WO2007025585A1 - Verfahren zur herstellung von 3,4-dichlor-isothiazolcarbonsäure - Google Patents
Verfahren zur herstellung von 3,4-dichlor-isothiazolcarbonsäure Download PDFInfo
- Publication number
- WO2007025585A1 WO2007025585A1 PCT/EP2006/006119 EP2006006119W WO2007025585A1 WO 2007025585 A1 WO2007025585 A1 WO 2007025585A1 EP 2006006119 W EP2006006119 W EP 2006006119W WO 2007025585 A1 WO2007025585 A1 WO 2007025585A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- alcohol
- formula
- hours
- dichloro
- chlorine
- Prior art date
Links
- YPWIGSYXDIIQNP-UHFFFAOYSA-N N#Cc([s]nc1Cl)c1Cl Chemical compound N#Cc([s]nc1Cl)c1Cl YPWIGSYXDIIQNP-UHFFFAOYSA-N 0.000 description 1
- HQZKNCJWLIWCSV-UHFFFAOYSA-N OC(c([s]nc1Cl)c1Cl)=O Chemical compound OC(c([s]nc1Cl)c1Cl)=O HQZKNCJWLIWCSV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D275/00—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings
- C07D275/02—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings not condensed with other rings
- C07D275/03—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
Definitions
- the invention relates to a process for the preparation and isolation of 3,4-dichloro-isothiazole-carboxylic acid.
- 3,4-Dichloro-isothiazole-carboxylic acid of the formula (I) is a known compound. Their preparation is described, for example, in US Pat. Nos. 3,341,547 and 3,393,547.
- a solvent for example N, N-dimethylformamide (DMF)
- DMF N, N-dimethylformamide
- the 3,4-dichloro-isothiazole-carbonitrile is saponified by heating in sodium hydroxide solution to 3,4-dichloro-isothiazole-carboxylic acid:
- the saponification of the nitrile of the formula (II) can in principle also be carried out acidically.
- this has the disadvantage that both the nitrile and the acid sublime under such conditions, which leads to problems on an industrial scale.
- nitrile impurities in the nitrile of the formula (II) lead to by-products in the resulting acid of the formula (I).
- nitrile impurities are mainly sulfur compounds and elemental sulfur according to the route of preparation.
- the by-products of these by-products are mainly the disulfide of formula (III).
- the reaction mixture after The first step of the preparation process is filtered through a filter aid. Subsequently, the filtrate is mixed with a lot of water. The resulting solid is filtered off with suction and washed with further water. This results in large amounts of polluted with organic compounds and therefore difficult to dispose of wastewater.
- the crude product thus obtained must now be further purified in additional lending steps.
- the nitrile can be subjected to steam distillation or recrystallized from cyclohexane in accordance with US Pat. No. 3,341,547 and US Pat. No. 3,393,547.
- the nitrile of the formula (I) thus obtained generally also contains significant amounts of sulfur and / or sulfur compounds.
- 3,4-dichloro-isothiazole-carboxylic acid of the formula (I) is, on the one hand, in its action as a plant growth regulator (see, for example, US Pat. Nos. 3,341,547 and 3,393,547). On the other hand, it is an important intermediate for the production of fungicidal active substances (see, for example, WO 99/24413 and WO 2004/002968).
- the invention accordingly provides a process for the preparation of 3,4-dichloroisothiazole cyanocarbonic acid of the formula (I), which comprises, in the first step of the process, a cyanide, carbon disulfide and chlorine to give 3,4-dichloroisothiazole. carbonitrile of the formula (II), this is isolated after distilling off the solvent, adding an alcohol and filtration as a solution in the alcohol and then saponified alkaline in the alcohol in the second step of the process.
- the process according to the invention avoids the aqueous work-up of the nitrile and thus large amounts of a wastewater which is heavily polluted with organic substances.
- the first step of the process according to the invention only one filtration step is needed. Elaborate cleaning operations for the nitrile can be omitted.
- the first process step is preferably designed in such a way that a cyanide is initially introduced in a solvent, CS 2 is added, preferably by dropwise addition, and gaseous chlorine is preferably introduced after the reaction has taken place.
- cyanide are preferably inorganic cyanides such as sodium cyanide and potassium cyanide. Particularly preferred is sodium cyanide.
- the reaction of the cyanide with carbon disulfide in the first step of the process is carried out in a known manner at temperatures between preferably 30 and 8O 0 C.
- the reaction time for the reaction of cyanide with carbon disulfide in the first step of the process is typically 0.5 to 6 hours, preferably 2 to 4 hours.
- the chlorination in the first step of the method according to the invention is generally carried out at temperatures between 10 and 80 0 C. Preferred are temperatures between 20 and 6O 0 C.
- the reaction time for the chlorination in the first step of the process according to the invention is generally between 1 and 6 hours and depends on the temperature during the chlorination. Is preferably carried out to initiate the chlorine at 3O 0 C within 2 hours, and then stirred for 1 to 5 hours at 20 ° C, or 1 to 2 hours at 2O 0 C and 1 to react for 2 hours at 60 0 C.
- the molar ratio of cyanide and CS 2 is generally between 1.5: 1 and 1: 1.5, preferably between 1.3: 1 and 1: 1.3, in particular it is about 1: 1.
- the amount of chlorine in the first step of the process according to the invention is generally between 0.5 and 1.5 moles per mole of sodium cyanide. Preference is given to 1 to 1.3 moles of chlorine per mole of sodium cyanide.
- Unreacted excess amounts of chlorine are preferably at temperatures between 20 and 6O 0 C by introducing an inert gas such as nitrogen or argon, removed.
- an inert gas such as nitrogen or argon
- amides such as formamide, N, N-dimethylformamide, N, N-dimethylacetamide or N-methylpyrrolidone are preferably used. Particularly preferred are N, N-dimethylformamide and N, N-dimethylacetamide.
- the solvent from the first step of the process can be distilled off at atmospheric pressure or reduced pressure. To avoid higher temperatures, it is usually distilled at reduced pressure. At the same time sulfur chlorides are distilled off with this distillation. Depending on the boiling point of the solvent used, this is obtained completely or largely free of such sulfur chlorides. For better separation of the sulfur chlorides may optionally be distilled through a column. This can be done directly from the reaction mixture, or in a second, downstream fractional distillation. Preferably, it is only distilled off to the extent that a stirrable residue still remains.
- the addition of the alcohol to isolate the nitrile as an alcoholic solution is generally carried out after distilling off the solvent.
- monohydric C 1 -C 6 -alcohols particularly preferred are methanol and ethanol.
- the isolation of the nitrile as a solution in the first step of the process is generally carried out at temperatures of 20 to 100 0 C; preferably at 40 to 8O 0 C.
- the amount of alcohol is usually such that it is sufficient to dissolve the expected amount of nitrile at the temperature of the insulation.
- the solution of the nitrile in the alcohol used is generally mixed with an alkali, such as sodium or potassium hydroxide, and heated.
- the alcohol is then distilled off, the aqueous residue is acidified with an acid, for example hydrochloric or sulfuric acid, and the precipitated 3,4-dichloro-isothiazole-carboxylic acid of the formula (I) is filtered off with suction and dried.
- the amount of liquor in the second step of the process is typically from 1.5 to 5 moles per mole of nitrile. Preference is given to 2 to 3.5 moles per mole of nitrile.
- the temperature in the saponification is generally 20 to 60 0 C, preferably 30 to 45 0 C.
- the saponification time in the second step of the process according to the invention is typically 2 to 8 hours.
- the acid (I) prepared according to the invention is used, for example, as indicated above, as a plant growth regulator and as an intermediate for the production of agrochemical active compounds, in particular fungicides.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Thiazole And Isothizaole Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT06818209T ATE452126T1 (de) | 2005-07-05 | 2006-06-24 | Verfahren zur herstellung von 3,4-dichlor- isothiazolcarbonsäure |
JP2008518690A JP5000645B2 (ja) | 2005-07-05 | 2006-06-24 | 3,4−ジクロロイソチアゾールカルボン酸の調製方法 |
EP06818209A EP1902042B1 (de) | 2005-07-05 | 2006-06-24 | Verfahren zur herstellung von 3,4-dichlor-isothiazolcarbonsäure |
CN2006800248250A CN101218215B (zh) | 2005-07-05 | 2006-06-24 | 3,4-二氯异噻唑羧酸的制备方法 |
KR1020087002611A KR101276667B1 (ko) | 2005-07-05 | 2006-06-24 | 3,4-디클로로이소티아졸카복실산의 제조방법 |
DE502006005668T DE502006005668D1 (de) | 2005-07-05 | 2006-06-24 | Verfahren zur herstellung von 3,4-dichlor-isothiazolcarbonsäure |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102005031348.5 | 2005-07-05 | ||
DE102005031348A DE102005031348B4 (de) | 2005-07-05 | 2005-07-05 | Verfahren zur Herstellung von 3,4-Dichlorisothiazolcarbonsäure |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2007025585A1 true WO2007025585A1 (de) | 2007-03-08 |
Family
ID=37000060
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2006/006119 WO2007025585A1 (de) | 2005-07-05 | 2006-06-24 | Verfahren zur herstellung von 3,4-dichlor-isothiazolcarbonsäure |
Country Status (9)
Country | Link |
---|---|
EP (1) | EP1902042B1 (de) |
JP (1) | JP5000645B2 (de) |
KR (1) | KR101276667B1 (de) |
CN (1) | CN101218215B (de) |
AT (1) | ATE452126T1 (de) |
DE (2) | DE102005031348B4 (de) |
ES (1) | ES2335924T3 (de) |
TW (1) | TWI370123B (de) |
WO (1) | WO2007025585A1 (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR102574266B1 (ko) * | 2023-08-07 | 2023-09-01 | 설현민 | 우수한 방수성능을 갖는 고기능성 개질 아스팔트계방수재 조성물 및 이를 이용한 아스팔트 교면방수 시공방법 |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010126170A1 (ja) * | 2009-05-01 | 2010-11-04 | イハラケミカル工業株式会社 | イソチアゾール誘導体の製造方法 |
CN102030718B (zh) * | 2009-09-28 | 2012-09-05 | 湖北成宇制药有限公司 | 3,4-二氯-5-氰基-异噻唑的制备方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3341547A (en) * | 1965-10-01 | 1967-09-12 | Pennsalt Chemicals Corp | 3, 4-dichloroisothiazoles and process for making them |
US3393992A (en) * | 1965-10-01 | 1968-07-23 | Pennsalt Chemicals Corp | Process for contacting plants with growth effecting chemical |
US5240951A (en) * | 1990-09-20 | 1993-08-31 | Mitsui Toatsu Chemicals, Incorporated | Isothiazolecarboxylic acid derivatives, rice blast control agents containing the same as active ingredients, and rice blast control method applying the control agents |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2231097A1 (de) * | 1972-06-24 | 1974-01-03 | Bayer Ag | Verfahren zur herstellung von 5-cyan-3,4-dichlorisothiazol |
DE2231098A1 (de) * | 1972-06-24 | 1974-01-03 | Bayer Ag | Verfahren zur herstellung von 3,4-dichlorisothiazolen |
JP2530071B2 (ja) * | 1990-09-20 | 1996-09-04 | 三井東圧化学株式会社 | イソチアゾ―ルカルボン酸誘導体およびこれらを有効成分とするイネいもち病防除剤 |
-
2005
- 2005-07-05 DE DE102005031348A patent/DE102005031348B4/de not_active Expired - Fee Related
-
2006
- 2006-06-24 CN CN2006800248250A patent/CN101218215B/zh active Active
- 2006-06-24 KR KR1020087002611A patent/KR101276667B1/ko active IP Right Grant
- 2006-06-24 ES ES06818209T patent/ES2335924T3/es active Active
- 2006-06-24 DE DE502006005668T patent/DE502006005668D1/de active Active
- 2006-06-24 EP EP06818209A patent/EP1902042B1/de active Active
- 2006-06-24 WO PCT/EP2006/006119 patent/WO2007025585A1/de active Application Filing
- 2006-06-24 AT AT06818209T patent/ATE452126T1/de active
- 2006-06-24 JP JP2008518690A patent/JP5000645B2/ja active Active
- 2006-07-04 TW TW095124223A patent/TWI370123B/zh active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3341547A (en) * | 1965-10-01 | 1967-09-12 | Pennsalt Chemicals Corp | 3, 4-dichloroisothiazoles and process for making them |
US3393992A (en) * | 1965-10-01 | 1968-07-23 | Pennsalt Chemicals Corp | Process for contacting plants with growth effecting chemical |
US5240951A (en) * | 1990-09-20 | 1993-08-31 | Mitsui Toatsu Chemicals, Incorporated | Isothiazolecarboxylic acid derivatives, rice blast control agents containing the same as active ingredients, and rice blast control method applying the control agents |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR102574266B1 (ko) * | 2023-08-07 | 2023-09-01 | 설현민 | 우수한 방수성능을 갖는 고기능성 개질 아스팔트계방수재 조성물 및 이를 이용한 아스팔트 교면방수 시공방법 |
Also Published As
Publication number | Publication date |
---|---|
ATE452126T1 (de) | 2010-01-15 |
KR20080031044A (ko) | 2008-04-07 |
JP5000645B2 (ja) | 2012-08-15 |
DE102005031348B4 (de) | 2007-04-19 |
JP2009500302A (ja) | 2009-01-08 |
CN101218215B (zh) | 2011-04-13 |
TWI370123B (en) | 2012-08-11 |
CN101218215A (zh) | 2008-07-09 |
DE502006005668D1 (de) | 2010-01-28 |
TW200714592A (en) | 2007-04-16 |
KR101276667B1 (ko) | 2013-06-19 |
DE102005031348A1 (de) | 2007-01-11 |
EP1902042B1 (de) | 2009-12-16 |
EP1902042A1 (de) | 2008-03-26 |
ES2335924T3 (es) | 2010-04-06 |
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