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WO2002032887A1 - Procede de preparation de 5-amino-3-alkylisothiazoles et de 5-amino-4-chloro-3-alkylisothiazoles - Google Patents

Procede de preparation de 5-amino-3-alkylisothiazoles et de 5-amino-4-chloro-3-alkylisothiazoles Download PDF

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Publication number
WO2002032887A1
WO2002032887A1 PCT/GB2001/004658 GB0104658W WO0232887A1 WO 2002032887 A1 WO2002032887 A1 WO 2002032887A1 GB 0104658 W GB0104658 W GB 0104658W WO 0232887 A1 WO0232887 A1 WO 0232887A1
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WIPO (PCT)
Prior art keywords
compound
formula
continuous phase
acid
amino
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/GB2001/004658
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English (en)
Inventor
Steven Fitzjohn
Nicholas Russell Foster
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.)
Syngenta Ltd
Original Assignee
Syngenta Ltd
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
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Priority to AU2002210689A priority Critical patent/AU2002210689A1/en
Publication of WO2002032887A1 publication Critical patent/WO2002032887A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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 present invention relates to a process for the preparation of a 5-amino-3- alkylisothiazole compound and to a process for the preparation of a 5-amino-4-chloro-3- alkylisothiazole compound.
  • 5-Amino-3-alkylisothiazoles and 5-amino-4-chloro-3- alkylisothiazoles are useful chemical intermediates, for example in the synthesis of agrochemicals.
  • the present invention provides a process for the preparation of a compound of formula (I):
  • R is - 6 alkyl; or an acid addition salt derived therefrom; the process comprising oxidising a compound of formula (IT):
  • a chlorinated alkane such as dichloromethane, 1,2-dichloroethane or 1,1,2,2-tetrachloroethane
  • an aromatic liquid for example benzene, toluene, chlorobenzene, fluorobenzene, perfluorobenzene, iso-butyl benzene or mesitylene or a xylene
  • an ester for example ethyl acetate or iso-propyl acetate
  • tert-butyl alcohol acetic acid, trifluoroacetic acid, sulfuric acid, propionitrile, butyronitrile or benzonitrile.
  • the continuous phase for the oxidation step comprises toluene, chlorobenzene, fluorobenzene, acetic acid, trifluoroacetic acid, sulfuric acid, tert-butvlalcohol. ethyl acetate, iso-propyl acetate, dichloromethane or 1,2-dichloroethane. More preferably the continuous phase for the oxidation step comprises toluene, fluorobenzene, ethyl acetate, iso-propyl acetate or dichloromethane.
  • the continuous phase for the oxidation step comprises ethyl acetate or iso-propyl acetate.
  • the continuous phase for the oxidation step may comprise a mixture of the liquids recited above.
  • the oxidation step is preferably performed at a temperature below 40°C, such as in the range 20 to 35°C, preferably in the range 24 to 26°C.
  • R is C ⁇ - 4 alkyl, more preferably R is Ci- 2 alkyl and most preferably R is ethyl.
  • Suitable acid addition salts include the hydrochloric acid salt.
  • the present invention provides a process for the preparation of a compound of formula (ffi):
  • R is C ⁇ - 6 alkyl
  • a chlorinated alkane such as dichloromethane, 1,2-dichloroethane or 1,1,2,2-tetrachloroethane
  • an aromatic liquid for example benzene, toluene, chlorobenzene, fluorobenzene, perfluorobenzene, iso-butvl benzene or mesitylene or a xylene
  • an ester for example ethyl acetate or iso-propyl acetate
  • tert-butyl alcohol acetic acid, trifluoroacetic acid, sulfuric acid, propionitrile, butyronitrile or benzonitrile to prepare a compound of formula (I):
  • the chlorination step is preferably performed at a temperature below 35°C, more preferably in the range 10 to 35°C and even more preferably in the range 20 to 30°C.
  • the continuous phase for the chlorination step may be a chlorinated alkane (such as dichloromethane, 1,2-dichloroethane or 1,1,2,2-tetrachloroethane), a saturated straight or branched chain hydrocarbon or a mixture thereof (for example a petroleum fraction, pentane or hexane), an optionally alkyl substituted C 5 - 7 cycloalkane (for example cyclohexane, cyclopentane or methylcyclohexane), an ether (such as tert-butylmethylether, glyme, diglyme, triglyme or tetrahydrofuran), an aromatic liquid (for example benzene, toluene, chlorobenzene, fluorobenzene, perfluorobenzene, iso-butyl benzene or mesitylene or a xylene), acetic acid or a polar aprotic liquid (such as a
  • the continuous phase for the chlorination step is a chlorinated alkane (such as dichloromethane, 1,2-dichloroethane or 1,1,2,2-tetrachloroethane), an ether (such as tert-butylmethylether.
  • a chlorinated alkane such as dichloromethane, 1,2-dichloroethane or 1,1,2,2-tetrachloroethane
  • an ether such as tert-butylmethylether.
  • glyme, diglyme, triglyme or tetrahydrofuran an aromatic liquid (for example benzene, toluene, chlorobenzene, fluorobenzene, perfluorobenzene, iso-butyl benzene or mesitylene or a xylene), acetic acid or a polar aprotic liquid (such as a nitrile (for example propionitrile, butyronitrile, benzonitrile or acetonitrile)).
  • aromatic liquid for example benzene, toluene, chlorobenzene, fluorobenzene, perfluorobenzene, iso-butyl benzene or mesitylene or a xylene
  • acetic acid or a polar aprotic liquid such as a nitrile (for example propionitrile, butyronitrile, benzonitrile or acetonitrile)).
  • the continuous phase for the chlorination step is an ether (especially tert-butylmethylether), an aromatic liquid (especially toluene, chlorobenzene or fluorobenzene), acetic acid, dichloromethane or acetonitrile.
  • an ether especially tert-butylmethylether
  • an aromatic liquid especially toluene, chlorobenzene or fluorobenzene
  • acetic acid especially dichloromethane or acetonitrile.
  • the continuous phase for the chlorination step is acetic acid, toluene, fluorobenzene, dichloromethane, tert-butylmethylether or acetonitrile.
  • the continuous phase for the chlorination step may comprise a mixture of the liquids recited above (for example a mixture of tert-butylmethylether and another liquid or a mixture of acetonitrile and dichloromethane).
  • the present invention provides a process for the preparation of a compound of formula (III) wherein R is C ⁇ - 6 alkyl, the process comprising oxidising a compound of formula (II) with hydrogen peroxide to prepare a compound of formula (I) or an acid addition salt derived therefrom; and chlorinating said compound of formula (I) with SO Cl 2 wherein the compound of formula (I) is not isolated prior to chlorination and both the oxidation step and the chlorination step are conducted with a continuous phase which comprises toluene, fluorobenzene, dichloromethane, ethyl acetate, iso-propyl acetate or acetonitrile, more preferably toluene, fluorobenzene, dichloromethane, ethyl acetate or iso- propyl acetate.
  • This Example illustrates the preparation of 5-amino-3-ethylisothiazole hydrochloride.
  • 3-Amino-2-pentenethioamide 498.5g, 3.84mol
  • ethyl acetate 1.251itre
  • the mixture was stirred, placed under a nitrogen blanket and the thermal control of the reaction vessel was set to maintain an internal temperature of ca.23-25°C.
  • a solution of hydrogen peroxide (575ml; 4.98mol) in water (270ml) was carefully added, from a pressure addition bottle using nitrogen pressure and via a PTFE tube, to the reaction mixture, initially at ca.23°C. There was an exothermic reaction but the temperature of the reaction mixture was maintaind between 22-53°C by the use of cooling means and by controlling the rate of addition of the hydrogen peroxide solution.
  • reaction mixture (a very thick-semi solid) was stirred vigorously and cooled to 0-2°C. Addition of HCl gas (at a rate of ⁇ 290ml/minute) was then continued for a further 3hours, during which the suspension became thinner and more mobile. The mixture was filtered (using some of the filtrate to wash the solid from the flask) and the solid material was then washed with hexane (2x500ml) and sucked dry to give a buff-coloured solid (573.3g; 90% yield).
  • Acetonitrile 1000ml was charged to the reaction vessel and stirred. The thermal control of the vessel was set to maintain ca.25-27°C (internal temperature).
  • the product from Example 1 (411.25g; 2.5mol) was added and washed-in with acetonitrile (2.31itres), to form a pale cream-coloured slurry.
  • the reaction mixture was then stirred at 29 to 30°C for 2hours, after which the reaction mixture was separated in to three equal portions, each of which was added to saturated NaHCO 3 (2.61itres) to which more solid NaHCO 3 (ca.83g for each of the three portions) was added, so as to maintain the solution at pH7-8.
  • the three portions were stirred for 20 minutes then each was extracted with ethyl acetate (1x400ml).
  • the aqueous portions were combined and extracted with ethyl acetate (3x600ml).
  • the combined organic phasess were washed with brine (1x750ml) and dried (MgSO ) overnight.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé pour préparer un composé de la formule (I), dans laquelle R est alkyle C1-6 ; ou un sel d'addition acide dérivé de ce composé ; ce procédé consistant à oxyder un composé de la formule (II) avec un peroxide d'hydrogène comportant un alcane chloré, un liquide aromatique, un ester, de l'alcool tert-butylique, de l'acide acétique, de l'acide trifluoroacétique, de l'acide sulfurique, du propionitrile, du butyronitrile ou du benzonitrile comme phase continue. La chloration ultérieure de (I) avec SO2CL2 produit les 5-amino-4-chloro-3-alkylisothiazoles.
PCT/GB2001/004658 2000-10-20 2001-10-18 Procede de preparation de 5-amino-3-alkylisothiazoles et de 5-amino-4-chloro-3-alkylisothiazoles Ceased WO2002032887A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2002210689A AU2002210689A1 (en) 2000-10-20 2001-10-18 Process for preparing 5-amino-3-alkylisothiazoles and 5-amino-4-chloro-3-alkylisothiazoles

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0025814.5 2000-10-20
GB0025814A GB0025814D0 (en) 2000-10-20 2000-10-20 Chemical processes

Publications (1)

Publication Number Publication Date
WO2002032887A1 true WO2002032887A1 (fr) 2002-04-25

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB2001/004658 Ceased WO2002032887A1 (fr) 2000-10-20 2001-10-18 Procede de preparation de 5-amino-3-alkylisothiazoles et de 5-amino-4-chloro-3-alkylisothiazoles

Country Status (3)

Country Link
AU (1) AU2002210689A1 (fr)
GB (1) GB0025814D0 (fr)
WO (1) WO2002032887A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3742984A1 (de) * 1987-12-18 1989-06-29 Bayer Ag Verfahren zur herstellung von 3-chlorisothiazol-verbindungen
WO1994021617A1 (fr) * 1993-03-19 1994-09-29 Dowelanco Procede de preparation d'isothiazoles halogenes
JPH07304758A (ja) * 1994-05-13 1995-11-21 Mitsui Toatsu Chem Inc ３−アルキル−５−アミノイソチアゾール鉱酸塩類の製造方法
WO1995031448A1 (fr) * 1994-05-17 1995-11-23 Dowelanco Pesticides de n-(5-isothiazolyle)amide
WO2000068214A1 (fr) * 1999-05-10 2000-11-16 Syngenta Limited Procede de preparation de composes 5-amino-3-alkylisothiazole et de composes 5-amino-4-chloro-3-alkylisothiazole

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3742984A1 (de) * 1987-12-18 1989-06-29 Bayer Ag Verfahren zur herstellung von 3-chlorisothiazol-verbindungen
WO1994021617A1 (fr) * 1993-03-19 1994-09-29 Dowelanco Procede de preparation d'isothiazoles halogenes
JPH07304758A (ja) * 1994-05-13 1995-11-21 Mitsui Toatsu Chem Inc ３−アルキル−５−アミノイソチアゾール鉱酸塩類の製造方法
WO1995031448A1 (fr) * 1994-05-17 1995-11-23 Dowelanco Pesticides de n-(5-isothiazolyle)amide
WO2000068214A1 (fr) * 1999-05-10 2000-11-16 Syngenta Limited Procede de preparation de composes 5-amino-3-alkylisothiazole et de composes 5-amino-4-chloro-3-alkylisothiazole

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 1996, no. 03 29 March 1996 (1996-03-29) *

Also Published As

Publication number Publication date
GB0025814D0 (en) 2000-12-06
AU2002210689A1 (en) 2002-04-29

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