WO2000005202A1 - Process for the preparation of thiono compounds - Google Patents

Process for the preparation of thiono compounds Download PDF

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Publication number
WO2000005202A1
WO2000005202A1 PCT/GB1999/002018 GB9902018W WO0005202A1 WO 2000005202 A1 WO2000005202 A1 WO 2000005202A1 GB 9902018 W GB9902018 W GB 9902018W WO 0005202 A1 WO0005202 A1 WO 0005202A1
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Prior art keywords
formula
compound
hydrogen
group
alkyl
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PCT/GB1999/002018
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French (fr)
Inventor
Andrew John Blacker
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Zeneca Limited
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Priority to AU45229/99A priority Critical patent/AU4522999A/en
Publication of WO2000005202A1 publication Critical patent/WO2000005202A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C337/00—Derivatives of thiocarbonic acids containing functional groups covered by groups C07C333/00 or C07C335/00 in which at least one nitrogen atom of these functional groups is further bound to another nitrogen atom not being part of a nitro or nitroso group
    • C07C337/02—Compounds containing any of the groups, e.g. thiocarbazates
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C329/00—Thiocarbonic acids; Halides, esters or anhydrides thereof
    • C07C329/12—Dithiocarbonic acids; Derivatives thereof
    • C07C329/14—Esters of dithiocarbonic acids
    • C07C329/20—Esters of dithiocarbonic acids having sulfur atoms of dithiocarbonic groups bound to carbon atoms of six-membered aromatic rings
    • 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
    • C07C333/02—Monothiocarbamic acids; Derivatives thereof
    • C07C333/08—Monothiocarbamic acids; Derivatives thereof having nitrogen atoms of thiocarbamic groups bound to carbon atoms of six-membered aromatic rings

Definitions

  • R 6 is as defined in relation to formula (I) and Y is a leaving group other than a group SR X where R x is CH 2 COOH or C M alkyl.
  • the reaction is suitably effected in the presence of an organic base, in particular a weak base such as pyridine, triethylamine or diisopropylethylamine, or an inorganic base such as Mn+(OH) n , Mn+(HCO 3 ) n or (Mn+) 2/n (CO 3 ) 2n/2 where M is a metal ion of valency n where n is especially 1 or 2, in particular an alkali or alkaline earth metal cation such as Na + or K + or Mg 2+ or Ca 2+ .
  • an organic base in particular a weak base such as pyridine, triethylamine or diisopropylethylamine, or an inorganic base such as Mn+(OH) n , Mn+(HCO 3 ) n or (Mn+) 2/n (CO 3 ) 2n/2
  • M is a metal ion of valency n where n is especially 1 or 2, in
  • Particularly suitable groups Y are halogens, -SM, SSM, -SC(S)OR 10 , SSC(S)OR 10 , OR 10, or OM where R 10 and M are as defined above.
  • R 1 , R 2 , R3, R4 and R5 include hydrogen and halogen such as chlorine as well as trihalomethyl, in particular trifluoromethyl.
  • halogen such as chlorine as well as trihalomethyl, in particular trifluoromethyl.
  • at least three of Ri, R2, R3, R4 and R5 are hydrogen.
  • one of these groups is at the meta position (R 2 or R 4 ). which in particular is trifluoromethyl.
  • R6 is an alkyl group in particular a methyl, ethyl or propyl group and especially methyl.
  • a particular group X is a group of formula -NR8-NR9-, in particular a hydrazine where R 8 and R9 are hydrogen.
  • the invention provides a method of preparing a compound of formula (III) by reacting a compound of formula (IV) Y 1
  • Y 1 , Y 2 , Y 3 and Y 4 are each leaving groups such as halogen and particularly chlorine, provided that at least one of Y', Y2 or Y3 is a group Y of formula (III), with a compound of formula (V)
  • R 6 and Mi is hydrogen or a group M as defined above; in the presence of a reducing agent.
  • Suitable reducing agents include hydrogen or a hydrogen transfer reagent such as isopropanol or formic acid or salts, a sulfur containing compound such as hydrogen sulphide or salts, a dihydrogen sulfite or dithionite or salts, in particular alkali metal salts such as sodium hydrogen sulfite, sodium sulfite or sodium dithionite, sulfur dioxide, or a transition metal or salt such as ferrous chloride, stannous chloride, acidic zinc , acidic copper or potassiurnhexacyanoferrate .
  • a hydrogen transfer reagent such as isopropanol or formic acid or salts
  • a sulfur containing compound such as hydrogen sulphide or salts
  • a dihydrogen sulfite or dithionite or salts in particular alkali metal salts such as sodium hydrogen sulfite, sodium sulfite or sodium dithionite, sulfur dioxide, or a transition metal or salt such as ferrous chloride,
  • a particularly preferred reducing agent is hydrogen sulfite salts such as alkali metal hydrogen sulfites like sodium hydrogen sulfite.
  • the reaction is preferably effected in the presence of a catalyst.
  • catalysts which may be used in this reaction include iodide salts, such as potassium iodide.
  • the compounds of formula (III) are produced using the improved method described above and reacted with a compound of formula (II) in-situ.
  • compounds of formula (I) are produced by mixing together a compound of formula (II) as defined above, a compound of formula (IV) as defined above, a compound of formula (V) as defined above and a reducing agent.
  • a compound of formula (II) as defined above a compound of formula (IV) as defined above
  • a compound of formula (V) as defined above a reducing agent.
  • methyl-2-(3-trifluoromethylphenyl)thionocarbazate can be produced when 3-trifluoromethylphenylhydrazine is added to a mixture of trichloromethansulfenylchloride, sodium hydrogen sulfite and sodium methoxide.

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

Abstract

A method of preparing a compound of formula (I) where R?1, R2, R3, R4 and R5¿ are independently selected from hydrogen or specified substitutents, X is -O-, -S-, -NR7-, -C=N-, -C=N-O-, -NR8-NR9-, where R?7, R8 and R9¿ are independently selected from hydrogen or alkyl; and R6 is an alkyl; which process comprises reacting a compound of formula (II) with a compound of formula (III) where R6 is as defined in relation to formula (I) and Y is a leaving group other than a group SRx where Rx is CH¿2?COOH or C1-4alkyl. Compounds of formula (III) are suitably prepared in situ by a method which forms a further aspect of the invention.

Description

PROCESS FOR THE PREPARATION OF THIONO COMPOUNDS
The present invention provides a process for preparing thiono- compounds, and in particular arylthionocarbazates, useful as intermediates in the production of many useful chemical compounds including agrochemicals and pharmaceuticals. US Patent No. 4,695,644 describes a process for preparing phenylchlorothionoformates in which trichloromethansulfenylchloride is reacted with sulphur dioxide in a biphasic aqueous organic solvent. The aqueous layer is separated and a phenol is added to the organic portion and subsequently a dehydrohalogenating agent. The production of inter alia alkoxythiocarbonylhydrazines are described by K.A.
Jensen et al, Acta Chem. Scand. 23 (1969) 6, 1916-1934. Various methods of preparing such compounds are described in this paper. Phenylhydrazine was said to react with an {[(alkylthio)-thiocarbonyljthio} acetic acid by displacing the thioacetic acid group to produce the alkoxythiocarbonylphenylhydrazine product. According to the present invention there is provided a method of preparing a compound of formula (I)
Figure imgf000003_0001
where Ri, R2, R3, R4 and R5 are independently selected from hydrogen, halogen, trihalomethyl, pentahaloethyl, mono- or difluoromethyl, mono-, di- tri- or tetrafluoroethyl, fluoroalkylthio, fluoroalkoxy, methylthio, methylsulphonyl, or halomethylsulphonyl, C1-2 alkyl or methoxy,
X is -O-,-S-, -NR7-, -C=N-, -C=N-O-, -NR8-NR9-, where R7, R8 and R9 are independently selected from hydrogen or alkyl; and R6 is an alkyl group; which process comprises reacting a compound of formula (II)
Figure imgf000004_0001
where R1, R , R3, R4 and R5 are as defined above in relation to formula (I); with a compound of formula (III)
Figure imgf000004_0002
where R6 is as defined in relation to formula (I) and Y is a leaving group other than a group SRX where Rx is CH2COOH or CMalkyl.
As used herein the term "halogen" refers to fluorine, chlorine, bromine and iodine. The term "alkyl" refers to straight or branched chains for example of from 1 to 18 carbon atoms in length, and suitably from 1 to 6 carbon atoms in length. The term "aryl" includes phenyl and naphthyl.
The reaction is suitably effected in the presence of an organic base, in particular a weak base such as pyridine, triethylamine or diisopropylethylamine, or an inorganic base such as Mn+(OH)n, Mn+(HCO3)n or (Mn+)2/n (CO3)2n/2 where M is a metal ion of valency n where n is especially 1 or 2, in particular an alkali or alkaline earth metal cation such as Na+ or K+ or Mg2+ or Ca2+.
Suitable leaving groups Y include halogens, -SR10 , -SM, SSM, -SC(S)OR10,
SSC(S)OR10, OR10' or OM where Rio is hydrogen or optionally substituted alkyl (provided that where Y is SRio, R10 is other than a group CH2COOH or C alkyl) and M is as defined above, as well as other such groups including mesylate, tosylate, 1,3-imidazole.
Suitable optional substitutents for alkyl groups R'O include nitro, =CRbRc, C(O)pRa, ORa, S(O)mRa, NRbRc, C(O)NRbRc, -NRbC(O).Ra, -NRaCONRbRc, where Ra, Rb and Rc are independently selected from hydrogen or hydrocarbyl, or Rb and Rc together form a substituted ring which optionally contains further heteroatoms such as S(O)m, oxygen and nitrogen, p is an integer of 1 or 2, m is 0 or an integer of 1-3.
Particularly suitable groups Y are halogens, -SM, SSM, -SC(S)OR10, SSC(S)OR10, OR10, or OM where R10 and M are as defined above.
Preferably however the leaving group Y is a halogen, and in particular chlorine. The reaction is suitably effected in water or an organic solvent or mixtures thereof at temperatures of for example between -78°C to 110°C, preferably at about 5°C. Examples of preferred organic solvents are halogenated solvents such as dichloromethane, aromatic solvents such as toluene and xylene, ether solvents such as t-butylmethylether and tetrahydrofuran, ester solvents such as isopropylacetate, n-butylacetate and iso-butylacetate, alcohols such as methanol.
Particular groups R1, R2, R3, R4 and R5 include hydrogen and halogen such as chlorine as well as trihalomethyl, in particular trifluoromethyl. Suitably at least three of Ri, R2, R3, R4 and R5 are hydrogen. Suitably where one or more substituents other than hydrogen are present, one of these groups is at the meta position (R2 or R4). which in particular is trifluoromethyl.
Preferably R6 is an alkyl group in particular a methyl, ethyl or propyl group and especially methyl. A particular group X is a group of formula -NR8-NR9-, in particular a hydrazine where R8 and R9 are hydrogen.
Compounds of formula (III) may be prepared by the known methods. For example, the reduction of trichloromethansulphenylchloride, followed by the isolation of thiophosgene and subsequent reaction with an alkoxide will yield a compound of formula (III) where Y is chlorine and R6 is methyl. The problem with this and similar processes is that it is necessary to isolate and deal with thiophosgene which is unstable.
The applicants have found an improved method for the production of compounds of formula (III) which does not require the isolation of thiophosgene.
In a further aspect, the invention provides a method of preparing a compound of formula (III) by reacting a compound of formula (IV) Y1
Figure imgf000006_0001
Y3
where Y1, Y2, Y3 and Y4 are each leaving groups such as halogen and particularly chlorine, provided that at least one of Y', Y2 or Y3 is a group Y of formula (III), with a compound of formula (V)
R6O-M1 (V)
where R6 and Mi is hydrogen or a group M as defined above; in the presence of a reducing agent.
Suitable reducing agents include hydrogen or a hydrogen transfer reagent such as isopropanol or formic acid or salts, a sulfur containing compound such as hydrogen sulphide or salts, a dihydrogen sulfite or dithionite or salts, in particular alkali metal salts such as sodium hydrogen sulfite, sodium sulfite or sodium dithionite, sulfur dioxide, or a transition metal or salt such as ferrous chloride, stannous chloride, acidic zinc , acidic copper or potassiurnhexacyanoferrate .
A particularly preferred reducing agent is hydrogen sulfite salts such as alkali metal hydrogen sulfites like sodium hydrogen sulfite.
Suitable leaving groups Y1, Y2, Y and Y are those described above in relation to Y in formula (III). Preferably however, Yi, Y2, Y and Y4 are the same and are all halogens such as chlorine.
The reaction is preferably effected in the presence of a catalyst. Examples of catalysts which may be used in this reaction include iodide salts, such as potassium iodide.
The reaction may be carried out in a solvent which may comprise water or mixtures of water and miscible solvents such as alcohols preferably methanol, or optionally with a second immiscible phase. Preferably the immiscible phase is an organic solvent. Examples of preferred organic solvents are halogenated solvents such as dichloromethane, aromatic solvents such as toluene and xylene, ether solvents such as t-butylmethylether and tetrahydrofuran, ester solvents such as isopropylacetate, n-butylacetate and iso-butylacetate. The reaction is suitably carried out at temperatures for example of from -20 to 150°C, conveniently at about 0°C.
In a preferred embodiment, the compounds of formula (III) are produced using the improved method described above and reacted with a compound of formula (II) in-situ. Thus in a particularly preferred embodiment, compounds of formula (I) are produced by mixing together a compound of formula (II) as defined above, a compound of formula (IV) as defined above, a compound of formula (V) as defined above and a reducing agent. For example, it has been found that methyl-2-(3-trifluoromethylphenyl)thionocarbazate can be produced when 3-trifluoromethylphenylhydrazine is added to a mixture of trichloromethansulfenylchloride, sodium hydrogen sulfite and sodium methoxide. The present invention provides a high yielding process for the formation of intermediates such as methyl-2-(3-trifluoromethylphenyl)thionocarbazate by reaction of mixtures of 3-trifluoromethylphenylhydrazine and methylchlorofhionoformate. The byproducts of this reaction are generally easy to handle and dispose of. For example in this particular example, the by-product is hydrogen chloride or an alkali metal chloride salt. The invention will now be particularly described by way of example. Example 1 Step l Preparation of methylchlorothiono formate Trichloromethansulfenylchloride (lg), dichloromethane (5ml), water (2ml), potassium iodide (13mg) and sodium hydrogen sulfite (1.3g) were stirred vigorously in a round-bottomed flask at 0°C.
Concentrated sulfuric acid (0.3g) was added dropwise and the resulting mixture was stirred at room temperature for ten hours. The phases were separated and the organic layer was dried over sodium sulfate before 1.06 ml of 25% (w/w) sodium methoxide in methanol was added. Step 2 Preparation of methyl-N.N'-S-trifluoromethylphenylthiocarbazate
A 3 neck round-bottom flask fitted with a thermometer and nitrogen inlet, was charged with 3-trifiuoromethylphenylhydrazine (1.6g) , pyridine (0.56ml) and dichloromethane (5ml). The flask was cooled to 5°C before the methylchlorothionoformate prepared in step 1 above was added dropwise whilst stirring. The reaction mixture was allowed to warm to room temperature. The reaction mixture was quenched into water (10ml), and the phases separated. The organic layer was washed with saturated sodium bicarbonate solution and then dried over sodium sulfate, before the solvent was removed under reduced pressure to afford a brown oil (1.9g).

Claims

1. A method of preparing a compound of formula (I)
Figure imgf000009_0001
where Ri, R2, R3, R4 and R5 are independently selected from hydrogen, halogen, trihalomethyl, pentahaloethyl, mono- or difluoromethyl, mono-, di- tri- or tetrafluoroethyl, fluoroalkylthio, fluoroalkoxy, methylthio, methylsulphonyl, or halomethylsulphonyl, Cj.2 alkyl or methoxy,
X is -O-,-S-, -NR7-, -C-N-, -C=N-O-, -NR8-NR9-, where R7, R8 and R9 are independently selected from hydrogen or alkyl; and R6 is an alkyl group; which process comprises reacting a compound of formula (II)
Figure imgf000009_0002
where R1, R2, R3, R4 and R5 are as defined above in relation to formula (I); with a compound of formula (III)
Figure imgf000010_0001
where R6 is as defined in relation to formula (I) and Y is a leaving group other than a group SRX where Rx is CH2COOH or C alkyl.
2. A method according to claim 1 wherein Y is a halogen.
3. A method of preparing a compound of formula (III) as defined in claim 1, which method comprises reacting a compound of formula (IV)
Y
Figure imgf000010_0002
where Y1, Y2,Y3 and Y4 are each leaving groups, provided that at least one group Yi, Y2 or Y is a group Y of formula (III); with a compound of formula (V) R6O-M1 (V) where R6 is as defined in claim 1 and Mi is hydrogen or a cation such as an alkali or alkaline earth metal cation such as Na+ or K+ or Mg + or Ca2+; in the presence of a reducing agent.
4. A method according to claim 1 wherein the compound of formula (I) is produced by mixing together a compound of formula (II) as defined in claim 1, a compound of formula (IV) as defined in claim 2, a compound of formula (V) as defined claim 2 and a reducing agent.
PCT/GB1999/002018 1998-07-22 1999-06-28 Process for the preparation of thiono compounds WO2000005202A1 (en)

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GBGB9816027.8A GB9816027D0 (en) 1998-07-22 1998-07-22 Novel process
GB9816027.8 1998-07-22

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2711421A (en) * 1954-02-02 1955-06-21 Ciba Pharm Prod Inc P-allyloxy-thiono-carbanilate esters
US3395234A (en) * 1959-09-29 1968-07-30 Gulf Oil Corp Thiocarbazate methods and compositions for controlling plasnt rust
US5350856A (en) * 1987-07-24 1994-09-27 Ici Americas Inc. 2-(substituted imino)-1,3,4-dihydrothiadiazoles

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2711421A (en) * 1954-02-02 1955-06-21 Ciba Pharm Prod Inc P-allyloxy-thiono-carbanilate esters
US3395234A (en) * 1959-09-29 1968-07-30 Gulf Oil Corp Thiocarbazate methods and compositions for controlling plasnt rust
US5350856A (en) * 1987-07-24 1994-09-27 Ici Americas Inc. 2-(substituted imino)-1,3,4-dihydrothiadiazoles

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
A.L. SCHROLL, ET AL.: "Novel symmetrical and mixed carbamoyl and amino polysulphanes by reactions of (alkoxydichloromethyl)polysulphanyl substrates with N-methylaniline", JOURNAL OF ORGANIC CHEMISTRY, vol. 51, no. 10, 16 May 1986 (1986-05-16), American Chemical Society, Washington, DC, US, pages 1866 - 1881, XP002117853, ISSN: 0022-3263 *
CHEMICAL ABSTRACTS, vol. 23, no. 12, 20 June 1929, Columbus, Ohio, US; P.C. GUHA, ET AL.: "Formation of heterocyclic compounds from ethylxanthioformate" page 2952; XP002117856 *
E.A. CASTRO, ET AL.: "Kinetics and mechanism of the pyridinolysis of alkyl aryl thionocarbonates", JOURNAL OF ORGANIC CHEMISTRY, vol. 62, no. 8, 18 April 1997 (1997-04-18), American Chemical Society, Washington, DC, US, pages 2512 - 2517, XP002117855, ISSN: 0022-3263 *
J.R. COX, ET AL.: "General formation of aryl dithiocarbonates and ethyl ethylxanthate in the Leuckart thiophenol synthesis", JOURNAL OF ORGANIC CHEMISTRY, vol. 25, no. 7, 8 July 1960 (1960-07-08), American Chemical Society, Washington, DC, US, pages 1083 - 1092, XP002117854, ISSN: 0022-3263 *
JOURNAL OF THE INDIAN CHEMICAL SOCIETY., vol. 6, 1929, The Indian Chemical Society, Calcutta, IN, pages 65 - 82, ISSN: 0019-4522 *
W. AUTENRIETH, ET AL.: "Über Versuche mit Thiophosgen", BERICHTE DER DEUTSCHEN CHEMISCHEN GESELLSCHAFT, vol. 58, no. 9, 14 October 1925 (1925-10-14), Verlag Chemie, Weinheim, DE, pages 2151 - 2156, XP002117886 *

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