WO2013161394A1 - トリメチルスルホキソニウムブロミドの製造方法、およびトリメチルスルホキソニウムブロミドを製造する反応系の温度制御方法 - Google Patents

トリメチルスルホキソニウムブロミドの製造方法、およびトリメチルスルホキソニウムブロミドを製造する反応系の温度制御方法 Download PDF

Info

Publication number
WO2013161394A1
WO2013161394A1 PCT/JP2013/056106 JP2013056106W WO2013161394A1 WO 2013161394 A1 WO2013161394 A1 WO 2013161394A1 JP 2013056106 W JP2013056106 W JP 2013056106W WO 2013161394 A1 WO2013161394 A1 WO 2013161394A1
Authority
WO
WIPO (PCT)
Prior art keywords
temperature
bromide
reaction
methyl bromide
reaction system
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2013/056106
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
隆志 大橋
荒木　信行
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kureha Corp
Original Assignee
Kureha Corp
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 Kureha Corp filed Critical Kureha Corp
Priority to CN201380015163.0A priority Critical patent/CN104185623B/zh
Priority to EP13782308.4A priority patent/EP2842941A4/en
Priority to US14/396,231 priority patent/US20150051424A1/en
Priority to IN8353DEN2014 priority patent/IN2014DN08353A/en
Publication of WO2013161394A1 publication Critical patent/WO2013161394A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C315/00—Preparation of sulfones; Preparation of sulfoxides
    • C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups

Definitions

  • the present invention relates to a method for producing trimethylsulfoxonium bromide, in which dimethylsulfoxide is reacted with methyl bromide to produce trimethylsulfoxonium bromide.
  • Trimethylsulfoxonium bromide is a useful compound as an intermediate for bactericidal azole derivatives. Trimethylsulfoxonium bromide is produced by reacting dimethyl sulfoxide with methyl bromide.
  • methyl bromide is added little by little to dimethyl sulfoxide heated to 50 to 75 ° C. under atmospheric pressure.
  • a method for producing trimethylsulfoxonium bromide is described in which 0.40 to 0.70 mol is reacted per mol of dimethyl sulfoxide.
  • Japanese Patent Publication Japanese Patent Laid-Open No. 9-235268 (published on September 9, 1997)”
  • Dimethyl sulfoxide which is a starting material in the production of trimethylsulfoxonium bromide, undergoes a decomposition reaction when the reaction temperature is high or an acid is mixed in the reaction solution. Once the decomposition reaction occurs, an acid is generated, and the acid promotes further decomposition reaction, so that the decomposition reaction proceeds at a stretch. Even if the reaction solution is left alone in an adiabatic state, the temperature of the reaction solution rises due to the heat stored by self-decomposition, and the decomposition reaction is accelerated.
  • the present invention has been made in view of the above problems, and an object thereof is to provide a method for producing trimethylsulfoxonium bromide, in which the reaction temperature between dimethyl sulfoxide and methyl bromide is appropriately and easily controlled. There is to do.
  • the present invention is a method for producing trimethylsulfoxonium bromide, wherein dimethylsulfoxide is reacted with methyl bromide to produce trimethylsulfoxonium bromide,
  • a method for producing trimethylsulfoxonium bromide in which methyl bromide is added to dimethyl sulfoxide so as to satisfy the following (1) and (2): (1) adding methyl bromide with an addition rate according to a predetermined input profile based on the reaction rate estimated from the reaction temperature; (2) The temperature in the reaction system of dimethyl sulfoxide and methyl bromide is detected, and when the detected temperature reaches a predetermined upper limit temperature, methyl bromide is added.
  • the present invention is a method for producing trimethylsulfoxonium bromide, in which dimethylsulfoxide is reacted with methyl bromide to produce trimethylsulfoxonium bromide, Also provided is a method for producing trimethylsulfoxonium bromide, wherein methyl bromide is added to dimethyl sulfoxide so as to satisfy (1) and (2) below: (1) The temperature in the reaction system is detected, and methyl bromide is added when the detected temperature reaches a predetermined upper limit temperature. (2) When the detected temperature is lower than a predetermined lower limit temperature, the addition rate of methyl bromide is decreased or the addition is stopped.
  • the present invention provides a temperature control method for a reaction system in which dimethyl sulfoxide and methyl bromide are reacted to produce trimethylsulfoxonium bromide, which detects the temperature in the reaction system. Add methyl bromide when the detected temperature reaches a predetermined upper limit temperature, or decrease the methyl bromide addition rate or stop adding when the temperature is below the predetermined lower limit temperature.
  • a method for controlling the temperature of the reaction system which controls the temperature of the reaction system.
  • methyl bromide is added to dimethyl sulfoxide so as to satisfy the following (1) and (2): (1) Reaction rate estimated from target reaction temperature (2) The temperature in the reaction system of dimethyl sulfoxide and methyl bromide is detected, and the detected temperature is a predetermined upper limit temperature. When it has reached, add methyl bromide. Since the temperature can be controlled by adding methyl bromide, the temperature of the reaction system can be controlled without performing temperature control from outside the reaction system such as a jacket. Therefore, it is possible to easily realize an efficient and stable reaction and to suppress the temperature rise of the reaction system.
  • the method for producing trimethylsulfoxonium bromide in the present embodiment is a method for producing trimethylsulfoxonium bromide by reacting dimethylsulfoxide with methyl bromide, and satisfies the following (1) and (2): Methyl bromide is added to dimethyl sulfoxide. (1) Methyl bromide is added at an addition rate according to a predetermined charging profile based on the reaction rate estimated from the target reaction temperature. (2) The temperature in the reaction system of dimethyl sulfoxide and methyl bromide is detected, and when the detected temperature reaches a predetermined upper limit temperature, methyl bromide is added.
  • the charging profile represents the relationship between the time from the start of the reaction set based on the reaction rate estimated from the target reaction temperature and the total amount of methyl bromide added so far.
  • the “target reaction temperature” is a predetermined target temperature in the reaction system, and is not actually detected temperature in the reaction system. By following this charging profile, it is possible to always maintain a gentle reflux of methyl bromide and to stably control the temperature in the reaction system.
  • An example of the input profile is shown in FIG. In the profile shown in FIG. 1, time progresses from left to right. The vertical axis represents the total amount of methyl bromide added at each time when the final total amount of methyl bromide is 100%.
  • the reaction rate that is, the consumption rate of methyl bromide
  • the reaction rate depends on the temperature in the reaction system and the raw material concentration. Therefore, once the target reaction temperature is determined, the approximate consumption rate of methyl bromide is also determined.
  • the heat removal of the reaction system is performed using latent heat of vaporization of methyl bromide, as will be described later. Therefore, in order to prevent the reaction system from being excessively cooled to decrease the reaction rate, and to prevent the temperature in the reaction system from rising due to insufficient methyl bromide, the reaction system has a consumption rate of methyl bromide. It is preferable that methyl bromide suitable for each is added each time. Furthermore, it is preferable that stable heat removal is always performed by gentle reflux of methyl bromide.
  • the input profile is predetermined from such a viewpoint.
  • the charging profile is an index for maintaining a gentle reflux so that stable heat removal is performed, and the charging of the above (1) in the method for producing trimethylsulfoxonium bromide in the present embodiment.
  • the conditions are not intended to limit the total amount of methyl bromide addition at a point in time to perfectly match a predetermined input profile.
  • the temperature in the reaction system of dimethyl sulfoxide and methyl bromide is detected, and when the detected temperature reaches a predetermined upper limit temperature, methyl is detected. Add bromide.
  • the heat of the reaction system is removed using the latent heat of vaporization of methyl bromide.
  • the evaporated methyl bromide is condensed in a condenser, and the condensed methyl bromide is evaporated in the reaction system to remove heat from the reaction system.
  • the amount of evaporation of methyl bromide increases, so the latent heat of evaporation also increases, and as a result, the temperature of the reaction system decreases.
  • the temperature of the reaction system is lowered by adding methyl bromide to the reaction system and controlled to a temperature lower than this upper limit temperature. can do. Therefore, by adding methyl bromide when the temperature in the reaction system rises, decomposition of dimethyl sulfoxide due to the temperature rise in the reaction system can be prevented.
  • the upper limit temperature is higher than the target reaction temperature, but from the viewpoint of preventing decomposition reaction, it is preferable to set the target reaction temperature + 20 ° C. or lower, and the target reaction temperature + 5.0 ° C. or lower. More preferably, the temperature is set.
  • the temperature in the reaction system of dimethyl sulfoxide and methyl bromide when the temperature in the reaction system of dimethyl sulfoxide and methyl bromide is detected, and the detected temperature is lower than a predetermined lower limit temperature Decrease the addition rate of methyl bromide or stop addition.
  • the addition rate of methyl bromide is reduced or the addition is stopped, the amount of evaporation of methyl bromide is reduced and the latent heat of evaporation is also reduced.
  • the temperature in the reaction system increases. That is, when the temperature in the reaction system is lower than the predetermined lower limit temperature, the temperature of the reaction system is increased by decreasing the addition rate of methyl bromide or stopping the addition.
  • the temperature can be controlled to be higher than this lower limit temperature. Therefore, by reducing the addition rate of methyl bromide when the temperature in the reaction system decreases or by stopping the addition, it is possible to prevent an increase in the time required for completion of the reaction due to a temperature decrease in the reaction system. be able to.
  • the lower limit temperature is lower than the target reaction temperature, but is preferably set to a target reaction temperature of ⁇ 10 ° C. or higher from the viewpoint of shortening the time until completion of the reaction. More preferably, the temperature is set to a temperature equal to or higher than C.
  • methyl bromide is added when the detected temperature reaches the upper limit temperature, and methyl bromide is added when the detected temperature is lower than the lower limit temperature.
  • the rate can be reduced or the addition can be stopped.
  • methyl bromide may be added, or addition of methyl bromide may be stopped.
  • whether or not methyl bromide is added may be determined depending on whether the temperature in the reaction system is increasing or decreasing at that time. In other words, the addition of methyl bromide may be determined based on whether or not a gentle reflux of methyl bromide is maintained.
  • the temperature in the reaction system may be detected constantly or at regular intervals.
  • the addition rate may be changed with time according to the detected temperature change, for example.
  • the addition rate may be maintained constant based on the temperature detected in the certain measurement, for example, from one measurement to the next.
  • the temperature in the reaction system is detected, and when the detected temperature reaches a predetermined upper limit temperature, methyl bromide is added to prevent the temperature of the reaction system from rising and decompose dimethyl sulfoxide. Can be prevented.
  • the addition rate of methyl bromide is decreased or the addition is stopped to prevent a decrease in the reaction system temperature. Can be prevented. Therefore, in the reaction in which dimethyl sulfoxide and methyl bromide are reacted to produce trimethylsulfoxonium bromide, the temperature in the reaction system is detected, and when the detected temperature reaches a predetermined upper limit temperature, methyl is detected.
  • a method of controlling the temperature of the reaction system by adding bromide and decreasing the addition rate of methyl bromide or stopping the addition when the detected temperature is below a predetermined minimum temperature is also possible. It is included in the category of the present invention.
  • the reaction tank for the reaction is used with a temperature control device such as a jacket, an oil bath, and a hot water bath. It is warming up.
  • a temperature control device such as a jacket, an oil bath, and a hot water bath. It is warming up.
  • the amount of evaporation of methyl bromide increases, and the amount of reflux increases accordingly. Therefore, the amount of heat removal can be increased.
  • the temperature to be heated it is preferable to heat the reaction vessel so as to maintain the reaction tank at a temperature 0 ° C. to 20 ° C. higher than the target reaction temperature, and to maintain the temperature 0 ° C. to 10 ° C. higher than the target reaction temperature.
  • the heating is performed.
  • “maintaining a temperature 0 ° C. higher than the target reaction temperature” means maintaining the target reaction temperature.
  • the heat removal (cooling) of the reaction system is performed only by evaporation, condensation and reflux of methyl bromide.
  • a temperature adjusting device such as a jacket is used for heating the reaction tank, and is not used as a means for cooling the reaction tank from the outside.
  • a temperature control device such as a jacket can be used as an external cooling means, for example, when the temperature of the reaction system rises unexpectedly and the temperature of the reaction system needs to be urgently reduced, a new Without preparing the cooling means, it is possible to quickly cope with a sudden temperature rise by switching the temperature adjusting device such as a jacket used for heating to the cooling means from the outside.
  • the amount of methyl bromide used per 1 mol of dimethyl sulfoxide is, for example, 0.40 to 0.70 mol, preferably 0.45 to 0.55 mol. And more preferably 0.48 to 0.53 mol.
  • the amount of methyl bromide used is 0.40 mol or more, the amount of product dissolved in the filtrate can be relatively reduced when the product is isolated, and the isolation yield can be increased. it can. Further, when the amount of methyl bromide used is 0.70 or less, the time required for the reaction can be shortened.
  • trimethyl orthoformate triethyl orthoformate, tripropyl orthoformate, tetramethyl orthocarbonate, tetraethyl orthocarbonate, tetraisopropyl orthocarbonate and orthocarbonate are included in the reaction system. It is preferable that at least one compound selected from the group consisting of tetrapropyl (hereinafter referred to as trimethyl orthoformate) is contained. These compounds are presumed to function as an aid for scavenging substances that promote the decomposition of dimethyl sulfoxide. Therefore, it can suppress more reliably that decomposition
  • the amount of trimethyl orthoformate used is, for example, 0.002 to 0.05 mol, preferably 0.004 to 0.02 mol, per mol of dimethyl sulfoxide.
  • the water concentration in the reaction system is preferably 400 ppm or less, more preferably 200 ppm or less, and further preferably 100 ppm or less. preferable.
  • Trimethyl orthoformate and the like are compounds that are decomposed by reacting with water. Therefore, decomposition of trimethyl orthoformate or the like can be suppressed by setting the water concentration in the reaction system to 400 ppm or less.
  • Examples of the method of setting the water concentration in the reaction system to 400 ppm or less include, for example, 1) a method of drying raw material compounds such as dimethyl sulfoxide and methyl bromide, and trimethyl orthoformate using a drying agent such as molecular sieves.
  • the method for producing trimethylsulfoxonium bromide in the present embodiment can be used under atmospheric pressure or under a slight pressure.
  • under slight pressure means that the pressure is about 10 kPa or less.
  • methyl bromide is refluxed at the target reaction temperature, it may be under a slight pressure or under an atmospheric pressure, but is preferably under a slight pressure. By making it under a slight pressure, it is possible to prevent moisture outside the reaction system from entering the reaction system.
  • the method for producing trimethylsulfoxonium bromide in the present embodiment after the addition of a predetermined amount of methyl bromide, stirring is further performed for 3 to 24 hours at the same temperature as during the addition.
  • isolation and purification may be performed by a conventionally known purification method. For example, after cooling the reaction mixture to room temperature, the insoluble matter is filtered off. The insoluble matter (filtered material) separated by filtration is washed with an organic solvent such as benzene, toluene and xylene. Trimethylsulfoxonium bromide can be isolated by drying this filtrate under a nitrogen stream or by drying at 30 to 60 ° C. under reduced pressure.
  • the upper limit temperature is preferably higher than the target reaction temperature and not higher than the target reaction temperature + 5.0 ° C.
  • the addition rate of methyl bromide is decreased or the addition is stopped. Is preferred.
  • the lower limit temperature is preferably lower than the target reaction temperature and not lower than the target reaction temperature ⁇ 5.0 ° C.
  • the reaction tank in which the reaction is carried out while the reaction between dimethyl sulfoxide and methyl bromide is being carried out. It is more preferable that the reaction vessel is always heated.
  • the reaction vessel is heated so as to be maintained at a temperature 0 ° C. to 20 ° C. higher than the target reaction temperature. More preferably, the reaction vessel is heated at a constant temperature.
  • trimethyl orthoformate in the above reaction system, trimethyl orthoformate, triethyl orthoformate, tripropyl orthoformate, tetramethyl orthocarbonate, tetraethyl orthocarbonate, tetraisopropyl orthocarbonate and ortho It is preferable that at least one compound selected from the group consisting of tetrapropyl carbonate is contained.
  • the water concentration in the reaction system is 400 ppm or less.
  • the reaction between dimethyl sulfoxide and methyl bromide is carried out under slight pressure conditions.
  • the temperature control method for a reaction system for producing trimethylsulfoxonium bromide it is preferable to further heat the reaction system.
  • the reaction system is more preferably heated at a constant temperature.
  • the apparatus was attached to a 500 ml four-necked flask. Under a nitrogen stream, 231 g of dimethyl sulfoxide and 3 g of trimethyl orthoformate were charged and heated. During the reaction, the end of the cooling device was sealed with a nitrogen stream.
  • the oil bath temperature was kept at 67-68 ° C.
  • the dropping rate of methyl bromide is decreased, or dropping is stopped, and when it exceeds 64 ° C, the dropping is restarted or the dropping rate is increased.
  • the reaction was carried out while maintaining the reaction solution temperature in the range of 62 to 65 ° C. while maintaining a gentle reflux of methyl bromide.
  • 155 g of methyl bromide was added to the reaction solution from the hyper glass cylinder over 79 hours. Since the reaction solution became a slurry as the reaction progressed, it was stirred so that it was sufficiently mixed.
  • the present invention can be used for the production of intermediates of active ingredients in agricultural and horticultural fungicides.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
PCT/JP2013/056106 2012-04-24 2013-03-06 トリメチルスルホキソニウムブロミドの製造方法、およびトリメチルスルホキソニウムブロミドを製造する反応系の温度制御方法 Ceased WO2013161394A1 (ja)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN201380015163.0A CN104185623B (zh) 2012-04-24 2013-03-06 三甲基溴化亚砜的制造方法以及制造三甲基溴化亚砜的反应系统的温度控制方法
EP13782308.4A EP2842941A4 (en) 2012-04-24 2013-03-06 PROCESS FOR PREPARING TRIMETHYL SUULFXONIUM BROMIDE AND TEMPERATURE CONTROL METHOD FOR REACTION SYSTEM FOR THE PRODUCTION OF TRIMETHYL SUULFOXONIUM BROMIDE
US14/396,231 US20150051424A1 (en) 2012-04-24 2013-03-06 Method of producing trimethylsulfoxonium bromide and a method of temperature control of reaction system producing trimethylsulfoxonium bromide
IN8353DEN2014 IN2014DN08353A (https=) 2012-04-24 2013-03-06

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2012-099132 2012-04-24
JP2012099132 2012-04-24

Publications (1)

Publication Number Publication Date
WO2013161394A1 true WO2013161394A1 (ja) 2013-10-31

Family

ID=49482734

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2013/056106 Ceased WO2013161394A1 (ja) 2012-04-24 2013-03-06 トリメチルスルホキソニウムブロミドの製造方法、およびトリメチルスルホキソニウムブロミドを製造する反応系の温度制御方法

Country Status (6)

Country Link
US (1) US20150051424A1 (https=)
EP (1) EP2842941A4 (https=)
JP (1) JPWO2013161394A1 (https=)
CN (1) CN104185623B (https=)
IN (1) IN2014DN08353A (https=)
WO (1) WO2013161394A1 (https=)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117018851A (zh) * 2023-08-17 2023-11-10 舞阳威森生物医药有限公司 一种三甲基溴化亚砜生产用尾气处理装置

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5448713A (en) * 1977-09-09 1979-04-17 Searle & Co Manufacture of trimethylsulfoxonium bromide
JPH09235268A (ja) 1995-12-28 1997-09-09 Kureha Chem Ind Co Ltd トリメチルスルホキソニウム ブロミドの製造方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2882663B2 (ja) * 1990-05-28 1999-04-12 株式会社リコー 画像符号量予測符号化方法および装置
EP0781765B1 (en) * 1995-12-28 2000-02-16 Kureha Kagaku Kogyo Kabushiki Kaisha Process for producing trimethylsulfoxonium bromide
JP2006265171A (ja) * 2005-03-24 2006-10-05 Toyotama Koryo Kk 香料組成物及び芳香製品の芳香性を改良又は増強する新しい方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5448713A (en) * 1977-09-09 1979-04-17 Searle & Co Manufacture of trimethylsulfoxonium bromide
JPH09235268A (ja) 1995-12-28 1997-09-09 Kureha Chem Ind Co Ltd トリメチルスルホキソニウム ブロミドの製造方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
M. G. SCAROS ET AL.: "Determination and control of the explosion hazards involved with the preparation of trimethylsulfoxonium bromide", CATALYSIS IN ORGANIC SYNTHESES, vol. 7, 1978, pages 301 - 309, XP008174831 *
See also references of EP2842941A4

Also Published As

Publication number Publication date
EP2842941A1 (en) 2015-03-04
IN2014DN08353A (https=) 2015-05-08
US20150051424A1 (en) 2015-02-19
JPWO2013161394A1 (ja) 2015-12-24
EP2842941A4 (en) 2015-12-23
CN104185623B (zh) 2016-01-06
CN104185623A (zh) 2014-12-03

Similar Documents

Publication Publication Date Title
US11111211B2 (en) Method of distilling dimethyl sulfoxide and multistage distillation tower
BR112015029714B1 (pt) Processo para preparar derivados de 4,6-bis(ariloxi)pirimidina
US9981917B2 (en) Preparation method for revaprazan hydrochloride
CN103429579A (zh) 1,2-苯并异噻唑-3-酮化合物制造方法
US5650530A (en) Process for preparing 6-oxo-(6H)-dibenz-[c,e][1,2]-oxaphosphorins (ODOPs)
JP5930930B2 (ja) メチレンジスルホニルクロライド化合物、メチレンジスルホン酸化合物およびメチレンジスルホネート化合物の製造方法
WO2013161394A1 (ja) トリメチルスルホキソニウムブロミドの製造方法、およびトリメチルスルホキソニウムブロミドを製造する反応系の温度制御方法
EP1829868A1 (en) Process for production of (4,5-dihydroisoxazol-3-yl)thio- carboxamidine salts
CN101633647B (zh) 一种高选择性高收率合成α-氨基芳基烷基酮类化合物的方法
CN109810031B (zh) 非罗考昔中间体的制备方法
CN105017229A (zh) 一种制备咯菌腈的方法
Wang et al. Synthesis of a novel poly (ethylene glycol) grafted triethylamine functionalized dicationic ionic liquid and its application in one-pot synthesis of 2-amino-2-chromene derivatives in water
AU2016374914B2 (en) Method for producing benzoxazole compound
AU2014219681B2 (en) Process for producing pyridazinone compound and production intermediates thereof
CN102627626A (zh) 一种2,3-二醛基噻吩的制备方法
WO2020148404A1 (en) Method for preparation of 1,4-sorbitan in aqueous medium
TW201718510A (zh) 製備1-甲基-3-(三氟甲基)-1h-吡唑-5-醇的方法
JPWO2005058806A1 (ja) クロロスルホニルイソシアナートの製造方法
CN104529924B (zh) 5-环丙基-4-[2-甲硫基-4-(三氟甲基)苯甲酰基]异恶唑的制备方法
Rostamizadeh et al. Synthesis of substituted trisphenols by use of a double acidic ionic liquid under solvent-free conditions
TWI626236B (zh) 異噻唑化合物之製造方法
RU2676692C1 (ru) Способ получения n-фенил-2-нафтиламина
CN106117058A (zh) 一种氯乙酸薄荷醇酯的精制方法
CN102367232A (zh) 一种过氧化二异丙苯的蒸馏方法
CN102558073A (zh) 一种喹螨醚的绿色合成方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13782308

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2014512399

Country of ref document: JP

Kind code of ref document: A

REEP Request for entry into the european phase

Ref document number: 2013782308

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2013782308

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 14396231

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE