WO2000068214A1 - Process for the preparation of 5-amino-3-alkylisothiazole compounds and of 5-amino-4-chloro-3-alkylisothiazole compounds - Google Patents

Process for the preparation of 5-amino-3-alkylisothiazole compounds and of 5-amino-4-chloro-3-alkylisothiazole compounds Download PDF

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WO2000068214A1
WO2000068214A1 PCT/GB2000/001591 GB0001591W WO0068214A1 WO 2000068214 A1 WO2000068214 A1 WO 2000068214A1 GB 0001591 W GB0001591 W GB 0001591W WO 0068214 A1 WO0068214 A1 WO 0068214A1
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compound
formula
amino
preparation
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Steven Fitzjohn
Mark Adrian Hugget
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Syngenta Limited
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    • 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- 5 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 C ⁇ - 6 alkyl; or an acid addition salt derived therefrom; the process comprising oxidising a compound of formula (II):
  • 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.
  • the present invention provides a process for the preparation of a compound of formula (III): 25
  • R is C ⁇ - 6 alkyl
  • the chlorination step is preferably performed at a temperature below 25°C, more preferably in the range 0 to 20°C and even more preferably in the range 5 to 15°C.
  • R is C)_ alkyl, more preferably R is Cj. 2 alkyl and most preferably R is methyl.
  • Suitable acid addition salts include the hydrochloric acid salt.
  • 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 .
  • 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 an optionally alkyl substituted C 5 .
  • 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 nitrile (for example propionitrile, butyronitrile, benzonitrile or acetonitrile)).
  • 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, 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)).
  • a chlorinated alkane such as dichloromethane, 1,2-dichloroethane or 1,1,2,2-tetrachloroethane
  • an ether such as tert
  • 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):
  • TBME tert-Butylmethylether
  • bet ⁇ -Imino-thiobutyramide (274g; 2.36mole) was added to the reactor, the final portion of this compound being washed in with further TBME (400ml), to give a yellow suspension.
  • An aqueous solution of hydrogen peroxide (35%w/v, 298ml; 3.07mole) further diluted with water (170ml) was charged into a Schott pressure addition bottle and then added to the reactor dropwise over 90minutes using nitrogen pressure via a PTFE tube.
  • Hydrogen chloride gas (110.6g; 3.03mole) was bubbled through the filtrate via a plain un-fritted gas inlet tube over 30minutes (any off-gasses were scrubbed with aqueous sodium hydroxide), causing an exothermic reaction and producing a buff solid which precipitated from solution.
  • reaction mixture was then quenched at 8°C (jacket temperature) with potassium carbonate (367.3g; 2.66mole) dissolved in water (llitre) over lhour. This resulted in exothermic and rapid gas evolution.
  • the layers were separated and the aqueous layer extracted twice with dichloromethane (600ml and 400ml). The combined organic layers were dried over magnesium sulphate, filtered and concentrated to dryness under reduced pressure to give a slightly sticky orange/red solid, yield 232.9g. This solid was ground with a pestle and mortar and then slurried in hexane (approximately 500ml) for lhour.
  • reaction mixture was then poured into a saturated aqueous solution of sodium bicarbonate (1 litre). This resulted in exothermic and rapid gas evolution. Additional sodium bicarbonate was then added until the reaction mixture became basic.
  • the reaction mixture was extracted with diethyl ether and the extract was washed with brine, dried over magnesium sulphate, charcoal treated, filtered (HyfloTM filter aid) and concentrated under reduced pressurte to give a brown solid (96g) which was then triturated with hexane, filtered, ground with a pestle and mortar, slurried again in hexane, filtered, hexane washed and finally air dried over several days to give the desired product as a brown powder (93g, 84%).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Thiazole And Isothizaole Compounds (AREA)

Abstract

A process for the preparation of a compound of formula (I): wherein R is C1-6alkyl; or an acid addition salt derived therefrom; the process comprising oxidising a compound of formula (II) with hydrogen peroxide with tert-butylmethylether as a continuous phase, and a process for the preparation of a compound of formula (III): wherein R is C1-6alkyl; the process comprising chlorinating a compound of formula (I) or an acid addition salt derived therefrom, with SO2Cl2 in the presence of a suitable continuous phase.

Description

PROCESS FOR THE PREPARATION OF 5-AMINO-3-ALKYLISOTHIAZOLE COMPOUNDS AND OF 5-AMINO-4-CHLORO-3-ALKYLISOTHIAZOLE COMPOUNDS
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- 5 alkylisothiazole compound. 5-Amino-3-alkylisothiazoles and 5-amino-4-chloro-3- alkylisothiazoles are useful chemical intermediates, for example in the synthesis of agrochemicals.
Processes to prepare 5-amino-3-methylisothiazole are disclosed by Adam and Slack, J.Chem.Soc, (1959), 3061; and Goerdeler and Pohland, Chem.Ber., (1961), 94, 2950; and in 10 BE629580.
Processes to prepare 5-amino-4-chloro-3-methylisothiazole are disclosed in WO9531448 and by Skotsch and Breitmaier, Synthesis, (1979), 370.
In one aspect the present invention provides a process for the preparation of a compound of formula (I):
Figure imgf000003_0001
wherein R is Cι-6 alkyl; or an acid addition salt derived therefrom; the process comprising oxidising a compound of formula (II):
Figure imgf000003_0002
20 with hydrogen peroxide with tert-butylmethylether as a continuous phase.
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.
In a further aspect the present invention provides a process for the preparation of a compound of formula (III): 25
Figure imgf000003_0003
wherein R is Cι-6 alkyl; the process comprising chlorinating a compound of formula (I) or an acid addition salt derived therefrom, with SO2Cl in the presence of a suitable continuous phase.
The chlorination step is preferably performed at a temperature below 25°C, more preferably in the range 0 to 20°C and even more preferably in the range 5 to 15°C.
It is preferred that R is C)_ alkyl, more preferably R is Cj.2 alkyl and most preferably R is methyl.
Suitable acid addition salts include the hydrochloric acid salt.
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 C5.7 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 nitrile (for example propionitrile, butyronitrile, benzonitrile or acetonitrile)).
It is preferred that 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, 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)).
More preferably 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.
Most preferably 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). In another aspect the present invention provides a process for the preparation of a compound of formula (III):
Figure imgf000005_0001
wherein R is Ch alky!; the process comprising oxidising a compound of formula (II):
Figure imgf000005_0002
with hydrogen peroxide with tert-butylmethylether as a continuous phase to prepare a compound of formula (I):
Figure imgf000005_0003
or an acid addition salt derived therefrom; and chlorinating said compound of formula (I) with SO2Cl in the presence of a suitable continuous phase. In a further aspect the compound of formula (I) is not isolated prior to chlorination and tert-butylmethylether is the continuous phase for both steps of the process.
The present invention is illustrated by the following Examples. Selected NMR data and melting point data are presented in the Examples. For NMR data, no attempt has been made to list every absorption. The following abbreviations are used throughout the Examples: mp = melting point (uncorrected) ppm = parts per million s = singlet t = triplet EXAMPLE 1 This Example illustrates the preparation of 5-amino-3-methylisothiazole hydrochloride.
Figure imgf000006_0001
tert-Butylmethylether (TBME, 600ml) was charged in to a 31itre jacketed reactor and stirred at 20°C (jacket temperature). betα-Imino-thiobutyramide (274g; 2.36mole) was added to the reactor, the final portion of this compound being washed in with further TBME (400ml), to give a yellow suspension. An aqueous solution of hydrogen peroxide (35%w/v, 298ml; 3.07mole) further diluted with water (170ml) was charged into a Schott pressure addition bottle and then added to the reactor dropwise over 90minutes using nitrogen pressure via a PTFE tube. (No syringe needle was fitted to the tubing.) The reaction was exothermic and, in order to maintain the temperature of the reaction mixture between 25 and 32°C, the jacket temperature was cooled to 5°C. The resultant brown two phase mixture was stirred at ambient temperature for 2hours and then the layers were separated. The aqueous phase was extracted twice with TBME (500ml and 250ml). The organic phases were combined, dried over magnesium sulphate and filtered. The filtrate was transferred to a 31itre 3-neck flask and stirred at approximately 5°C (water/ice bath). Hydrogen chloride gas (110.6g; 3.03mole) was bubbled through the filtrate via a plain un-fritted gas inlet tube over 30minutes (any off-gasses were scrubbed with aqueous sodium hydroxide), causing an exothermic reaction and producing a buff solid which precipitated from solution.
Throughout the reaction, the temperature of the reaction mixture was maintained below 27°C. The suspension was stirred at 20°C for lOminutes, filtered, washed with TBME (2x250ml) and then washed with hexane (500ml). The filtrate was dried under suction and then left to air dry for 3days to yield the desired product as a sand-like yellow-brown solid (312.8g, 88%).
Η NMR (DMSO-d6): δ 6.23(s,lH); 2.32(s,3H)ppm. [Spectroscopy showed the presence of 2-5 mole% ammonium chloride as an impurity: Η NMR(DMSO-dό): δ 7.55, 7.35, 7.15, (t,4H)ppm.]
This material was used in Example 2 without further purification. EXAMPLE 2 This Example illustrates the preparation of 5-amino-4-chloro-3-methylisothiazole.
Figure imgf000007_0001
5-Amino-3-methylisothiazole hydrochloride (250g; 1.66mole) was suspended in dichloromethane (1.251itre) and stirred in a 3 litre jacketed reactor at 8°C (jacket temperature). Sulfuryl chloride (146.8ml; 1.83mole) was added to the reactor dropwise over lhour and any off-gasses were scrubbed with aqueous sodium hydroxide. During this addition the temperature of the reaction mixture was maintained between 10 and 15°C. As the sulfuryl chloride was added the solid dissolved and a dense dark oil began to separate from the reaction mixture. The resultant two phase mixture was stirred at 10°C for 15minutes (in some repeats of this preparation a solid began to precipitate from the reaction mixture at this stage). An aliquot of the reaction mixture was basified with saturated sodium bicarbonate solution and extracted with dichloromethane. The organic extract was dried (magnesium sulphate) and concentrated to dryness under reduced pressure. In some repeat preparations there was little change in appearance of the reaction mixture during the reaction since a solid precipitated from the reaction mixture simultaneously with the consumption of the starting material but 1H NMR (CDC13) analysis of the residue confirmed that no starting material remained (that is, there was no singlet at δ 6.15ppm).
The remaining reaction mixture was then quenched at 8°C (jacket temperature) with potassium carbonate (367.3g; 2.66mole) dissolved in water (llitre) over lhour. This resulted in exothermic and rapid gas evolution. The layers were separated and the aqueous layer extracted twice with dichloromethane (600ml and 400ml). The combined organic layers were dried over magnesium sulphate, filtered and concentrated to dryness under reduced pressure to give a slightly sticky orange/red solid, yield 232.9g. This solid was ground with a pestle and mortar and then slurried in hexane (approximately 500ml) for lhour. After filtering, the solid was further washed with hexane (approximately 250ml) and then dried under suction. The solid was further dried in a dessicator under vacuum to give the desired product as a red/brown solid (228.7g, 93%). 1H NMR (CDCI3): δ 4.6(broad s,2H); 2.30(s,3H)ppm. Mp: 69-71°C.
EXAMPLE 3 This Example illustrates an alternative preparation of 5-amino-4-chloro-3- methylisothiazole.
Figure imgf000008_0001
5-Amino-3-methylisothiazole hydrochloride (113g; 0.75mole) was suspended in acetonitrile (l.Olitre) and stirred in a 21itre reactor at 3°C. Sulfuryl chloride (72ml; 0.9mole) was slowly added to the reactor over 75minutes and the reaction mixture was then left stirring as it was allowed to warm to room temperature (2hours). An aliquot of the reaction mixture was basified with saturated sodium bicarbonate solution and extracted with diethyl ether. 1H NMR (CDC13) analysis of this sample confirmed that no starting material remained (that is, there was no singlet at δ 6.15ppm). The remaining reaction mixture was then poured into a saturated aqueous solution of sodium bicarbonate (1 litre). This resulted in exothermic and rapid gas evolution. Additional sodium bicarbonate was then added until the reaction mixture became basic. The reaction mixture was extracted with diethyl ether and the extract was washed with brine, dried over magnesium sulphate, charcoal treated, filtered (Hyflo™ filter aid) and concentrated under reduced pressurte to give a brown solid (96g) which was then triturated with hexane, filtered, ground with a pestle and mortar, slurried again in hexane, filtered, hexane washed and finally air dried over several days to give the desired product as a brown powder (93g, 84%).
1H NMR (CDCI3): δ 4.6(broad s,2H); 2.30(s,3H)ppm. EXAMPLE 4 This Example illustrates alternative preparations of 5-amino-4-chloro-3- methylisothiazole.
SOoCI,
Figure imgf000009_0002
Room Temperature
Figure imgf000009_0001
Solvent A
5-Amino-4-chloro-3-methylisothioazole hydrochloride (0.5g; 0.0033mole) was added to Solvent A (3ml) in a test tube and the suspension was stirred. Sulphuryl chloride (0.3ml; O.0037mole) was added dropwise by syringe to the test tube over approximately lOminutes. Once the addition was completed the reaction mixture was stirred at room temperature for approximately 2.5hours. The reaction mixture was then worked up by careful basification with aqueous potassium carbonate solution followed by extraction with ethyl acetate or dichloromethane. The organic extraction solution was treated with charcoal, silica and magnesium sulphate, filtered through Hyflo™ filter aid, and the filtrate was then evaporated under reduced pressure to give the desired product (confirmed by 1H NMR spectroscopy) whose purity was established by HPLC.
The preparation was carried out on five occasions, using a different Solvent A on each occasion; the results are shown in Table 1 below. TABLE 1
Solvent A Yield of Product Purity (HPLC)
t-Butylmethylether 0.26g; 53% 95.0%
Toluene 0.26g; 53% 90.3%
Fluorobenzene 0.20g; 40.5% 93.5%
Acetic acid 0.25g; 51% 97.6%
Dichloromethane 0.21g; 42.6% 97.2%

Claims

1. A process for the preparation of a compound of formula (I):
Figure imgf000010_0001
wherein R is Cι_6alkyl; or an acid addition salt derived therefrom; the process comprising oxidising a compound of formula (II):
Figure imgf000010_0002
with hydrogen peroxide with tert-butylmethylether as a continuous phase.
2. A process for the preparation of a compound of formula (III):
Figure imgf000010_0003
wherein R is Cι-6alkyl; the process comprising chlorinating a compound of formula (I):
Figure imgf000010_0004
or an acid addition salt derived therefrom, with SO Cl in the presence of a suitable continuous phase.
3. A process for the preparation of a compound of formula (III):
Figure imgf000011_0001
wherein R is Cj-6 alkyl; the process comprising oxidising a compound of formula (II):
Figure imgf000011_0002
with hydrogen peroxide with tert-butylmethylether as a continuous phase to prepare a compound of formula (I):
Figure imgf000011_0003
or an acid addition salt derived therefrom; and chlorinating said compound of formula (I) with SO2Cl in the presence of a suitable continuous phase.
4. A process as claimed in claim 3 wherein both the oxidation step and the chlorination step are conducted with tert-butylmethylether as the continuous phase and the compound of formula (I) is not isolated prior to chlorination.
PCT/GB2000/001591 1999-05-10 2000-04-25 Process for the preparation of 5-amino-3-alkylisothiazole compounds and of 5-amino-4-chloro-3-alkylisothiazole compounds WO2000068214A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002032887A1 (en) * 2000-10-20 2002-04-25 Syngenta Limited Process for preparing 5-amino-3-alkylisothiazoles and 5-amino-4-chloro-3-alkylisothiazoles

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE629580A (en) * 1961-03-16
US3476765A (en) * 1966-09-27 1969-11-04 R & L Molecular Research Ltd Certain substituted isoxazoles
US3551440A (en) * 1966-07-25 1970-12-29 Bristol Myers Co 3 phenyl - 5(alkyl)isothiazole - 4 - carboxylic acids and intermediates thereof
WO1995031448A1 (en) * 1994-05-17 1995-11-23 Dowelanco N-(5-isothiazolyl)amide pesticides

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE629580A (en) * 1961-03-16
GB997378A (en) * 1961-03-16 1965-07-07 May & Baker Ltd Isothiazole derivatives
US3551440A (en) * 1966-07-25 1970-12-29 Bristol Myers Co 3 phenyl - 5(alkyl)isothiazole - 4 - carboxylic acids and intermediates thereof
US3476765A (en) * 1966-09-27 1969-11-04 R & L Molecular Research Ltd Certain substituted isoxazoles
WO1995031448A1 (en) * 1994-05-17 1995-11-23 Dowelanco N-(5-isothiazolyl)amide pesticides

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
C. SKOETSCH ET AL., SYNTHESIS, no. 5, 1979, pages 370 - 2 *
CHEMICAL ABSTRACTS, vol. 91, no. 21, 19 November 1979, Columbus, Ohio, US; abstract no. 175253r, page 655; XP002143656 *
J. GOERDELER ET AL., CHEMISCHE BERICHTE, vol. 94, 1961, pages 2950 - 9, XP002143649 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002032887A1 (en) * 2000-10-20 2002-04-25 Syngenta Limited Process for preparing 5-amino-3-alkylisothiazoles and 5-amino-4-chloro-3-alkylisothiazoles

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