GB2162521A - Tetra-aryl bisimidocarbonate sulphones and sulphoxides, and their cyclisation to thiatriazines - Google Patents

Tetra-aryl bisimidocarbonate sulphones and sulphoxides, and their cyclisation to thiatriazines Download PDF

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GB2162521A
GB2162521A GB08519241A GB8519241A GB2162521A GB 2162521 A GB2162521 A GB 2162521A GB 08519241 A GB08519241 A GB 08519241A GB 8519241 A GB8519241 A GB 8519241A GB 2162521 A GB2162521 A GB 2162521A
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compound
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Jeffrey Daniel Michael
Barry Clive Ross
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Sanofi Aventis UK Holdings Ltd
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Hoechst UK Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
    • C07D285/15—Six-membered rings
    • 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
    • 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
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
    • C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
    • C07D513/04—Ortho-condensed systems

Abstract

A process for the production of a herbicidal compound of formula <IMAGE> in which R represents an aryl group, unsubstituted or substituted by one or two substituents selected from methyl, trifluoromethyl, nitro and cyano groups, and chlorine, fluorine and bromine atoms; R<1> represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 7 carbon atoms, which alkyl or cycloalkyl groups is unsubstituted or substituted, or R<1> represents an alkenyl group having 2 to 6 carbon atoms or an alkynyl group having 3 to 6 carbon atoms; R<2> represents an aryloxyl group, unsubstituted or substituted as defined above for the group R; or R<2> represents an -NHR<3> group in which R<3> represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms that is unsubstituted or substituted; or R<2> represents a group NHR<3>a, and R<1> and R<3>a, together with the atoms to which they are attached, form a 5- or 6-membered ring containing two nitrogen atoms, and p represents the integer 1 or 2, comprises (a) reacting a compound of formula II <IMAGE> in which R and p are as defined above, with an amine of formula III R<1>-NH<2> III in which R<1> is as defined above and, if desired, (b) reacting a resulting compound of formula I in which R<2> represents an optionally substituted aryloxy group with an amine of formula IV R3-NH2 IV in which R<3> is as defined above, to give a compound of formula I in which R<2> represents group NHR<3>; or (c) reacting compound of formula II as defined above with a diamine of formula V H2N-Z-NH2 V in which Z represents an alkylene group having 2 or 3 carbon atoms, to give a compound of formula I in which R<2> represents a group NHR<3>a, and R<1> and R<3>a, together with the atoms to which they are attached, form a 5- or 6-membered ring containing two nitrogen atoms and, if desired or required, at any stage, (d) oxidising a compound in which p represents the integer 1 to give the corresponding compound in which p represents the integer 2. The compounds of formula I are useful in the manufacture of other 5-substituted 1,2,4,6- thiatriazines, in particular in which OR is replaced by A'-(CH2)n-X-(CH2)m-NHr where A' is phenyl or certain hetero ring groups, X is O or S, n is 0 or 1 and m is 2 or 3. Compounds of formula II are claimed per se.

Description

SPECIFICATION Chemical compound and process for its production The present invention relates to a process for the production of 4-substituted 1, 2, 4, 6thiatriazine derivatives which are useful, inter alia, in the production of compounds having histamine H2-antagonist activity, and also relates to certain of the 4-substituted 1, 2, 4, 6thiatriazine derivatives per se.
Our UK Patent Specification No. 2 129 426A describes and claims thiatriazine derivatives that have histamine H2-antagonist activity and that are useful in the treatment of gastric hyperacidity and gastric ulcers, and also describes and claims processes for the production of these compounds. These processes utilise certain 4-substituted 1, 2, 4, 6-thiatriazine 1, 1dioxides.
The present invention provides a process for the production of a compound of formula I
in which R represents an aryl group, which may be unsubstituted or substituted by one or two substituents, which may be the same or different, selected from methyl, trifluoromethyl, nitro and cyano groups, and chlorine, fluorine and bromine atoms; R' represents a hydrogen atom, a striaght or branched chain alkyl group having from 1 to 6 carbon atoms or a cycloalkyl group having from 3 to 7 carbon atoms, which alkyl or cycloalkyl group is unsubstituted or is substituted by one or more substituents, which may be the same or different, for example, by one or two substitutents, especially by one substituent, selected from halogen atoms; nitro and cyano group; -OR4 groups in which R4 represents a hydrogen atom or an alkyl group having from 1 to 4 carbon atoms; cycloalkyl groups having from 3 to 7 carbon atoms; NR5R6 groups in which R5 and R6, which may be the same or different, each represents a hydrogen atom or an alkyl group having from 1 to 4 carbon atoms; -COOR7 groups in which R7 represents a hydrogen atom or a carboxylic acid esterifying group; -CONR5R6 groups in which R5 and R6 are as defined above; -SO2NR5R6 groups in which R5 and R6 are as defined above; aromatic and non-aromatic heterocyclic groups having from 5 to 8 ring members and 1 or 2 heteroatoms, which may be the same or different, selected from oxygen, nitrogen and sulphur atoms and optionally having an alkyl group having from 1 to 4 carbon atoms as a substituent on a ring nitrogen atom; and phenyl groups R8 that are unsubstituted or substituted by one or more substituents, which may be the same or different, selected from halogen atoms, trifluoromethyl groups, nitro and cyano groups, alkyl and alkoxy groups having from 1 to 4 carbon atoms, and NR5R6 groups in which R5 and R6 are as defined above; or R1 represents a straight or branched chain alkenyl group having from 2 to 6 carbon atoms or a straight or branched chain alkynyl group having from 3 to 6 carbon atoms; R2 represents an aryloxy group which is unsubstituted or is substituted as defined above for the aryl group R; or R2 represents an -NHR3 group in which R3 represents a hydrogen atom, a straight or branched chain alkyl group having from 1 to 6 carbon atoms that is unsubstituted or is substituted as defined above for an alkyl group R', or an aromatic or non-aromatic heterocyclic group as defined above; or R2 represents a group NHR3,, and R' and R3a, together with the atoms to which they are attached, form a 5- or 6-membered ring containing two nitrogen atoms, and p represents the integer 1 or 2, which comprises (a) reacting a compound of formula
in which R and p are as defined above, with an amine of formula III R1-NH2 Ill in which R1 is as defined above to give a compound of formula la
in which R, p and R' are as defined above, that is to say, a compound of formula I in which R2 represents an optionally substituted aryloxy group and, if desired, (b) reacting the resulting compound of formula la with an amine of formula IV R3-NH2 IV in which R3 is as defined above, to give a compound of formula Ib
in which R, p, R' and R3 are as defined above, that is to say, a compound of formula I in which R2 represents a group -NHR3; or (c) reacting a compound of formula II as defined above with a diamine of formula V H2N-Z-NH2 V in which Z represents an alkylene group having 2 or 3 carbon atoms to give a compound of formula Ic
in which R, p and Z are as defined above, that is to say, a compound of formula I in which R2 represents a group NHR3a, and R' and R3a, together with the atoms to which they are attached, form a 5- or 6-membered ring containing two nitrogen atoms; and, if desired or required, at any stage, (d) oxidising a compound in which p represents the integer 1 to give the corresponding compound in which p represents the integer 2.
The term "aryl" is used herein to denote a radical derived from benzene or from a polynuclear arene, for example, derived from diphenylmethane or naphthalene (see Roberts and Caserio, Basic Principles of Organic Chemistry, W.A. Benjamin, Inc., New York, 1964). An aryl group is preferably a phenyl group. Carboxylic acid esterifying groups are well known, that is to say, in actual use in the art or described in the literature of the art.
In a compound of formula I, an aromatic or non-aromatic heterocyclic group is, for example, a furyl, tetrahydrofuryl, thienyl, pyridyl, dihydropyranyl, pyrrolidinyl, N-alkyl-pyrrolidinyl or piperidyl group, especially a furyl or pyridyl group. An alkyl substituent on a ring nitrogen atom is especially a methyl group.
The oxidation of a sulphoxide of formula I to the corresponding sulphone may be carried out by means of an oxidising agent, for example, a peracid, for example, peracetic acid or m chloroperbenzoic acid; hydrogen peroxide; an alkylhydroperoxide, for example, t-butyl hydroperoxide; a permanganate, for example, potassium permanganate; or a perborate, for example, sodium perborate. The oxidation is carried out in a suitable solvent or diluent. A sulphoxide of formula la may be oxidised before reaction with the amine of formula Ill, or after formation of a compound of formula Ib.
Compound II is preferably reacted with the amine of formula Ill in a solvent or diluent, for example, an aprotic solvent or diluent that does not react with the amine Ill, for example, acetonitrile, dichloromethane, dioxane or tetrahydrofuran. Generally the reaction is carried out at a temperature within the range of from 0 to 1 00 C, preferably from 20 to 80"C, depending on the nature of any substituent(s) on the phenyl rings. Generally one mole of the amine is used per mole of compound II.
The reaction of a compound of formula II with a diamine of formula V, for example, with 1,2diaminoethane or 1,3-diaminopropane is generally carried out under the reaction conditions described above for the reaction of compounds II and III, and the reaction of compounds la and IV is also generally carried out under those conditions.
A compound of formula II in which p represents the integer 1 may be produced by reacting a compound of formula VI
in which R is as defined above, with thionyl chloride in the presence of an organic base, for example, a trialkylamine, for example, trimethylamine, triethylamine, or diethylisopropylamine.
The reaction is generally carried out in a solvent or diluent, for example, an aprotic solvent, for example, acetonitrile, chloroform, dichloromethane, diethyl ether or tetrahydrofuran. The reaction temperature is generally within the range of from - 50 to + 30"C. A resulting compound of formula il in which p represents the integer 1 may be oxidised to give the corresponding compound of formula II in which p represents the integer 2 using reagents and reaction conditions as described above.
Many of the compounds of formula VI are unstable, giving triazines on standing, and must be prepared and then reacted immediately with thionyl chloride at low temperatues, for example, from - 50 to - 20"C to prevent such a side reaction. A simple method for preparing diphenyl imidocarbonates of formula VI and observations on their instability are give by NEF in Annalen 287,310 (1895).
Particularly useful compounds of formula VI are those in which the aryl groups R are phenyl groups and are each substituted by a methyl, trifluoromethyl, cyano or nitro group, or by a halogen atom, for example, a chlorine, bromine or fluorine atom, especially by a 2-nitro or 4methyl group. When such a substituent is present, the reaction of a resulting compound of formula II (optionally after oxidation), with an amine of formula Ill or a diamine of formula V may be carried out at a lower temperature than is possible with the corresponding unsubstituted compound 11. A subsequent reaction of a resulting compound la with an amine of formula IV is also facilitated by the presence of a halogen, trifluromethyl, cyano or nitro (especially 2-nitro) substituent on the phenyl ring R.The presence of a halogen, trifuloromethyl, nitro or cyano substitutent, especially a 2-nitro substitutent, is particularly advantageous when a compound of formula II or la is to be reacted with a sterically hindered amine, for example, isopropylamine or t-butylamine.
Accordingly, preferred compounds of formulae II are those in which each radical R represents a halogenophenyl, trifluoromethylphenyl, cyanophenyl, methylphenyl or nitrophenyl group, and especially those in which each radical R represents a 2-nitrophenyl or 4-methylphenyl group.
The process of the present invention is suitable for large-scale manufacturing use. The starting materials and reagents are readily available and inexpensive and, in general, the intermediate tetraphenyl-bis-imidocarbonate sulphoxides and sulphones of formula II are stable, highly crystalline compounds and as such are easily isolated from reaction mixtures without the need for chromatography.
Moreover, as described above, the reactivity of the displaceable phenoxy groups RO-can be controlled by careful selection of the phenyl ring substituents, thus increasing the versatility of the process of the invention to include the use of sterically hindered amines and diamines in the production of a compound of formula I.
In a resulting compound of formula I as in the intermediates described above, the reactivity of the displaceable phenoxy group RO- can be controlled by the selection and positioning of substituents on the phenyl ring. If two substituents are present on a phenyl ring, these are preferably in the 2- and 4-positions. Generally, it is preferable to have only one substituent. As mentioned above, a nitro group is preferably in the 2-position, and a methyl substituent is preferably in the 4-position. A particularly useful compound of formula I is 3,5-bis-(4 methylphenoxy)-4-methyl- 1 ,2,4, 6-thiatriazine 1 ,1-dioxide.
A compound of formula I produced by the process of the present invention may be used to produce a compound of formula VII
in which A represents a phenyl, imidazolyl, thiazolyl, furyl, thienyl, or pyridyl radical, which radical may have one or two substitutents, selected from (C,-C4) alkyl, guanidino, and -CH2NR9R' groups, R9 and R'O, which may be the same or different, each representing a hydrogen atom or a (C,-C6) alkyl group, or together with the nitrogen atom to which they are attached, may form a pyrrolidine, piperidine, morpholine, or N-methylpiperazine ring; X represents -O- or -S-; n represents 0 or 1; m represents 2 or 3; and R' and R2 are as defined above, by a process which comprises (a) reacting a compound of formula I as defined above with a compound of formula VIII A(CH2)nX(CH2)rnNH2 (VIII) in which A, X, m and n are as defined above and, if desired, when R2 in a resulting compound VII represents an aryloxy group, reacting that compound VII with an amine of formula IV H2NR3 (IV) in which R3 is as defined above to obtain a compound of formula VII in which R2 represents an -NHR3 group, or (b) reacting a compound of formula I obtained in accordance with the present invention with a compound of formula IX HX-(CH2),,-NH2 (IX) in which X and m are as defined above and reacting the resulting compound of formula X
with a compound of formula Xl A(CH2)nL (Xl) in which A is as defined above and L represents a leaving group, for example, a halogen atom, a hydroxy group, an alkoxy group or a sulphonate ester, and (c) if required, at any stage oxidising a compound in which p represents 1.
The present invention includes such use of a compound of formula I.
Further details of this process and of compounds that may be prepared by this process are given in our UK Specification No. 2 129 426A.
Other substituted thiatriazines analogous to compound VII but having different side chains attached to the 5-position of the thiatriazine ring may be prepared analogously to compound VII.
An example of such a compound is as defined above for compound VII but having as radical A a thiazolyl radical that is substituted by a guanidino group that is itself substituted by one or more alkyl groups, wherein the or each alkyl group may itself be substitued, for example, by a trifluoromethyl group or by a halogen atom.
In particular, the present invention provides the use of a compound of formula I (when produced by the process of the present invention) in the manufacture of a compound of formula XII
that is to say, 3-N-[2-f(2-guanidino-4-thiazolyl)methylthio]ethyl]amino-4-methyl-5-amino-1, 2, 4, 6-thiatriazine 1, 1-dioxide.
The compound of formula XII may be produced by a process which comprises (i) reacting a compound of formula XIII obtained by the process of the present invention
in which compound R is defined as above, with a compound of formula XIV
or (ii) reacting a compound of formula XV obtained by the process of the present invention
with the compound of formula XIV, and reacting the resulting compound of formula XVI
with ammonia, or (iii) reacting a compound of formula I in which p represents 2, obtained by the process of the present invention, with an amino thiol of formula XVII HS-(CH2)2-NH2 (XVII) and reacting the resulting compound of formula XVIII
with a compound of formula XIX
in which L represents a leaving group, for example, a halogen atom, a hydroxy group, an alkoxy group or a sulphonate ester.
Compounds XIII and XIV are generally reacted in a solvent or diluent, preferably an alcohol, dimethylformamide or dimethyl sulphoxide, at a temperature within the range of from 0 to 100to, preferably from 0 to 60"C. The compound of formula XIV should be reacted in the form of the free base, as shown. If it is initially present in the form of an acid addition salt, for example, as the hydrochloride or hydrobromide, this should be converted into the free base during or, preferably, before reaction with compound XIII. Conversion to the free base is carried out using a base, for example, triethylamine, sodium hydroxide or potassium hydroxide.
Compound XV is reacted with compound XIV under conditions similar to those described above for the reaction of compounds XIII and XIV, except that generally lower temperatures are preferred in order that the groups RO- may be displaced selectively.
The reaction of the resulting compound XVI with ammonia is generally carried out in an alcoholic solvent at a temperature from 0 to 60"C.
In all cases, the group RO- in the thiatriazine starting material used for the production of compounds VII, XII and analogous compounds is preferably one of the substituted phenyl groups described above, in particular a 2-nitrophenyl group or a 4-methylphenyl group.
A number of compounds of formula XI are known, see for example, UK Specification 2 001 624A; US Patent 3 950 333; US Patent 4 128 658; and Belgian Patents 867 106 and 875 846. Others may be prepared analogously. The preparation of compound XIV is described in UK Specification 2 001 624A.
Compounds of formula I as defined above find application as herbicides, and the present invention provides the use of a compound of formula I as defined above as a herbicidal agent.
The invention also provides a method of treating plants, especially crops, for example, monocotyledenous plants, which comprises applying to the plants a compound of formula I as defined above, for example, in the form of a dispersion or a solution. The invention further provides a herbicidal composition comprising an aqueous suspension of a compound of formula I, or comprising a compound of formula I in admixture with a solid carrier.
Compounds of formulae Ic and II are also part of the present invention.
The present invention also provides compounds of formula I as defined above with the exception of those compounds in which (i) R represents a methyl-substituted phenyl group, R' represents a methyl or ethyl group, and R2 represents an amino group, and those in which (ii) R and R2 both represent methylphenoxy groups and R1 represents a methyl group. The present invention provides, for example, those compounds of formula I in which R2 represents a group NHR3 in which R3 represents an aromatic or non-aromatic heterocyclic group having from 5 to 8 ring members and 1 or 2 heteroatoms, which may be the same or different, selected from oxygen, sulphur and nitrogen atoms, the latter optionally having an alkyl group having from 1 to 4 carbon atoms as a substituent, for example, as described further above.
The following Examples illustrate the invention, but are not limiting.
EXAMPLE 1 Tetra (2-nitrophenyl)-bisimidocarbonate sulphoxide 24.2 g of di(2-nitrophenyl) imidocarbonate was dissolved in 200 ml of dichloromethane containing 8.8 g of triethylamine, and the solution cooled to 5"C in an ice bath. 4.76 g of thionyl chloride was dissolved in 50 ml of dichloromethane and added dropwise to the stirred imidocarbonate solution over a period of 30 minutes. Ice cooling was discontinued and the reaction solution stirred an additional 60 minutes before washing 3 times with water, drying over magnesium sulphate, and evaporating in vacuo to obtain the title compound as a crystalline solid. Recrystallisation from dichloromethane/toluene gave 20.2 g of the title compound, m.p. 179-180"C.
C26H,6N6SO,3 requires: C 47.85, H 2.47, N 12.88 found: C 47.87, H 2.56, N 12.80 EXAMPLE 2 Tetra (2-nitrophenyl)-bisimidocarbonate sulphonate 1 9.6 g of tetra (2-nitrophenyl)-bisimidocarbonate sulphoxide was dissolved in 1 50 ml of dichloromethane and cooled to 5"C with an ice bath. 8 9 of meta-chloroperoxybenzoic acid dissolved in 100 ml of dichloromethane was added dropwise to the stirred sulphoxide solution. When addition was complete, the reaction mixture was stirred for 60 minutes before filtering off the crystalline product, which was then washed thoroughly with ether and dried to give 16.1 9 of the title compound, m.p. 200-203"C.
A second crop of 2.9 g of the title compound was obtained by washing the dichloromethane mother liquors with an aqueous sodium bicarbonate solution, drying over magnesium sulphate, and evaporating in vacuo. A sample recrystallised from chloroform/ether melted sharply at 203"C.
C26H,6N6SO14 requires: C 46.71, H 2.41, N 12.57 found: C 46.63, H 2.50, N 12.59 EXAMPLE 3 Tetra (4-methylphenyl)-bisimidocarbonate sulphoxide 43.2 g of p-cresol and 1 8 g of sodium hydroxide were dissolved in 800 ml of water and cooled to 5"C in an ice bath. The mixture was stirred well, and 21.2 9 of cyanogen bromide was added portionwise over a period of about 30 minutes. Ice cooling was then discontinued, and the reaction mixture was stirred for a further 60 minutes before filtering off the imidocarbonate, which was then washed thoroughly with water. The moist product was then dissolved in 300 ml of dichloromethane and dried over magnesium sulphate for one hour at 20"C.The filtered dichloromethane solution was then cooled to - 40"C and 1 3.6 9 of triethylamine added. 7.32 g of thionyl chloride was then added to the stirred dichloromethane solution at a rate sufficient to maintain the reaction at - 40"C with continued cooling. When the addition was complete, the solution was allowed to come to ambient temperature and was washed three times with water, dried over magnesium sulphate, and evaporated in vacuo. 21 g of the title compound was crystallised from ether, m.p. 130-145"C. A sample recrystallised from ether had a melting point fo 1 35 to 143"C with decomposition.
C30H28N2SO5 requires: C 68.16, H 5.34, N 5.30 found: C 68.10, H 5.38, N 5.26 EXAMPLE 4 Tetra (4-methylphenyl)-bisimidocarbonate sulphonate 21 9 of tetra (4-methylphenyl)-bisimidocarbonate sulphoxide was dissolved in 100 ml of dichloromethane and cooled to 5"C with an ice bath. 8 g of meta-chloroperoxybenzoic acid dissolved in 100 ml of dichloromethane was added dropwise to the stirred sulphoxide solution.
When the addition was complete, the reaction mixture was stirred for a further 60 minutes and then washed twice with a 5% aqueous sodium bicarbonate solution, dried over magnesium sulphate, and evaporated in vacuo. The residual crystalline solid was recrystallised from dichloromethane/ether to give 1 9.9 g of the title compound, m.p. 188-190"C. A recrystallised sample melted at 193-194"C.
C30H28N2SO6 requires: C 66.16, H 5.18, N 5.14 found: C 66.07, H 5.22, N 5.12 EXAMPLE 5 4-Methyl-3, 5-di(4-methylphenoxy)-1, 2, 4, 6-thiatriazine 1, l-dioxide 1.0889 of tetra (4-methylphenyl)-bisimidocarbonate sulphone was suspended in 30 ml of acetonitrile. This solution was stirred well, and to it was added, at 20"C, 62 mg of methylamine. The clear solution which formed immediately after the addition of the amine was heated to reflux for 1 6 hours, then evaporated in vacuo to yield the title compound as a crystalline solid, which was recrystallised from acetonitrile/ether to give 592 mg of the title compound, m.p. 282-286"C. Further recrystallisation gave a sample having a melting point of 290-291 C.
H n.m.r. (250MHz) DMSO-d6 8: 2.34 (6H, s), 3.35 (3H, s), 7.25 (8H, ABq).
EXAMPLE 6 4-Ethyl-3, 5-di(4-methylphenoxy)-i, 2, 4, 6-thiatriazine 1, i-dioxide By a procedure analogous to that described in Example 5, but using ethylamine instead of methylamine, 430 9 of the title compound was obtained, m.p. 302-304"C after recrystallisation from ethanol.
'H n.m.r. (250MHz) DMSO-d6 6: 1.45 (3H, t), 2.34 (6H, s), 4.22 (2H, q), 7.27 (8H, ABq).
EXAMPLE 7 4-Propargyl-3, 5-di(4-methylphenoxy)- 1, 2, 4, 6-thiatriazine 1, l-dioxide By a procedure analogous to that described in Example 5, but using propargylamine instead of methylamine, 495 g of the title compound was obtained, m.p. 279-280"C after recrystallisation from ethanol.
1H n.m.r. (250MHz) DMSO-d6 8: 2.35 (6H, s), 3.31 (1H, s), 5.05 (2H, d), 7.27 (8H, ABq).
EXAMPLE 8 4-lsopropyl-3. 5-di(2-nitrophenoxy)- 1, 2, 4, 6-thiatriazine 1, 1-dioxide 2.68 g of tetra (2-nitrophenyl)-bisimidocarbonate sulphone was suspended in 100 ml of acetonitrile, and 236 mg of isopropylamine added dropwise to the stirred suspension at 20"C.
The resulting clear orange solution was stirred for one hour at 20"C and then concentrated to a volume of 20 ml in vacuo. The crystalline product was filtered off and recrystallised from acetonitrile to give 890 mg of the title compound, m.p. 259-263"C with decomposition.
H n.m.r. (250MHz) DMSO-d6 8: 1.67, (6H, d), 5.37 (1H, m), 7,67-8.34 (8H, m).
EXAMPLE 9 4-Isopropyl-3-methylamino-5-(2-nitrophenoxy) 1, 2, 4, 6-thiatriazine 1, 1-dioxide 450 mg of 4-isopropyl-3, 5-di(4-nitrophenoxy)-1, 2, 4, 6-thiatriazine 1,1-dioxide was suspended in 20 ml of acentonitrile and 32 mg of methylamine was added to the stirred solution at 20"C. The reaction mixture was stirred at 20"C for 1 6 hours and the solvent evaporated in vacuo to yield a crystalline residue, which was chromatographed on silica gel using chloroform/acetonitrile as eluant. 1 62 mg of the title compound was obtained after recrystallisation from ethanol, m.p. 242"C.
1H n.m.r. (250MHz) DMSO-d6 8: 1.54 (6H, d), 2,80 (3H, s), 4.61 (1H, m), 7.62-8.28 (4H, m), 8.06 (1 H, br.s).
EXAMPLE 10 7-(2-Nitrophenoxyl-imidazolidinyll,2-c 2, 2, 4, 6]-thiatriazine 5, 5-dioxide 1.43 g of tetra (2-nitrophenoxy)-bisimidocarbonate sulphone was suspended in 25 ml of acetonitrile and 120 mg of 1 ,2-diaminoethane added to the stirred suspension at 20"C. After stirring at this temperature for 1 6 hours, the resulting fine crystalline solid was collected by filtration, washed thoroughly with ether, and dried in vacuo to give 506 mg of the title compound, m.p. 325"C with decomposition.
1H n.m.r. (250MHz) DMSO-d6 8: 3.67 (2H, m) 4.24 (2H, m), 7.63-8.28 (4H, m), 8.98 (1 H, br.s).

Claims (24)

1. A process for the production of a compound of formula I
in which R represents an aryl group, which may be unsubstituted or substituted by one or two substituents, which may be the same or different, selected from methyl, trifluoromethyl, nitro and cyano groups, and chlorine, fluorine and bromine atoms; Ri represents a hydrogen atom, a straight or branched chain alkyl group having from 1 to 6 carbon atoms or a cycloalkyl group having from 3 to 7 carbon atoms, which alkyl or cycloalkyl group is unsubstituted or is substituted by one or more substituents, which may be the same or different, selected from halogen atoms; nitro and cyano groups; -OR4 groups in which R4 represents a hydrogen atom or an alkyl group having from 1 to 4 carbon atoms; cycloalkyl groups having from 3 to 7 carbon atoms;NR5R6 groups in which R5 and R6, which may be the same or different, each represents a hydrogen atom or an alkyl group having from 1 to 4 carbon atoms; -COOR? groups in which R7 represents a hydrogen atom or carboxylic acid esterifying group; -cONRsR6 groups in which R5 and R6 are as defined above; -SO2NRsR6 groups in which R5 and R6 are as defined above; aromatic and non-aromatic heterocyclic groups having from 5 to 8 ring members and 1 or 2 heteroatoms, which may be the same or different, selected from oxygen, nitrogen and sulphur atoms and optionally having an alkyl group having from 1 to 4 carbon atoms as a substituent on a ring nitrogen atom; and phenyl groups R8 that are unsubstituted or substituted by one or more substituents, which may be the same or different, selected from halogen-atoms, trifluoromethyl groups, nitro and cyano groups, alkyl and alkoxy groups having from 1 to 4 carbon atoms, and NR5R6 groups in which R5 and R6 are as defined above; or R7 represents a straight or branched chain alkenyl group having from 2 to 6 carbon atoms or a straight or branched chain alkynyl group having from 3 to 6 carbon atoms; R2 represents an aryloxy group which is unsubstituted or is substituted as defined above for the aryl group R; or R2 represents an -NHR3 group in which R3 represents a hydrogen atom, a straight or branched chain alkyl group having from 1 to 6 carbon atoms that is unsubstituted or is substituted as defined above for an alkyl group Ri, or an aromatic or non-aromatic heterocyclic group as defined above; or R2 represents a group NHR3, and R1 and R3a, together with the atoms to which they are attached, form a 5- or 6-membered ring containing two nitrogen atoms, and p represents the integer 1 or 2, which comprises (a) reacting a compound of formula II
in which R and p are as defined above, with an amine of formula Ill Ra-NH2 Ill in which R1 is as defined above to give a compound of formula la
in which R and Ri are as defined above and, if desired, (b) reacting the resulting compound of formula I in which R2 represents an optionally substituted aryloxy group with an amine of formula IV R3-NH2 IV in which R3 is as defined above, to give a compound of formula Ib
in which R, Ri and R3 are as defined above; or (c) reacting a compound of formula II as defined above with a diamine of formula V H2N-Z-NH2 V in which Z represents an alkylene group having 2 or 3 carbon atoms to give a compound of formula Ic
in which R, p and Z are as defined above; and, if desired or required, at any stage, (d) oxidising a compound in which p represents the integer 1 to give the corresponding compound in which p represents the integer 2.
2. A process as claimed in claim 1, wherein a compound of formula II in which p represents the integer 2 is produced by oxidising the corresponding compound of formula II in which p represents the integer 1.
3. A process as claimed in claim 1 or claim 2, wherein a compound of formula II in which p represents the integer 1 is produced by reacting a compound of formula VI
in which R is as defined in claim 1, with thionyl chloride in the presence of an organic base.
4. A process as claimed in claim 3, wherein the base is a trialkylamine.
5. A process as claimed in any one of claims 1 to 4, wherein an aryl ring R in formula II is substituted by a methyl, trifluoromethyl, cyano or nitro group or by a halogen atom, and an aryl group R in formula la is substituted by a trifluoromethyl, cyano or nitro group or by a halogen atom.
6. A process as claimed in claim 5, wherein an aryl ring R in formula I is a phenyl group substituted by a 4-methyl or 2-nitro group.
7. A process as claimed in claim 1, carried out substantially as described in any one of Examples 5 to 1 0.
8. A process as claimed in claim 2, carried out substantially as described in Example 2 or Example 4.
9. A process as claimed in claim 3, carried out substantially as described in Example 1 or Example 3.
10. A compound of formula I as defined in claim 1, whenever produced by a process as claimed in any one of claims 1 to 9.
11. 3,5-Bis-(4-methylphenoxy)-4-methyl-1, 2, 4, 6-thiatriazine-1, 1-dioxide, whenever produced by a process as claimed in any one of claims 1 to 3.
12. 3,5-Bis-(4-methylphenoxy)-4-methyl-1, 2, 4, 6-thiatriazine-1, 1-dioxide, whenever produced by a process substantially as described in Example 5 herein.
1 3. A process as claimed in claim 12, wherein the tetra (4-methylphenyl)-bisimidocarbonate sulphone used as starting material is prepared as described in Examples 3 and 4 herein.
1 4. A herbicidal composition which comprises an aqueous suspension of a compound of formula I as defined in claim 1 , or which comprises a compound of formula I as defined in claim 1 in admixture with a solid carrier.
1 5. A compound of formula I as defined in claim 1 for use as a herbicidal agent.
1 6. A method of treating plants which comprises applying to plants a compound of formula I as defined in formula I.
1 7. A method as claimed in claim 16, wherein the compound of formula I is in the form of a dispersion or a solution.
1 8. A compound as claimed in claim 8, for use in the production of a 5-substituted 1, 2, 4, 6-thiatriazine.
19. A process for the production of a compound of formula Vlla
in which A1 represents a phenyl, imidazolyl, thiazolyl, furyl, thienyl, or pyridyl radical, which radical may have one or two substitutents, selected from (C1-C4)alkyl, guanidino, and -CH2NR4R5 groups, R4 and R5, which may be the same or different, each representing a hydrogen atom or a (C1 -C8) alkyl group, or together with the nitrogen atom to which they are attached, may form a pyrrolidine, piperidine, morpholine, or N-methylpiperazine ring; or A1 represents a thiazolyl radical that is substituted by a guanidino group that is itself substituted by one or more alkyl groups, and wherein the or each alkyl group may itself be substituted; X represents -O- or -S-; n represents 0 or 1; m represents 2 or 3; and R1 and R2 are as defined in claim 1, which comprises (a) producing a compound of formula I by a process as claimed in claim 1 and reacting the resulting compound of formula I with a compound of formula VIII AI-(CH,),-X-(CH,),-NH, (VII I) in which A1, X, m and n are as defined above and, if desired, when R2 in a resulting compound VII represents an aryloxy group, reacting that compound VII with an amine of formula IV H2NR3 (IV) in which R3 is as defined in claim 1 to obtain a compound of formula VII in which R2 represents an -NHR3 group, or (b) producing a compound of formula I by a process as claimed in claim 1 and reacting the resulting compound of formula I with a compound of formula IX HX~(CH2)mNH2 (IX) in which X and m are as defined above and reacting the resulting compound of formula X
with a compound of formula XI AI-(CH,),-L (Xl) in which A1 is as defined above and L represents a leaving group and, if desired or required, at any stage, (c) oxidising a compound in which p represents 1 to the corresponding compound in which p represents 2.
20. A process as claimed in claim 19, wherein a substituted guanidino group has one or more alkyl groups as substituent(s), and the or each alkyl group is itself substituted by a trfiluoromethyl group or by a halogen atom.
21. A process for the production of a compound of formula XII
(i) which comprises reacting a compound of formula II as defined in claim 1 and in which p represents 2, with methylamine and reacting the resulting compound with ammonia to give a compound of formula XIII
in which R is as defined in claim 1, reacting the compound of formula XV with the compound of formula XIV, and reacting the resulting compound of formula XVI
or (ii) reacting a compound of formula II as defined in claim 1 and in which p represents 2, with methylamine to give a compound of formula XV
in which R is as defined in claim 1, reacting the compound of formula XV with the compound of formula XIV, and reacting the resulting compound of formula XVI
with ammonia, or (iii) reacting a compound of formula II as defined in claim 1 and in which p represents 2, with methylamine and reacting the resulting compound with ammonia, to obtain a compound of formula XIII
in which R is as defined in claim 1, reacting the compound of formula XIII with an amino thiol of formula XVII HS-(CH2-NH2 (XVII) and reacting the resulting compound of formula XVIII
with a compound of formula XIX
in which L represents a leaving group.
22. A compound of formula II
in which R and p are as defined in claim 1.
23. A compound of formula Ic
in which R, Z and p are as defined in claim 1.
24. A compound of formula Id
in which R, Rl and p are as defined in claim 1 and R3b represents an aromatic or non-aromatic heterocyclic group having from 5 to 8 ring members and 1 or 2 heteroatoms, which may be the same or different, selected from oxygen, sulphur and nitrogen atoms, the latter optionally having an alkyl group having from 1 to 4 carbon atoms as a substituent.
GB08519241A 1984-07-31 1985-07-31 Tetra-aryl bisimidocarbonate sulphones and sulphoxides, and their cyclisation to thiatriazines Withdrawn GB2162521A (en)

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