances C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/63—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明介绍了一种用硫酰氯使通式II的烷芳酮类在脂肪醇存在下进行氯化，制备通式I的α-氯烷芳酮类的方法其中，n为1至5，相互独立的R1为H、烷基、烷氧基、芳基、芳氧基、酰氧基、酰氨基、卤素或硝基，相互独立的R2，3为H、烷基或芳基。
Description
本发明涉及一种制备α-氯烷芳酮类的新方法。
α-氯烷芳酮类是作为合成药物和农作物保护有效化合物的中间体。它们要预先特别是通过烷芳酮类和氯化剂进行反应来制取。
Lands等人(J.Med.Chem.35(1992)3081-3084)揭露了下述反应，其生成的产物B的产率是41％。
我们自己用SO2Cl2为氯化剂做的实验表明，在氯化过程中，随反应过程而定，不是产率令人不满意，就是选择性过低。
本发明的目的就是给出一种通过用SO2Cl2氯化烷芳酮类制备α-氯烷芳酮类的有效方法，其中又不会出现上述缺点。
我们已经发现通过用硫酰氯对通式II
的烷芳酮类在脂族醇存在下的卤化作用制备通式I的α-氯烷芳酮类，就能达到此目的。
其中n为1-5，
相互独立的R1为H、烷基、烷氧基、芳基、芳氧基、酰氧基、
酰氨基卤素或硝基，
相互独立的R2，3为H、烷基或芳基。
饱和或不饱和脂族醇适合于本发明的方法。最好使用饱和的无支链或支链醇类，尤其是那些有1-10个碳原子的。
最好的醇类是甲醇、乙醇、丙醇、异丙醇、丁醇或异丁醇。
按照本发明方法里使用的醇类，既可以单独一种使用，也可以混合使用。
如果每摩尔烷芳酮使用0.1-10摩尔量的脂族醇，最好是2-6摩尔，那么就能得到好的结果。比那些指定值低的摩尔比通常会引起明显的副反应，而摩尔比高通常导致转化不完全。
通常每摩尔烷基酮II使用的硫酰氯量为1-2摩尔，最好是1.0--1.5摩尔。
硫酰氯也可以使用这些特定量之外的量，但不能引起按照本发明方法的改进。
因为式I的α-氯烷芳酮类通常是固体，所以最好在溶剂里进行反应。合适的溶剂是所有那些易溶解所用烷基酮类II和生成的α-氯烷芳酮类I二者、又不在反应条件下参加任何与硫酰氯发生的反应的溶剂。芳烃类，例如苯、甲苯、乙苯、二甲苯，例如邻二甲苯和1，2，3，4-四氢化萘，卤代芳族类，例如氯苯和二氯苯，例如1，2-二氯苯，分子式CnH2n＋2的/饱和脂族烃类，其中n＝5-20，例如己烷、庚烷和辛烷，以及氯代脂族烃，例如二氯甲烷、氯仿、四氯甲烷、 1，1-二氯乙烷、1，2-二氯乙烷、1，1，1-三氯乙烷和1，1，2-三氯乙烷及它们的混合物都特别合适。
因为反应压力增加或减少都不会对选择性、产率和工艺技术有任何益处，所以反应最好在常压下进行。
反应在-80℃至+100℃的温度内，最好在0℃至50℃的范围内进行。此范围之外的反应温度对选择性、产率和工艺技术不会出现明显的好处，但却会由于冷却或加热所需能量的增加而引起不必要的费用增加。
反应可以在适当的设备中以分批或连续形式进行。
用于本发明方法中的式II烷芳酮类是已知的商品，或已知—例如按照Friedel-Crafts法(Houben Weyl＂Methoden derorganischenChemie＂(有机化学方法)Georg Thieme Verlag，Stuttgart 1973，7/2a卷第一部分，第23页-107页和135-154页)—从芳烃和羰酰卤制得。
以下的实施例用作本发明更详细的说明以及论证现有技术(对比实施例)。
实施例1
一般操作步骤
使用表1中列出的烷芳酮类1a至1d的量和图表1中指出的2a至2c的醇量，还有在表1中显示的硫酰氯、二氯甲烷和水的量。确立表1中指定的反应温度。先把1a至1d的烷芳酮引进二氯甲烷和2a至2c中的一种脂族醇类的混合物中，再引入到一个带搅拌的有恒温双套的设备中。所需反应温度已经由带恒温装置的加热和冷却设备来确定。使二氯甲烷中的硫酰氯在1小时期间内计量进搅拌的反应混合物中，同时用自动计量仪器的装置维持反应温度。接着混合物在恒温下搅拌1小时，然后往反应混合物里加水。用有机相的气相色谱分析测定氯化反应的转化率和选择性。
图表1
1a-d 2a-c 3a-dR1.1 R1.2 R2 R3 R1.1 R1.2 R2 R31a：H H H H 2a：甲醇 3a： H H H H1b：CH3 H H H 2b：乙醇 3b： CH3 H H H1c：OCH3 H H H 2c：异丙醇 3c： OCH3 H H H1d：H H C2H5 H 3d： H H C2H5 H1e：F H H H 3e： F H H H1f：OCH3 OCH3 H H 3f： OCH3 OCH3 H H
表1
1)基于烷基酮12)基于α-氯烷芳酮3
| 烷芳酮[mmol] | 二氯甲烷[ml] | 醇[mmol] | 硫酰氯[mmol] | 二氯甲烷[ml] | 水[ml] | 温度[℃] | 转化率[％] | 选择性[％] |
| 1a-100 | 50 | 2a-400 | 140 | 20 | 50 | 20 | 96.5 | ＞99 |
| 1b-100 | 50 | 2a-400 | 140 | 20 | 50 | 20 | 95.8 | ＞99 |
| 1c-100 | 50 | 2a-400 | 140 | 20 | 50 | 20 | 97.3 | 98.9 |
| 1d-100 | 50 | 2a-400 | 140 | 20 | 50 | 20 | ＞99 | 97.5 |
| 1e-100 | 50 | 2a-400 | 140 | 20 | 50 | 20 | 97.8 | 97.3 |
| 1f-100 | 50 | 2a-400 | 140 | 20 | 50 | 20 | 97.6 | 97.1 |
| 1c-100 | 50 | 2b-400 | 140 | 20 | 50 | 20 | 87.8 | 96.7 |
| 1c-100 | 50 | 2c-400 | 140 | 20 | 50 | 20 | 75.1 | 93.4 |
| 1c-100 | 50 | 2a-400 | 140 | 20 | 50 | 10 | ＞99 | 94.7 |
| 1c-100 | 50 | 2a-400 | 140 | 20 | 50 | 40 | 98.6 | 95.6 |
| 1c-100 | 50 | 2a-400 | 100 | 20 | 50 | 20 | 67.0 | ＞99 |
| 1c-100 | 50 | 2a-400 | 160 | 20 | 50 | 20 | ＞99 | 87.6 |
| 1c-100 | 50 | 2a-200 | 140 | 20 | 50 | 20 | ＞99 | 78.4 |
| 1c-100 | 50 | 2a-600 | 140 | 20 | 50 | 20 | 91.3 | 98.5 |
实施例2(对比实施例，不按本发明的)
采用实例1的一般实验步骤进行表2的对比实验，但不加脂肪醇。编号涉及到图表1。
表2
1)基于烷芳酮12)基于α-氯烷芳酮3
| 烷基酮[mmol] | 二氯甲烷[ml] | 醇[mmol] | 硫酰氯[mmol] | 二氯甲烷[ml] | 水[ml] | 温度[℃] | 转化率1)[％] | 选择性2)[％] |
| 1a-100 | 50 | - | 140 | 20 | 50 | 20 | ＞99 | 76.2 |
| 1b-100 | 50 | - | 140 | 20 | 50 | 20 | ＞99 | 57.0 |
| 1c-100 | 50 | - | 140 | 20 | 50 | 20 | ＞99 | 64.3 |
Claims (4)
1.一种制备通式I的α-氯烷芳酮类的方法，
其中n为1-5，
相互独立的R1为H、烷基、烷氧基、芳基、芳氧基、酰
氧基、酰氨基、卤素或硝基，
相互独立的R2，3为H、烷基或芳基，采用通式II
的烷基酮类被硫酰氯氯化，其中包括氯化作用要在脂肪醇存在下完成。
2.按照权利要求1的方法，其中每摩尔烷芳酮II要使用0.1-10摩尔的醇。
3.按照权利要求1或2的方法，其中使用C1-C4的醇。
4.按照权利要求3的方法，其中使用的醇是甲醇。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19511861A DE19511861A1 (de) | 1995-03-31 | 1995-03-31 | Verfahren zur Herstellung von a-Chloralkylarylketonen |
| DE19511861.8 | 1995-03-31 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1142483A true CN1142483A (zh) | 1997-02-12 |
| CN1084725C CN1084725C (zh) | 2002-05-15 |
Family
ID=7758274
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96108016A Expired - Fee Related CN1084725C (zh) | 1995-03-31 | 1996-03-30 | α－氯烷芳酮的制备方法 |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US5710341A (zh) |
| EP (1) | EP0735016B1 (zh) |
| JP (1) | JPH08277240A (zh) |
| CN (1) | CN1084725C (zh) |
| AT (1) | ATE181724T1 (zh) |
| CA (1) | CA2172014C (zh) |
| DE (2) | DE19511861A1 (zh) |
| DK (1) | DK0735016T3 (zh) |
| ES (1) | ES2135126T3 (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108586220A (zh) * | 2018-06-27 | 2018-09-28 | 安徽国星生物化学有限公司 | 一种2-氯-1-(1-氯环丙基)乙酮的合成方法 |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU6596800A (en) * | 1999-09-03 | 2001-04-10 | Asahi Kasei Kabushiki Kaisha | Processes for the preparation of tricyclic amino alcohol derivatives |
| FR2827602A1 (fr) * | 2001-07-23 | 2003-01-24 | Rhodia Chimie Sa | Procede de preparation de alpha-halogenoalkylarylcetones et de leurs produits intermediaires halogenes de type cetal cyclique |
| DE10309645A1 (de) * | 2003-03-06 | 2004-09-16 | Basf Ag | Verfahren zur Herstellung von a-(3-Arylthio)-acetophenonen |
| DE10349249A1 (de) * | 2003-10-20 | 2005-05-12 | Basf Ag | Verfahren zur Herstellung von alpha-(3-Arylthio)-acetophenonen |
| DE102004024565A1 (de) * | 2004-05-18 | 2005-12-15 | Basf Ag | Verfahren zur Herstellung von α-Chloralkylpyridylketonen und/oder deren Hydrochloriden |
| JP5503534B2 (ja) | 2007-06-20 | 2014-05-28 | ビーエーエスエフ ソシエタス・ヨーロピア | アゾアルクス（Ａｚｏａｒｃｕｓ）ＳｐＥｂＮ１脱水素酵素を用いる光学活性アルコールの製造方法 |
| CA2735769C (en) * | 2008-09-17 | 2018-10-09 | Basf Se | Method for producing l-phenylephrine using an alcohol dehydrogenase of aromatoleum aromaticum ebn1 (azoarcus sp. ebn1) |
| WO2013035674A1 (ja) * | 2011-09-09 | 2013-03-14 | 株式会社クレハ | ２－ハロ－１－（１－ハロシクロプロピル）エタノンの製造方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1109200B (it) * | 1979-02-20 | 1985-12-16 | Montedison Spa | Processo per la preparazione di esteri di acidi arilacetici da alfa-alo-alchilarilchetoni |
| US4310702A (en) * | 1980-07-28 | 1982-01-12 | Allied Corporation | Selective monochlorination of ketones and aromatic alcohols |
| JPS6197239A (ja) * | 1984-10-18 | 1986-05-15 | Seitetsu Kagaku Co Ltd | ω−ハロアセトフエノン類の製造法 |
| DE3824625A1 (de) * | 1988-07-20 | 1990-01-25 | Bayer Ag, 5090 Leverkusen | Verfahren zur hydrierung von (alpha),(beta)-ungesaettigten ketonen |
| DE4030061A1 (de) * | 1990-06-13 | 1991-12-19 | Bayer Ag | Verfahren zur herstellung von benzylketonen sowie verfahren zur herstellung eines oxiranes |
| JPH05286902A (ja) * | 1992-04-10 | 1993-11-02 | Sumitomo Pharmaceut Co Ltd | α−クロロ−β−ケトエステル誘導体の製造方法 |
-
1995
- 1995-03-31 DE DE19511861A patent/DE19511861A1/de not_active Withdrawn
-
1996
- 1996-03-18 CA CA002172014A patent/CA2172014C/en not_active Expired - Fee Related
- 1996-03-19 ES ES96104306T patent/ES2135126T3/es not_active Expired - Lifetime
- 1996-03-19 AT AT96104306T patent/ATE181724T1/de not_active IP Right Cessation
- 1996-03-19 DE DE59602311T patent/DE59602311D1/de not_active Expired - Lifetime
- 1996-03-19 DK DK96104306T patent/DK0735016T3/da active
- 1996-03-19 EP EP96104306A patent/EP0735016B1/de not_active Expired - Lifetime
- 1996-03-22 US US08/620,317 patent/US5710341A/en not_active Expired - Lifetime
- 1996-03-30 CN CN96108016A patent/CN1084725C/zh not_active Expired - Fee Related
- 1996-04-01 JP JP8079248A patent/JPH08277240A/ja active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108586220A (zh) * | 2018-06-27 | 2018-09-28 | 安徽国星生物化学有限公司 | 一种2-氯-1-(1-氯环丙基)乙酮的合成方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2135126T3 (es) | 1999-10-16 |
| US5710341A (en) | 1998-01-20 |
| CN1084725C (zh) | 2002-05-15 |
| EP0735016B1 (de) | 1999-06-30 |
| EP0735016A1 (de) | 1996-10-02 |
| ATE181724T1 (de) | 1999-07-15 |
| CA2172014A1 (en) | 1996-10-01 |
| DE19511861A1 (de) | 1996-10-02 |
| JPH08277240A (ja) | 1996-10-22 |
| DE59602311D1 (de) | 1999-08-05 |
| DK0735016T3 (da) | 1999-11-22 |
| CA2172014C (en) | 2006-01-17 |
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