JP4597522B2 - ハロゲン化2−(3−ブテニルスルファニル)−1,3−チアゾールを製造する方法 - Google Patents
ハロゲン化2−(3−ブテニルスルファニル)−1,3−チアゾールを製造する方法 Download PDFInfo
- Publication number
- JP4597522B2 JP4597522B2 JP2003560000A JP2003560000A JP4597522B2 JP 4597522 B2 JP4597522 B2 JP 4597522B2 JP 2003560000 A JP2003560000 A JP 2003560000A JP 2003560000 A JP2003560000 A JP 2003560000A JP 4597522 B2 JP4597522 B2 JP 4597522B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- compound
- optionally
- acid
- chloroacetaldehyde
- 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.)
- Expired - Fee Related
Links
- 0 *CCC(*)=C(F)F Chemical compound *CCC(*)=C(F)F 0.000 description 3
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C331/00—Derivatives of thiocyanic acid or of isothiocyanic acid
- C07C331/02—Thiocyanates
- C07C331/04—Thiocyanates having sulfur atoms of thiocyanate groups bound to acyclic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C333/14—Dithiocarbamic acids; Derivatives thereof
- C07C333/18—Esters of dithiocarbamic acids
- C07C333/20—Esters of dithiocarbamic acids having nitrogen atoms of dithiocarbamate groups bound to hydrogen atoms or to acyclic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
- C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
- C07D277/36—Sulfur atoms
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- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Environmental Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Plant Pathology (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Thiazole And Isothizaole Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Paper (AREA)
Description
(a) 式(II)の化合物
RはHまたはFであり、
Xは臭素、塩素、メシレートまたはトシレートであり、好ましくは臭素である]
を、式(III)のチオシアナート塩
M+SCN− (III)
[式中、M+は水素、アンモニウムイオン、テトラアルキルアンモニウムイオンまたはアルカリ金属イオン、例えば、K+もしくはNa+である]
と、場合によって反応助剤の存在下、および場合によって希釈剤の存在下で反応させて、
式(IV)の3−ブテニルチオシアナート
Rは上記に定義されたとおりである]
を得て、
(b)この得られた化合物に、場合によって反応助剤の存在下、および場合によって希釈剤の存在下で、硫化水素またはその塩を添加することにより、
式(V)の3−ブテニル1−ジチオカルバマート
式(IV)の化合物を調製するための本発明によるプロセス(a)の好ましい実施形態では、溶媒、好ましくはアルコール中で式(III)のチオシアナートと式(II)の化合物とを、好ましくは室温で撹拌すると、沈殿が形成する。次いで、バッチを還流状態まで加熱し、冷却させて、濾液を吸引で濾別し、蒸発によって濃縮する。
Rf(SiO2,CH2Cl2):0.85.
1HNMR(CDCl3,400MHz):δ=2.8−2.92(m,2H)、3.1(t,1H).
13CNMR(CDCl3,100MHz):δ=26.6(CH2−CF)、29.5(S−CH2)、110.9(SCN)、125.4(CF)、153.7(CF2).
MS(DCI,NH3):167(11%,M+)、108(92%)、95(100%)、69(40%).
m.p.=49〜53℃
Rf(SiO2,トルエン−酢酸エチル4:1):0.5
1HNMR(CDCl3,400MHz):δ=2.65−2.82(m,2H)、3.41(t,2H)、6.7(broad s,1H)、7.25(broad s,1H).
MS(DCI,NH3):201(0.2%,M+)、119(50%)、93(58%)、60(100%).
Claims (11)
- 式(I)の化合物を調製する方法であって、
RはHまたはFである]
(a)式(II)の化合物
RはHまたはFであり、
Xは臭素、塩素、メシレートまたはトシレートである]
を式(III)の化合物
M+SCN− (III)
[式中、
M+は水素、アンモニウムイオン、テトラアルキルアンモニウムイオンまたは、アルカリ金属もしくはアルカリ土類金属イオンである]
と、場合によって無機または有機の塩基または酸アクセプターから選択される反応助剤の存在下、および場合によって水および不活性有機溶媒から選択される希釈剤の存在下で反応させて、
式(IV)の化合物
Rは上記に定義されたとおりである]
を得て、
(b)次いで、この得られた化合物に、場合によって無機または有機の塩基または酸アクセプターから選択される反応助剤の存在下、および場合によって水および不活性有機溶媒から選択される希釈剤の存在下で、硫化水素またはその塩を添加することにより、
式(V)の化合物
Rは上記に定義されたとおりである]
に変換し、さらに、
(c)この変換した化合物を、場合によってカルボン酸、HCl、BF 3 、H 2 SO 4 、トリフルオロ酢酸、p−トルエンスルホン酸およびメタンスルホン酸から選択される酸性反応助剤の存在下、および場合によって水および不活性有機溶媒から選択される希釈剤の存在下で、クロロアセトアルデヒド(ClCH2CHO)または、そのアセタールもしくは環状アセタールと反応させること、
を特徴とする方法。 - 式(II)の化合物を塩基の存在下で、HSCNと反応させることを特徴とする請求項1に記載の方法。
- 式(II)の化合物をNH4SCNと反応させることを特徴とする請求項1に記載の方法。
- 工程(a)に使用する希釈剤が、アルコールであることを特徴とする請求項3に記載の方法。
- 式(IV)の化合物をH2Sと反応させることを特徴とする請求項1に記載の方法。
- 工程(b)を塩基の存在下で実施することを特徴とする請求項1または5に記載の方法。
- 式(V)の化合物をクロロアセトアルデヒドジアルキルアセタールと反応させることを特徴とする請求項1に記載の方法。
- 工程(c)を酸の存在下で実施する請求項1または7に記載の方法。
- 式(V)の化合物を、0.1〜10モル%のp−トルエンスルホン酸またはメタン−スルホン酸の存在下で、クロロアセトアルデヒドまたはそのアセタールと反応させることを特徴とする請求項1に記載の方法。
- Rがフッ素であることを特徴とする請求項1から9のいずれかに記載の方法。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10201238A DE10201238A1 (de) | 2002-01-15 | 2002-01-15 | Verfahren zur Herstellung von halogenierten 2-(3-Butenylsulfanyl)-1,3-thiazolen |
PCT/EP2003/000028 WO2003059896A1 (de) | 2002-01-15 | 2003-01-03 | Verfahren zur herstellung von halogenierten 2-(3-butenylsulfanyl)-1,3-thiazolen |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2009290564A Division JP5087609B2 (ja) | 2002-01-15 | 2009-12-22 | ハロゲン化2−(3−ブテニルスルファニル)−1,3−チアゾールを製造する方法 |
JP2009290565A Division JP5087610B2 (ja) | 2002-01-15 | 2009-12-22 | ハロゲン化2−(3−ブテニルスルファニル)−1,3−チアゾールを製造する方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2005519896A JP2005519896A (ja) | 2005-07-07 |
JP4597522B2 true JP4597522B2 (ja) | 2010-12-15 |
Family
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Family Applications (3)
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JP2003560000A Expired - Fee Related JP4597522B2 (ja) | 2002-01-15 | 2003-01-03 | ハロゲン化2−(3−ブテニルスルファニル)−1,3−チアゾールを製造する方法 |
JP2009290565A Expired - Fee Related JP5087610B2 (ja) | 2002-01-15 | 2009-12-22 | ハロゲン化2−(3−ブテニルスルファニル)−1,3−チアゾールを製造する方法 |
JP2009290564A Expired - Fee Related JP5087609B2 (ja) | 2002-01-15 | 2009-12-22 | ハロゲン化2−(3−ブテニルスルファニル)−1,3−チアゾールを製造する方法 |
Family Applications After (2)
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JP2009290565A Expired - Fee Related JP5087610B2 (ja) | 2002-01-15 | 2009-12-22 | ハロゲン化2−(3−ブテニルスルファニル)−1,3−チアゾールを製造する方法 |
JP2009290564A Expired - Fee Related JP5087609B2 (ja) | 2002-01-15 | 2009-12-22 | ハロゲン化2−(3−ブテニルスルファニル)−1,3−チアゾールを製造する方法 |
Country Status (8)
Country | Link |
---|---|
US (3) | US7078527B2 (ja) |
EP (1) | EP1467980B1 (ja) |
JP (3) | JP4597522B2 (ja) |
AT (1) | ATE300527T1 (ja) |
AU (1) | AU2003212206A1 (ja) |
DE (2) | DE10201238A1 (ja) |
ES (1) | ES2246467T3 (ja) |
WO (1) | WO2003059896A1 (ja) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10201238A1 (de) * | 2002-01-15 | 2003-07-24 | Bayer Cropscience Ag | Verfahren zur Herstellung von halogenierten 2-(3-Butenylsulfanyl)-1,3-thiazolen |
DE10229776A1 (de) * | 2002-07-03 | 2004-01-22 | Bayer Cropscience Ag | Verfahren zum Herstellen von heterocyclischen Fluoralkenylsulfonen |
DE10319591A1 (de) | 2003-05-02 | 2004-11-18 | Bayer Cropscience Ag | Wirkstoffkombinationen mit nematiziden, insektiziden und fungiziden Eigenschaften basierend auf Trifluorbutenyl-Verbindungen |
DE10319590A1 (de) | 2003-05-02 | 2004-11-18 | Bayer Cropscience Ag | Wirkstoffkombinationen mit nematiziden und insektiziden Eigenschaften basierend auf Trifluorbutenyl-Verbindungen |
JP2005008567A (ja) * | 2003-06-19 | 2005-01-13 | Bayer Cropscience Ag | 殺センチュウ性チアゾリン含有フルオロブテン類 |
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US2426397A (en) | 1944-10-14 | 1947-08-26 | Goodrich Co B F | Process for preparing unsubstituted mercaptothiazole |
US3513172A (en) | 1965-09-27 | 1970-05-19 | Stauffer Chemical Co | 3-phenyl-5-(3,4,4-trifluoro-3-butenylthio)1,2,4-thiadiazole |
US3510503A (en) | 1968-05-27 | 1970-05-05 | Wayne C Jaeschke | Trifluorobutenylthiocarbamates and thiocarbonates |
US3697538A (en) | 1968-06-03 | 1972-10-10 | Synvar Ass | 2,4,5-substituted n-oxy and hydroxyimidazoles |
US3689662A (en) * | 1970-12-10 | 1972-09-05 | Wayne C Jaeschke | Nematocidel use of 3,4,4-trifluoro-3-butenylthio methylidene compounds |
JPS59155355A (ja) * | 1983-02-21 | 1984-09-04 | Shionogi & Co Ltd | 4−チアゾリルオキシ−および4−チアゾリルチオ−フエニル酢酸誘導体の新規製造法 |
US4952580A (en) | 1985-06-20 | 1990-08-28 | Fmc Corporation | Pesticidal polyhaloalkene derivatives |
JPS63500037A (ja) * | 1985-06-20 | 1988-01-07 | エフ エム シ− コ−ポレ−シヨン | 殺虫剤ポリハロアルケン誘導体類 |
US4748186A (en) * | 1986-06-30 | 1988-05-31 | Fmc Corporation | S-trifluorobutenyl derivatives and pesticidal uses thereof |
EP0712395B1 (en) | 1993-08-05 | 2002-05-22 | Syngenta Limited | Process for the preparation of fluoroalkenylthio heterocyclic derivatives |
IL112721A0 (en) | 1994-03-10 | 1995-05-26 | Zeneca Ltd | Azole derivatives |
GB2304713B (en) | 1995-09-11 | 1999-05-05 | Zeneca Ltd | Novel process |
GB2322372B (en) | 1997-02-24 | 1999-03-24 | Zeneca Ltd | Preparation of 2-Mercaptothiazole |
GB9708280D0 (en) | 1997-04-24 | 1997-06-18 | Zeneca Ltd | Novel process |
FR2771631B1 (fr) | 1997-12-03 | 2001-02-02 | Oreal | Compositions de teinture des fibres keratiniques contenant des 3-amino pyrazolo-[1,5-a]-pyrimidines, procede de teinture, nouvelles 3-amino pyrazolo- [1,5-a]-pyrimidines et leur procede de preparation |
JP3899626B2 (ja) | 1997-12-26 | 2007-03-28 | 宇部興産株式会社 | 2−メルカプトチアゾ−ルの製法 |
US6448262B1 (en) * | 1998-11-16 | 2002-09-10 | American Cyanamid Company | Pesticidal and parasiticidal use of 2-(substituted thio) thiazolo-[4,5-b]pyridine compounds |
JP2001019685A (ja) * | 1999-07-06 | 2001-01-23 | Nippon Bayer Agrochem Co Ltd | 殺センチュウ性トリフルオロブテン類 |
JP2001322988A (ja) * | 2000-03-09 | 2001-11-20 | Nippon Bayer Agrochem Co Ltd | 殺センチュウ性トリフルオロブテン類 |
DE10034133A1 (de) * | 2000-07-13 | 2002-01-24 | Bayer Ag | Heterocyclische Fluoralkenylthioether (l) |
DE10201238A1 (de) * | 2002-01-15 | 2003-07-24 | Bayer Cropscience Ag | Verfahren zur Herstellung von halogenierten 2-(3-Butenylsulfanyl)-1,3-thiazolen |
-
2002
- 2002-01-15 DE DE10201238A patent/DE10201238A1/de not_active Withdrawn
-
2003
- 2003-01-03 ES ES03708046T patent/ES2246467T3/es not_active Expired - Lifetime
- 2003-01-03 US US10/501,115 patent/US7078527B2/en not_active Expired - Lifetime
- 2003-01-03 DE DE50300857T patent/DE50300857D1/de not_active Expired - Lifetime
- 2003-01-03 WO PCT/EP2003/000028 patent/WO2003059896A1/de active IP Right Grant
- 2003-01-03 JP JP2003560000A patent/JP4597522B2/ja not_active Expired - Fee Related
- 2003-01-03 AU AU2003212206A patent/AU2003212206A1/en not_active Abandoned
- 2003-01-03 EP EP03708046A patent/EP1467980B1/de not_active Expired - Lifetime
- 2003-01-03 AT AT03708046T patent/ATE300527T1/de not_active IP Right Cessation
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2006
- 2006-04-13 US US11/403,743 patent/US7439408B2/en not_active Expired - Lifetime
- 2006-04-13 US US11/403,514 patent/US7385093B2/en not_active Expired - Lifetime
-
2009
- 2009-12-22 JP JP2009290565A patent/JP5087610B2/ja not_active Expired - Fee Related
- 2009-12-22 JP JP2009290564A patent/JP5087609B2/ja not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
DE50300857D1 (de) | 2005-09-01 |
JP2010111682A (ja) | 2010-05-20 |
WO2003059896A1 (de) | 2003-07-24 |
US20050124816A1 (en) | 2005-06-09 |
EP1467980A1 (de) | 2004-10-20 |
US7439408B2 (en) | 2008-10-21 |
ES2246467T3 (es) | 2006-02-16 |
JP5087610B2 (ja) | 2012-12-05 |
EP1467980B1 (de) | 2005-07-27 |
US7385093B2 (en) | 2008-06-10 |
US20060183914A1 (en) | 2006-08-17 |
US20060183915A1 (en) | 2006-08-17 |
AU2003212206A1 (en) | 2003-07-30 |
US7078527B2 (en) | 2006-07-18 |
ATE300527T1 (de) | 2005-08-15 |
JP2010132661A (ja) | 2010-06-17 |
JP5087609B2 (ja) | 2012-12-05 |
DE10201238A1 (de) | 2003-07-24 |
JP2005519896A (ja) | 2005-07-07 |
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