WO2010071192A1 - クロロチオールホルメートの製造方法 - Google Patents
クロロチオールホルメートの製造方法 Download PDFInfo
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- WO2010071192A1 WO2010071192A1 PCT/JP2009/071101 JP2009071101W WO2010071192A1 WO 2010071192 A1 WO2010071192 A1 WO 2010071192A1 JP 2009071101 W JP2009071101 W JP 2009071101W WO 2010071192 A1 WO2010071192 A1 WO 2010071192A1
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- phosgene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C329/00—Thiocarbonic acids; Halides, esters or anhydrides thereof
- C07C329/02—Monothiocarbonic acids; Derivatives thereof
- C07C329/04—Esters of monothiocarbonic acids
- C07C329/06—Esters of monothiocarbonic acids having sulfur atoms of thiocarbonic groups bound to acyclic carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C329/00—Thiocarbonic acids; Halides, esters or anhydrides thereof
- C07C329/02—Monothiocarbonic acids; Derivatives thereof
Definitions
- the present invention is a compound of formula (I) in an organic solvent in the presence of a base catalyst in a reactor.
- R 1 and R 2 each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
- R 1 and R 2 each have the same meaning as described above.
- a compound represented by the formula [hereinafter sometimes referred to as chlorothiolformate (II). ] About the method of manufacturing.
- Patent Document 1 produces chlorothiolformate (II) by reacting alkenyl mercaptan (I) with phosgene in an organic solvent in the presence of a base catalyst in a reactor.
- 0.05 mol of carboxylic acid amide is used per 1 mol of alkenyl mercaptan (I)
- alkenyl mercaptan (I) phosgene and carboxylic acid amide are supplied to a reactor containing no carboxylic acid amide.
- Patent Document 2 uses 0.05 mol of triethylamine with respect to 1 mol of alkenyl mercaptan (I), and is 25 wt% of the total amount of alkenyl mercaptan (I) and 25 wt% of the total amount of triethylamine.
- I) Discloses a method for supplying phosgene to a reactor in which a total amount and a total amount of triethylamine are previously placed.
- An object of the present invention is to provide a method that can satisfactorily suppress the production of by-product (III) and produce excellent quality chlorothiolformate (II) in a good yield.
- the present invention is a compound of formula (I) in the presence of a carboxylic acid amide in an organic solvent in a reactor.
- R 1 and R 2 each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
- a manufacturing method for supplying into a vessel is provided.
- the alkenyl mercaptan (I) represented by the above formula (I) is reacted with phosgene.
- examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, s-butyl group, and t-butyl group. Can be mentioned.
- alkenyl mercaptans (I) examples include 2-propenyl mercaptan (allyl mercaptan), 2-butenyl mercaptan, 3-methyl-2-butenyl mercaptan, 2-pentenyl mercaptan, 2-hexenyl mercaptan, 2-heptenyl mercaptan Etc.
- 2-propenyl mercaptan allyl mercaptan
- 2-propenyl mercaptan is used.
- the amount of phosgene used is usually 1 mol or more, preferably 1.05 to 2 mol, per 1 mol of alkenyl mercaptan (I).
- a gaseous thing may be used for phosgene and a liquid thing may be used.
- the carboxylic acid amide may be an N, N-disubstituted carboxylic acid amide, an N-monosubstituted carboxylic acid amide or an unsubstituted carboxylic acid amide.
- a typical example is a compound represented by the following formula (IV).
- R 3 , R 4 and R 5 each represent a hydrogen atom, an alkyl group or an aryl group
- alkyl group examples include a methyl group, an ethyl group, a propyl group, and a butyl group.
- aryl group examples include a phenyl group and a naphthyl group.
- the amount of the carboxylic acid amide used is usually 0.01 to 0.09 mol per 1 mol of alkenyl mercaptan (I).
- the reaction can proceed smoothly when the amount of the carboxylic acid amide used is 0.01 mol or more per 1 mol of alkenyl mercaptan (I).
- the amount of the carboxylic acid amide used is 0.09 mol or less with respect to 1 mol of alkenyl mercaptan (I)
- the amount of by-product (III) produced can be reduced.
- an organic solvent that is immiscible with water is preferably used because it is easy to employ an operation of mixing the reaction solution with water and separating the oil and water in post-treatment after the reaction.
- Specific examples include aliphatic hydrocarbons such as hexane, heptane, and octane; alicyclic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; dichloromethane, chloroform, 1, Halogenated aliphatic hydrocarbons such as 2-dichloroethane; halogenated aromatic hydrocarbons such as monochlorobenzene and dichlorobenzene; ethers such as diethyl ether and dibutyl ether; esters such as ethyl acetate and butyl acetate It is done.
- Aromatic hydrocarbons are preferably used.
- the amount of the organic solvent used is usually 1 to 10 parts by weight, preferably 1 to 5 parts by weight per 1 part by weight of alkenyl mercaptan (I).
- an alkenyl mercaptan (I), phosgene and the remaining carboxylic acid amide are placed in a reactor in which 10 to 50% by weight of the total amount of carboxylic acid amide is previously placed. %)),
- the formation of the by-product (III) represented by the above formula (III) can be satisfactorily suppressed, and excellent quality chlorothiolformate (II) can be obtained in a good yield.
- the amount of the carboxylic acid amide previously placed in the reactor is preferably 30 to 50% by weight based on the total amount of the amide.
- the total amount of alkenyl mercaptan (I) may be supplied into the reactor together with phosgene and a predetermined amount of carboxylic acid amide, or a part of the alkenyl mercaptan (I) is put in the reactor in advance, and then the remainder is phosgene and A fixed amount of carboxylic acid amide may be supplied into the reactor.
- the total amount of phosgene may be supplied into the reactor together with alkenyl mercaptan (I) and a predetermined amount of carboxylic acid amide, or a part of the phosgene is put in the reactor in advance, and then the rest May be fed into the reactor together with alkenyl mercaptan (I) and a predetermined amount of carboxylic acid amide.
- the organic solvent may be put in the reactor in advance, or may be supplied into the reactor together with alkenyl mercaptan (I), phosgene and carboxylic acid amide.
- the supply of alkenyl mercaptan (I) and the supply of phosgene may be performed continuously without any interval, or may be performed intermittently. Further, the start of supply of alkenyl mercaptan (I) and the start of supply of phosgene, and the end of supply of alkenyl mercaptan (I) and the end of supply of phosgene do not necessarily coincide with each other, as long as the effects of the present invention are not impaired. It may be shifted.
- the amount of alkenyl mercaptan (I) supplied together with phosgene may be 80% by weight or more of the total amount of alkenyl mercaptan (I) used. Moreover, what is necessary is just to make it the quantity of the phosgene supplied with alkenyl mercaptan (I) be 80 weight% or more of the total amount of phosgene to be used.
- Alkenyl mercaptan (I) is preferably supplied after cooling. As a result, the formation of by-product (III) can be suppressed, and in addition, a reaction in which two molecules of alkenyl mercaptan (I) are oxidized to produce disulfide, and alkenyl mercaptan (I) reacts with chlorothiolformate. The reaction which dithiol carbonate produces
- the cooling temperature of the alkenyl mercaptan (I) is usually ⁇ 20 to 5 ° C., although it depends on the type.
- the reaction temperature is usually 0 to 80 ° C., preferably 30 to 50 ° C.
- the reaction is usually carried out at around normal pressure, but may be carried out under pressure or under reduced pressure if necessary.
- As the reaction system any of a continuous system, a semi-continuous system, and a batch system can be employed.
- a reaction mixture containing chlorothiolformate (II) represented by the formula (II) can be obtained with good quality and yield.
- the post-treatment operation after the reaction is appropriately selected. Water, preferably acidic water, is added to the reaction mixture, and if excess phosgene remains, it is hydrolyzed, followed by oil-water separation to obtain an organic solvent solution of chlorothiolformate as the organic phase. It is preferable to obtain.
- the solution thus obtained can be used for various applications after being purified by washing, distillation, crystallization, or the like, if necessary.
- Example 1 In a glass reactor equipped with a phosgene gas introduction tube, a reflux condenser, a thermometer, a stirrer, and a jacketed dropping funnel, 65.34 g (0.402 mol) of allyl mercaptan obtained by the method described in Reference Example 1, 2.37 g of N, N-dimethylformamide (0.032 mol, 40% by weight based on the total amount of the amide) and 403.21 g of xylene were added and stirred. Nitrogen was introduced into the gas phase in the reactor and a nitrogen stream was introduced. Below. Next, 41.80 g (0.423 mol) of phosgene was introduced into the liquid over 2 hours while maintaining the temperature of the reaction liquid at 39 to 41 ° C.
- a mixed liquid of 195.31 g (1.207 mol) of allyl mercaptan and 3.53 g of N, N-dimethylformamide (0.048 mol, 60% by weight based on the total amount of the amide) was put in a dropping funnel with a jacket, The reaction solution was cooled to 0 to 5 ° C. and dropped over 5 hours while maintaining the temperature of the reaction solution at 39 to 41 ° C., and 104.50 g (1.056 mol) of phosgene was introduced into the reaction solution over 5 hours. Further, 20.90 g (0.211 mol) of phosgene was introduced into the liquid over 1 hour while maintaining the temperature of the reaction liquid at 39 to 41 ° C.
- reaction solution was kept at 39 to 41 ° C. for 3 hours.
- the obtained reaction solution was cooled to 0 to 5 ° C., and 264.08 g of water was added to the reaction solution to decompose unreacted phosgene.
- the reaction solution was separated into oil and water to obtain 740.76 g of an allylchlorothioformate xylene solution as an organic phase.
- the content of allyl chlorothioformate in the solution was 25.60% by weight.
- the yield of allyl chlorothioformate based on allyl mercaptan was 86.24%.
- the area ratio of the amide form of the by-product (III) to the amide form of the chlorothiolformate (II) was 0.03%.
- Comparative Example 1 In a glass reactor equipped with a phosgene gas introduction tube, a reflux condenser, a thermometer, a stirrer, and a jacketed dropping funnel, 80.00 g (0.521 mol) of allyl mercaptan obtained by the method described in Reference Example 1, N, N-dimethylformamide (7.62 g, 0.104 mol, 100% by weight with respect to the total amount of the amide) and xylene (46,000.00 g) were added and stirred. Nitrogen was introduced into the gas phase in the reactor and a nitrogen stream was introduced. Below.
- the obtained reaction solution was cooled to 0 to 5 ° C., and 379.91 g of 2% hydrochloric acid was added to the reaction solution to decompose unreacted phosgene. Subsequently, the reaction solution was separated into oil and water to obtain 910.60 g of an allylchlorothioformate xylene solution as an organic phase.
- the allyl chlorothioformate content in the solution was 25.21% by weight.
- the yield of allyl chlorothioformate with respect to allyl mercaptan was 80.64%.
- the area ratio of the amide form of the by-product (III) to the amide form of the chlorothiolformate (II) was 0.17%.
- Comparative Example 2 97.50 g (0.550 mol) of allyl mercaptan obtained by the method described in Reference Example 1, in a glass reactor equipped with a phosgene gas introduction tube, a reflux condenser, a thermometer, a stirrer, and a jacketed dropping funnel, 17.68 g of N, N-dimethylformamide (0.242 mol, 11 mol% with respect to the total amount of allyl mercaptan, 100 wt% with respect to the total amount of amide) and 604.50 g of xylene were added and stirred, and the gas phase part in the reactor Nitrogen was introduced into the atmosphere under a nitrogen stream.
- Comparative Example 3 In a glass reactor equipped with a phosgene gas introduction tube, a reflux condenser, a thermometer, a stirrer, and a jacketed dropping funnel, 37.52 g (0.220 mol) of allyl mercaptan obtained by the method described in Reference Example 1, 1.78 g of triethylamine (0.018 mol, 40% by weight with respect to the total amount of the amine) and 232.51 g of xylene were added and stirred, and nitrogen was introduced into the gas phase portion in the reactor under a nitrogen stream. Next, while maintaining the temperature of the reaction solution at 39 to 41 ° C., 22.83 g (0.231 mol) of phosgene was introduced into the solution over 2 hours.
- a mixed liquid of 112.51 g (0.659 mol) of allyl mercaptan and 2.67 g of triethylamine (0.0264 mol, 60% by weight based on the total amount of the amine) was put into a jacketed dropping funnel and cooled to 0 to 5 ° C. While maintaining the temperature of the reaction solution at 39 to 41 ° C., it was added dropwise over 5 hours, and 57.08 g (0.577 mol) of phosgene was introduced into the reaction solution over 5 hours. Further, 11.42 g (0.115 mol) of phosgene was introduced into the reaction solution over 1 hour while maintaining the temperature of the reaction solution at 39 to 41 ° C.
- reaction solution was kept at 39 to 41 ° C. for 3 hours.
- the obtained reaction solution was cooled to 0 to 5 ° C., and 143.29 g of water was added to decompose unreacted phosgene.
- the reaction solution was separated into oil and water to obtain 416.11 g of an allylchlorothioformate xylene solution as an organic phase.
- the allyl chlorothioformate content in the solution was 23.87% by weight.
- the yield of allyl chlorothioformate based on allyl mercaptan was 82.71%.
- the area ratio of the amide form of the by-product (III) to the amide form of the chlorothiolformate (II) was 0.05%.
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Abstract
Description
で示される化合物〔以下、アルケニルメルカプタン(I)ということがある。〕とホスゲンとを反応させることにより、式(II)
で示される化合物〔以下、クロロチオールホルメート(II)ということがある。〕を製造する方法に関する。
で示される化合物〔以下、副生物(III)ということがある。〕の生成量が増加してしまうことがあり、クロロチオールホルメート(II)の品質や収率の点でも必ずしも満足のいくものではなかった。
カルボン酸アミド総量の10~50重量%を予め入れた反応器内に、式(I)で示される化合物、ホスゲン及び残部のカルボン酸アミド(すなわち該アミドの総量の50~90重量%)を反応器内に供給する製造方法を提供するものである。
<アリルメルカプタン〔R1及びR2が水素原子である式(I)の化合物〕の調製>
還流冷却器、温度計、攪拌器及びジャケット付き滴下ロートを備えたガラス製反応器に、水硫化ナトリウム水和物(水硫化ナトリウム含有量=70重量%、硫化ナトリウム含有量=4.20重量%、硫化ナトリウム/水硫化ナトリウム=6.0重量%)230.30g(2.868モル)、水200.11g、キシレン160.02g、69.6重量%トリエチルベンジルアンモニウムクロリド水溶液111.24g(0.333モル)を入れて攪拌し、反応器内の気相部に窒素を導入して窒素気流下とした。
次いで、アリルクロリド200.01g(2.561モル)をジャケット付き滴下ロートに入れて-2~5℃に冷却した。この冷却したアリルクロリドを、反応液の温度を40℃に保ちながら、7時間かけて滴下し、さらに40℃で3時間保温した。得られた反応液を0~10℃に冷却した後、反応液に水240.11gを添加して、析出した塩化ナトリウムを溶解させた。次いで、該反応液を油水分離し、有機相として、アリルメルカプタンのキシレン溶液345.67gを得た。該キシレン溶液をガスクロマトグラフィーで分析したところ、アリルクロリドに対するアリルメルカプタンの収率は83.92%であった。
ホスゲンガス導入管、還流冷却器、温度計、攪拌器及びジャケット付き滴下ロートを備えたガラス製反応器に、参考例1に記載の方法で得られたアリルメルカプタン65.34g(0.402モル)、N,N-ジメチルホルムアミド2.37g(0.032モル、該アミド総量に対し40重量%)及びキシレン403.21gを入れて攪拌し、反応器内の気相部に窒素を導入して窒素気流下とした。次いで、反応液の温度を39~41℃に保ちながら、ホスゲン41.80g(0.423モル)を2時間かけて液中に導入した。次にアリルメルカプタン195.31g(1.207モル)、N,N-ジメチルホルムアミド3.53g(0.048モル、該アミド総量に対し60重量%)の混合液を、ジャケット付き滴下ロートに入れ、0~5℃に冷却し、反応液の温度を39~41℃に保ちながら5時間かけて滴下すると共に、ホスゲン104.50g(1.056モル)を5時間かけて反応液中に導入した。さらに反応液の温度を39~41℃に保ちながら、ホスゲン20.90g(0.211モル)を1時間かけて液中に導入した。その後、反応液を39~41℃で3時間保温した。得られた反応液を0~5℃に冷却し、反応液に水264.08gを添加して未反応のホスゲンを分解した。次いで、該反応液を油水分離し、有機相として、アリルクロロチオールホルメートのキシレン溶液740.76gを得た。
該溶液中のアリルクロロチオールホルメートの含有量は25.60重量%であった。アリルメルカプタンに対するアリルクロロチオールホルメートの収率は86.24%であった。また、ガスクロマトグラフィーにより分析したところ、クロロチオールホルメート(II)のアミド体に対する副生物(III)のアミド体の面積比は0.03%であった。
ホスゲンガス導入管、還流冷却器、温度計、攪拌器及びジャケット付き滴下ロートを備えたガラス製反応器に、参考例1に記載の方法で得られたアリルメルカプタン80.00g(0.521モル)、N,N-ジメチルホルムアミド7.62g(0.104モル、該アミド総量に対し100重量%)及びキシレン496.00gを入れて攪拌し、反応器内の気相部に窒素を導入して窒素気流下とした。次いで、反応液の温度を39~41℃に保ちながら、ホスゲン51.54g(0.521モル)を2時間かけて液中に導入した。次にアリルメルカプタン240.00g(1.563モル)を、ジャケット付き滴下ロートに入れ0~5℃に冷却し、反応液の温度を39~41℃に保ちながら6時間かけて滴下すると共に、ホスゲン154.61g(1.563モル)を6時間かけて液中に導入した。その後、反応液を39~41℃で3時間保温した。得られた反応液を0~5℃に冷却し、反応液に2%塩酸379.91gを添加して未反応のホスゲンを分解した。次いで、該反応液を油水分離し、有機相として、アリルクロロチオールホルメートのキシレン溶液910.60gを得た。
該溶液中のアリルクロロチオールホルメートの含有量は25.21重量%であった。アリルメルカプタンに対するアリルクロロチオールホルメートの収率は80.64%であった。また、ガスクロマトグラフィーにより分析したところ、クロロチオールホルメート(II)のアミド体に対する副生物(III)のアミド体の面積比は0.17%であった。
ホスゲンガス導入管、還流冷却器、温度計、攪拌器及びジャケット付き滴下ロートを備えたガラス製反応器に、参考例1に記載の方法で得られたアリルメルカプタン97.50g(0.550モル)、N,N-ジメチルホルムアミド17.68g(0.242モル、アリルメルカプタン総量に対し11mol%、該アミド総量に対し100重量%)及びキシレン604.50gを入れて攪拌し、反応器内の気相部に窒素を導入して窒素気流下とした。次いで、反応液の温度を39~41℃に保ちながら、ホスゲン54.37g(0.550モル)を2時間かけて液中に導入した。次にアリルメルカプタン292.50g(1.649モル)を、ジャケット付き滴下ロートに入れ0~5℃に冷却し、反応液の温度を39~41℃に保ちながら6時間かけて滴下すると共に、ホスゲン163.11g(1.649モル)を6時間かけて反応液中に導入した。その後、該反応液を39~41℃で3時間保温した。
得られた反応液を0~5℃に冷却し、2%塩酸400.79gを添加して未反応のホスゲンを分解した。次いで、該反応液を油水分離し、有機相として、アリルクロロチオールホルメートのキシレン溶液1079.40gを得た。
該溶液中のアリルクロロチオールホルメートの含有量は21.59重量%であった。アリルメルカプタンに対するアリルクロロチオールホルメートの収率は77.60%であった。また、ガスクロマトグラフィーにより分析したところ、クロロチオールホルメート(II)のアミド体に対する副生物(III)のアミド体の面積比は0.72%であった。
ホスゲンガス導入管、還流冷却器、温度計、攪拌器及びジャケット付き滴下ロートを備えたガラス製反応器に、参考例1に記載の方法で得られたアリルメルカプタン37.52g(0.220モル)、トリエチルアミン1.78g(0.018モル、該アミン総量に対し40重量%)及びキシレン232.51gを入れて攪拌し、反応器内の気相部に窒素を導入して窒素気流下とした。次いで、反応液の温度を39~41℃に保ちながら、ホスゲン22.83g(0.231モル)を2時間かけて液中に導入した。次にアリルメルカプタン112.51g(0.659モル)、トリエチルアミン2.67g(0.0264モル、該アミン総量に対し60重量%)の混合液を、ジャケット付き滴下ロートに入れ0~5℃に冷却し、反応液の温度を39~41℃に保ちながら5時間かけて滴下すると共に、ホスゲン57.08g(0.577モル)を5時間かけて反応液中に導入した。さらに反応液の温度を39~41℃に保ちながら、ホスゲン11.42g(0.115モル)を1時間かけて反応液中に導入した。その後、該反応液を39~41℃で3時間保温した。得られた反応液を0~5℃に冷却し、水143.29gを添加して未反応のホスゲンを分解した。次いで、該反応液を油水分離し、有機相として、アリルクロロチオールホルメートのキシレン溶液416.11gを得た。
該溶液中のアリルクロロチオールホルメートの含有量は23.87重量%であった。アリルメルカプタンに対するアリルクロロチオールホルメートの収率は82.71%であった。また、ガスクロマトグラフィーにより分析したところ、クロロチオールホルメート(II)のアミド体に対する副生物(III)のアミド体の面積比は0.05%であった。
Claims (5)
- カルボン酸アミドが、N,N-ジアルキルカルボン酸アミドである、請求項1に記載の製造方法。
- カルボン酸アミドの使用量が、式(I)で示される化合物1モルに対して0.01~0.09モルである、請求項1または2に記載の製造方法。
- 式(I)で示される化合物が、アリルメルカプタンである、請求項1~3のいずれかに記載の製造方法。
- 有機溶媒が芳香族炭化水素である、請求項1~4のいずれかに記載の製造方法。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP09833494A EP2380875A1 (en) | 2008-12-19 | 2009-12-18 | Chlorothioformate manufacturing method |
CN2009801498685A CN102245569A (zh) | 2008-12-19 | 2009-12-18 | 硫代氯甲酸酯的制造方法 |
US13/140,361 US8455674B2 (en) | 2008-12-19 | 2009-12-18 | Chlorothioformate manufacturing method |
IL213632A IL213632A0 (en) | 2008-12-19 | 2011-06-16 | Process for producing chlorothioformate |
Applications Claiming Priority (2)
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JP2008-323470 | 2008-12-19 | ||
JP2008323470 | 2008-12-19 |
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WO2010071192A1 true WO2010071192A1 (ja) | 2010-06-24 |
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PCT/JP2009/071101 WO2010071192A1 (ja) | 2008-12-19 | 2009-12-18 | クロロチオールホルメートの製造方法 |
Country Status (7)
Country | Link |
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US (1) | US8455674B2 (ja) |
EP (1) | EP2380875A1 (ja) |
JP (1) | JP2010163427A (ja) |
CN (1) | CN102245569A (ja) |
IL (1) | IL213632A0 (ja) |
TW (1) | TW201033166A (ja) |
WO (1) | WO2010071192A1 (ja) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5634663A (en) * | 1979-08-28 | 1981-04-06 | Hoechst Ag | Manufacture of thiochloroformic ester |
HU202488B (en) * | 1986-07-18 | 1991-03-28 | Eszakmagyar Vegyimuevek | Catalytic process for producing chloroformic acid thio esters |
JP2007204428A (ja) | 2006-02-02 | 2007-08-16 | Sumitomo Chemical Co Ltd | クロロチオールホルメートの製造法 |
JP2007290987A (ja) | 2006-04-24 | 2007-11-08 | Sumitomo Chemical Co Ltd | クロロチオールホルメートの製造法 |
-
2009
- 2009-12-17 JP JP2009286045A patent/JP2010163427A/ja active Pending
- 2009-12-18 WO PCT/JP2009/071101 patent/WO2010071192A1/ja active Application Filing
- 2009-12-18 US US13/140,361 patent/US8455674B2/en not_active Expired - Fee Related
- 2009-12-18 CN CN2009801498685A patent/CN102245569A/zh active Pending
- 2009-12-18 EP EP09833494A patent/EP2380875A1/en not_active Withdrawn
- 2009-12-18 TW TW098143592A patent/TW201033166A/zh unknown
-
2011
- 2011-06-16 IL IL213632A patent/IL213632A0/en unknown
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5634663A (en) * | 1979-08-28 | 1981-04-06 | Hoechst Ag | Manufacture of thiochloroformic ester |
HU202488B (en) * | 1986-07-18 | 1991-03-28 | Eszakmagyar Vegyimuevek | Catalytic process for producing chloroformic acid thio esters |
JP2007204428A (ja) | 2006-02-02 | 2007-08-16 | Sumitomo Chemical Co Ltd | クロロチオールホルメートの製造法 |
JP2007290987A (ja) | 2006-04-24 | 2007-11-08 | Sumitomo Chemical Co Ltd | クロロチオールホルメートの製造法 |
Also Published As
Publication number | Publication date |
---|---|
JP2010163427A (ja) | 2010-07-29 |
US8455674B2 (en) | 2013-06-04 |
IL213632A0 (en) | 2011-07-31 |
US20110251429A1 (en) | 2011-10-13 |
CN102245569A (zh) | 2011-11-16 |
EP2380875A1 (en) | 2011-10-26 |
TW201033166A (en) | 2010-09-16 |
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