+

WO1999048848A1 - Procede de reduction de la quantite d'oxyhalogenures de phosphore et de pentenes dialogenes dans les 1,1-diahalo-1-cyclopropylethanes - Google Patents

Procede de reduction de la quantite d'oxyhalogenures de phosphore et de pentenes dialogenes dans les 1,1-diahalo-1-cyclopropylethanes Download PDF

Info

Publication number
WO1999048848A1
WO1999048848A1 PCT/US1999/005838 US9905838W WO9948848A1 WO 1999048848 A1 WO1999048848 A1 WO 1999048848A1 US 9905838 W US9905838 W US 9905838W WO 9948848 A1 WO9948848 A1 WO 9948848A1
Authority
WO
WIPO (PCT)
Prior art keywords
cyclopropylethane
mixture
dihalo
alcohol
group
Prior art date
Application number
PCT/US1999/005838
Other languages
English (en)
Inventor
David R. Tueting
Christopher J. Woltermann
David W. Maloney
Dennis M. Borden
Karl E. Reineke
Rex A. Ii Shipplett
Ignacio H. Sanchez
Original Assignee
Great Lakes Chemical Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Great Lakes Chemical Corporation filed Critical Great Lakes Chemical Corporation
Publication of WO1999048848A1 publication Critical patent/WO1999048848A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/38—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/38—Separation; Purification; Stabilisation; Use of additives
    • C07C17/395—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to a chemical modification of at least one compound

Definitions

  • This invention relates to a method to purify 1,1- dihalo-1-cyclopropylethanes, and more particularly relates to a method to remove phosphorus oxyhalides and dihalogenated pentenes.
  • 1-Dihalo-l-cyclopropylethanes are used to prepare 1-cyclopropylethyne .
  • the latter is a known intermediate, which may be used to prepare many organic compounds.
  • 1-cyclopropylethyne is a critical ingredient to prepare a highly potent HIV reverse transcription inhibitor. See PCT application WO 96/37457 to Thompson and others.
  • 1-Cyclopropylethyne is, in one approach, formed by reacting a 1, 1-dihalo-l-cyclopropylethane (DCCP) with one or more strong bases, such as potassium hydroxide (see Hanack and Bassler, J. Amer . Chem. Soc . 91, 2117 (1969)) or potassium t-butoxide (Sala ⁇ n, J.Org.Chem. 41, No.7, 1237 (1976)). It is desirable to start with reasonably pure 1, 1-dihalo-l-cyclopropylethane to avoid further processing and complicated purification methods.
  • DCCP 1, 1-dihalo-l-cyclopropylethane
  • strong bases such as potassium hydroxide (see Hanack and Bassler, J. Amer . Chem. Soc . 91, 2117 (1969)) or potassium t-butoxide (Sala ⁇ n, J.Org.Chem. 41, No.7, 1237 (1976)). It is desirable to
  • this invention is a method to reduce the amount of phosphorus oxyhalide in a mixture containing 1, 1-dihalo-l-cyclopropylethane, an organic solvent, and phosphorus oxyhalide by contacting the mixture with an alcohol and an aqueous amine.
  • this invention is a method to reduce the amount of phosphorus oxyhalide in a mixture containing 1, 1-dihalo-l-cyclopropylethane, an organic solvent, and phosphorus oxyhalide by contacting the mixture with an alcohol and an epoxide.
  • this invention is a method to reduce the amount of phosphorus oxyhalide in a mixture containing 1, 1-dihalo-l-cyclopropylethane, an organic solvent, and phosphorus oxyhalide by contacting the mixture with an alcohol and a nonaqueous amine.
  • this invention is a method to remove dihalogenated pentenes from a mixture containing 1, 1-dihalo-l-cyclopropylethane and dihalogenated pentenes by contacting the mixture with a halogen under conditions sufficient to convert a substantial portion of the dihalogenated pentenes into polyhalogenated pentanes and distilling the mixture to recover the 1, 1-dihalo-l-cyclopropylethane .
  • An object of this invention is to remove phosphorus oxyhalide and/or dihalogenated pentene impurities from 1, 1-dihalo-l-cyclopropylethane .
  • a feature of this invention is that these impurities are removed without substantially affecting the 1, 1-dihalo-l-cyclopropylethane .
  • An advantage of this invention is that it is economical to use in a synthesis that starts with cyclopropyl methyl ketone and ends with 1- cyclopropylethyne .
  • 1, 1-Dihalo-l-cyclopropylethanes are frequently formed by reacting cyclopropyl methyl ketone with slurry of solvent and phosphorus halide.
  • Preferable solvents include C 5 to C 20 hydrocarbons, aromatic hydrocarbons, and halogenated hydrocarbons or aromatic hydrocarbons.
  • the ketone is added to the slurry and the resulting mixture is maintained between minus 10°C and 70°C until the reaction is complete.
  • the reaction also produces phosphorus oxyhalide co-products and dihalogenated pentenes.
  • One embodiment of this invention is a method to remove the phosphorus oxyhalide without substantially affecting the 1, 1-dihalo-l-cyclopropylethane.
  • the method begins by leaving the 1, 1-dihalo-l- cyclopropylethane in the organic solvent in which it is produced, but if necessary, one could also use fresh solvent, preferably a C 5 to C 20 hydrocarbon, an aromatic hydrocarbon, a halogenated hydrocarbon, preferably a Ci to C 5 halogenated species; or a halogenated aromatic hydrocarbon.
  • fresh solvent preferably a C 5 to C 20 hydrocarbon, an aromatic hydrocarbon, a halogenated hydrocarbon, preferably a Ci to C 5 halogenated species; or a halogenated aromatic hydrocarbon.
  • the 1, 1-dihalo-l-cyclopropylethane and solvent are then combined with an aqueous amine and an alcohol.
  • the alcohol is preferably dihydric, but a monohydric alcohol may also be used.
  • the preferred amines are alkanolamines of which the most preferred are ethanolamine, propanolamine, and butanolamine .
  • the amine concentration before addition is preferably from about 20-wt% to about 60-wt%.
  • the most preferred dihydric alcohols are ethylene glycol, propylene glycol, and butylene glycol.
  • the alcohol and the aqueous amine can be added simultaneously or separately, and preferably all the reactants are maintained between about minus 20°C to about 10°C from the time they are combined until the reaction is complete, (i.e. the oxyhalide is removed).
  • the reaction leaves a biphasic mixture, and most of the 1, 1-dihalo-l-cyclopropylethane is contained in the organic solvent phase.
  • the 1, 1-dihalo-l- cyclopropylethane may be removed using well-known techniques such as draining the aqueous phase from the product mixture and distilling to recover 1, 1-dihalo-l- cycloproylethane from the mixture.
  • a second embodiment of this invention is another method to remove the phosphorus oxyhalide without substantially affecting the 1, 1-dihalo-l- cyclopropylethane.
  • This second method also begins by leaving the 1, 1-dihalo-l-cyclopropylethane in the organic solvent in which it is produced, but if necessary, one may also use fresh solvent, preferably a C 5 to C 2 o hydrocarbon, an aromatic hydrocarbon, a halogenated hydrocarbon, preferably a Ci to C 5 halogenated species; or a halogenated aromatic hydrocarbon.
  • the 1, 1-dihalo-l-cyclopropylethane and solvent are then combined with an epoxide and an alcohol that is preferably mono- or dihydric.
  • the preferred epoxides are ethylene oxide, propylene oxide, butylene oxide, and styrene oxide.
  • the most preferred monohydric alcohols are methanol, ethanol, propanol, and butanol.
  • the most preferred dihydric alcohols are ethylene glycol, propylene glycol, and butylene glycol.
  • the alcohol and the epoxide can be added simultaneously or separately, and preferably all the reactants are maintained between about minus 10°C and about 50°C from the time they are combined until the reaction is complete.
  • the reaction leaves a biphasic mixture, and most of the 1, 1-dihalo-l-cyclopropylethane is contained in the organic solvent phase.
  • the 1, 1-dihalo-l- cyclopropylethane may be removed using well-known techniques such as draining the alcohol phase from the product mixture and distilling to recover the 1,1- dihalo-1-cycloproprylethane from the mixture. Additionally, the alcohol phase may be washed with fresh solvent and the washing solvent added to the organic solvent phase prior to distillation.
  • a third embodiment of this invention is yet another method to remove the phosphorus oxyhalide without substantially affecting the 1, 1-dihalo-l- cyclopropylethane.
  • This third method also begins by leaving the 1, 1-dihalo-l-cyclopropylethane in the organic solvent in which it is produced, but if necessary, one may also use fresh solvent, preferably a C 5 to Ci 6 hydrocarbon, an aromatic hydrocarbon, a halogenated hydrocarbon preferably a Ci to C 5 halogenated species; or a halogenated aromatic hydrocarbon.
  • fresh solvent preferably a C 5 to Ci 6 hydrocarbon, an aromatic hydrocarbon, a halogenated hydrocarbon preferably a Ci to C 5 halogenated species; or a halogenated aromatic hydrocarbon.
  • the 1, 1-dihalo-l-cyclopropylethane and solvent are then combined with an amine, which is preferably tertiary, and an alcohol, which is preferably mono- or dihydric.
  • the most preferable tertiary amines are trimethylamine, triethylamine, tri-n-propylamine, tri- n-butylamine, and dimethyl-sec-butylamine .
  • the most preferred monohydric alcohols are methanol, ethanol, propanol, and butanol .
  • the most preferred dihydric alcohols are ethylene glycol, propylene glycol, and butylene glycol.
  • the alcohol and the amine can be added simultaneously or separately, and preferably all the reactants are maintained between about minus 5°C to about 30°C from the time they are combined until the reaction is complete.
  • the product slurry is then filtered to remove any solids, such as amine salts, that may have formed during the reaction.
  • the 1, 1-dihalo-l-cyclopropylethane may then be removed using well-known techniques such as distilling the filtrate liquors that remain. Without limiting the scope of the invention, it is believed that a variety of compounds are formed when the phosphorus oxyhalide reacts with the alcohol and the amine. For example, it is conceivable that the reaction may produce alkylamine hydrohalide salts and alkylphosphate esters. These compounds are then either filtered out or removed during the distillation of the 1, 1-dihalo-l-cyclopropylethane.
  • a related embodiment of this invention is a method to remove dihalogenated pentenes that also may be present in the 1, 1-dihalo-l-cyclopropylethane by converting them into tetrahalogenated pentanes.
  • the method begins by contacting the 1, 1-dihalo-l- cyclopropylethane with a halogen, preferably chlorine, bromine, or bromine chloride.
  • a halogen preferably chlorine, bromine, or bromine chloride.
  • the reactants are preferably maintained between about minus 10°C to about 60°C until the reaction is complete, which is preferably when the level of dihalogenated pentenes is less than 5-wt% or more preferably less than l-wt%.
  • the 1,1- dihalo-1-cyclopropylethane may then be separated from the tetrahalogenated pentanes using well-known techniques such as distilling the product mixture at reduced pressure. This may be done with or without a solvent .
  • a 100-gallon GLS (glass-lined steel) reactor was charged with 280.0 lb. of Norpar 13®, which is a C ⁇ 2 to C 14 linear hydrocarbon solvent and 300 lb. of solid phosphorus pentachloride .
  • the resulting PCl 5 /solvent slurry was then cooled to ⁇ 0°C.
  • 120.6 lb. of cyclopropyl methyl ketone (CPMK) was added to the slurry while maintaining the internal reactor temperature below 20°C. After the CPMK addition was complete, the mixture was allowed to warm with mild heating to ⁇ 65°C. The mixture was held at ⁇ 65°C for 0.5 hr during which time the slurry became clear yellow.
  • CPMK cyclopropyl methyl ketone
  • the solution was cooled to ambient temperature.
  • the crude product contained about 25 to 35-wt% phosphorus oxychloride; however, gas chromatographic (GC) analysis of the mixture also indicated complete conversion of the CPMK to a mixture of 1, 1-dichloro-l-cyclopropylethane (DCCP) and E/Z isomers of 2, 5-dichloropent-2-ene (DCP) .
  • GC gas chromatographic
  • the crude product was then transferred to a 200 gallon GLS reactor and cooled to -10°C. Thereafter, 179.0 lb. of ethylene glycol was added to the mixture while maintaining the internal pot temperature below 0°C. Next, 218.0 lb. of a 40:60 wt . /wt . mixture of ethanolamine and water was added to the reactor while maintaining the internal pot temperature below 0°C. After the addition, the mixture was agitated for 0.5 hr 10
  • the crude product mixture was flash distilled at reduced pressure (-10 mm Hg) to an overhead temperature of 45°C, and a mixture of 1, 1-dichloro-l- cyclopropylethane and E/Z 2 , 5-dichloropent-2-ene was recovered.
  • DCCP contained in the recovered distillate was 109.5 lb.
  • the DCCP to DCP ratio in the distillate was 67:33 by weight, and only a negligible amount of phosphorus oxychloride was present.
  • the preparation of DCCP was repeated according the method described in Example 1, however, chlorobenzene was used as the reaction solvent.
  • the crude DCCP and chlorobenzene were then transferred to a 200 gallon GLS reactor and the procedure described in Example 1 was repeated using a mixture of butanolamine and water for the aqueous amine and butylene glycol for the alcohol.
  • the crude product mixture was then flash distilled at reduced pressure, and a mixture of 1, 1-dichloro-l- cyclopropylethane and E/Z 2, 5-dichloropent-2-ene was recovered.
  • Example 3 The preparation of DCCP was repeated according the method described in Example 1, however, chlorobutane 11
  • Example 4 The crude DCCP and chlorobutane were then transferred to a 200 gallon GLS reactor and the procedure described in Example 1 was repeated using a mixture of propanolamine and water for the aqueous amine and butanol for the alcohol. The crude product mixture was then flash distilled at reduced pressure, and a mixture of 1, 1-dichloro-l- cyclopropylethane and E/Z 2, 5-dichloropent-2-ene was recovered.
  • Example 4 Example 4
  • Example 1 The reaction to synthesize DCCP shown in Example 1 was repeated with the same temperature parameters using 804.4 g of PC1 5 in 774.0 g of Norpar-13® solvent in a 3 liter reactor and 300.0 g of CPMK.
  • the resulting solution contained about 25 to 35-wt% phosphorus oxychloride; however, gas chromatography revealed a 76% yield of DCCP with a DCCP to DCP ratio of about -87:13 DCCP to DCP.
  • the preparation of DCCP was repeated according the method described in Example 1, however, chlorobenzene was used as the reaction solvent.
  • the crude DCCP and chlorobenzene were then treated with alcohol and epoxide as described in Example 4, however, propanol was used for the alcohol and styrene oxide was used for the epoxide.
  • the crude product mixture was then distilled, and a mixture of 1, 1-dichloro-l- cyclopropylethane and 2 , 5-dichloropent-2-ene was recovered.
  • Example 6 The preparation of DCCP was repeated according the method described in Example 1, however, chlorobutanol was used as the reaction solvent.
  • the crude DCCP and chlorobenzene were then treated with alcohol and epoxide as described in Example 4, however, butanol was used for the alcohol and ethylene oxide was used for the epoxide.
  • the crude product mixture was then distilled, and a mixture of 1, 1-dichloro-l- cyclopropylethane and 2, 5-dichloropent-2-ene was recovered.
  • Example 7 CPMK (50.0 g) was again dichlorinated as previously described in Example 1 using 129.3 g of PCI 5 ,. 13
  • the PC1 5 was suspended in 392.3 g of o-dichlorobenzene (ODCB) .
  • ODCB o-dichlorobenzene
  • the post- reaction solution exhibited a DCCP: DCP ratio of 87:13 and about 25 to 35-wt% phosphorus oxychloride.
  • 186.5 g of triethylamine in 109.0 g of n- propanol was then added to the crude product over 2 hr while maintaining the internal temperature ⁇ 25°C.
  • the mixture was then heated to 50 °C, which caused an exothermic reaction to increase the internal temperature to 62 °C.
  • the slurry was held at 50°C for 5.5 hr to complete the consumption of P0C1 3 .
  • the suspension was cooled to room temperature and then filtered to remove salts.
  • the filter cake was washed with ODCB.
  • the filtrate and washes were combined and distilled through a 10 tray Oldershaw column using a 3:1 reflux ratio collecting the fraction exhibiting a 70-82 °C overhead temperature.
  • a total of 35.8 g of DCCP was recovered from the distillation with only negligible amounts of phosphorus oxychloride.
  • Example 8 DCCP was again prepared in ODCB as described in Example 7. Thereafter the crude DCCP was combined with an amine and alcohol as described in Example 7. But in place of triethylamine and n-propanol, tri-n-butylamine and butylene glycol were used. The product slurry was then filtered and the filtrate liquors were distilled to recover the DCCP.
  • Example 9 A mixture (775.6 lbs.) containing -67% 1,1- 14
  • the target DCCP to DCP ratio of >100:1 was confirmed by the analysis. Nitrogen was then sparged through the solution for 0.5 hr to remove the residual chlorine. The clear solution was transferred to a 100 gallon GLS distillation vessel and flash distilled at reduced pressure (-10 mm Hg) while collecting the distillate up to an overhead temperature of ⁇ 55°C. Analysis of the distillate indicated 498.9 lbs. of DCCP were recovered; equivalent to a 96% recovered yield of the DCCP initially charged to the chlorination reaction. The distillate exhibited a DCCP: DCP ratio of >100:1 after chlorination and distillation.
  • Example 10 792.6 lbs. of a mixture containing 67% 1,1- dichloro-1-cyclopropylethane and 33% 2, 5-dichloropent- - 2-ene were charged in a 100 gallon GLS reactor and the 15
  • the mixture was analyzed to determine the DCP content by gas chromatography .
  • the target DCCP to DCP ratio of >95:1 was confirmed by the analysis.
  • Excess bromine was consumed by the addition of a small quantity of a C i4 to C ⁇ ⁇ long chain olefin (e.g. Neodene 16® (Shell)). Nitrogen was then sparged through the solution for 0.5 hr .
  • the clear solution was transferred to a 100 gallon GLS distillation vessel and flash distilled at reduced pressure ( ⁇ 10mm Hg) collecting the distillate up to an overhead temperature of ⁇ 55°C. Analysis of the distillate indicated 472.6 lbs. of DCCP were recovered; equivalent to an 89% recovery of the DCCP initially charged to the chlorination reaction.
  • the distillate exhibited a DCCP: DCP ratio of >95:1 after bromination and distillation.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)

Abstract

Procédé de réduction de la quantité d'oxyhalogénures de phosphore et de pentènes dihalogénés dans un mélange de 1,1-diahalo-1-cyclopropyléthane et de solvant. Dans un mode de réalisation, l'oxyhalogénure de phosphore est extrait par trempe du 1,1-diahalo-1-cyclopropyléthane dans de l'alcool et une amine aqueuse. Dans un second mode de réalisation, l'oxyhalogénure de phosphore est extrait par trempe du 1,1-diahalo-1-cyclopropyléthane dans de l'alcool et un époxyde. Dans un troisième mode de réalisation, l'oxyhalogénure de phosphore est extrait par trempe du 1,1-diahalo-1-cyclopropyléthane dans de l'alcool et une amine. Dans le dernier mode de réalisation, les pentènes diahalogénés sont extraits par mise en contact du 1,1-diahalo-1-cyclopropyléthane avec un halogène.
PCT/US1999/005838 1998-03-24 1999-03-17 Procede de reduction de la quantite d'oxyhalogenures de phosphore et de pentenes dialogenes dans les 1,1-diahalo-1-cyclopropylethanes WO1999048848A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US4706398A 1998-03-24 1998-03-24
US09/047,063 1998-03-24

Publications (1)

Publication Number Publication Date
WO1999048848A1 true WO1999048848A1 (fr) 1999-09-30

Family

ID=21946879

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1999/005838 WO1999048848A1 (fr) 1998-03-24 1999-03-17 Procede de reduction de la quantite d'oxyhalogenures de phosphore et de pentenes dialogenes dans les 1,1-diahalo-1-cyclopropylethanes

Country Status (1)

Country Link
WO (1) WO1999048848A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109678651A (zh) * 2018-12-28 2019-04-26 瑞孚信江苏药业股份有限公司 一种高纯度α,α-二氯乙基环丙烷的制备方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996037457A1 (fr) * 1995-05-25 1996-11-28 Merck & Co., Inc. Synthese asymetrique de (-) 6-chloro-4-cyclopropyle-ethynyle-4-trifluoromethyle-1,4-dihydro-2h-3,1-benzoxazin-2-one

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996037457A1 (fr) * 1995-05-25 1996-11-28 Merck & Co., Inc. Synthese asymetrique de (-) 6-chloro-4-cyclopropyle-ethynyle-4-trifluoromethyle-1,4-dihydro-2h-3,1-benzoxazin-2-one

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109678651A (zh) * 2018-12-28 2019-04-26 瑞孚信江苏药业股份有限公司 一种高纯度α,α-二氯乙基环丙烷的制备方法
CN109678651B (zh) * 2018-12-28 2021-11-12 瑞孚信江苏药业股份有限公司 一种高纯度α,α-二氯乙基环丙烷的制备方法

Similar Documents

Publication Publication Date Title
JP7549635B2 (ja) １，３－ベンゾジオキソール複素環式化合物の調製方法
EP2043984A1 (fr) Produit à base de glycérol brut, procédé pour sa purification et son utilisation dans la fabrication de dichloropropanol
JP5021745B2 (ja) フルオロメチル２，２，２−トリフロオロ−１−（トリフルオロメチル）エチルエーテルの製造方法
JP2002540179A (ja) セボフルランおよびその中間体を合成するための方法
EP0663379A1 (fr) Procédé pour la production d'hydrocarbures aromatiques substitués par dédiazonisation des anilines correspondantes
CN103635451B (zh) 用于制备七氟烷的方法
HUE028257T2 (en) Process for the preparation of (5-fluoro-2-methyl-3-quinolin-2-ylmethylindol-1-yl) acetic acid esters
JP2723652B2 (ja) Ｃ▲下３▼〜ｃ▲下４▼‐モノアルカノールと塩化水素との連続反応による反応生成物の後処理法
EP1311468B1 (fr) Procede de purification d'acide alcanoique fluore
JP2010504916A (ja) クロロメチル２，２，２―トリフロオロ−１−（トリフルオロメチル）エチルエーテルの製造方法
KR101269493B1 (ko) 메틸 메타크릴레이트 정제시 생성되는 스트림으로부터 유용한 화합물을 회수하는 방법
WO1999048848A1 (fr) Procede de reduction de la quantite d'oxyhalogenures de phosphore et de pentenes dialogenes dans les 1,1-diahalo-1-cyclopropylethanes
CN110831944A (zh) 通过极有效制备中间体2,4,5-三氟苯乙酸来制备西他列汀的有效方法
CZ2002931A3 (cs) Způsob výroby n-butylakrylátu
JP2511093B2 (ja) ジアリ―ルアルキルホスホネ―ト反応残留の精製方法
JPH0560817B2 (fr)
CS236891B2 (en) Method of decomposition of compound of o-benzoyl-benzoic acid and hydrogen fluoride and boron trifluoride
JPH04139137A (ja) 塩素含有量の低いベンジルトルエンとジベンジルトルエンの合成方法
JPH0228588B2 (ja) Nnarukiruechirenjiaminruinoseizohoho
JPS5920665B2 (ja) フエニルヒドラジンの精製方法
CZ2002930A3 (cs) Způsob výroby n-butylakrylátu
JP4710142B2 (ja) アリルクロライドの製造方法
US20020045784A1 (en) Process for producing allyl chloride
EP1254103B1 (fr) Procede de preparation de 3,5-difluoroaniline a partir de 1,3,5-trichlorobenzene
JP2000044585A (ja) ハロゲン含有リン酸エステルの製造方法

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): CA MX

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE

121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase
点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载