HERBICIDAL 1, 2, 4, 6-THIATRIAZINES

The present invention relates to novel, herbicidally active thiatriazine derivatives, processes for their preparation, compositions comprising these compounds, and their use for controlling weeds, in particular in crops of useful plants, for example cereals, maize, rice, cotton, soya, oilseed rape, sorghum, sugar cane, sugar beet, sunflower, vegetables and fodder plants, or for inhibiting plant growth.

Thiatriazine compounds are described, for example, in Z. Chem. 15(5), 193-194 (1975), ibid. 15(2), 57-58 (1975), Chem. Ber. 121 , 383-386 (1988), Z. Naturforsch. 43, 763-768 (1988), Chem. Ber. 126, 2601-2607 (1993), J. Am. Chem. Soc. 111 , 1180-1185 (1989), DD- A-113 006 and in the inaugural dissertation by W. Jϋrgler, Philipps-University arburg/Lahn, 1988 ("1λ ⁴ - and 1 λ ⁶ -2,4,6-thiatriazines from sulfodiimides").

Novel and simple synthesis methods for preparing novel diversely substituted thiatriazine derivatives have now been found. In addition to the easy accessibility of diversely substituted thiatriazine derivatives, the low number of synthesis stages is another advantage of the synthesis methods.

Herbicidal and growth-inhibiting properties have been found for these thiatriazine derivatives.

The present invention thus relates to compounds of the formula I

in which

RT is a group -OR ₇ , -NRgoR.i or an N-heterocyclic radical, onto which 1 or 2 further carbocyclic, heterocyclic or aromatic rings can be fused and which contains or does not contain further heteroatoms;

R ₇ is d-Ciβalkyl, d-Ciealkyl substituted by halogen, NO ₂ , CN, Cι-C ₅ alkoxy, C,-C ₅ alkylthio, C ₃ -C ₈ cycloalkoxy, C ₃ -C ₈ cycloalkylthio, Cι-C ₃ trialkylsilyl ₍ C ₃ -Cιoalkenyloxy, C ₃ -C ₅ alkynyloxy,

Cι-C ₅ alkylcarbonyloxy, C,-C ₃ alkoxycarbonyl, d-C ₃ alkylcarbonyl, C ₅ -Cτcycloalkenyl or C ₅ - dcycloalkenyl substituted by d-C alkyl, or

R ₇ is d-d ₆ alkyl substituted by C ₃ -C _θ cycloalkyl, C ₆ -C ₁₂ bicycloalkyl, C ₆ -Cι ₂ chlorobicycloalkyl, C ₆ -Cι ₂ bicycloalkenyl or adamantyl, or

R ₇ CrC ₁₆ alkyl substituted by substituted or unsubstituted aryl, aryloxy, arylmethyleneoxy, arylcarbonyl, arylcarbonyloxy or a heterocyclic ring, or

R ₇ is C ₃ -Cι ₅ alkenyl, C ₃ -d ₅ alkenyl substituted by halogen, d-C ₃ alkoxy, C ₃ -C ₈ cycloalkyl, Cι-C ₃ trialkylsilyl or substituted or unsubstituted aryl or aryloxy, or

R ₇ is C ₃ -C ₅ alkynyl, C ₃ -d ₂ cycloalkyl, C ₃ -C ₁₂ cycloalkyl substituted by halogen, CN, d-Cstrialkylsilyl, =O, C C ₆ alkyl, cyano-d-C ₅ alkyl, d-Csalkyl-CONH-d-Csalkyl, phenyl- CONH-Cι-C ₅ alkyl, d-C ₅ chloroalkyl, d-C ₃ alkoxy, d-C ₃ alkylthio, Cι-C ₃ alkoxycarbonyl, d-Csalkoxycarbonyl-d-dalkyl, C ₅ -C7cycloalkyl, C ₂ -C4alkenyl, C ₂ -C ₄ alkynyl, benzyl or d-C ₃ halogenoalkyl, or

R ₇ is Cs-dcycloalkenyl, d-dcycloalkenyl substituted by d-C ₃ alkyl, or

R ₇ is C ₆ -Cι ₂ bicycloalkyl, C ₆ -C ₁₂ bicycloalkyl substituted by d-C ₃ alkyl, cyano or halogen, C ₆ -Cι ₂ bicycloalkenyl, C ₆ -d_bicycloalkenyl substituted by d-C ₃ alkyl, or

R ₇ is a substituted or unsubstituted non-aromatic heterocyclic ring or an alicyclic ring system;

R9 ₀ and R ₉₁ independently of one another are hydrogen, Cι-C ₁₂ alkyl substituted by halogen, NO ₂ , CN, hydroxyl, Cι-C ₃ alkoxy, Cι-C ₃ alkoxycarbonyl, d -C ₃ trialky Isilyl ,

C C ₆ alkylamino, di(Cι-C ₆ alkyl)amino, d-dcycloalkyl,

or a heterocyclic ring, or C ₃ -Cι ₀ alkenyl, C ₃ -C ₁₀ alkynyl, C ₆ -C ₁₂ bicycloalkyl, C ₆ -C ₁₂ bicycloalkenyl, C ₃ -C ₁₂ cycloalkyl, C ₃ -C ₁₂ cycloalkyl substituted by d-dalkyl, C ₅ -C ₇ cycloalkenyl or C ₅ -Cτcycloalkenyl substituted by d-dalkyl, with the proviso that R ₉₀ and R ₉₁ are not simultaneously hydrogen; or

R ₉₀ and R ₉₁ , together with the nitrogen atom to which they are bonded, form a saturated heterocyclic ring which contains 2-12 carbon atoms and can contain, as further heteroatoms, a nitrogen, an oxygen or a sulfur atom and can be substituted by d-dalkyl, d- or dhalogenoalkyl, d- or C ₂ hydroxyalkyl, methoxy-d-C ₄ alkyl, halogen, hydroxyl, CN,

d-C ₄ alkoxy, d-dalkylcarbonyl, C or C ₂ halogenoalkyl, ,

, Cι-C ₃ alkoxycarbonyl, (Cι-C ₃ alkyl) ₂ NCO, di(C ₁ -C ₄ alkyl)amino or =O and

^R 24 can additionally be bridged by 1 or 2 — C — groups and onto which 1 or 2 further

R ₂₄ carbocyclic, heterocyclic or aromatic rings can be fused, or

R90 and R ₉₁ , together with the nitrogen atom to which they are bonded, form a mono- or diunsaturated heterocyclic ring which contains 5-7 carbon atoms and is substituted or unsubstituted by d-dalkyl, d- or C ₂ halogenoalkyl, halogen, hydroxyl, CN, amino, d-dalkylamino, di(d-C alkyl)amino, phenyl, Cι-C ₄ alkoxy or d-C ₃ alkoxycarbonyl and

^R 24 additionally bridged by 1 or 2 — C — groups and onto which 1 or 2 further carbocyclic,

^R 24 heterocyclic or aromatic rings can be fused; the radicals R ₂₄ independently of one another are hydrogen or methyl;

Rgβ is hydrogen, fluorine, chlorine, bromine, CN, Cι-C ₃ alkoxy, Cι-C ₃ alkoxycarbonyl,

Cι-C ₃ alkoxy-C C ₃ alkyl, d- or C ₂ halogenoalkyl, d-C ₅ alkyl, NO _2l C ₃ -C ₅ alkenyl, cyclopropyl or

C or C ₂ halogenoalkoxy;

R ₂ is halogen, C,-C ₁₀ alkoxy, d-Cioalkoxy substituted by halogen, CN, NO ₂ , d-C ₆ alkoxy, Cι-C ₆ alkylthio, C ₃ -C ₆ alkenyloxy, d-C_alkoxycarbonyl, heterocyclyl or substituted or unsubstituted aryl or aryloxy, C ₃ -C ₁₀ alkenyloxy, C ₃ -C ₁₀ alkenyloxy substituted by halogen, CN, NO ₂ , Cι-C ₆ alkoxy, C ₃ -C ₆ alkenyloxy, Ci-Cealkoxycarbonyl or substituted or unsubstituted aryl or aryloxy, d-C ₁₀ alkylthio, d-C ₁₀ alkylthio substituted by halogen, CN, NO ₂ , C ₁ - C ₆ alkoxy, C ₃ -C ₆ alkenyloxy, d-C ₆ alkoxycarbonyl or substituted or unsubstituted aryl or aryloxy, C ₃ -C ₁₀ alkenylthio or C ₃ -Cιoalkenylthio substituted by halogen, CN, NO ₂ , C,- C ₆ alkoxy, C ₃ -C ₆ alkenyloxy, Cι-C ₆ alkoxycarbonyl or substituted or unsubstituted aryl or aryloxy, or

R ₂ is C ₃ -C ₅ alkynyloxy, C ₃ -C ₅ -alkynylthio, C ₃ -C _β cycloalkyl-X-, C ₆ -Cι ₂ bicycloalkyl-X-, heterocyclyl-X-, alicyclyl-X-, aryl-X-, phthalidyl-X-, biphenyl-X- or heteroaryl-X-; X is -O-, -S-, -SO- or -SO ₂ -, or

R ₂ is a group RββRβ-N-

Rββ and R ₈ . independently of one another are hydrogen, Cι-C ₆ alkyl, d-C ₆ alkyl substituted

by halogen, CN, Cι-C ₃ alkoxy or , C ₃ -Cι ₂ cycloalkyl, C ₃ -Cιoalkenyl,

C ₃ -Cι ₀ alkynyl, C ₆ -C ₂ bicycloalkyl or C ₆ -d ₂ bicycloalkyl substituted by Cι-C ₃ alkyl; the radicals R∞ independently of one another are hydrogen or d-C ₄ alkyl; n ₇ is 4 or 5;

Y is -O-, -S-, -NH- or -NR _1o ;

R ₁₀ ι is d-C ₄ alkyl, d-C ₄ alkylcarbonyl or d-C ₃ alkoxycarbonyl; and

R ₉₈ is as defined above;

R ₃ is halogen, hydroxyl, d-doalkoxy, d-Cioalkoxy substituted by halogen, CN, NO ₂ , Cι-C ₆ alkoxy, d-C ₆ alkylthio, C ₃ -C ₆ alkenyloxy, d-C ₆ alkoxycarbonyl, heterocyclyl or substituted or unsubstituted aryl or aryloxy, C ₃ -Cιoalkenyloxy, C ₃ -Cιoalkenyloxy substituted by halogen, CN, NO ₂ , Cι-C ₆ alkoxy, C ₃ -C ₆ alkenyloxy, Ci-Cealkoxycarbonyl or substituted or unsubstituted aryl or aryloxy, d-doalkylthio, d-Cioalkylthio substituted by halogen, CN, NO ₂ , Cι-C _e alkoxy, C ₃ -C ₆ alkenyloxy, d-C ₆ alkoxycarbonyl or substituted or unsubstituted aryl or aryloxy, C ₃ -Cιoalkenylthio or C ₃ -Cιoalkenylthio substituted by halogen, CN, NO ₂ , Ci C ₆ alkoxy, C ₃ -C ₆ alkenyloxy, Cι-C ₆ alkoxycarbonyl or substituted or unsubstituted aryl or aryloxy, or

R ₃ is C ₃ -C ₅ alkynyloxy, C ₃ -C ₅ alkynylthio, C ₃ -C ₈ cycloalkyl-X-, C ₆ -C ₁₂ bicycloalkyl-X-, heterocyclyl-X-, alicyclyl-X-, aryl-X-, phthalidyl-X-, biphenyl-X- or heteroaryl-X-; and

X is as defined above, and stereoisomers of the compounds of the formula I, excluding the compounds of formulae Ii to l ₇

5 -

wherein R0 ₁ is hydrogen, methyl, ethyl, n-propyl, i-butyl, tert-butyl, allyl, cyclohexyl or benzyl;

R ₀₂ is ethyl and

R ₀₃ is cyclohexyl, or

R ₀₂ and R∞, together with the nitrogen atom to which they are bonded, form a piperidine ring;

R04 is chlorine, methylthio, ethylthio, i-propylthio, n-butylthio, i-butylthio, phenylthio or benzylthio;

R05 is ethoxy, methylthio, ethylthio or phenylthio; and

Roe is chlorine or cyclohexylamino.

The alkyl groups occurring in the substituent definitions can be straight-chain or branched, which also applies to the alkyl, alkenyl and alkynyl moiety of the halogenoalkyl, halogenoalkenyi, alkenyloxy, alkylcarbonyloxy, alkoxyalkyl-, alkoxyalkenyl-, alkoxycarbonyl-, alkoxycarbonylalkyl-, alkylamino-, dialkylamino-, alkoxyalkoxy-, nitroalkyl-, cyanoalkyl-, hydroxyalkyl-, alkylaminoalkyl-, dialkylaminoalkyl-, cycloalkylalkyl-, heterocyclylalkyl-, alkoxyalkenyloxy-, alkoxycarbonylalkenyloxy-, halogenoalkylthio-, alkoxyalkylthio-, alkenylthio, halogenoalkenylthio-, alkoxyalkenylthio-, halogenoalkylcarbonyl- and halogenoalkoxycarbonyl groups.

Examples of alkyl groups are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl or hexadecyl and branched isomers thereof. These alkyl groups can be substituted by halogen, cyano, nitro, hydroxyl, C C ₃ alkoxy, d-C ₆ alkylamino, di(Cι-C ₆ -alkyl)amino, C ₃ -C ₁₀ alkenyl, C ₃ -Cιoalkynyl, C ₃ -C ₁₀ alkenyloxy, C ₃ -C ₅ alkynyloxy, d-C ₃ trialkylsilyl, d-Cealkoxycarbonyl, heterocyclyl, C ₃ -Cι ₂ cycloalkyl, C ₃ -C ₈ cycloalkoxy or C ₆ -Cι ₀ bicycloalkyl. The alkenyl and alkynyl radicals can be mono- or polyunsaturated.

Examples of alkenyls are allyl, methallyl, 1-methylallyl, but-2-en-1-yl, pent-4-en-1-yl, hex- 4-en-1-yl and hept-4-en-1-yl, preferably alkenyl radicals having a chain length of 3 to 6 carbon atoms. The alkenyl groups can be substituted on the saturated carbon atoms, for example by d-C ₆ alkoxy or C ₃ -C _β cycloalkyl, and on the saturated or unsaturated carbon atoms by halogen. The alkenyl radicals are preferably bonded to a heteroatom by a saturated carbon atom.

Examples of alkynyls are propargyl, but-3-yn-1-yl, but-2-yn-1-yl, 1-methylpropargyl, 2- methylbutyn-2-yl, pent-4-yn-1-yl or 2-hexynyl, preferably alkynyl radicals having a chain length of 3 to 6 carbon atoms. The alkynyl radicals are preferably bonded to a heteroatom via a saturated carbon atom.

Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine. A corresponding statement also applies to halogen in combination with other definitions, such as halogenoalkyl, halogenoalkenyi, halogenoalkoxy, halogenoalkylcarbonyl, halogenoalkoxycarbonyl, halogenoalkyicarbonyloxy, halogenocycloalkyl or halogenobicycloalkyl.

Halogenoalkyl is alkyl groups which are mono- or polysubstituted, in particular mono- to trisubstituted, by halogen, halogen specifically being iodine and, in particular, fluorine, chlorine and bromine, for example fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 1 ,1-dichloro-2,2,2- trifluoroethyl, pentafluoroethyl, 2-fluoroethyl, 2-chloroethyl and 2,2,2-trichloroethyl.

Alkoxy is, for example, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec- butoxy, tert-butoxy, and one of the isomeric pentoxy, hexyloxy, heptyloxy, octyloxy, nonyloxy and decyloxy radicals.

Halogenoalkenyi is alkenyl groups which are mono- or polysubstituted by halogen, halogen being bromine, iodine and, in particular, fluorine and chlorine, for example 2,2-difluoro-1 -

methylvinyl, 3-fluoropropenyl, 3-chloropropenyl, 3-bromopropenyl, 2,3,3-trifluoropropenyl and 4,4,4-trifluoro-but-2-en-1 -yl. Preferred C ₃ -d ₅ alkenyl radicals which are mono- di- or trisubstituted by halogen are those which have a chain length of 3 to 6 carbon atoms.

Alkoxycarbonyl is, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentoxycarbonyl and hexyloxycarbonyl and branched isomers thereof, preferably methoxycarbonyl, ethoxycarbonyl and propoxycarbonyl.

Alkylamino is, for example, methylamino, ethylamino, propyl-, butyl-, pentyl- and hexylamino and their branched isomers.

Dialkylamino is, for example, dimethylamino, methylethylamino, diethylamino, n-propylmethylamino, dipropyl-, dibutyl-, dipentyl- and dihexylamino and their branched isomers.

In substituents such as dialkylamino or dialkylaminoalkyi, the alkyl radicals can be identical or different. They preferably have the same meaning. Corresponding statements also apply to the alkyl radicals in dialkylaminocarbonyl and trialkylsilyl substituents.

Alkoxyalkoxy is, for example, methoxymethoxy, ethoxymethoxy, ethoxyethoxy, propoxymethoxy, propoxyethoxy, butoxyethoxy and butoxybutoxy.

Halogenoalkoxy is, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluorethoxy, 1 ,1 ,2,2-tetrafluorethoxy, 2-fluorethoxy, 2-chloroethoxy and 2,2,2-trichloroethoxy.

Alkylthio is, for example, methylthio, ethylthio, propylthio, butylthio, pentylthio, hexylthio, heptylthio, octylthio, nonylthio or decylthio and branched isomers thereof.

Alkenyloxy is, for example, allyloxy, 1 -methylallyloxy, methallyloxy, but-2-en-1-yloxy or hex- 2-en-1-yloxy. Alkenyl radicals having a chain length of 3 to 6 carbon atoms are preferred.

Alkynyloxy is, for example, propargyloxy, 1 -methylpropargyloxy, but-3-yn-1-yloxy or pent- 4-yn-1-yloxy.

Alkenylthio is, for example, allylthio, ethallylthio, but-3-en-1-ylthio, pent-4-en-1-ylthio or hex-2-en-1 -ylthio.

Alkynylthio is, for example, propargylthio, 1-methylpropargylthio, but-3-yn-1-ylthio, pent-4- yn-1-ylthio or hex-2-yn-1 -ylthio.

Suitable cycloalkyl substituents contain 3 to 12 carbon atoms and are, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl or cyclododecyl. Corresponding cycloalkenyl substituents can be mono- or else polyunsaturated, for example cyclopentenyl, cyclopentadienyl, cyclohexenyl, cycloheptenyl or cyclooctatetraenyl.

Cycloalkyl and also cycloalkenyl substituents can, unless stated otherwise, be substituted by d-dalkyl and contain fused-on aryl rings.

If alkyl, alkenyl or alkynyl occur as substituents on a cycloalkyl, cycloalkenyl, bicycloalkyl, bicycloalkenyl, phenyl, biphenyl, naphthyl or heterocyclyl, these ring systems can also be polysubstituted by alkyl, alkenyl or alkynyl.

If R _∑ o, R ₂₄ , R ₂ 5, R97. R98 or R ₉₉ occur on phenyl, naphthyl or heteroaryl, these ring systems can also be polysubstituted by R∞, R ₂₄ , R _2S , R97, Rgβ or R99.

If R _∞ , R ₂₄ , R_s, R ₉ 8 or R ₁ 00 occur on alicyclic or carbocyclic rings, these ring systems can also be polysubstituted by R ₂₀ , R ₂ , R ₂₅ , R_β or Rι _∞ .

Carbocyclic radicals are to be understood as meaning saturated and unsaturated, mono- and polycyclic ring systems which consist of cycloalkanes, cycloalkenes, polycycloalkanes and polycycloalkenes. Carbocyclic radicals preferably contain 3 to 12 carbon atoms, for example cyclopropane, cyclobutane, cyclopentane, cyclohexane, cyclohexene, cycloheptane, cyclooctane, cyclononane, cyclodecane, cyclododecane and cis- and trans- decalin, it being possible for these carbocyclic radicals, unless stated otherwise, to be substituted by Cι-C ₄ alkyl.

Heterocyclyl is to be understood as meaning mono- and polycyclic ring systems which, in addition to carbon atoms, contain at least one heteroatom, such as nitrogen, oxygen or sulfur. They can be saturated or unsaturated and substituted by d-C ₃ alkyl, halogen or =O. Such ring systems preferably contain 3 to 12 ring atoms. This also applies to those heterocyclic radicals which, as in the case of groups such as -NR_oR ₉ ι, are formed by 2 substituents bonded to a nitrogen atom.

Examples of N-heterocyclic radicals onto which 1 or 2 further carbocyclic, heterocyclic or aromatic rings can be fused or spiro-bonded and which contain or do not contain further heteroatoms, in the definition of R _{1 t} are:

in which the radicals R _∞ independently of one another are hydrogen, d-C ₄ alkyl or d-C ₃ alkoxy;

Ras is hydrogen, chlorine, methyl or methoxy;

Rico is hydrogen or C C ₃ alkyl;

Y, is -O-, -S- or -NR ₃₀ ;

R ₃₀ is hydrogen, methyl, Cι-C ₃ alkylcarbonyl or (C ₁ -C ₃ alkyl) ₂ NCO-; n, is 1 , 2, 3, 4 or 5; n ₂ is 0, 1 or 2; and n ₃ is a number from 3 to 10. The hetererocyclic radical is bonded to the thiatriazine ring via its nitrogen atom.

Examples of aryl, aryloxy, arylmethyleneoxy, arylcarbonyl-, arylcarbonyloxy or aryloxycarbonyl ring systems in the definition of R ₂ , R ₃ , R ₇ , Rι ₃ , R^ and R ₉₇ are:

in which R ₂₅ is as defined above;

R ₉₉ is hydrogen, halogen, NO ₂ , CN, d-C ₅ alkyl, Ci-Cealkoxy, d- or C ₂ halogenoalkoxy, C1

Ce-alkenyloxycarbonyl, d-C ₃ alkylthio,

. Ci-C ₆ alkoxycarbonyl,

NH ₂ , C C ₃ alkyl-CONH, di(CrC ₆ alkyl)amino or Ci-Cealkylamino;

R ₉₈ is hydrogen, fluorine, chlorine, bromine, CN, C C ₃ alkoxy, d-dalkoxycarbony, C C ₃ - alkoxy-d-C ₃ -alkyl, Cr or C ₂ -halogenoalkyl, C C ₅ -alkyl, NO ₂ , C ₃ -C ₅ alkenyl, cyclopropyl or

C-- or C ₂ halogenoalkoxy; and n ₆ is 3, 4, 5 or 6.

Examples of heterocyclic rings R ₇ and R ₂ or R ₃ bonded to alkyl or alkoxy are:

in which R _9β and Rι _∞ are as defined above;

R ₂₄ is hydrogen or methyl; and

R10 ₁ is d-dalkyl, d-C ₄ alkylcarbonyl or d-C ₃ -alkoxycarbonyl.

Examples of non-aromatic heterocyclic rings in the definition of R ₇ are:

in which R ₁₀₀ and Rι_ι are as defined above.

Alicyclic ring systems in the definition of R ₇ are saturated and unsaturated, mono- and polycyclic ring systems containing bridge bonds and heteroatoms, such as nitrogen, oxygen or sulfur. Examples of such alicyclic ring systems are:

in which R ₂ ι and R_ ₂ independently of one another are hydrogen or d-C alkyl; n ₉ is 3 or 4; and

R20. 24, R25. Rgβ, R100. R101 and n ₆ are as defined above.

Examples of heterocyclic rings R ₉₀ and R ₉₁ , which are independent of one another, bonded to alkyl are:

in which R ₂₅ and Rι _∞ are as defined above.

Saturated and unsaturated and substituted or unsubstituted mono- or bicyclic heterocyclic radicals formed from -NR9 ₀ R ₉₁ include, for example, pyrrolidyl, dimethylpyrrolidyl, piperidyl, morpholinyl, dimethylmorphoiinyl, thiomorpholinyl, cis- and trans-decahydro(iso)quinolyl, tetrahydropyridyl, 1 ,2,3,4-tetrahydro(iso)quinolyl, 1-methylpiperazinyl, perhydroindolyl, 3-pyrrolinyl, hexahydro-azepinyl, aziridyl, azetidyl, 4-piperidonyl and homopiperazinyl, it being possible for these heterocyclic radicals to have 1 or 2 further carbocyclic, heterocyclic or aromatic rings, for example cyclohexane, (nor-)bornane, cyclopentane, cycloheptane, cyclododecane or phenyl, fused-on or spiro-linked carbocyclic rings, for example cyclohexane or (nor-)bornene.

Further examples of saturated, substituted or unsubstituted heterocyclic rings formed from -NR90R91 which contain or do not contain heteroatoms or which can additionally be bridged

^R 24 with 1 or 2 groups — C — are:

^R 24

Preferred examples in which R _∞ and R ₉ ι, together with the nitrogen atom, form a ring are pyrrolidyl, piperidyl, dimethyipiperidyl, ethoxycarbonylpiperidyl, morpholinyl, dimethylmorpholinyl, cis- and trans-decahydro(iso)quinolyl and 1 ,2,3,4- tetrahydro(iso)quinolyl.

Examples of aryl-X-, phthalidyl-X-, biphenyl-X- or heteroaryl-X- R ₂ and R ₃ are:

in which X is -O-, -S-, -SO- or -SO ₂ -; X ₂ is -O-, -S- or -NR ₁₀ o- ; R∞. R ₂ 4. R_β and Rι _∞ are as defined above; R ₉₂ is hydrogen or C C ₄ alkyl;

R ₉₃ is hydrogen, d-dalkyl, hydroxyl, C C ₄ alkoxy or d-C ₄ alkylthio; R ₉₇ is hydrogen, halogen, NO ₂ , CN, C ₃ -C ₆ cycloalkoxy, CrCioalkyl, d-Cioalkyl substituted by halogen, CN, NO ₂ , CrC ₆ alkoxy, C ₃ -C ₆ alkenyloxy, CrC ₆ alkoxycarbonyl or substituted or unsubstituted aryl or aryloxy, C ₃ -Cι ₀ alkenyl, C ₃ -Cιoalkenyl substituted by halogen, CN, NO ₂ , CrC ₆ alkoxy, C ₃ -C ₆ alkenyloxy, Ci-Cealkoxycarbonyl or substituted or unsubstituted aryl or aryloxy, d-Cioalkoxy, Crd ₀ alkoxy substituted by halogen, CN, NO ₂ , CrC ₆ alkoxy, C ₃ -C ₆ alkenyloxy, Cι-C ₆ alkoxycarbonyl or substituted or unsubstituted aryl or aryloxy, C ₃ -C ₁₀ alkenyloxy, C ₃ -Cιoalkenyloxy substituted by halogen, CN, NO ₂ , d-C ₆ alkoxy, C ₃ -C ₆ alkenyloxy, d-C ₆ - alkoxycarbonyl or substituted or unsubstituted aryl or aryloxy, CrCι ₀ alkylcarbonyl, CrCioalkylcarbonyl substituted by halogen, CN, NO ₂ , CrC ₆ alkoxy, C ₃ -C ₆ alkenyloxy, CrC ₆ alkoxycarbonyl or substituted or unsubstituted aryl or aryloxy, d-Cioalkoxycarbonyl, d-Cioalkoxycarbonyl substituted by halogen, CN, NO ₂ , CrC ₆ alkoxy, C ₃ -C ₆ alkenyloxy, CrC ₆ alkoxycarbonyl or substituted or unsubstituted aryl or aryloxy, C Ci ₀ alkylcarbonyloxy or Cι-Cι ₀ alkylcarbonyloxy substituted by halogen, CN, NO ₂ , d-C ₆ alkoxy, C ₃ -C ₆ alkenyloxy, CrC ₆ alkoxycarbonyl or substituted or unsubstituted aryl or aryloxy, or R ₉₇ is CHO, C ₃ -C _B -

cycloalkyl, d-C ₄ alkylthio, C ₃ - or dalkenylthio, (R9 ₄ ) ₂ N-, (R ₉₅ ) ₂ N-CO-, aryl, aryloxy, arylcarbonyl or aryloxycarbonyl, or a group

(CH ₂ ) NCO- ; the radicals R94 independently of one another are hydrogen, d-doalkyl,

C ₃ -C _β cycloalkyl, Crd ₀ alkylcarbonyl or substituted or unsubstituted arylcarbonyl; the radicals R95 independently of one another are hydrogen, d-C ₅ alkyl or C ₃ -C ₈ cycloalkyl; and n is a number from 5 to 12.

Examples of alicyclyl-X- R ₂ and R ₃ are:

in which R∞, R ₂₄ , R ₂₅ , Rββ. R100, R101. X, n ₆ and π ₉ are as defined above.

Examples of nonaromatic heterocyclyl-X- R ₂ and R ₃ are:

in which R ₂₄ , X, Rι _∞ and R ₁ 0 ₁ are as defined above.

Examples of cyclic radicals Rn, in the compounds of the formula XII in the preparation process, onto which 1 or 2 further carbocyclic, heterocyclic or aromatic rings can be fused and which contain or do not contain heteroatoms are:

in which the radicals R ₂₀ , R.s. R100, Yi, riι, n ₂ and n ₃ are as defined above.

Suitable substituted or unsubstituted bicycioalkyi and bicycloalkenyl substituents contain 6 to 12 carbon atoms and are, for example:

in which R ₂ is as defined above.

The substituents in composite definitions, for example cycloalkoxy, cycloalkylalkyl, cycloalkyl-X-, bicycloalkylalkyl, bicycloalkyl-X-, alkylcarbonyl, alkylcarbonyloxy, cycloalkylalkenyl, cycloalkenylalkyl, alkoxyalkyl, alkoxyalkenyl, halogenobicycloalkyl, alkenyloxycarbonyl, alkenyloxyalkoxy, alkoxycarbonylalkoxy, alkylaminoalkyl, dialkylaminoalkyi, heterocyclylalkyl, heterocyclyl-X-, halogenoalkenyloxy, alkoxyalkenyloxy, alkenyloxyalkenyloxy, alkoxycarbonylalkenyloxy, halogenoalkylthio, alkenyloxyalkylthio, alkoxycarbonylalkylthio, halogenoalkenylthio, alkoxyalkenylthio, alkenyloxyalkenylthio, alkoxycarbonylalkenylthio, halogenoalkylcarbonyl, alkoxyalkylcarbonyl, alkenyloxyalkylcarbonyl, alkoxycarbonylalkylcarbonyl, halogenoalkoxycarbonyl, alkoxyalkoxycarbonyl, alkenyloxyalkoxycarbonyl, alkoxycarbonylalkoxycarbonyl, halogenoalkylcarbonyloxy, alkoxyalkylcarbonyloxy, alkenyloxyalkoxycarbonyloxy and alkoxycarbonylalkylcarbonyloxy can also be assigned corresponding definitions.

ln the definitions cyanoalkyl, alkoxycarbonyl, alkylcarbonyloxy, alkylcarbonyl, alkoxycarbonylalkoxy and alkenyloxycarbonyl, the cyano or carbonyl carbon atom is not included in the particular lower and upper limits stated for the number of carbons.

Unless stated specifically, ¹ H- and ¹³ C-NMR spectra (Tables 1-6) were recorded with a 300 MHz spectrometer in CDCI ₃ .

The compounds of the formula I in which R ₂ and R ₃ differ from one another have a centre of asymmetry in the sulfur atom of the thiatriazine ring.

Furthermore, asymmetric centres can be present in the substituents of the thiatriazine ring, for example in the definition of Ri or R ₇ . This means that diastereomers can be formed, which can sometimes be separated by column chromatography, as shown, for example, in the tabular examples Compound Nos. 5.45/5.46, 6.6, 6.10, 6.55/6.56, 6.92/6.93, 6.120/6.121 and 6.153/6.154.

If substituents are bonded via a wavy line to a ring system in the formulae, for example in the definition of Ri, this means that all conformations or geometric isomerisms ('up' und 'down', or 'equatorial' and 'axial') are possible for these substituents.

Unless chiral starting materials are used, the compounds of the formula I are in general obtained as racemates in the process described in this application, and these are separated by customary separation processes, for example chromatographic processes, for example high pressure liquid chromatography (HPLC) over acetylcellulose, on the basis of physico- chemical properties. In the present invention, the active compounds of the formula I are to be understood as meaning both the pure optical antipodes and the racemates. Unless the individual optical antipodes are referred to specifically, those racemic mixtures which are formed in the preparation process described are to be understood under the formula given. If an aliphatic C=C double bond is present or if alicyclic or carbocyclic rings contain substituents, geometric isomerism may also occur.

The formula I is intended to include all these possible isomers, enantiomers and diastereoisomers and mixtures thereof.

Preferred compounds are those of the formula I

in which

Ri is a group -OR ₇ , -NR90R9 ₁ , or an N-heterocyclic radical, onto which 1 or 2 further carbocyclic, heterocyclic or aromatic rings can be fused and which contains or does not contain further heteroatoms;

R ₇ is CrCiealkyl, CrCiealkyl substituted by halogen, NO ₂ , CN, CrC ₅ alkoxy, CrC ₅ alkylthio, C ₃ -C ₈ cycloalkoxy, CrC ₃ trialkylsilyl, C ₃ -Cι ₀ alkenyloxy, C ₃ -C ₅ alkynyloxy, d-C ₃ alkyl- carbonyloxy, d-C ₃ alkoxycarbonyl, C C ₃ alkylcarbonyl, d-C^ycloalkenyl or C ₅ -C ₇ cycloalkenyl substituted by d-C ₄ alkyl, or

R ₇ is CrCiealkyl substituted by C ₃ -C ₈ cycloalkyl, C ₆ -C ₁₂ bicycloalkyl, C ₆ -Cι ₂ chlorobicycloalkyl, C ₆ -Cι ₂ bicycloalkenyl or adamantyl, or

R ₇ is CrCiealkyl substituted by substituted or unsubstituted aryl, aryloxy, arylmethyleneoxy, arylcarbonyl, arylcarbonyloxy or a heterocyclic ring, or

R ₇ is C ₃ -Cι ₅ alkenyl, C ₃ -Cι ₅ alkenyl substituted by halogen, d-C ₃ alkoxy, C ₃ -C ₈ cycloalkyl or substituted or unsubstituted aryl or aryloxy, or

R ₇ is C ₃ -C ₅ alkynyl, C ₃ -Cι ₂ cycloalkyl, C ₃ -C ₁₂ cycloalkyl substituted by halogen, CN, CrC ₃ -trialkylsilyl, =O, d-Cealkyl, cyano-C C _s alkyl, CrC ₅ alkyl-CONH-CrC ₅ alkyl, phenyl- CONH-Cι-C ₅ alkyl, d-C ₅ chloroalkyl, d-dalkoxy, d-C ₃ alkylthio, d-C ₃ alkoxycarbonyl, CrC ₃ alkoxycarbonyl-CrC ₅ alkyl, C ₅ -C ₇ cycloalkyl, C ₂ -C ₄ alkenyl, d-dalkynyl, benzyl or C C ₃ halogenoalkyl, or

R ₇ is d-dcycloalkenyl, d-dcycloalkenyl substituted by d-C ₃ alkyl, or

R ₇ is C ₆ -Cι ₂ bicycloalkyl, C ₆ -Cι ₂ bicycloalkyl substituted by d-C ₃ alkyl or halogen, C ₈ -Cι ₂ bicycloalkenyl, C ₆ -C ₁₂ bicycloalkenyl substituted by C -C ₃ alkyl, or

R ₇ is a substituted or unsubstituted nonaromatic heterocyclic ring or an alicyclic ring system;

R90 and R91 independently of one another are hydrogen, d-Cι ₂ alkyl, CrCι ₂ alkyl substituted by halogen, NO ₂ , CN, hydroxyl, Cι-C ₃ alkoxy, C C ₃ trialkylsilyl, CrC ₆ alkylamino, di(d-C ₆ -

alkyl)amino, or a heterocyclic ring, or

C ₃ -Cι ₀ alkenyl, C ₃ -Cι ₀ alkynyl, C ₆ -C ₁₂ bicycloalkyl, C ₆ -Cι ₂ bicycloalkenyl, C ₃ -Cι ₂ cycloalkyl, C ₃ -C ₁₂ cycloalkyl substituted by d-C ₄ alkyl, C ₅ -Cτcycloalkenyl or C ₅ -Cτcycloalkenyl substituted by d-dalkyl, with the proviso that Rgo and R91 are not simultaneously hydrogen; or

R9 ₀ and R9 ₁ , together with the nitrogen atom to which they are bonded, form a saturated heterocyclic ring which contains 2-12 carbon atoms and can contain, as further heteroatoms, a nitrogen, an oxygen or a sulfur atom and can be substituted by d-C alkyl, C or C ₂ -halogenoalkyl, methoxy-d-dalkyl, halogen, hydroxyl, CN, d-C ₄ alkoxy, d-d-

alkylcarbonyi, d- or C ₂ halogenoalkyl, , d-

C ₃ alkoxycarbonyl, (CrC ₃ alkyl) ₂ NCO, di(Cι-C ₄ alkyl)amino or =O and can additionally be

^R 24 bridged by 1 or 2 — C — groups and onto which 1 or 2 further carbocyclic, heterocyclic

^R 24 or aromatic rings can be fused, or

R90 and R9 ₁ , together with the nitrogen atom to which they are bonded, form a monounsaturated heterocyclic ring which contains 5-7 carbon atoms and is substituted or unsubstituted by d-C alkyl, d- or C ₂ halogenoalkyl, halogen, hydroxyl, CN, amino, d-dalkylamino, di(C C ₄ alkyl)amino, phenyl, d-C ₄ alkoxy or CrC ₃ alkoxycarbonyi

^R 24 and is additionally bridged by 1 or 2 — C — groups and onto which 1 or 2 further

^R 24 carbocyclic, heterocyclic or aromatic rings can be fused; the radicals R ₂₄ independently of one another are hydrogen or methyl;

R_β is hydrogen, fluorine, chlorine, bromine, CN, d-C ₃ alkoxy, CrC ₃ alkoxycarbonyl, CrC ₃ - alkoxy-d-C ₃ alkyl, d- or C ₂ halogenoalkyl, CrC ₅ alkyl, NO ₂ , C ₃ -C ₅ alkenyl, cyclopropyl or d- or C ₂ halogenoalkoxy;

R ₂ is halogen, d-Cioalkoxy, d-Cioalkoxy substituted by halogen, CN, NO ₂ , CrC ₆ alkoxy, CrC ₆ alkylthio, C ₃ -C ₆ alkenyloxy, Cι-C ₆ alkoxycarbonyl, heterocyclyl or substituted or unsubstituted aryl or aryloxy, C ₃ -C _alkenyloxy, C ₃ -Cιoalkenyloxy substituted by halogen, CN, NO ₂ , CrC ₆ aikoxy, C ₃ -C ₆ alkenyloxy, Cι-C ₆ alkoxycarbonyl or substituted or unsubstituted aryl or aryloxy, d-Cioalkylthio, CrC ₁₀ alkylthio substituted by halogen, CN, NO ₂ , CrC ₆ alkoxy, C ₃ -C ₆ alkenyloxy, Ci-Cealkoxycarbonyl or substituted or unsubstituted aryl or aryloxy, C ₃ -Cιoalkenylthio or C ₃ -Cιoalkenylthio substituted by halogen, CN, NO ₂ , CrC ₆ alkoxy, C ₃ -C ₆ alkenyloxy, Cι-C _e alkoxycarbonyl or substituted or unsubstituted aryl or aryloxy, or

R ₂ is C ₃ -C ₅ alkynyloxy, C ₃ -C ₅ alkynylthio, C ₃ -C ₈ cycloalkyl-X-, Ce-Cι ₂ bicycloalkyl-X-, heterocyclyl-X-, alicyclyl-X-, aryl-X-, phthalidyl-X-, biphenyl-X- or heteroaryl-X-; X is -O-, -S-, -SO- or -SO ₂ -, or

R ₂ is a group RωRβgN-

Rββ and R ₈₉ independently of one another are hydrogen, d-Cealkyl, Cι-C ₆ alkyl substituted

by halogen, CN, Cι-C ₃ alkoxy or , C ₃ -Cι ₂ cycioalkyl, C ₃ -Cιoalkenyl,

C ₃ -Cι ₀ alkynyl, C ₆ -C ₁₂ bicycloalkyl or C ₆ -d ₂ bicycloalkyl substituted by d-C ₃ alkyl; the radicals R∞ independently of one another are hydrogen or Cι-C ₄ alkyl; n ₇ is 4 or 5;

Y is -O-, -S-, -NH- or -NRι ₀ r;

R101 is CrC alkyl, d-dalkylcarbonyl or C C ₃ alkoxycarbonyl and

R ₉₈ is as defined above; and

R ₃ is halogen, CrCι ₀ alkoxy, d-Cioalkoxy substituted by halogen, CN, NO ₂ , Cι-C ₆ alkoxy, d-C ₆ alkylthio, C ₃ -C ₆ alkenyloxy, CrC ₆ alkoxycarbonyl, heterocyclyl or substituted or unsubstituted aryl or aryloxy, C ₃ -Cι ₀ alkenyloxy, C ₃ -Cιoalkenyloxy substituted by halogen,

CN, NO _2l Ci-C _e alkoxy, C ₃ -C ₆ alkenyloxy, C C ₆ alkoxycarbonyl or substituted or unsubstituted aryl or aryloxy, d-doalkylthio, d-Cι ₀ alkylthio substituted by halogen, CN, NO ₂ , d-Cealkoxy, C ₃ -C ₆ alkenyloxy, d-C ₆ alkoxycarbonyl or substituted or unsubstituted aryl or aryloxy, C ₃ -Cι ₀ alkenylthio or C ₃ -Cιoalkenylthio substituted by halogen, CN, NO ₂ , Ci-Cealkoxy, C ₃ -C ₆ alkenyloxy, CrC ₆ alkoxycarbonyl or substituted or unsubstituted aryl or aryloxy, or

R ₃ is C ₃ -C ₅ alkynyloxy, C ₃ -C ₅ alkynylthio, C ₃ -C ₈ cycloalkyl-X-, C _e -Cι ₂ bicycloalkyl-X-, heterocyclyl-X-, alicyclyl-X-, aryl-X-, phthalidyl-X-, biphenyl-X- or heteroaryl-X-; and X is as defined above.

Preferred compounds of the formula I are also those in which

in which the radicals R_« independently of one another are hydrogen or d-dalkyl;

R ₂₅ is hydrogen, chlorine, methyl or methoxy;

Rico is hydrogen or d-C ₃ alkyl;

Y, is -O-, -S- or -NR∞;

R ₃₀ is hydrogen, methyl, C C ₃ alkylcarbonyl or (C C ₃ alkyl) ₂ NCO; n, is 1 , 2, 3, 4 or 5; n ₂ is 0, 1 or 2; and n ₃ is a number from 3 to 10.

Preferred compounds of the formula I are also those in which

Ri is the group -OR ₇ , in which

R is as defined under formula I and

R ₂ and R ₃ independently of one another are chlorine, CrCι_alkoxy, Ci-Cioalkoxy substituted by halogen, CN, NO ₂ , CrC ₆ alkoxy, CrC ₆ alkylthio, C ₃ -C ₆ alkenyloxy, Cι-C ₆ alkoxycarbonyl, heterocyclyl or substituted or unsubstituted aryl or aryloxy, C ₃ -Cιoalkenyloxy, C ₃ -Cι ₀ alkenyloxy substituted by halogen, CN, NO ₂ , CrC _e alkoxy, C ₃ -C ₆ alkenyloxy, Ci-Cealkoxycarbonyl or substituted or unsubstituted aryl or aryloxy, Crd ₀ alkylthio, Cι-Cι_alkylthio substituted by halogen, CN, NO ₂ , CrC ₆ alkoxy, C ₃ -C ₆ alkenyloxy, Cι-C ₆ alkoxycarbonyl or substituted or unsubstituted aryl or aryloxy, C ₃ -d ₀ alkenylthio or d-Cι ₀ alkenylthio substituted by halogen, CN, NO ₂ , CrC ₆ alkoxy, C ₃ -C ₆ alkenyloxy, Ci-Cealkoxycarbonyl or substituted or unsubstituted aryl or aryloxy, or R ₂ and R ₃ independently of one another are C ₃ -C ₅ alkynyloxy, C ₃ -C ₅ alkynylthio, d-Cβcycloalkyl-X-, C ₆ -Cι ₂ bicycloalkyl-X-, heterocyclyl-X-, alicyclyl-X-, aryl-X-, phthalidyl-X-, biphenyl-X- or heteroaryl-X-.

Compounds of the formula I which are likewise preferred are those in which R, is the group -OR ₇ ;

R ₂ is a group RββRβsN- or Y N — ; and R ₃ is aryl-X-

phthalidyl-X-, biphenyl-X-, or heteroaryl-X-, in which

R , R∞, Raβ, Res. Y, n ₇ and X are as defined under formula I.

Thiatriazine derivatives of the formula I which are furthermore preferred are those in which Ri is a group -NR ₉₀ R ₉₁ or an N-heterocyclic radical, onto which 1 or 2 further carbocyclic, heterocyclic or aromatic rings can be fused and which contains or does not contain further heteroatoms.

R ₂ is a group RββRβgN- — or Y N — ; and R ₃ is aryl-X-,

phthalidyl-X-, biphenyl-X- or heteroaryl-X-, in which R ₂₀ , Rββ, R ₈ 9, Y, n ₇ and X are as defined under formula I.

Particularly preferred thiatriazine derivatives of the formula I are those in which Ri is a group -OR ₇ ;

R ₇ CrCiealkyl, CrCiealkyl substituted by halogen, NO ₂ , CN, d-C ₅ alkoxy, CrC ₅ alkylthio, C ₃ - C ₈ cycloalkoxy, CrC ₃ trialkylsilyl, C ₃ -Cι ₀ alkenyloxy, C ₃ -C ₅ alkynyloxy, CrC ₅ alkylcarbonyloxy, d-C ₃ alkoxycarbonyl, d-C ₃ alkylcarbonyl, Cs-dcycloalkenyl or C ₅ -C ₇ cycloalkenyl substituted by d-dalkyl, or

R ₇ is CrCiealkyl substituted by C ₆ -d ₂ bicycloalkyl, C ₆ -Cι ₂ chlorobicycloalkyl,

C ₆ -Cι ₂ bicycloalkenyl or adamantyl, or R ₇ is CrCiealkyl substituted by

in which R ₂₄ is hydrogen or methyl;

Rgβ is hydrogen, fluorine, chlorine, bromine, CN, d-C ₃ alkoxy, d-C ₃ alkoxycarbonyl, Cι-C ₃ alkoxy-CrC ₃ alkyl, C or C ₂ halogenoalkyl, CrC ₅ alkyl, NO ₂ , C ₃ -C ₅ alkenyl, cyclopropyl or d- or C ₂ halogenoalkoxy;

R99 is hydrogen, halogen, NO ₂ , CN, CrC ₅ alkyl, d-C ₆ alkoxy, CrC ₆ alkenyloxycarbonyl,

d-C ₃ alkylthio,

Ci-Cealkoxycarbonyl, NH ₂ , Cι-C ₃ alkyl-CONH, di(CrC ₆ alkyl)amino or CrC ₆ alkylamino; R ₁ 00 is hydrogen or Cι-C ₃ alkyl; and

R ₁ 0 ₁ is d-C ₄ alkyl, d-C alkylcarbonyl or CrC ₃ alkoxycarbonyl; or R ₇ is C ₃ -Cι ₂ cycloalkyl, C ₃ -Cι ₂ cycloalkyl substituted by halogen, CN, d-C ₃ trialkylsilyl, =O, d-Cealkyl, cyano-d-dalkyl, Cι-C ₅ alkyl-CONH-Cι-C ₅ alkyl, phenyl-CONH-d-C ₅ alkyl, Cι-C ₅ chloroalkyl, CrC ₃ alkoxy, d-C ₃ alkylthio, d-C ₃ alkoxycarbonyl, d-C ₃ alkoxycarbonyl- CrC ₅ alkyl, Cs-dcycloalkyl, C ₂ -C ₄ alkenyl, C ₂ -C ₄ alkynyl, benzyl or C C ₃ halogenoalkyl, Cs-d¬ cycloalkenyl or C ₅ -Cτcycloalkenyl substituted by Cι-C ₃ alkyl, or R ₇ is C ₆ -Cι ₂ bicycloalkyl, C ₆ -Cι ₂ bicycloalkyl substituted by d-C ₃ alkyl or halogen, C ₆ -Cι ₂ bicycloalkenyl or C ₈ -Cι ₂ bicycloalkenyl substituted by d-C ₃ alkyl, or R ₇ is a substituted or unsubstituted nonaromatic heterocyclic ring or an alicyclic ring system; R ₂ is a group RβeRagN-; Rβa and R ₈ g independently of one another are hydrogen, Ci-Cealkyl, CrC ₆ alkyl substituted

by halogen, CN, C C ₃ alkoxy or C ₃ -C ₁₂ cycloalkyl, C ₃ -Cιoalkenyl,

Cs-Cioalkynyl, C ₆ -Cι ₂ bicycloalkyl or C ₆ -Cι ₂ bicycloalkyl substituted by d-C ₃ aikyl; and R ₃ is aryl-X-, phthalidyl-X-, biphenyl-X- or heteroaryl-X-.

Of these, especially preferred thiatriazine derivatives of the formula I are those in which R is C ₃ -Cι ₂ cycloalkyl, C ₃ -Cι ₂ cycloalkyl substituted by halogen, CN, CrC ₆ alkyl, cyano- Crdalkyl, Cι-C ₃ alkoxy or d-C ₃ halogenoalkyl, or R ₇ is C ₅ -C ₇ cycloalkenyl or C ₅ -C cyclo- alkenyl substituted by methyl, or

R ₇ is C ₆ -Cι ₂ bicycloalkyl, C ₆ -Cι ₂ bicycloalkyl substituted by methyl or chlorine, C ₆ -Cι ₂ bicycloalkenyl or C ₆ -Cι ₂ bicycloalkenyl substituted by methyl, or

in which

Rιoo is hydrogen or d-C ₃ alkyl; and

R ₁₀₁ is d-C ₄ alkyl, d-C ₄ alkylcarbonyl or d-C ₃ alkoxycarbonyl; or

in which R ₂₀ is hydrogen or d-C ₄ alkyl;

R ₂ ι and R^ independently of one another are hydrogen or d-dalkyl;

R ₂₄ is hydrogen or methyl;

R ₂₅ is hydrogen, chlorine, methyl or methoxy;

Rgβ is hydrogen, fluorine, chlorine, bromine, CN, d-C ₃ alkoxy, CrC ₃ alkoxycarbonyl, d-

C ₃ alkoxy-d-C ₃ alkyl, d- or C ₂ halogenoalkyl, d-C ₅ alkyl, NO ₂ , C ₃ -C ₅ alkenyl, cyclopropyl or d- or C ₂ -halogenoalkoxy;

n ₈ is 3, 4, 5 or 6; n ₉ is 3 or 4; and

Rιoo and R101 are as defined above;

R ₂ is a group R∞RβgN-;

Reβ and R ₈ g independently of one another are hydrogen or CrC ₆ alkyl and

in which X is -O- or -S-;

X ₂ is -O-, -S- or -NR _1∞ -;

R20. R ₂ 4 and R100 are as defined above;

R _g2 is hydrogen or d-C ₄ alkyl;

R ₈₃ is hydrogen, d-C ₄ alkyl, hydroxyl, d-C alkoxy or d-C ₄ alkylthio;

R ₉₇ is hydrogen, halogen, NO ₂ , CN, C ₃ -C ₆ cycloalkoxy, CrCι ₀ alkyl, d-Cioalkyl substituted by halogen, CN, NO _2p CrC ₆ alkoxy, C ₃ -C ₆ alkenyloxy, Cι-C ₆ alkoxycarbonyl or substituted or unsubstituted aryl or aryloxy, C ₃ -Cι ₀ alkenyl, C ₃ -Cιoalkenyl substituted by halogen, CN, NO ₂ ,

CrC ₆ alkoxy, C ₃ -C _β alkenyloxy, CrC ₆ alkoxycarbonyl or substituted or unsubstituted aryl or aryloxy, d-Cioalkoxy, Ci-Cioalkoxy substituted by halogen, CN, NO ₂ , CrC ₆ alkoxy,

C ₃ -C ₆ alkenyloxy, Ci-Cealkoxycarbonyl or substituted or unsubstituted aryl or aryloxy,

C ₃ -Cιoalkenyloxy, C ₃ -Cιoalkenyloxy substituted by halogen, CN, NO ₂ , CrC ₆ alkoxy,

C ₃ -C ₆ alkenyloxy, Ci-Cealkoxycarbonyl or substituted or unsubstituted aryl or aryloxy, d-Cι ₀ alkylcarbonyl, d-Cioalkylcarbonyl substituted by halogen, CN, NO ₂ , CrC ₆ alkoxy,

C ₃ -C_alkenyloxy, Ci-Cealkoxycarbonyl or substituted or unsubstituted aryl or aryloxy, d-

C1.alkoxycarbonyl, Ci-Cioalkoxycarbonyl substituted by halogen, CN, NO ₂ , CrC ₆ alkoxy, C ₃ - dalkenyloxy, CrC ₆ alkoxycarbonyl or substituted or unsubstituted aryl or aryloxy, d-Cioalkylcarbonyloxy or Crd ₀ alkylcarbonyloxy substituted by halogen, CN, NO ₂ , d-C ₆ - alkoxy, C ₃ -C ₆ alkenyloxy, d-C ₆ alkoxycarbonyl or substituted or unsubstituted aryl or aryloxy, or

R ₉₇ is CHO, C ₃ -C ₈ cycloalkyl, d-C ₄ alkylthio, C ₃ - or dalkenylthio, (R ) ₂ N-, (R ₉₅ ) ₂ N-CO-, aryl, aryloxy, arylcarbonyl or aryloxycarbonyl, or a group

(CH ₂ ) NCO-; the radicals R ₉ independently of one another are hydrogen, d-Cioalkyl, ⁿ 5

C ₃ -C ₈ cycloalkyl, d-doalkylcarbonyl or substituted or unsubstituted arylcarbonyl; the radicals

R ₉₅ independently of one another are hydrogen, d-dalkyl or C ₃ -C ₈ cycloalkyl; n ₅ is a number from 5 to 12; and

Rgβ is as defined above.

Of these, those compounds in which X and X ₂ are -O- are especially important.

Particularly preferred compounds of the formula I are also those in which

R _I is a group -NRgoRgi or

Rgo and R ₉ ι independently of one another are Cι-Cι ₂ alkyl, Ci-Cealkyl substituted by halogen, CN or CrC ₃ alkoxy, C ₆ -C ₁₂ bicycloalkyl, C ₆ -Cι ₂ bicycloalkenyl, C ₃ -Cι ₂ cycloalkyl,

C ₃ -C ₁₂ cycloalkyl substituted by C C alkyl, d-dcycloalkeπyl or d-C^ycloalkenyl substituted by C C ₄ alkyl; the radicals R ₂₀ independently of one another are hydrogen or d-C ₄ alkyl; n ₂ is 0, 1 or 2; and n ₃ is a number from 3 to 10;

R ₂ is a group RrøRβgN-;

Rββ and R ₈₉ independently of one another are hydrogen or C C ₆ alkyl and

in which X is -O-, -S-, -SO- or -SO ₂ -; X ₂ is -O-, -S- or -NR ₁ 00-; R ₁ 00 is hydrogen or d-C ₃ alkyl; R _∞ is as defined above; R ₂₄ is hydrogen or methyl; Rgj. is hydrogen or d-C ₄ alkyl;

Rgs is hydrogen, d-dalkyl, d-C ₄ alkoxy or C C alkylthio;

R ₉₇ is hydrogen, halogen, NO ₂ , CN, C ₃ -C ₆ cycloalkoxy, d-Cioalkyl, Ci-Cioalkyl substituted by halogen, CN, NO ₂ , CrC ₆ alkoxy, C ₃ -C ₆ alkenyloxy, Ci-Cealkoxycarbonyl or substituted or unsubstituted aryl or aryloxy, C ₃ -Cιoalkenyl, C ₃ -Cιoalkenyl substituted by halogen, CN, NO _2l CrCβalkoxy, C ₃ -C ₆ alkenyloxy, CrC ₆ alkoxycarbonyl or substituted or unsubstituted aryl or aryloxy, Ci-Cioalkoxy, Ci-Cioalkoxy substituted by halogen, CN, NO ₂ , CrC ₆ alkoxy, C ₃ -C ₆ - alkenyloxy, Ci-Cealkoxycarbonyl or substituted or unsubstituted aryl or aryloxy, C ₃ -Cι_alkenyloxy, C ₃ -Cιoalkenyloxy substituted by halogen, CN, NO _2> CrC ₆ alkoxy, C ₃ -C ₆ alkenyloxy, CrC ₆ alkoxycarbonyl or substituted or unsubstituted aryl or aryloxy, Cι-Cι ₀ alkylcarbonyl, d-Cιoalkylcarbonyl substituted by halogen, CN, NO ₂ , CrC ₆ alkoxy, C ₃ -C ₆ alkenyloxy, Ci-Cealkoxycarbonyl or substituted or unsubstituted aryl or aryloxy, CrC ₁₀ alkoxycarbonyl, Ci-Cioalkoxycarbonyl substituted by halogen, CN, NO ₂ , d-dalkoxy, C ₃ -C ₆ alkenyloxy, Ci-Cealkoxycarbonyl or substituted or unsubstituted aryl or aryloxy, d-doalkylcarbonyloxy or d-Cι ₀ alkylcarbonyloxy substituted by halogen, CN, NO ₂ , Ci-Ce¬ alkoxy, C ₃ -C ₆ alkenyloxy, C C ₆ alkoxycarbonyl or substituted or unsubstituted aryl or aryloxy, or R ₉₇ is CHO, C ₃ -C ₈ cycloalkyl, C,-C ₄ alkylthio, C ₃ - or C ₄ alkenylthio, (R ₉₄ ) ₂ N-, (R ₉₅ ) ₂ N-CO-, aryl, aryloxy, arylcarbonyl or aryloxycarbonyl, or a group

(CH ₂ ) NCO-; the radicals R ₉₄ independently of one another are hydrogen, Ci-Cioalkyl,

C ₃ -C _θ cycloalkyl, Crd ₀ alkylcarbonyl or substituted or unsubstituted arylcarbonyl; the radicals R ₉₅ independently of one another are hydrogen, d-C ₅ alkyl or C ₃ -C ₈ cycloalkyl; n ₅ is a number from 5 to 12; and

Rgβ is hydrogen, fluorine, chlorine, bromine, CN, Cι-C ₃ alkoxy, C C ₃ alkoxycarbonyl, CrC ₃ - alkoxy-d-C ₃ alkyl, d- or C ₂ halogenoalkyl, d-Csalkyl, NO ₂ , C ₃ -C ₅ alkenyl, cyclopropyl or C or C ₂ halogenoalkoxy.

Especially preferred compounds of these are those in which Ri is a group

RgoRgi or

Rso and R ₉ ι independently of one another are Crd ₂ alkyl, Ci-Cealkyl substituted by halogen, CN or d-C ₃ alkoxy, C ₃ -C ₈ cycloalkyl, C ₃ -C _β cycloalkyl substituted by methyl, d-dcycloalkenyl or d-dcycloalkenyl substituted by methyl; the radicals R ₂₀ independently of one another are hydrogen or methyl; n, is 2, 3 or 4; n ₂ 0 or 1 ; and n ₃ is 3, 4 or 5;

R ₂ is a group RββRβgN-;

Rββ and R ₈₉ independently of one another are hydrogen or d-C ₃ alkyl; and

in which X is -O- or -S-;

R ₉₇ is hydrogen, halogen, NO ₂ , CN, d-Cι ₀ alkyl, Ci-Cioalkyl substituted by halogen, CN,

NO ₂ , CrC ₆ alkoxy or substituted or unsubstituted aryl or aryloxy, C ₃ -Cι ₀ alkenyl, C ₃ -Cιoalkenyl substituted by halogen, CN, NO ₂ , d-C ₆ alkoxy or substituted or unsubstituted aryl or aryloxy,

Ci-Cioalkoxy, d-Cioalkoxy substituted by halogen, CN, NO ₂ , d-C ₆ alkoxy or substituted or unsubstituted aryl or aryloxy, C ₃ -d ₀ alkenyioxy, C ₃ -Cιoalkenyloxy substituted by halogen,

CN, NO ₂ , CrCealkoxy or substituted or unsubstituted aryl or aryloxy, Ci-Cioalkoxycarbonyl,

Ci-Cioalkoxycarbonyl substituted by halogen, CN, NO ₂ , d-C ₆ alkoxy or substituted or unsubstituted aryl or aryloxy, CrCι ₀ alkylcarbonyloxy or C Cioalkylcarbonyloxy substituted by halogen, CN, NO ₂ , d-dalkoxy or substituted or unsubstituted aryl or aryloxy, or R ₉₇ is

(R_ ₄ ) ₂ N-, (R ₉₅ ) ₂ N-CO-, aryl, aryloxy, arylcarbonyl or aryloxycarbonyl; the radicals R ₉₄ independently of one another are hydrogen, d-C alkyl, C ₃ -C ₈ cycloalkyl, d-C ₃ alkylcarbonyl or substituted or unsubstituted arylcarbonyl; and the radicals R ₉₅ independently of one another are hydrogen, d-C ₃ alkyl or C ₃ -C ₆ cycloalkyl.

Especially preferred individual compounds from the scope of formula I are:

3-amino-5-pentafluorophenoxy-1-(trans-3,3,5-trimethylcycl ohexanolyl)thiatriazine;

3-amino-5-pentafluorophenoxy-1-[(N-cis-3,3,5-trimethylcyc lohexyl)methylamino]thiatriazine;

3-amino-5-pentafluorophenoxy-1-octamethyleneimino-thiatri azine;

3-amino-5-pentafluorophenoxy-1-decahydroquinolyl-thiatria zine;

3-amino-5-pentafluorophenoxy-1 -tetrahydroisoquinolyl-thiatriazine; and

the compound of the formula

The compounds of the formula I can be prepared on the one hand by process steps known per se using known starting materials, and on the other hand by processes which are not known per se. The latter processes which are not known per se comprise a procedure in which, for preparation of compounds of the formula I in which Ri is the group R ₇ ; R ₂ and R ₃ independently of one another are halogen, d-Cioalkoxy, CrCι ₀ alkoxy substituted by halogen, CN, NO ₂ , CrC ₆ alkoxy, d-dalkylthio, C ₃ -C ₆ alkenyloxy, Cι-C ₆ alkoxycarbonyl, heterocyclyl or substituted or unsubstituted aryl or aryloxy, C ₃ -Cι ₀ alkenyloxy,

C ₃ -Cι ₀ alkenyloxy substituted by halogen, CN, NO ₂ , Ci-Cealkoxy, C ₃ -C ₆ alkenyloxy, Cι-C ₆ alkoxycarbonyl or substituted or unsubstituted aryl or aryloxy, CrCι ₀ alkylthio, Cι-Cι ₀ alkylthio substituted by halogen, CN, NO ₂ , CrC ₆ alkoxy, C ₃ -C ₆ alkenyloxy, Ci-Cealkoxycarbonyl or substituted or unsubstituted aryl or aryloxy, C ₃ -Cιoalkenylthio or C ₃ -Cι ₀ alkenylthio substituted by halogen, CN, NO ₂ , CrC ₆ alkoxy, C ₃ -C ₆ alkenyloxy, Ci-Cealkoxycarbonyl or substituted or unsubstituted aryl or aryloxy, or R ₂ and R ₃ independently of one another are C ₃ -C ₅ alkynyloxy, C ₃ -C ₅ alkynylthio, C ₃ -C ₈ cycloalkyl-X-, C ₆ -Cι ₂ bicycloalkyl-X-, heterocyclyl-X-, alicyclyl-X-, aryl-X-, phthalidyl-X-, biphenyl-X- or heteroaryl-X-, and X is as defined under formula I, ai) 1 ,3,5-trichlorthiatriazine is used as the starting substance, and this is converted with an alcohol of the formula XVII

R ₇ -OH (XVII), in which R ₇ is as defined under formula I, if appropriate in the presence of an equimolar amount of base and an inert organic solvent, into the compound of the formula VII

^N _s ^ (VII),

0-R ₇ in which R ₇ is as defined, and this compound is then either bi) reacted with a compound of the formula XXIII

Rι ₄ -XιH (XXIII), in which R is Ci-Cioalkyl, CrCiealkyl substituted by halogen, CN, NO ₂ , CrC ₆ alkoxy, Cι-C ₆ alkylthio, C ₃ -C ₆ alkenyloxy, CrC ₆ alkoxycarbonyl, heterocyclyl or substituted or unsubstituted aryl or aryloxy, C ₃ -Cιoalkenyl or C ₃ -Cιoalkenyl substituted by halogen, CN, NO _2t CrC ₆ alkoxy, C ₃ -C ₆ alkenyloxy, CrC ₆ alkoxycarbonyl or substituted or unsubstituted aryl or aryloxy, C ₃ -C ₃ alkynyl, C ₃ -C ₈ cycloalkyl, C ₆ -Cι ₂ bicycloalkyl, heterocyclyl or alicyclyl and Xi is oxygen or sulfur, in the presence of an equimolar amount of base and an inert organic solvent, or b ₂ ) converted with a compound of the formula XVI

R ₁₂ -X ₁ H (XVI), in which Rι ₂ is an aryl, phthalidyl, biphenyl or heteroaryl radical; and X1 is oxygen or sulfur, in the presence of an equimolar amount of base and an aprotic solvent, into the compound of the formula VI

in which R ₃ is -XrRι_, and this compound is either c ₂ ) reacted with the compound of the formula XXIII

R -XιH (XXIII), in which R and Xi are as defined above, in the presence of an equimolar amount of base and an inert organic solvent, or c ₃ ) converted with the compound of the formula XVI

Rι ₂ -XιH (XVI), in which Rι ₂ and Xi are as defined above, in the presence of an equimolar amount of base and an aprotic solvent, into the compound of the formula V

in which R ₃ is -X Rι ₂ and

R _7p Xi and R ₁₂ are as defined above, and this compound is then d ₃ ) reacted with the compound of the formula XXIII

R ₁₄ -X1H (XXIII), in which Rι and Xi are as defined, in the presence of an equimolar amount of base and in an inert organic solvent, or the compound of the formula VII b ₃ ) converted with 2 mol of compound of the formula XVI

R, ₂ -XιH (XVI), in which R ₁₂ and Xi are as defined, in the presence of an equimolar amount of base and in an aprotic organic solvent, into the compound of the formula V, and this compound is then reacted in a manner analogous to that described under d ₃ ), or a ₂ ) 1 ,3,5-trichlorothiatriazine is converted with a C ₈ -Cι ₂ bicycloalkyl epoxide, a C ₆ -Cι ₂ bicycloalkyl epoxide substituted by d-C ₃ alkyl or an epoxide of the formula XVIII or XIX

(XIX).

in which the radicals R ₃ independently of one another are hydrogen, C ₃ -C ₈ alkenyl, d-C^alkyl, Cι-Cι ₄ alkyl substituted by halogen, NO ₂ , CN, d-C ₅ alkoxy, aryloxy or d- C ₃ alkoxycarbony I ; the radicals R ₂₃ independently of one another are hydrogen or d-C ₆ alkyl; n ₈ is a number from 3-10; and nn is 1 or 2, in an inert organic solvent, into the compound of the formula VII in which

R ₇ is C ₂ -Cιe-b-chloroalkyl, C ₂ -Cι ₆ -b-chloroalkyl substituted by halogen, NO ₂ , CN, d-dalkoxy, aryloxy or d-C ₃ alkoxycarbonyl, C ₅ -Cι ₂ -b-chlorocycloalkyl or C ₅ -d ₂ -b- chlorocycloalkyl substituted by d-C ₆ alkyl , and this compound reacted further in a manner analogous to that described under bi); b ₂ ) and c ₂ ); b ₂ ), c ₃ ) and d ₃ ); or b ₃ ) and d ₃ ), or a ₃ ) 1 ,3,5-trichlorothiatriazine is reacted with an alcohol of the formula XVII

R OH (XVII), in which R ₇ is d-doalkyl, CrCioalkyl substituted by halogen, CN, NO ₂ , d-C ₅ alkoxy, CrC ₅ alkylthio, C ₃ -C ₆ alkenyloxy, d-C ₃ alkoxycarbonyl, heterocyclyl or substituted or unsubstituted aryl or aryloxy, C ₃ -Cιoalkenyl, C ₃ -Cιoalkenyl substituted by halogen, d-dalkoxy or substituted or unsubstituted aryl or aryloxy, C ₃ -C ₅ alkynyl, C ₃ -C ₈ cycloalkyl, C ₆ -Cι ₂ bicycloalkyl, heterocyclyl or alicyclyl, if appropriate in an inert solvent in the presence of an eqimolar amount of base.

Another process according to the invention for the preparation of the compounds of the formula I in which Ri is the group -OR ₇ ;

R ₂ is a group RββR ₈₉ N-

and R ₃ is aryl-X-, phthalidyl-X-, biphenyl-X- or heteroaryl-X- comprises a procedure in which c ₄ ) a compound of the formula VI

in which R ₇ is as defined under formula I and

R ₃ is as defined above, is reacted with an amine of the formula XIII, XIV or XV

RββRβ ₉ NH (XIII), (XIV) or Y N-H (XV),

in which R∞, Rββ, R ₈₉ , Y and n ₇ are as defined under formula I, if appropriate in a solvent; or c ₃ ) the compound of the formula VI is first converted with a compound of the formula XVI

R, ₂ -XιH (XVI), in which Rι ₂ is an aryl, phthalidyl, biphenyl or heteroaryl radical, and X is oxygen or sulfur, in the presence of an equimolar amount of base and in an aprotic organic solvent, into the compound of the formula V

in which R ₃ is -X Rι ₂ and

R ₇ , Rι ₂ and Xi are as defined, and d ₄ ) this is then reacted with an amine of the formula XIII, XIV or XV in a manner analogous to that described under C ); or in which a ) 1 ,3,5-trichlorothiatriazine is converted with an alcoholate of the formula XVII1

(R ₇ -O ^' ) _n Mι ⁺ⁿ (XVII,), in which R ₇ is as defined under formula I; ι ⁺ⁿ is an alkali metal or alkaline earth metal ion or a metal ion of the first or second sub¬ group of the Periodic Table; and n is 1 , 2, 3 or 4, in the presence of an inert organic solvent, into the compound of the formula VII

in which R ₇ is as defined, and b ₄ ) this is reacted with an amine of the formula XIII, XIV or XV

Rβ-RβgNH (XIII), -H (XIV) or N-H (XV),

in which R∞, Rββ, R∞. Y and n ₇ are as defined under formula I, if appropriate in a solvent, to give the compound of the formula VIM

in which R ₂ and R ₇ are as defined, and c ₅ ) this is then reacted with a compound of the formula XVI in which Rι ₂ is an aryl, phthalidyl, biphenyl or heteroaryl radical; and Xi is oxygen or sulfur, in a solvent in the presence of a tertiary amine and, if appropriate, another base.

The process according to the invention for the preparation of the compounds of the formula I in which

Ri is a group -NRgoRgi or an N-heterocyclic radical onto which 1 or 2 further carbocyclic, heterocyclic or aromatic rings can be fused and which can contain further heteroatoms;

R ₂ is a group RββRβgN-, or Y N — ; and

R ₃ is aryl-X-, phthalidyl-X-, biphenyl-X- or heteroaryl-X-

comprises a procedure in which e) a compound of the formula III

in which R ₇ is as defined under formula I and

R ₂ and R ₃ are as defined, is reacted with an amine of the formula XI or XII

in which Rgo and R ₉ ι are as defined under formula I and

R ₁₁ is a cyclic radical onto which 1 or 2 further carbocyclic, heterocyclic or aromatic rings can be fused and which can contain further heteroatoms, if appropriate in a solvent; or in which a _s ) 1 ,3,5-trichlorothiatriazine is converted with an amine of the formula XI or XII

in which Rgo and R ₉ ι are as defined under formula I and

R11 is a cyclic radical onto which 1 or 2 carbocyclic, heterocyclic or aromatic rings can be fused and which can contain further heteroatoms, or with an amide of the formula XI1 or XII1

(R _9θ R _9l N ) _n M ₂ ⁺ (Xlι) or (XII1),

in which Rgo, R9 ₁ and R _ιn are as defined;

M ₂ ⁺ⁿ is an alkali metal or alkaline earth metal ion or a metal ion of the first or second sub¬ group of the Periodic Table; and n is 1 , 2, 3 or 4, in the presence of an inert organic solvent and if appropriate a base, into the compound of the formula IX

in which Ri is as defined, and b _s ) this is reacted with an amine of the formula XIII, XIV or XV

RββRβgNH (XIII), (XIV) or N-H (XV),

in which R ₂₀ , Rββ. Reg. Y and n ₇ are as defined under formula I, if appropriate in a solvent, to give the compound of the formula X

in which R and R ₂ are as defined, and

c ₆ ) this is then reacted with a compound of the formula XVI in which Rι ₂ is an aryl, phthalidyl, biphenyl or heteroaryl radical; and Xi is oxygen or sulfur, in a solvent in the presence of a tertiary amine and a further equivalent amount of base.

Another process according to the invention for the preparation of compounds of the formula

I in which

Ri is a group -OR ₇ ;

R ₂ is a group RββRβgN- thalidyl-X-,

biphenyl-X- or heteroaryl-X-; and R ₃ is aryl-X-, phthalidyl-X-, biphenyl-X- or heteroaryl-X-, comprises a procedure in which a compound of the formula I in which

Ri is a group -OR ₇ , in which

R is other than in the end product; and

R ₂ and R ₃ are as defined is reacted with an alcohol of the formula XVII

R ₇ -OH (XVII) in which R ₇ is other than in the starting substance of the formula I, in the presence of an inert organic solvent and a catalytic or equimolar amount of base.

The abovementioned processes according to the invention for the preparation of compounds of the formula I follow equations 1 and 2, the scope of the compounds of the formula I being composed of the scopes of the compounds of the formulae II, III and IV shown in the equations mentioned.

Equation 1 : ^CI

IX

IV V

In equation 1 the following applies: ai) Rτ-OH (XVII), solvent, -60°-+80°C;

⁰ A a ₂ ) Bicycioalkyi epoxides, . pCVIII) or ) _r X (XIX), solvent, 0°-130°C;

Pialn,, ly ^Jn β

R~, a ₃ ) R ₇ -OH (XVII), solvent, base, for example NaH, 10°-40°C; bi) R -XιH (XXIII), solvent, base, for example NaH, -60°-+80°C; b ₂ ) R ₁₂ -X-H (XVI), solvent, base, for example NaH, -60°-+50°C; b ₃ ) 2 mol R12-X1H (XVI), solvent, base, for example NaH, -60°-+50°C;

c ₂ ) Rι ₄ -XιH (XXIII), solvent, base, for example K tert-butylate, -60°-+80°C; c ₃ ) Rι ₂ -XιH (XVI), solvent, base, for example NaH, -60°-+50°C; and d ₃ ) R _i -XιH (XXIII), solvent, base, for example K tert-butylate, -60°-+80°C; a ) (Rτ-O ^' )n Mι ⁺ⁿ (Vlli), for example (R ₇ -O ^' )(MgCI)\ solvent, for example tetrahydrofuran,

-78°-0°C;

(XIV) or Y NH (XV). solvent, -78°-+40°C;

a ₅ ) R ₉₀ R ₉₁ NH (XI) or ^R „ N-H (XII), base, for example Et_N, solvent, or

(R ₉ oR ₉ iN ^' )„ M ₂ ⁺ⁿ (Xlι) or (XII1), solvent, -78°-0°C;

b ₅ ) RββRβgNH (XIII), H (XIV) or Y NH (XV), solvent, -78°-+40°C,

in which R _7> Rn, R, ₂ , Rι ₃ , R, ₄ , R20, R ₂₃ , R ₈₈ , Rβ9, R90, R91, n, n ₇ , n ₈ , n,,, Y, Xi, M ⁿ and M ₂ ⁺ are as defined above.

Equation 2:

V

In equation 2, the following applies: c ₃ ) Rι ₂ -XιH (XVI), solvent, base, for example NaH, -60°-+50°C;

c ₄ ) RββRωNH (XIII), / ^~~ λ tχιv) or Y N-H (XV), solvent, -50°-+50°C;

d ₄ ) RββR _β gNH (XIII), -H (XV), solvent, -20°-+ 100°C;

e) R9oR ₉ ιNH (XI) or R N-H (XII), solvent, 20°-150°C;

c ₅ ) Rι ₂ -XιH (XVI), solvent, tertiary amine, for example (CH ₃ ) ₃ N, if appropriate base, for example NaOH, -10°-+70°C; c ₆ ) Rι ₂ -XιH (XVI), solvent, tertiary amine, for example (CH ₃ ) ₃ N, base, for example NaOH,

-10°-+70°C; p) R^OH (XVII), solvent, basest., for example NaH, -60 ^o -+50°C; and q) R ₇ -OH (XVII), solvent, base, for example NaH, 0°-+50°C; in which R _7l R _{11 f} R ₂ , R∞, Rββ, Rββ. R90, R91, Y. n ₇ and Xi are as defined above.

The substitution of the most reactive chlorine atom on the sulfur of the 1 ,3,5-trichloro- thiatriazine leads on the one hand by a process variant ai), by reaction with the alcohol of the formula XVII, by process variant a ₂ ), by reaction with bicycioalkyi epoxides or epoxides of the formula XVIII or XIX, or by process variant a ₄ ), by reaction with alcoholates of the formula XVII1, to the compounds of the formula VII, and on the other hand by process variant a ₃ ), by reaction with the alcohol of the formula XVII, directly to the compounds of the formula IV (equation 1).

Process variant a ₂ ) always gives 1 -b-chloroalkoxy derivatives of the formula VII here.

The reaction according to process variant ai) is advantageously carried out in a non-polar organic solvent which is inert in the reaction, such as chlorinated hydrocarbons, for example methylene chloride, chloroform or carbon tetrachloride, aromatic hydrocarbons, for example benzene, toluene or xylenes, cyclic hydrocarbons, for example cyclohexane, or cyclic ethers, for example tetrahydrofuran or dioxane, at reaction temperatures of -60°C to +80°C, preferably at temperatures of -30°C to +50°C, if appropriate in the presence of an equimolar amount of base. Examples of suitable bases are organic bases, such as tertiary amines, for example trimethylamine, triethylamine, quinuclidine, 1 ,4-diazabicyclo-[2.2.2]octane, 1 ,5- diazabicyclo[4.3.0]non-5-ene or 1 ,5-diazabicyclo[5.4.0]undec-7-ene or alcoholates, for example potassium tert-butylate, sodium methylate or sodium ethylate. However, inorganic bases, such as hydrides, for example sodium or calcium hydride, hydroxides, such as sodium or potassium hydroxide, carbonates, such as sodium or potassium carbonate, or

bicarbonates, such as potassium or sodium bicarbonate, can also be used as bases. In a preferred embodiment (Example H2), 2-chloroethanol and an equimolar amount of triethylamine are dissolved in carbon tetrachloride and a solution of 1 ,3 ,5- trichlorothiatriazine in carbon tetrachloride is added to this cooled solution (-15°C), and the mixture is subsequently warmed to 0°C.

The reaction of 1 ,3,5-trichlorothiatriazine with bicycioalkyi epoxides or with epoxides of the formula XVIII or XIX is expediently carried out in the same solvents as listed under variant ai) at reaction temperatures of 0° to 130°C, preferably at reaction temperatures of 25° to

80°C.

In a preferred embodiment (Example H1), 1 ,3,5-trichlorothiatriazine is dissolved in carbon tetrachloride and an equimolar amount of cyclohexene oxide is added at room temperature.

In process variant a ₄ ), 1 ,3,5-trichlorothiatriazine is reacted with an alcoholate of the formula XVIIi

(Rτ-0-)„ M ⁿ (XVIIi), in which R ₇ is as defined under formula I;

Mι ⁺ⁿ is a mono- or polyvalent metal ion, for example an alkali metal or alkaline earth metal ion or a metal ion of the first or second sub-group of the Periodic Table, preferably lithium, magnesium, zinc, aluminium, silicon, tin or titanium, but especially preferably magnesium; and n is the number 1 , 2, 3 or 4 (=oxidation number of the corresponding metal ion) in the presence of an inert organic solvent, such as ethers, for example diethyl ether or tetrahydrofuran (THF).

In the compounds of the formula XVIIi in the case of polyvalent metal ions Mι ⁺ⁿ , if n>1 , further substituents, for example halogen, C C^lkyl or cyano, are also possible in addition to one or more R^O groups. Furthermore, the alcoholates of the formula XVIIi can also be employed in combination with salts, for example aluminium, tin or zinc chloride or aluminium or zinc bromide.

The reaction temperatures for this reaction range from -70° to +20°C, but are preferably below 0°C.

The resulting compound of the formula VII can be isolated, if appropriate, or else used directly for the next reaction stage.

In process variant a ₃ ), the most reactive chlorine atom on the sulfur of the thiatriazine ring is replaced in particular by the group -OR ₇ with addition of an equimolar amount of base; the less reactive chlorine atoms on the carbon atoms in the 3- and 5-positions can also be

partly or completely replaced by the group -OR ₇ , depending on the reaction conditions (for example low reaction temperatures; slow warming of the reaction mixture). The replacement according to variant a ₃ ) is advantageously carried out in the presence of a non-polar organic solvent which is inert in the reaction. Such solvents are listed under variants a^ and a ₂ ). The alcohol of the formula XVII is accordingly converted into the corresponding alcoholate in the solvent by treatment with a strong base, such as metal hydrides, for example sodium hydride, and this alcoholate solution is added dropwise to a solution of 1 ,3,5-trichlorothiatriazine at temperatures of 10° to 40°C, in particular at temperatures of 20° to 30°C, while cooling.

In a preferred embodiment (Example H9), the 1 ,3,5-trichlorothiatriazine is dissolved in tetrahydrofuran and a methanolic sodium methylate solution in tetrahydrofuran is added dropwise at 30°C, while cooling. Completely substituted 1 ,3,5-trimethoxythiatriazine is obtained.

Preparation of the thiatriazine derivatives of the formula VI (equation 1 ) according to process variant b ₂ ) is advantageously carried out by reaction of the corresponding 3,5- dichloro-thiatriazine of the formula VII with an alcohol of the formula XVI

Rι ₂ -XιH (XVI), in which Rι ₂ and Xi are as defined, in the presence of an organic solvent which is inert in the reaction, such as cyclic ethers, for example tetrahydrofuran or dioxane, and an equimolar amount of base, for example alkali metal hydrides, preferably sodium or lithium hydride, or alcoholates, for example potassium tert-butylate. The reaction temperatures range from -60° to +50°C, preferably from -40° to +10°C.

In a preferred embodiment (Example H4), ethyl salicylate is dissolved in tetrahydrofuran together with the equimolar amount of sodium hydride, 1 -chloroethoxy-3,5-dichloro- thiatriazine is added dropwise at -30°C and the mixture is then warmed to room temperature.

The substitution of the remaining chlorine atom in the thiatriazine derivative of the formula VI with a further radical -XιRι ₂ is carried out in accordance with process variant c ₃ ). This reaction advantageously proceeds analogously to variant b ₂ ), and leads to symmetrically or asymmetrically substituted thiatriazine derivatives of the formula V, depending on the compound of the formula XVI employed (equation 1).

The thiatriazine derivatives of the formula V can also be prepared directly from the compounds of the formula VII according to process variant b ₃ ), and leads exclusively to symmetrically substituted derivatives being formed.

The reaction according to process variant b ₃ ) is advantageously carried out analogously to process variant b ₂ ) or c ₃ ), but with the difference that two molar equivalents of the compound of the formula XVI and accordingly two molar equivalents of base are employed.

The preparation of the thiatriazine derivatives of the formula IV (equation 1), in which R ₂ , R ₃ and R ₇ are as defined, is advantageously carried out in accordance with process variant d ₃ ) from the thiatriazine derivatives of the formula V by reaction with alcohols or thiols of the formula XXIII

Rι ₄ -XιH (XXIII), in which R _u and X are as defined, in an inert organic solvent analogously to process variant a _n ) at temperatures of -60° to +80°C, preferably -50°C to room temperature, in the presence of an equimolar amount of base. Suitable bases are, for example, organic bases, such as tertiary amines, for example triethylamine, alcoholates, for example potassium tert-butylate, or inorganic bases, such as alkali metal hydrides, for example sodium or lithium hydride. If appropriate, the alcohol of the formula XXIII can also be used as the solvent. Partial or complete exchange can take place both on the sulfur atom (1 -position) and on the carbon atoms in the 3- and 5- positions, depending on the reaction conditions (reaction temperature, reaction time) and the ease of substitution of the substituents in the starting compound of the formula V. In a preferred embodiment (Example H10), 1-(b-chloroethoxy)-3,5-di(2',5'-difluorophenoxy)- thiatriazine is dissolved in methanol and a sodium methylate solution in methanol is added dropwise at low temperatures (-60°C). The derivative substituted by methoxy in the 1 -position is first formed by this procedure and is converted into 1 ,3-dimethoxy-5-(2',5'-di- fluorophenoxy)thiatriazine when the reaction solution is warmed.

In another preferred embodiment (Example H1 1 ), 1 -(b-chloroethoxy)-3,5-di(2',4'-dichloro- phenoxy)thiatriazine is dissolved in tetrahydrofuran and a solution of 2,2,2-trichloroethanol and sodium hydride is added dropwise at low temperatures (-50°C). After the reaction mixture has been warmed up, the derivative of the formula IV substituted by 2,2,2- trichloroethoxy in the 3- and 5-positions on the thiatriazine ring is isolated.

The reactions according to process variants bi) and c ₂ ) (equation 1 ) starting from the thiatriazine intermediates of the formulae VII and VI also give thiatriazines of the formula IV. Both variants bi) and c ₂ ) are advantageously carried out analogously to process variant d ₃ ) by reaction of the thiatriazine intermediates of the formula VII or VI with alcohols or thiols of

the formula XXIII in organic solvents which are inert in the reaction at reaction temperatures of -60° to +80°C.

In these two process variants bi) and c ₂ ) also, partial or complete exchange of the substituents in the 1-, 3- and 5-positions can be obtained, depending on the reactivity of the substituents in the 1 -, 3- and 5-positions of the thiatriazine intermediates of the formulae VII and VI and on the reaction conditions, for example the use of an equimolar amount of alcohol or thiol of the formula XXIII and an equimolar or catalytic amount of base. In an embodiment preferred for variant bi) (Example H12), 1-(b-chloroethoxy)-3,5-di- chlorothiatriazine is dissolved in tetrahydrofuran and a solution of 3 molar equivalents of tert-butylmercaptan and triethylamine in tetrahydrofuran is added dropwise at low temperatures (-50°C). After the reaction mixture has been warmed up to 0 ^C C, a 4/1 product mixture comprising 1 -(b-chloroethoxy)-3-chloro-5-tert-butylmercaptothiatriazine and 1 -(b-chloroethoxy)-3,5-di-tert-butylmercaptothiatriazine is obtained.

The preparation of the thiatriazine derivatives of the formula VIII (equation 1 ) according to process variant b ₄ ) is advantageously carried out by reaction of the 3,5-dichlorothiatriazine of the formula VII with an amine of the formula XIII, XIV or XV, if appropriate in the presence of a solvent, preferably tetrahydrofuran or acetonitrile, if appropriate mixed with water, at reaction temperatures of - 78° to +40°C.

In a preferred embodiment (Example H20), 3,5-dichloro-1 -(3-hexyloxy)thiatriazine is reacted with ammonia in tetrahydrofuran at 0°C.

In process variant a ₅ ) in equation 1 , the most reactive chlorine atom on the sulfur atom of the trichlorothiatriazine is substituted by addition of an amine of the formula XI or XII in an inert organic solvent and if appropriate in the presence of a base, for example a tertiary amine, for example triethylamine. Suitable solvents for this substitution are ethers, for example tetrahydrofuran, at reaction temperatures of -78° to +25°C, but preferably at reaction temperatures below -40°C.

Alternatively, instead of the amines of the formula XI or XII, the amides of the formula Xh or Xllι

(R∞Rθi Jn M ₂ ⁺ⁿ (Xlι) or . (Xllι)

in which R ₉₀ and R ₉₁ are as defined under formula I;

R ₁₁ is a cyclic radical onto which 1 or 2 carbocyclic, heterocyclic or aromatic rings can be fused and which can contain further heteroatoms;

M ₂ ⁺ⁿ is an alkali metal or alkaline earth metal ion or a metal ion of the first or second sub¬ group of the Periodic Table; and n is the number 1 , 2, 3 or 4 (=oxidation number of the corresponding metal ion), can be reacted with the 1 ,3,5-trichlorothiatriazine in an organic solvent, for example an ether, for example diethyl ether or, preferably tetrahydrofuran. The reaction temperatures range from -78° to 0°C, but are preferably below -40°C. In the compounds of the formula Xh or XI , in the case of polyvalent metal ions M ₂ ⁺ⁿ , if n>1 , further substituents, for example halogen or d-C ₄ alkyl, are also possible in addition to one or more amide groups.

The compound of the formula IX can be isolated, if appropriate, or else used directly for the next reaction stage (b ₅ )).

In a preferred embodiment (Example H21), a mixture comprising equimolar amounts of octahydroindole and triethylamine is added dropwise to 1 ,3,5-trichlorothiatriazine in diethyl ether at -70° to -60°C.

Further reaction of the thiatriazine of the formula IX in accordance with process variant b ₅ ) in equation 1 gives the thiatriazine of the formula X. This process variant is advantageously carried out analogously to process variant b ₄ ).

In a preferred embodiment (Example H23), an aqueous ammonia solution is added to

3,5-dichloro-1 -(octahydroindol-1 -yl)thiatriazine in tetrahydrofuran.

In another preferred embodiment (Example H22), a suspension of piperidine and n- butyllithium is added dropwise to a solution of trichlorothiatriazine in tetrahydrofuran which has been cooled to -60°C, and the mixture is subsequently treated further with ammonia gas at -10°C until the conversion is complete.

In the reactions according to process variants p) and q) (equation 2), only the substituent in the 1 -position, i.e. on the sulfur atom of the thiatriazine ring, is substituted selectively.

The thiatriazine derivatives of the formula III can be obtained either by reaction of the 3-chlorothiatriazine derivatives of the formula VI with the amines of the formula XIII, XIV or XV in accordance with process variant c ₄ ), or by reaction of the 5-chlorothiatriazine derivatives of the formula VIII with an alcohol of the formula XVI in accordance with process variant c ₅ ) (equation 2).

The substitution reaction according to variant c ) can advantageously be carried out in an inert organic solvent, such as a cyclic ether, for example tetrahydrofuran or dioxane, at temperatures of -50° to +50°C, preferably at temperatures of -20° to +20°C.

In a preferred embodiment (Example H15), 3-chloro-1 -(b-chloroethoxy)-5-(2'-carbo- ethoxyphenoxy)thiatriazine is dissolved in tetrahydrofuran, and dimethylamine is passed in at 0°C until conversion is complete.

The substitution reaction according to variant c ₅ ) can advantageously be carried out in an organic solvent, such as an ether, for example tetrahydrofuran, or a halogenated hydrocarbon, for example methylene chloride, to which water is admixed, if appropriate, in the presence of a catalytic to excess amount of a tertiary amine, for example trimethylamine, and in the presence or absence of a further base, for example sodium hydroxide, at temperatures from -10° to +70°C, preferably at 0° to 25°C. In a preferred embodiment (Example H16), a mixture of 3-amino-5-chloro-1 -(3-hexyloxy)- thiatriazine, difluorophenol and trimethylamine in methylene chloride is allowed to react at 20°C.

Another possibility for the preparation of the thiatriazines of the formula III starts from the thiatriazine intermediates of the formula V, one of the radicals -XιRι ₂ being substituted by amines of the formula XIII, XIV or XV according to process variant d ₄ ) (equation 2). This substitution reaction is advantageously carried out analogously to variant c ₄ ) in an inert organic solvent at temperatures from -20° to +100°C, preferably at 0° to 50°C.

According to process variant e), in equation 2, the group -OR ₇ bonded to the sulfur of the thiatriazine ring of the formula III can be substituted selectively by an amino group. As a result, compounds of the formula II in which

Ri is a group -NRgoRgi or an N-heterocyclic radical, are obtained. This reaction is advantageously carried out with amines of the formula XI or

XII in an inert organic solvent, such as an aromatic hydrocarbon, for example toluene or xylenes, at temperatures of 20° to 150°C, preferably at temperatures of 50° to 100 ^C C.

In a preferred embodiment (Example H18), 1 -(2'-chlorocyclohexanolyl)-3-amino-5-(2',6'- difluorophenoxy)thiatriazine is heated at 80°-90°C together with decahydroquinoline in toluene until conversion is complete.

Another possibility for the preparation of the thiatriazines of the formula II starts from the 1 ,3-disubstituted 5-chlorothiatriazines of the formula X, the 5-chlorine atom being replaced by alcohols of the formula XVI according to process variant c ₆ ) in equation 2. This replacement is advantageously carried out in the presence of a catalytic to excess amount of a tertiary amine, for example trimethylamine, and a further equivalent amount of base, for example sodium hydroxide, in an organic solvent, such as an ether, for example tetrahydrofuran, or a halogenated hydrocarbon, for example methylene chloride, to which water is admixed if appropriate. The reaction temperatures are -10° to +70°C, preferably 0° to 25°C.

In a preferred embodiment (Example H19), 3-amino-5-chloro-1 -(piperidin-1-yl)thiatriazine and pentafluorophenol are brought together in methylene chloride with 2N sodium hydroxide solution and aqueous trimethylamine and allowed to react. In the thiatriazine derivatives of the formulae V and III, the group -OR ₇ bonded to the sulfur can be substituted selectively by another alcohol of the formula XVII

Rτ-OH (XVII), in which R ₇ is as defined under formula I, according to process variants p) and q) in equation 2. Other compounds of the formulae V and III and of the formula I can be prepared in this way and by customary derivatization.

In the case of the compounds of the formula V, this exchange is advantageously carried out according to process variant p) with an excess of alcohol, but at least the equimolar amount of alcohol, in an inert organic solvent, such as a cyclic ether, for example tetrahydrofuran or dioxane, at temperatures from -60° to +50°C, preferably at temperatures from -40° to +10°C, in the presence of a catalytic amount of base, for example 1-30 mol%, preferably 5-20 mol%. Suitable bases are, for example, metal hydrides, such as sodium hydride, or alcoholates, such as potassium tert-butylate.

The exchange of the group -OR ₇ in the case of the compounds of the formula III in accordance with process variant q) can be carried out analogously to process variant p), with the difference that reaction temperatures of 0° to 50°C, preferably 10° to 30°C, are used and that the amount of base used for the exchange reaction is less critical. Equimolar amounts of bases are preferably used.

In a preferred embodiment (Example H14), isopropanol and sodium hydride are initially introduced into tetrahydrofuran and 3-amino-1 -(b-chloroethoxy)-5-(2',5'-difluorophenoxy)- thiatriazine is added to this suspension at room temperature.

The thiatriazines of the formula I or of the formulae II, III and IV, in which

R ₂ and/or R ₃ is aryl-X-, phthalidyl-X-, biphenyl-X- or heteroaryl-X-; and

X is sulfur, obtained in the process variants described above can subsequently be oxidized to give the corresponding sulfoxides and sulfone derivatives of the formula I or of the formulae II, III and IV, in which

R ₂ and/or R ₃ is aryl-X-, phthalidyl-X-, biphenyl-X- or heteroaryl-X-; and

X is -SO- or -SO ₂ -, analogously to known standard processes, for example with hydrogen peroxide or m-chloro- perbenzoic acid. In order to avoid undesirable side reactions, the conditions for this oxidation must be evaluated in respect of the reactivities of the other substituents on the thiatriazine ring. Examples of such sulfur oxidations are described in Houben-Weyl,

"Methoden der Organischen Chemie" [Methods of Organic Chemistry], Fourth edition,

Volume IV, Georg Thieme Verlag Stuttgart.

The present processes according to the invention have the following advantages:

1. Easy accessibility of the 1 ,3,5-trichlorothiatriazine and of the other starting compounds of the formulae XVII, XVIII, XIX, XVI, XXIII, XI, XII, XIII, XIV and XV, and of the bicycioalkyi epoxides from the scope of formula I;

2. Low number of synthesis stages;

3. Selectivity of the exchange reactions on the thiatriazine ring;

4. Wide possibilities for derivatization in respect of the choice of substituents Ri, R ₂ and R ₃ on the thiatriazine ring and associated wide possibilities of variation for the thiatriazines of the formula I; and

5. Exchange reactions are carried out under mild reaction conditions (for example low temperatures) and are compatible for a large number of functional groups.

The thiatriazine derivatives of the formulae V, VI, VII, VIII, IX and X are novel. They are important intermediates for the synthesis of the compounds of the formula I. The invention therefore also relates to these novel compounds and processes for their preparation, and to the use of the compounds of the formulae V, VI, VII, VIII, IX and X for the preparation of compounds of the formula I.

For the intermediates of the formulae V, VI, VII, VIII, IX and X, the same preferences apply in respect of R ₃ and R ₇ as for the compounds of the formula I.

The starting compounds of the formulae XVII, XVIII and XIX required in process variants ai), a ₂ ), a ₃ ), p) and q) and the corresponding bicycioalkyi epoxides from the scope of formula I either are obtainable commercially or can be prepared by generally known methods. The preparation of such compounds is described, for example, in Houben-Weyl, "Methoden der Organischen Chemie" [Methods of Organic Chemistry], Fourth edition, Volume VI and VI/3, Georg Thieme Verlag Stuttgart.

The starting compounds of the formulae XVI and XXIII required in process variants bi), b ₂ ), b ₃ ), c ₂ ), c ₃ ) and d ₃ ) either are obtainable commercially or can be prepared by generally known methods.

The preparation of such compounds is described, for example, in Houben-Weyl, "Methoden der Organischen Chemie" [Methods of Organic Chemistry], Fourth edition, Volume VI and IX, Georg Thieme Verlag Stuttgart.

The amines of the formulae XI, XII, XIII, XIV and XV required in process variants c ), d ₄ ) and e) either are obtainable commercially or can be prepared analogously to known standard processes.

The preparation of such compounds is described, for example, in Houben-Weyl, "Methoden der Organischen Chemie" [Methods of Organic Chemistry], Fourth edition, Volume XI,

Georg Thieme Verlag Stuttgart.

The alcoholates of the formula XVI required in process variant a ) can be prepared analogously to known standard processes, for example by reaction of the corresponding alcohol of the formula XVI I with an Mrorganometallic compound, for example CrC ₄ alkyllithium or Cι-C ₈ alkylmagnesium halide, or by reaction with an Mi-metal compound which contains at least one leaving group, for example cyano or, preferably, halogen, and if appropriate one or more Cι-C alkyl groups, in the presence of a base. The compounds of the formula XVIIi do not have to be isolated in a pure form, but can be further used directly.

The amides of the formulae Xh and Xlli required in process variant a ₅ ) can be prepared analogously to known standard processes, for example by reaction of the corresponding amines of the formula XI and XII with an M ₂ -organometallic compound, for example Cι-C ₄ alkyllithium or Cι-C ₈ alkylmagnesium halide, or by reaction with an M ₂ -metal compound which has at least one leaving group, for example halogen, and where appropriate one or more d-C ₄ alkyl groups, in the presence of a base.

The preparation of the starting compound 1 ,3,5-trichlorothiatriazine is described in DD-A-113 006 (Example 1).

The resulting compounds of the formula I can be isolated in the customary manner by concentration or evaporation of the solvent, and purified by recrystallization or trituration of the solid residue in solvents in which they do not dissolve readily, such as ethers or aliphatic hydrocarbons, by distillation or by means of column chromatography with a suitable eluting agent.

If no controlled synthesis is carried out for isolation of pure isomers or diastereomers, the product can be obtained as a mixture of two or more isomers or diastereomers. The isomers or diastereomers can be separated by methods known per se.

If desired, for example, pure optically active isomers or diastereomers can also be prepared by synthesis from corresponding optically active starting materials, for example cis- or trans- decalin, cis- or trans-2,6-dimethylmorpholine or cis- or trans-decahydro(iso)quinoline.

The end products of the formula I can be isolated in the customary manner by concentration and/or evaporation of the solvent and purified by recrystallization or trituration of the solid residue in solvents in which they do not dissolve readily, such as ethers, aromatic hydrocarbons or chlorinated hydrocarbons.

For use according to the invention of the compounds of the formula I, including the compounds of the formulae to l ₇ , or compositions comprising these, all the methods of application customary in agriculture, for example preemergence and postemergence application, as well as various methods and techniques such as, for example, controlled release of the active compound, are suitable. For this, the active compound is adsorbed in solution onto mineral granule carriers or polymerized granules (urea/formaldehyde) and the granules are dried. If appropriate, a coating can additionally be applied (coated granules), allowing the active compound to be released in a metered form over a certain period of time.

The compounds of the formula I, including the compounds of the formulae Ii to l ₇ , can be employed in unchanged form, i.e. as they are obtained in the synthesis, but they are preferably processed in the customary manner with the auxiliaries customary in formulation technology, for example to give emulsifiable concentrates, solutions which can be sprayed or diluted directly, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules. The methods of application, such as spraying, atomizing, dusting, wetting,

scattering or pouring, like the nature of the compositions, are chosen according to the required aims and the given circumstances.

The formulations, i.e. the compositions, formulations, preparations, combinations or mixtures comprising the active compound of the formula I or at least one active compound of the formula I, including the compounds of the formulae Ii to l ₇ and as a rule one or more solid or liquid formulation auxiliaries, are prepared in a known manner, for example by intimate mixing and/or grinding of the active compounds with the formulation auxiliaries, for example solvents or solid carriers. Surface-active compounds (surfactants) can, furthermore, additionally be used in the preparation of the formulations.

Solvents can be: aromatic hydrocarbons, preferably fractions C ₈ to Cι ₂ , for example xylene mixtures or substituted naphthalenes phthalic acid esters, such as dibutyl or dioctylphthalate, aliphatic hydrocarbons, such as cyclohexane or paraffins, alcohols and glycols, and ethers and esters thereof, such as ethanol, ethylene glycol or ethylene glycol monomethyl or -ethyl ether, ketones, such as cyclohexanone, strongly polar solvents, such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or N.N-dimethylformamide, and epoxidized or non-epoxidized vegetable oils, such as epoxidized coconut oil or soya oil; or water.

Solid carriers, for example for dusts and dispersable powders, which are used are as a rule natural rock powders, such as calcite, talc, kaolin, montmorillonite or attapulgite. Highly disperse silicic acid or highly disperse absorbent polymers can also be added to improve the physical properties of the formulation. Granular adsorptive carriers for granules are porous types, for example pumice, crushed brick, sepiolite or bentonite, and non-sorbent carrier materials are, for example, calcite or sand. A large number of pregranulated materials of inorganic or organic nature, such as, in particular, dolomite or comminuted plant residues, can moreover be used.

Surface-active compounds are nonionic, cationic and/or anionic surfactants and surfactant mixtures having good emulsifying, dispersing and wetting properties, depending on the nature of the active compound of the formula I to be formulated.

Suitable anionic surfactants can be both so-called water-soluble soaps and water-soluble synthetic surface-active compounds.

Soaps are the alkali metal, alkaline earth metal or substituted or unsubstituted ammonium salts of higher fatty acids (Cι ₀ -C ₂₂ ), for example the Na or K salts of oleic or stearic acid, or

of naturally occuring fatty acid mixtures, which can be obtained, for example, from coconut oil or tallow oil. They are also the fatty acid methyl-taurine salts.

However, so-called synthetic surfactants are more frequently used, in particular fatty alcohol sulfonates, fatty alcohol sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.

The fatty alcohol sulfonates or sulfates are as a rule in the form of alkali metal, alkaline earth metal or substituted or unsubstituted ammonium salts and contain an alkyl radical having 8 to 22 C atoms, alkyl also including the alkyl moiety of acyl radicals, for example the Na or Ca salt of ligninsulfonic acid, of dodecyl-sulfuric acid ester or of a fatty alcohol sulfate mixture prepared from naturally occurring fatty acids. These also include the salts of the sulfuric acid esters and sulfonic acids of fatty alcohol-ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and a fatty acid radical having 8-22 C atoms. Alkylarylsulfonates are, for example, the Na, Ca or triethanolamine salts of dodecylbenzenesulfonic acid, of dibutylnaphthalenesulfonic acid or of a naphthalenesulfonic acid-formaldehyde condensation product.

Salts can furthermore also be corresponding phosphates, for example salts of the phosphoric acid ester of a p-nonylphenol-(4-14)-ethylene oxide adduct, or phospholipids.

Nonionic surfactants are, in particular, polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, which can contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the alkyl radical of the alkylphenols.

Other suitable nonionic surfactants are the water-soluble adducts, containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups, of polyethylene oxide on polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol having 1 to 10 carbon atoms in the alkyl chain. The compounds mentioned usually contain 1 to 5 ethylene glycol units per propylene glycol unit.

Examples of nonionic surfactants are nonylpheπolpolyethoxyethanols, castor oil polyglycol ether, polypropylene-polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.

Fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate, can also be used.

The cationic surfactants are, in particular, quaternary ammonium salts, which contain at least one alkyl radical having 8 to 22 C atoms as N substituents and lower, halogenated or non-halogenated alkyl, benzyl or lower hydroxyalkyl radicals as further substituents. The salts are preferably in the form of halides, methyl sulfates or ethyl sulfates, for example stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)ethyl ammonium bromide.

The surfactants customary in formulation technology which can also be used in the compositions according to the invention are described, inter alia, in "Mc Cutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood New Jersey, 1981 , Stache, H. , "Tensid-Taschenbuch" [Surfactant Handbook], Carl Hanser Verlag, Munich/Vienna, 1981 and M. and J. Ash, "Encyclopedia of Surfactants", Volume 1—111, Chemical Publishing Co., New York, 1980-81.

The herbicidal formulations as a rule comprise 0.1 to 99% by weight, in particular 0.1 to 95% by weight, of herbicide, 1 to 99.9% by weight, in particular 5 to 99.8% by weight, of a solid or liquid formulation auxiliary and 0 to 25% by weight, in particular 0.1 to 25% by weight, of a surfactant.

While concentrated compositions are more preferable as commercial goods, the end user as a rule uses dilute compositions.

The compositions can also comprise further additives, such as stabilizers, for example epoxidized or nonepoxidized vegetable oils (epoxidized coconut oil, rapeseed oil or soya oil), defoamers, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers and fertilizers or other active compounds.

In particular, preferred formulations have the following composition: (% = per cent by weight)

Emulsifiable concentrates:

Active compound: 1 to 90%, preferably 5 to 50%

Surface-active agent: 5 to 30%, preferably 10 to 20%

Solvent: 15 to 94%, preferably 70 to 85%

Dusts:

Active compound: 0.1 to 50%, preferably 0.1 to 1 %

Solid carrier: 99.9 to 90%, preferably 99.9 to 99%

Suspension concentrates: Active compound: 5 to 75%, preferably 10 to 50% Water: 94 to 24%, preferably 88 to 30% Surface-active agent: 1 to 40%, preferably 2 to 30%

Wettable powders: Active compound: 0.5 to 90%, preferably 1 to 80% Surface-active agent: 0.5 to 20%, preferably 1 to 15% Solid carrier material: 5 to 95%, preferably 15 to 90%

Granules: Active compound: 0.1 to 30%, preferably 0.1 to 15%. Solid carrier: 99.5 to 70%, preferably 97 to 85%

The active compounds of the formula I, including the compounds of the formulae d to l ₇ , are as a rule successfully employed on the plants or their environment with rates of application of 0.001 to 4 kg/ha, in particular 0.005 to 2 kg/ha. The dosage required for the desired action can be determined by experiments. It depends on the mode of action, the stage of development of the crop plant and the weed and on the application (location, time, method), and can vary within relatively wide limits as a result of these parameters.

The compounds of the formula I, including the compounds of the formulae d to l ₇ , have herbicidal and growth-inhibiting properties which enable them to be used in crops of useful plants, in particular in cereals, cotton, soya, sugar beet, sugar cane, plantation crops, oilseed rape, maize and rice.

Crops are also to be understood as those which have been rendered tolerant to herbicides or classes of herbicide by conventional breeding or genetic engineering methods.

The weeds to be controlled can be both monocotyledon and dicotyledon weeds, for example Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Phaseolus, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum

halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica.

The following examples illustrate the invention further, without limiting it.

Preparation examples:

Example H 1 : Preparation of 1 -(trans-2-chlorocyclohexyloxy)-3,5-dichlorothiatriazine (process a ₂ )

(Compound No. 1.15)

5.1 1 g (0.025 mol) of 1 ,3,5-trichlorothiatriazine are dissolved in 50 ml of carbon tetrachloride, and 2.94 g (0.03 mol) of cyclohexene oxide are added at 25°C. The weakly exothermic reaction is carried out at 25-35°C and has ended after 30 minutes. The cloudy solution formed is filtered and the filtrate is concentrated. 8.7 g of crude product are obtained as a residue, recrystallization of which from a mixture of ethyl acetate and hexane gives 6.75 g (89% of theory) of the desired product of melting point 82-83°C.

Example H2: Preparation of 1-(2-chloroethoxy)-3.5-dichlorothiatriazine (process a

(Compound No. 1.7)

0.80 g (0.01 mol) of 2-chloroethanol and 1.21 g (0.012 mol) of triethylamine are dissolved in 30 ml of carbon tetrachloride and the solution is cooled to -15°C. Thereafter, a solution of 2.04 g (0.01 mol) of 1 ,3,5-trichlorothiatriazine in 5 ml of carbon tetrachloride is added dropwise at this temperature and the temperature is then allowed to rise to 0°C. The triethylamine hydrochloride is filtered off and the filtrate is concentrated to give 1 .85 g of

crude product. Recrystallization from 10 ml of hexane gives 1.65 g (67% of theory) of the desired product of melting point 54-55°C.

Example H3: Preparation of 1 -methoxy-3.5-dichlorothiatriazine (process ai)

(Compound No. 1.1)

4.09 g (0.02 mol) of 1 ,3,5-trichlorothiatriazine are stirred as a suspension in 50 ml of carbon tetrachloride at -25°C, and a solution of 0.70 g (0.022 mol) of methanol in a little carbon tetrachloride is added dropwise. During this operation, the trichlorothiatriazine dissolves apart from a little insoluble product. The mixture is then warmed to 0"C and filtered and the filtrate is concentrated on a rotary evaporator at a maximum of 50°C. 3.25 g of the desired product, which, according to the ¹³ C-NMR spectrum and thin layer chromatogram (silica gel; eluting agent ethyl acetate/hexane 1/3), contains practically no further impurities, are obtained as the residue. The compound is unstable and decomposes within a few hours when left to stand.

The compounds listed in the following Table I can be prepared analogously to Examples H1 to H3.

Table 1 : Compounds of the formula VII

Comp. R ₇ Process Physical data No.

T3; a. C-NMR: 167.5 ppm; 52.6 ppm

ai Melting point 54-55°C

Comp. Ry Process Physical data No.

13, C-NMR: 167.7 ppm; 71 .7 ppm;

1.15 a ₂ Melting point 82-83°C

166.8 ppm; 88.9 ppm; ; 33.1 ppm; 31 .2 ppm; ; 25.3 ppm; 25.1 ppm;

1.20 ai ³ C-NMR: 166.5 ppm; 82.8 ppm;

33.4 ppm; 25.2 ppm; 23.4 ppm

1.21 167.2 ppm; 88.6 ppm; ; 33.2 ppm; 30.8 ppm;

1.22 ¹³ C-NMR: 166.5 ppm; 85.9 ppm;

33.2 ppm; 26.8 ppm; 22.5 ppm

1.23

— CH:

\\ /

Comp. Rr Process Physical data No.

36.0 ppm;

1.30

^CH 3 CH ₃

1.31 -CH ₂ CH ₂ SC ₂ H ₅

1.34 -CH ₂ C-CH ai ¹³ C-NMR: 167.7 ppm; 79.0 ppm; 75.3 ppm; 55.5 ppm

Comp. R ₇ Process Physical data

1.39 CH(C ) ₃ CF ₃

C^H,),

1.44

-CH ₂ CH =CH ₂

1.47 -CH ₂ — <|

Comp. R ₇ Process Physical data No.

1.51 CHCR _j CI 13^ »,. _ ,-, a ₂ ^J C <_/--NiMMivιRπ:. 1 l 6o7/ ..0u p μpμmm;, 166.8 ppm; 84.3 ppm; 4 -IK5.77 p npnmm-; 29fi6.44 n pnprmrv;

C ₂ H ₅ 9.5 ppm

1.52 -CH ₂ CH ₂ OCH ₃ 1.53 -CH ₂ CH ₂ Br 1.54 — CH-CHCI a ₂ ¹ H-NMR: 3.9-4.1 ppm (3H);

1.6-2.0 ppm (2H); 1.05 ppm (3H)

C ₂ H ₅

1.55 CHCH I

I

(CH ₂ ) ₆ CH ₃

H ₂ CN

Comp. R ₇ Process Physical data No.

1.66

1.77 -CHCH.CI a ₂ Melting point 67-68°C

CH ₂ Br

Comp. R ₇ Process Physical data No.

a ₂ ¹ H-NMR: 8.2 ppm (2H); 7.6 ppm (1H); 7.5 ppm (2H); 4.85 ppm (1H); 4.6 ppm (1H); 4.4 ppm (1H); 3.7 ppm (2H)

Comp. R ₇ Process Physical data No.

1.93 -CHCrCH^OCK,

COOCH ₃ 1.94 -C(CH-JCH ₂ CI

COOCH ₃

1.107

Comp. R ₇ Process Physical data

1.119

-CH _) ^{~ ~}

Comp. R ₇ Process Physical data

.121 CH,

1.123

'COOCH,

Comp. R ₇ Process Physical data No.

1.136 -CHCH ₂ CI

CH ₂ 0C(CH ₃ )

Example H4: Preparation of 1-chloroethoxy-2-chloro-3-(2'-carboethoxyphenoxy)thiatriazin e

(Compound No. 2.4)

3.32 g (0.02 mol) of ethyl salicylate are stirred with 0.96 g of 55% sodium hydride (0.022 mol) in 50 ml of tetrahydrofuran under nitrogen. With evolution of hydrogen, a clear solution forms, which is added dropwise to a solution of 4.97 g (0.02 mol) of 1-chloroethoxy- 3,5-dichlorothiatriazine at -30°C. The mixture is warmed to room temperature and extracted with water and ethyl acetate at pH 6, with addition of a little acetic acid. After the solvent has been evaporated, 7.2 g of crude product are obtained, which is chromatographed on silica gel with a mixture of ethyl acetate and hexane 3/7. The desired product is obtained as an oil in a yield of 6.6 g (95% of theory).

The compounds listed in the following Table 2 can be prepared analogously to Example H4. Table 2: Compounds of the formula VI

Comp. R ₇ Physical Data

Melting point 128-129°C

Comp. R ₇ Physical Data

21.5

ppm

Comp. R ₇ R ₃ Physical Data

Comp. R ₇ Physical Data

H); 1 H);

Melting point 72-73°C

Comp. R ₇ Physical Data

Comp. R ₇ Physical Data

2.49 - H ₂ CH ₂ d ppm (3H); 4.2 ppm (1H); .15 ppm (2H);

Comp. R ₇ Physical Data No.

R ₃ Physical Data

COCH ₃

C ₆ F ₅ S-

2.75 -CH ₂ CH ₂ OCH ₃ C ₆ F ₅ O-

2.77 C ₆ F ₅ O-

Example H5: Preparation of 1-(b-chloroethoxy)-3.5-diphenoxythiatriazine (process b _g )

2.07 g (0.022 mol) of phenol are dissolved in 30 ml of tetrahydrofuran under nitrogen at a temperature of 40°C to 45°C, and 0.90 g (0.0225 mol) of 60% sodium hydride is added. When no further hydrogen is evolved, the mixture is cooled to -40°C, 2.5 g (0.01 mol) of 1-(b-chloroethoxy)-3,5-dichlorothiatriazine are added in portions and the exothermic reaction is allowed to proceed at -30°C to -40°C. The temperature is then allowed to rise to 0°C and the reaction mixture is extracted with water and ethyl acetate. After removal of the solvent, 4.5 g of crude product are obtained, which, after purification by chromatography (silica gel; ethyl acetate/hexane 1/1 ) and recrystallization from 10 ml of ethyl acetate and 15 ml of hexane, gives 3.35 g (92 % of theory) of the desired pure product of melting point 89- 90°C.

Analysis: Cι ₆ H ₁₄ CIN ₃ O ₃ S calculated T%1 found [%1

N 11.55 11.69

Cl 9.74 9.73

Example H6: Preparation of 1 -cvclohexyloxy-3-(p-nitrophenoxyι-5-(a-naphthoxy)thiatriazi ne (process c ₃ )

0.65 g (0.0045 mol) of a-naphthol is dissolved in 40 ml of tetrahydrofuran, and 0.196 g (0.0045 mol) of 55 % sodium hydride is added, under nitrogen. When the exothermic reaction has ended, the mixture is cooled to room temperature (23 ^C C) and a solution of 1.60 g (0.0043 mol) of 1-cyclohexyloxy-3-chloro-5-(p-nitrophenoxy)thiatriazine in a little tetrahydrofuran is added dropwise. During this operation, the temperature rises from 23°C to 31 °C. The mixture is extracted with water and ethyl acetate, the extract is concentrated and the residue is chromatographed (silica gel; ethyl acetate/hexane 1/9). This gives 1.05 g of the desired pure product, which is recrystallized from 5 ml of ethyl acetate and 5 ml of hexane. The yield of crystalline product of melting point 115-116°C is 0.87 g. The ¹³ C-NMR spectrum in CDCI ₃ shows, in addition to the lines for the a-naphthyl radical (118-156 ppm), 4 lines for the cyclohexyl radical (79.3 ppm; 33.4 ppm; 24.9 ppm and 23.6 ppm) and 2 lines for the two C atoms of the thiatriazine ring (169.3 ppm and 168.2 ppm).

Example H7: Preparation of 1-(n-butoxy)-3.5-di(2',5'-dichlorophenoxy)thiatriazine (process p)

0.75g (0.0015 mol) of 1-(b-chloroethoxy)-3,5-di(2',5'-dichlorophenoxy)thiatriazine and 2.22 g (0.03 mol) of n-butanol are dissolved in 15 ml of tetrahydrofuran, the solution is cooled to -40°C and 3.1 ml of a 0.098 molar solution of potassium tert-butylate in tetrahydrofuran

(0.00030 mol) are added. After 45 minutes, the reaction has ended. The reaction mixture is extracted with water and ethyl acetate, the extract is concentrated and the residue is chromatographed (silica gel; ethyl acetate/hexane 8/92). The yield is 0.64 g (92% of theory) of a resin, the 300 MHz ¹ H-NMR spectrum of which confirms the structure of the desired compound.

Example H8: Preparation of 1 -(2.2-dimethylpropoxy)-3.5-di(pentafluorophenoxy)thiatriazin e (process p)

0.74 g (0.001494 mol) of 1 -methoxy-3,5-di(pentafluorophenoxy)thiatriazine is dissolved with 5.27 g (0.0598 mol) of 2,2-dimethyl-1-propanol in 15 ml of tetrahydrofuran, and 0.30 ml of a 0.0982 molar solution (2.94 x 10 ^'5 mol) of potassium tert-butylate in tetrahydrofuran is added at -60°C. After 30 minutes, the reaction has ended. The mixture is extracted with water and ethyl acetate, the extract is concentrated on a rotary evaporator and the residue is treated under a high vacuum at 50°C. The yield is 0.75 g (91 % of theory) of a resin, the 300 MHz ¹ H- and ³ C-NMR spectra of which are in agreement with the structure of the desired compound.

The compounds listed in the following Table 3 can be prepared analogously to Examples

H5 to H8.

Table 3: Compounds of the formula V

R ₁₂ X, N

^N *s I ' ^N (V) OR ₇

Comp. Process R ₇ R12-X1

Comp. Process R ₇ Rι ₂ -Xι

Comp. Process R ₇ Rι ₂ -Xι

Comp. Process R ₇ R12-X1

Comp. Process R ₇ R ₃ R12-X1

C ₆ F ₅ O- C ₆ F ₅ O-

Comp. Process R ₇ R ₃ R12-X1

3.54 -CH ₂ CH ₂ CI C ₆ F ₅ O-

F ςX-

-88

R ₁ 2-X1

3.68 -CH ₂ CH ₂ CI

3.79 -CH ₂ CH ₂ CI _F _ς ₀ ,

Comp. Process R ₇ Rι ₂ -Xι No.

Comp. Process R ₇ R12-X1 No.

Comp. Process R ₇ R12-X1 No.

3.100 -CH ₂ CH ₂ Br C ₆ F ₅ O- C ₆ F ₅ O-

Comp. Process R ₇ R12-X1 No.

Comp. Process R ₇ Rι ₂ -Xι No.

3.124 p -CH(CH ₃ )(CH ₂ ) ₅ CH ₃

Comp. Process R R ₃ R12-X1 No.

3.136

o-

Comp. Process R ₇ R ₃ R12-X1 No.

-CH-CH ₂ CI (CH ₃ ) _? N (CH ₃ ) ₂ N _,

3.147

CH ₂ Br

O-

W // >-

Comp. Process R ₇ R _a R12-X1 No.

3.150 -CH ₂ CH ₂ CI C _e FsO-

Comp. Process R ₇ R12-X1 No.

Comp. Process R ₇ Rι ₂ -Xι No.

3.170 -CH ₂ CH ₂ CI C ₆ F ₅ O-

3.171 -CH ₂ CH ₂ CI C ₆ F ₅ O- C ₆ F ₅ S-

Comp. Process R ₇ R12-X1 No.

3.178

3.179 b ₃

3.180

Comp. Process R ₇ R ₃ R12- 1 No.

3.188 -CH ₂ CH ₂ CI

Comp. Process R ₇ R12-X1 No.

3.189 C ₆ F ₅ O- C ₆ F ₅ O-

^

Comp. Process R ₇ Rι ₂ -Xι No.

Comp. Process R ₇ R ₃ R12-X1 No.

Comp. Process R ₇ R _a R ₁₂ -X ₁ No.

Comp. Process R ₇ R12-X1 No.

Comp. Process R ₇ R ₃ Rι ₂ -Xι No.

3.232 -OC 'e6R' 5 -OC « ₆ Rrs

-OC ₆ F ₅ -OC ₆ F ₅

-OC ₆ F ₅ -OC ₆ F ₅

C(CH ₃ ) ₃

Comp. Process R ₇ R ₃ R12-X1 No.

3.237 -OC ₆ eRs -OCβ βRr ₅

CH,

-OC ₆ F ₅

-OC ₆ F ₅

3.240 -OC ' ₆ βFr ₅ -OC ₆ 6R» 5

3.241 p -CH ₂ Si(CH ₃ ) ₃ -OC ₆ F _s -OC ₆ F ₅

3.243 -OC ^■ β6Fr, ₅ -OC ₆ F ₅

Comp. Process R ₇ R12-X1 No.

Comp. Process R ₇ R12-X1 No.

3.271 -OC ₆ 6Rr5 -OC ₆ 6R' 5

3.272 -OC ₆ eRr ₅ -OC ₆ F ₅

-00

3.273 -OC ₆ 6R~5 -OC ₆ 6R' 5

3.275 CF, -OC ₆ F. -OC ₆ F ₅

-O

Comp. Process R ₇ R ₃ R12-X1 No.

3.276 -OCββF",5 -OC ₆ F ₅

3.278 -OCββFr.5

3.279 C -OC ' ₆ 6F'.5 -OC ₆ F ₅ vF. ₃

3.280 -o -OCβ 6F1 5. -OCe 6F».5

Comp. Process R ₇ R12-X1 No.

3.284 -OC -e6Rr ₅ -OC ₆ 6Rr- ₅

3.286 p ^ -CnH ₂ .--rCj(rCuH ₂ rCuH ₂ rCMN)i ₂ -OC -'6 ₆ 'F5. -OC eeRr ₅ CH,

3.287 -OC « ₆ Fr. ₅ -OC eeRr ₅

Comp. Process R ₇ R ₃ R12-X1 No.

3.292 Cl Cl -OCe βRr ₅ -OC eeRr ₅

- ^CH *

3.293 -OC ₆ Rr ₅ -OCeFg

3.294 -OC ^■ e6Rr ₅ -OC ^• e6Rr ₅

3.295 -OC eeRr ₅ -OC 'eβRr ₅

3.296 -OC ^■ eeRre -CH

3.299 p CF ₃ -OC ₆ F ₅ -OC ₆ F ₅

- ^cH« -C_

3.304 -OCe βRr ₅ -OCe 6RI 5

³ -307 -OC ₆ F ₅ -OCeF _g

Physical data of compounds in Table 3:

Comp. Physical Data

No.

3.1 Melting point 89-90°C

3.3 Melting point 82-83°C

3.5 ¹ H-NMR: 6.9-7.3 ppm (8H); 4.3 ppm (1 H); 3.95 ppm (1 H); 3.8 ppm (6H); 1.2- 2.2 ppm (12H)

3.6 Melting point 104-105°C

3.7 ¹ H-NMR: 7.3 ppm (2H); 7.1 ppm (4H); 3.8 ppm (2H); 1.6 ppm (2H); 1.4 ppm (2H); 0.9 ppm (3H)

3.10 ¹ H-NMR: 6.8-7.4 ppm (6H); 3.9 ppm (2H); 3.0 ppm (2H)

3.13 Melting point 184-186°C

3.19 ¹ H-NMR: 7.1-8.0 ppm (8H); 4.1 ppm (2H); 3.6 ppm (2H); 3.35 ppm (3H)

3.23 Melting point 89-90°C

3.24 ¹ H-NMR: 7.6 ppm (2H); 7.4 ppm (1 H); 6.9 ppm (1 H); 5.5 ppm (1 H); 4.4 ppm

(1 HHV); 11.44--11.99 n pnpmm M (1-4lHH)i

3.28 ¹ H-NMR: 10.05 ppm (2H); 7.1 -7.9 ppm (8H); 4.1 ppm (2H); 3.65 ppm (2H) 3.31 Melting point 115-116°C

3.36 ¹ H-NMR: 7.6-7.7 ppm (2H); 7.1-7.3 ppm (4H); 5.3-5.5 ppm (1 H); 4.3-4.5 ppm

(1H) 3.40 ¹³ C-NMR: 173.8 ppm; 135-150 ppm; 79.0 ppm; 22.0-47.4 ppm (7 signals)

3.45 Melting point 83-84°C

3.48 'H-NMR: 6.5-7.4 ppm (11 H); 5.7 ppm (1 H); 1.6 ppm (3H)

3.50 ¹ H-NMR: 7.05 ppm (2H); 6.85 ppm (2H); 4.7 ppm (2H); 4.2 ppm (4H); 4.0 ppm

(2H); 3.6 ppm (2H); 1.6 ppm (6H); 1.3 ppm (6H) 3.57 ¹ H-NMR: 7.1-7.9 ppm (12H); 4.95 ppm (1H); 4.1 ppm (2H)

3.61 Melting point 100-102°C

3.67 ¹³ C-NMR: 167.9 ppm; 136-143 ppm; 86.7 ppm; 62.5 ppm; 33.4 ppm; 30.6 ppm; 21.0 ppm

3.68 Melting point 141 -142°C

Comp. Physical Data

No.

3.72 Melting point 86-87°C

3.77 ¹ H-NMR: 8.85 ppm (2H); 7.4 ppm (2H); 7.15 ppm (2H); 4.05 ppm (2H); 3.6 ppm (2H); 2.6 ppm (6H) 3.82 ¹ H-NMR: 7.9 ppm (2H); 7.6 ppm (2H); 7.4 ppm (4H); 4.0 ppm (2H); 3.9 ppm

(6H); 3.6 ppm (2H) 3.84 ¹³ C-NMR: 168.2 ppm; 136-143 ppm; 73.8 ppm; 31.6 ppm; 25.9 ppm

3.89 Melting point 126-127°C

3.93 Melting point 173-174°C

3.97 Melting point 108-109°C

3.103 Melting point 100-102°C

3.105 Melting point 169-170°C

3.109 ³ C-NMR: 177.9 ppm; 162.9 ppm; 103.2 ppm; 83.5 ppm

3.112 ¹ H-NMR: 8.6 ppm (2H); 7.7 ppm (4H); 7.3 ppm (2H); 4.0 ppm (2H); 3.6 ppm

(2H) 3.119 Melting point 80-81 °C

3.124 ¹ H-NMR: 7.1-7.3 ppm (6H); 4.35 ppm (1H); 1.6 ppm (2H); 1.3 ppm (11 H); 0.9 ppm (3H)

3.129 ¹ H-NMR: 6.4 ppm (2H); 6.3 ppm (4H); 4.0 ppm (2H); 3.8 ppm (12H); 3.6 ppm (2H)

3.130 ¹³ C-NMR: 167.4 ppm; 147.7 ppm; 109.7 ppm; 88.2 ppm; 62.2 ppm; 36.5 ppm; 34.0 ppm; 32.0 ppm; 26.3 ppm; 25.4 ppm; 20.6 ppm

3.131 ¹³ C-NMR: 167.7 ppm; 147.8 ppm; 109.5 ppm; 83.1 ppm; 68.1 ppm; 37.1 ppm; 35.7 ppm; 33.0 ppm; 29.5 ppm; 26.2 ppm; 20.5 ppm

3.136 Melting point 96-97°C

3.140 Melting point 86-87°C

3.142 ¹ H-NMR: 7.3 ppm (2H); 7.15 ppm (4H); 4.0 ppm (2H); 3.6 ppm (2H)

3.147 ¹ H-NMR: 7.2 ppm (2H); 6.6 ppm (2H); 6.4 ppm (2+2H); 4.4 ppm (1 H); 3.7 ppm

(2H); 3.5 ppm (2H); 2.9 ppm (12H)

3.155 Melting point 101-102°C

3.160 'H-NMR: 7.1 ppm (2H); 6.9 ppm (4H); 4.0 ppm (2H); 3.6 ppm (2H)

Comp. Physical Data No.

3.168 ¹³ C-NMR: 177.9 ppm; 162.9 ppm; 103.2 ppm; 83.5 ppm

3.169 Melting point 197-198°C 3.179 Melting point 100-101 °C

3.186 ¹ H-NMR: 6.8-7.4 ppm (6H); 4.7 ppm (2H)

3.189 ¹³ C-NMR: 167.8 ppm; 136.2-143.1 ppm; 83.2 ppm; 34.0 ppm; 23.2 ppm

3.196 Melting point 106-108°C

3.202 Melting point 89-90°C

3.207 ¹ H-NMR: 6.9-7.2 ppm (6H); 3.7 ppm (2H); 1.7 ppm (2H); 1.3 ppm (4H); 0.9 ppm (3H) 3.219 ¹ H-NMR: 6.8-7.1 ppm (6H); 4.15 ppm (1 H); 1.2-1.9 ppm (10H)

3.224 Melting point 85-86°C

3.232 ¹³ C-NMR: 168.2 ppm; 142.4 ppm; 120.3 ppm; 63.3 ppm; 45.6 ppm; 40.6 ppm; 38.0 ppm; 36.3 ppm; 31.5 ppm; 31.3 ppm; 26.1 ppm; 21.0 ppm

3.233 ¹³ C-NMR: 168.1 ppm; 136-143 ppm; 64.2 ppm; 18.2 ppm; -1.9 ppm

3.234 Melting point 126-127°C

3.235 ¹³ C-NMR: 168.1 ppm; 136-143 ppm; 68.0 ppm; 24.0 ppm; 12.3 ppm; -1.99 ppm

3.236 Melting point 99-100°C

3.237 ¹³ C-NMR: 171.4 ppm; 168.2 ppm; 137.6 ppm; 136.2-142.8 ppm; 62.0 ppm; 36.8 ppm; 8.6 ppm

3.239 Melting point 113-11 °C

3.240 Melting point 93-94°C

3.241 ¹³ C-NMR: 168.53 ppm; 54.59 ppm; -3.54 ppm

3.243 ³ C-NMR: 167.9 ppm; 167.6 ppm; 119.1 ppm; 84.1 ppm; 44.2 ppm; 33.6 ppm; 28.4 ppm; 24.9 ppm; 21.7 ppm; 15.8 ppm

3.244 ¹³ C-NMR: 168.0 ppm; 167.7 ppm; 119.0 ppm; 85.8 ppm; 45.7 ppm; 32.6 ppm; 28.7 ppm; 28.5 ppm; 22.1 ppm; 21.7 ppm; 15.8 ppm

3.246 ¹³ C-NMR: 167.7 ppm; 81.2 ppm; 33.6 ppm; 33.0 ppm; 31.2 ppm; 21.5 ppm

3.247 ¹³ C-NMR: 167.7 ppm; 78.2 ppm; 31.3 ppm; 30.9 ppm; 28.6 ppm; 21.7 ppm

3.248 Melting point 48-49°C

3.249 ¹ H-NMR: 5.8 ppm (1 H); 5.0 ppm (2H); 4.2 ppm (1 H); 0 ppm (9H)

Comp. Physical Data No.

3.251 Melting point 185-186°C

3.252 ¹³ C-NMR: 174.5 ppm; 62.5 ppm; 15.0 ppm

3.253 Melting point 90-92°C

3.254 ³ C-NMR: 173.8 ppm; 75.7 ppm; 23.6 ppm

3.255 ¹ H-NMR: 4.55 ppm (2H); 3.2 ppm (4H); 1.0 ppm (2H); 0 ppm (9H)

3.256 ¹ H-NMR: 4.6 ppm (2H); 3.75 ppm (2H); 3.6 ppm (2H); 1.6 ppm (2H); 0.5 ppm (2H); 0 ppm (9H)

3.257 H-NMR: 4.6 ppm (2H); 3.8 ppm (2H); 3.2 ppm (2H); 2.0 ppm (3H); 1.4-1.8 ppm (6H)

3.258 ¹ H-NMR: 4.5 ppm (2H); 3.7 ppm (2H); 3.0 ppm (2H); 0 ppm (9H)

3.259 ¹³ C-NMR: 167.7 ppm; 78.2 ppm; 31.3 ppm; 30.9 ppm; 28.6 ppm; 21.7 ppm

3.260 Melting point 48-49°C

3.261 Melting point 95-96°C

3.262 Melting point 131-132°C

3.263 'H-NMR: 7.0 ppm (2H); 4.55 ppm (1H); 0.8-2.0 ppm (16H)

3.264 Melting point 83-84°C

3.265 Melting point 103-104°C

3.267 ¹³ C-NMR: 167.7 ppm; 138.9-147.6 ppm; 103.1-103.7 ppm; 51.0 ppm; 46.3 ppm; 34.7 ppm; 32.9 ppm; 27.5 ppm

3.268 Melting point 74-75°C

3.269 Melting point 112-113°C

3.270 ¹³ C-NMR: 167.7 ppm; 136-143 ppm; 81.9 ppm; 35.0 ppm; 34.4 ppm; 33.9 ppm; 31.2 ppm; 28.9 ppm; 26.1 ppm; 21.1 ppm

3.273 ¹³ C-NMR: 168.0 ppm; 167.8 ppm; 139.0 ppm; 130.7 ppm; 125-143.0 ppm; 79.6 ppm; 47.6 ppm; 47.5 ppm; 42.2 ppm; 35.1 ppm

3.274 ¹³ C-NMR: 168.0 ppm; 187.8 ppm; 142.3 ppm; 131.6 ppm; 80.4 ppm; 49.0 ppm; 46.0 ppm; 40.7 ppm; 35.3 ppm

3.275 ¹³ C-NMR: 167.8 ppm; 125-143 ppm; 75.9 ppm; 36.3 ppm (q); 30.8 ppm; 30.7 ppm; 2g.6 ppm; 23.7 ppm; 18.4 ppm

3.276 ¹³ C-NMR: 168.1 ppm; 138.3 ppm; 131.4 ppm; 125-143 ppm; 68.4 ppm; 49.4 ppm; 43.7 ppm; 42.3 ppm; 38.3 ppm; 2g.1 ppm

Comp. Physical Data

No.

3.277 ¹³ C-NMR: 167.8 ppm; 125-143 ppm; 80.7 ppm; 42.0 ppm; 37.4 ppm; 37.3 ppm; 36.4 ppm; 29.0 ppm; 20.6 ppm

3.278 ¹³ C-NMR: 167.8 ppm; 125-143 ppm; 83.1 ppm; 43.3 ppm; 40.3 ppm; 35.4 ppm; 34.9 ppm; 27.8 ppm; 24.1 ppm

3.279 ³ C-NMR: 167.7 ppm; 127-143 ppm; 73.5 ppm; 45.5 ppm (q); 31.8 ppm; 23.9 ppm; 19.8 ppm; 19.5 ppm

3.281 ¹³ C-NMR: 167.9 ppm; 167.4 ppm; 125-143 ppm; 81.8 ppm; 47.5 ppm; 44.8 ppm; 41.4 ppm; 38.4 ppm; 36.8 ppm; 33.9 ppm; 27.2 ppm; 23.7 ppm; 19.4 ppm

3.284 Melting point 123-124°C

3.285 Melting point 117-118°C

3.286 Melting point 109-110°C

3.287 ¹³ C-NMR: 167.9 ppm; 167.7 ppm; 136-143 ppm; 119.1 ppm; 83.0 ppm; 41.6 ppm; 33.4 ppm; 28.8 ppm; 21.8 ppm; 17.2 ppm

3.288 ¹³ C-NMR: 167.9 ppm; 167.7 ppm; 136-143 ppm; 117.4 ppm; 84.3 ppm; 42.8 ppm; 32.5 ppm; 28.6 ppm; 21.9 ppm; 19.8 ppm

3.292 Melting point 82-83°C

3.295 ¹³ C-NMR: 167.5 ppm; 157.5 ppm; 136-143 ppm; 131.5 ppm; 128.6 ppm; 124.3 ppm; 120.5 ppm; 110.3 ppm; 78.6 ppm; 55.1 ppm; 38.8 ppm; 30.4 ppm; 21.4 ppm

3.296 ¹³ C-NMR: 168.3 ppm; 126-143 ppm; 136.3 ppm; 135.2 ppm; 133.4 ppm; 129.6 ppm; 128.9ppm; 127.5 ppm; 67.0 ppm; 39.9 ppm; 33.3 ppm; 20.0 ppm; 13.8 ppm

3.299 ¹³ C-NMR: 168.4 ppm; 126-143 ppm; 65.9 ppm

Example H9: Preparation of 1 ,3.5-trimethoxythiatriazine (process a ₃ )

(Compound No. 4.2)

2.04 g (0.02 mol) of trichlorothiatriazine are dissolved in 15 ml of tetrahydrofuran and a solution of 5.94 g (0.033 mol) of 30% methanolic sodium methylate solution in 20 ml of tetrahydrofuran is added dropwise at 30°C, while cooling. After 15 minutes, the reaction mixture is extracted with water and ethyl acetate, the extract is concentrated and the residue is chromatographed over silica gel with ethyl acetate/hexane 1/3 as the eluting agent. The yield of the desired product is 1.70 g (89% of theory). Analysis: C ₅ H _g N ₃ O ₃ S calculated [%] found [%]

N 21.98 21.98

S 16.77 16.25

Example H10: Preparation of 1.3-dimethoxy-5-(2'.5'-difluorophenoxy)thiatriazine (process d ₃ )

(Compound No. 4.5)

3.05 g (0.007 mol) of 1 -(β-chloroethoxy)-3,5-di(2',5'-difluorophenoxy)thiatriazine are dissolved in 20 ml of methanol. 10.4 ml of a 1.35 molar sodium methylate solution in methanol are slowly added dropwise at -60°C, the intermediate 1 -methoxy-3 ₍ 5-di(2' _> 5'- difluorophenoxy)thiatriazine crystallizing out. The mixture is warmed gradually to +5°C, the intermediate reacting further to give the desired end product. The reaction mixture is extracted with water and ethyl acetate, the extract is concentrated and the residue is chromatographed over silica gel. The yield of desired product is 1.38 g (68% of theory). After recrystallization from a mixture of cyclohexane/toluene 6/1 , the product melts at 75- 76°C. Analysis: Cι ₀ H ₉ N ₃ O ₃ F ₂ S

calculated [%] found [%]

0.30 g of 1 ,3,5-trimethoxythiatriazine (.Example H9) is isolated as a by-product.

Example H11 : Preparation of 1-(β-chloroethoxy)-3.5-di(trichloroethoxy)thiatriazine (process d ₃ )

(Compound No. 4.38)

1.80 g (0.0036 mol) of 1-(β-chloroethoxy)-3,5-di(2',4'-dichlorophenoxy)thiatriazin e are dissolved in 20 ml of tetrahydrofuran and the solution is cooled to -50°C. A solution prepared from 1.12 g (0.0075 mol) of trichloroethanol and 0.33 g of 55% sodium hydride (0.0075 mol) is added dropwise to this solution. The reaction is exothermic. The reaction mixture is warmed to 0°C, extracted with water and ethyl acetate, and the product is chromatographed over silica gel. The yield is 1.62 g (95% of theory). The desired compound is a resin, the ¹ H- and ¹³ C-NMR spectra of which confirm the structure.

Example H12: Preparation of 1 -(β-chloroethoxy)-3.5-di-tert-butylmercaptothiatriazine and 1- (β-chloroethoxy)-3-chloro-5-tert-butylmercaptothiatriazine (process bi)

(CH ₃ ) ₃ CS N SC(CH ₃ ) ₃ (CH ₃ ) ₃ CS N Cl

N^N (Compound No. 4.49) and N^N (Compound No. 4.22)

I I

OCH ₂ CH ₂ CI OCH ₂ CH ₂ CI

3.00 g (0.012 mol) of 1-(β-chloroethoxy)-3,5-dichlorothiatriazine are dissolved in 20 ml of tetrahydrofuran, and a solution of 3.25 g (0.036 mol, of tert-butylmercaptan and 3.64 g (0.036 mol) of triethylamine in 15 ml of tetrahydrofuran is added dropwise at -50°C. Thereafter, the mixture warmed to 0°C, extracted with water and ethyl acetate, and the substance mixture is separated over silica gel with ethyl acetate/hexane 3/1 as the eluting agent. 1.05 g of 1-(β-chloroethoxy)-3-chloro-5-tert-butylmercaptothiatriazin e and 0.25 g of 1- (β-chloroethoxy)-3,5-di-tert-butylmercaptothiatriazine are obtained as resins. The ¹ H-NMR spectra and the mass spectra confirm the structures.

The compounds listed in the following Table 4 can be prepared analogously to Examples

H9 to H12.

Table 4: Compounds of the formula IV

Comp. Process R_ R ₃ NO.

4.4 b, -CH ₂ CH ₂ CI Cl -SCH(CH ₃ ) ₂

Comp. Process R_ R ₃ No.

4.14 -CH ₂ CH ₂ CI -SCH ₃

Cl -OCH ₂ CH ₂ CH ₃

C ₆ F ₅ O- -OCH ₃

Comp. Process R_ No.

Cl -SC(CH ₃ ) ₃

-OCH ₂ CF ₃ -OCH ₂ CF ₃

Comp. Process R. No.

4.33 -C ₂ H ₅ -OCH ₃ -OCH ₃

4.38 -CH ₂ CH ₂ CI -OCH ₂ CCI ₃ -OCH ₂ CCI ₃ 4.39 -SCH ₃ -SCH ₃

4.40 - OCH(CH ₃ ) ₂ -O-CH(CH ₃ ) ₂

4.41 -C ₂ 2Hrl5 -OC ₂ H ₅

4.43 -CH ₃ -OCH ₃

Comp. Process R. R ₃ R ₂ No.

4.44 -CH ₃ -OCH ₃

4.45 - C ₆ F ₅ O-

4.48 -CH(CH ₃ ) ₂ -O-CH(CH ₃ ) ₂

4.49 bi -CH ₂ CH ₂ CI -SC(CH ₃ ) ₃ -SC(CH ₃ ) ₃ 4.50 d ₃ -C ₂ Hs -OC ₂ H ₅ -OC ₂ H ₅

4.52 -CH ₂ CH ₂ CI C ₆ F ₅ O- -SCH ₃

4.54 -CH ₂ CH ₂ CI -SCH(CH ₃ ) ₂

4.55 -CH(CH ₃ ) ₂ -OCH(CH ₃ ) ₂

Comp. Process R. No.

4.57 -CH ₃ CH, -OCH ₃

4.60 -CH ₂ C-CH C ₆ F ₅ O- -OCH ₃

Comp. Process R_ R ₂ No.

4.67 -S-CH(CH ₃ ) ₂ -S-CH(CH ₃ ) ₂

4.71 -CH ₂ CH ₂ CI -OCH(CH ₃ )C ₂ H ₅

4.72 O -SC(CH ₃ ) ₃ -SC(CH ₃ ) ₃

Comp. Process R. R ₂ No.

4.76 -CH(CH ₃ ) ₂ -O-CH(CH ₃ ) ₂

4.77 -CH ₃ -SCH ₃

4.84 -CH ₂ CH ₂ CI C -SCH ₃

Comp. Process R. R ₂ No.

4.90 -CH(CH ₃ )C ₂ H ₅ -OCH(CH ₃ )C ₂ H ₅

4.93 -CH ₂ CH=CH ₂ -SCH ₃ -SCH ₃

Comp. Process R. R ₂ No.

Comp. Process R_ No.

4.116 -CH ₃ CeFsO

Comp. Process R_ No.

4.120 -CH ₂ CH ₂ F

4.121 -C ₇ Hι,(n) 4.122 -C ₅ Hn(n)

4.123 -CHCH-CI

C ₆ H ₅

4.126 -S-CH(CH ₃ ) ₂ -S-CH(CH ₃ ) ₂

Comp. Process R_ R ₂ No.

4.130 -O-CH(CH ₃ ) ₂ -O-CH(CH ₃ ) ₂

4.132 -CH(CH ₃ ) ₂ -O-CH(CH ₃ ) ₂

4.135 -OCH ₂ CF ₃ -OCH ₂ CF ₃

4.136 -CH ₃ -OCH _a -OCH,

Comp. Process R_ R ₃ R ₂ No.

Cl

-SC3H ₇ (n) -SC(CH ₃ ) ₃

4.154 -CH(CH ₃ )_ -SCH _{2 2} CRr ₃ -SCH ₂ CF ₃

Comp. Process R. No.

4.156 d ₃ -OCeβRrδ -OCH ₂ CH ₂ CI

4.157 d ₃ -CH ₂ CH ₂ Si (CH ₃ ) ₃ -OC ₆ P ₅ -OCH ₂ CH ₂ CI 4.158 d ₃ -(CH ₂ ) ₃ Si(CH ₃ ) ₃ -OCePs -OCH ₂ CH ₂ CI 4.159 d ₃ -OC ₆ F ₅ -OCH ₂ CH ₂ CI

4.160 d ₃ -CH ₂ Si(CH ₃ ) ₃ -OC ₆ F ₅ -OCH ₂ CH ₂ CI

R ₂

-OCH ₂ CH ₂ CI

-OCH ₂ CH ₂ CI -OCH ₂ CH ₂ CI

H

Physical data of compounds in Table 4:

Comp. Physical data

No.

4.1 ¹ H-NMR: 7.4 ppm (2H); 7.25 ppm (1 H); 7.15 ppm (2H); 3.9 ppm (3H); 3.5 ppm (3H)

4.2 ¹³ C-NMR: 169.5 ppm; 54.7 ppm; 49.1 ppm

4.4 ¹³ C-NMR: 181.8 ppm; 164. 9 ppm; 65.9 ppm; 41.6 ppm; 36.5 ppm; 22.9 ppm

4.5 Melting point 75-76°C

4.8 Η-NMR: 4.6 ppm (2H); 4.4 ppm (2H); 3.3 ppm (4H);1.35 ppm (3H); 1.25 ppm (3H)

4.9 'H-NMR: 7.2 ppm (1 H); 7.0 ppm (2H); 3.9 ppm (3H); 3.4 ppm (3H) 4.12 ¹ H-NMR: 7.1 ppm (1 H); 6.9 ppm (2H); 4.9 ppm (2H); 3.4 ppm (3H); 2.5 ppm (1H)

4.15 ¹ H-NMR: 4.3 ppm (2H); 3.7 ppm (2H); 1.4-1.9 ppm (4H); 0.9-1.1 ppm (6H)

4.16 ¹³ C-NMR: 170.0 ppm; 167.9 ppm; 136.0-143.2 ppm; 125.9 ppm; 55.2 ppm; 49.1 ppm

4.18 ¹ H-NMR: 3.95 ppm (2H); 3.85 ppm (2H); 3.6 ppm (2H); 1.4 ppm (6H)

4.20 'H-NMR: 7.1 ppm (1H); 6.9 ppm (2H); 4.3 ppm (2H); 3.7 ppm (2H); 1.3 ppm (6H)

4.22 ¹ H-NMR: 4.0 ppm (2H); 3.7 ppm (2H); 1.6 ppm (9H)

4.23 ¹³ C-NMR: 160.0 ppm; 122.6 ppm; 65.1 ppm ; 63.6 ppm; 41.6 ppm 4.26 ¹ H-NMR: 4.3 ppm (4H); 3.6 ppm (2H); 1.8 ppm (4H); 1.6 ppm (2H); 1.0 ppm (6H); 0.9 ppm (3H) 4.29 'H-NMR: 5.2 ppm (4H); 4.0 ppm (2H); 3.6 ppm (2H)

4.33 'H-NMR: 3.95 ppm (6H); 3.7 ppm (2H); 1.3 ppm (3H)

4.38 ¹³ C-NMR: 168.2 ppm; 94.3 ppm; 76.5 ppm; 64.9 ppm; 41.6 ppm

4.41 'H-NMR: 7.2-8.0 ppm (4H); 4.35 ppm (2H) 4.25 ppm (2H); 3.7-3.9 ppm

(2H);1.2-1.4 ppm (9H) 4.43 'H-NMR: 7.5 ppm (1 H); 7.3 ppm (1 H); 7.1 ppm (1 H); 3.9 ppm (3H); 3.4 ppm (3H)

4.45 ¹³ C-NMR: 168.5 ppm; 167.2 ppm; 136.1 -143.0 ppm; 125.8 ppm; 81.7 ppm; 67.2 ppm; 40.7 ppm; 33.8 ppm

4.49 'H-NMR: 3.95 ppm (2H); 3.65 ppm (2H); 1.6 ppm (18H)

4.50 'H-NMR: 4.4 ppm (4H); 3.7 ppm (2H); 1.4 ppm (6H); 1.3 ppm (3H) 4.86 Melting point 141 -1 2°C

4.156 ' ³ C-NMR: 169.0 ppm; 167.7 ppm; 142.8 ppm; 119.g ppm; 67.3 ppm; 62.8 ppm; 45.6 ppm; 40.8 ppm; 40.6 ppm; 38.0 ppm; 36.5 ppm; 31.5 ppm;

31.3 ppm; 26.1 ppm; 21.0 ppm

4.157 ¹³ C-NMR: 169.0 ppm; 167.6 ppm; 67.3 ppm; 63.7 ppm; 40.9 ppm; 18.4 ppm; -1.7 ppm

4.158 'H-NMR: 4.6 ppm (2H); 3.75 ppm (2H); 3.6 ppm (2H); 1.65 ppm (2H); 0.5 ppm (2H); 0.0 ppm (9H)

4.159 'H-NMR: 4.6 ppm (2H); 3.8 ppm (2H); 3.2 ppm (2H); 2.0 ppm (3H); 1.6- 1.8 ppm (6H); 1.5 ppm (6H)

4.160 'H-NMR: 4.55 ppm (2H); 3.7 ppm (2H); 3.0 ppm (2H); 0.0 ppm (9H)

4.161 'H-NMR: 7.3-7.0 ppm (3H); 3.95 ppm (3H); 3.4 ppm (3H); 2.25 ppm (3H)

4.162 'H-NMR: 7.1-7.4 ppm (5H); 4.35 ppm (2H); 3.75 ppm (2H); 1.2-1.4 ppm (6H)

4.163 'H-NMR: 6.9-7.3 ppm (4H); 3.95 ppm (3H); 3.8 ppm (3H); 3.4 ppm (3H)

4.164 'H-NMR: 5.2 ppm (4H); 4.0 ppm (2H); 3.65 ppm (2H)

4.165 'H-NMR: 5.3 ppm (1H); 4.6 ppm (2H); 3.8 ppm (2H); 3.6 ppm (2H); 1.9- 2.4 ppm (7H); 1.25 ppm (3H); 1.1 ppm (1 H); 0.8 ppm (3H)

4.166 'H-NMR: 7.0 ppm (1 H); 4.55 ppm (1 H+2H); 3.75 ppm (2H); 0.8-1.9 ppm (16H)

4.167 ¹³ C-NMR: 168.8 ppm; 168.4 ppm; 167.6 ppm; 167.1 ppm; 125-143 ppm; 80.5 ppm; 80.3 ppm; 67.3 ppm; 47.5 ppm; 44.8 ppm; 41.4 ppm; 40.7 ppm; 38.4 ppm; 37.0 ppm; 33.9 ppm; 27.3 ppm; 23.8 ppm; 19.6 ppm

4.168 ¹³ C-NMR: 169.0 ppm; 167.7 ppm; 125-143 ppm; 67.7 ppm; 64.7 ppm;

41.4 ppm; 40.8 ppm

4.169 ¹³ C-NMR: 168.4 ppm; 167.1 ppm; 84.8 ppm; 67.3 ppm; 47.9 ppm; 41.8 ppm; 40.8 ppm; 34.5 ppm; 33.4 ppm; 32.6 ppm; 29.2 ppm; 26.0 ppm; 25.7 ppm; 23.9 ppm

Example H13: Preparation of 3-amino-1-(β-chloroethoxy)-5-(2'.4'-dichlorophenoxy)- thiatriazine (process d ₄ )

(Compound No. 5.333)

6.5 g (0.013 mol) of 1-(β-chloroethoxy)-3,5-di(2\4'-dichlorophenoxy)thiatriazine are dissolved in 100 ml of tetrahydrofuran. Thereafter, ammonia gas is passed in at 20°C until the starting material can no longer be detected in a thin layer chromatogram (about 15 minutes). The reaction mixture is concentrated on a rotary evaporator and hexane is added to the still hot residue until crystallization starts. The crystals formed are filtered off with suction, washed with hexane and dried. 4.00 g (86.5% of theory) of the desired compound are obtained as crystals of melting point 141-142°C. Cl analysis: 29.3 % (calculated 29.9%); 'H-NMR (300 MHz, CDCI ₃ ): 7.2-7.5 ppm (3H), 6.6 and 6.3 ppm (2H), 3.9 ppm (2H), 3.6 ppm (2H).

Example H14: Preparation of 3-amino-1-isopropoxy-5-(2'.5'-difluorophenoxy)thiatriazine (process q)

(Compound No. 5.3)

0.50 g (0.0084 mol) of isopropanol is reacted with 0.37 g (0.0084 mol) of 55 % sodium hydride in oil in 30 ml of tetrahydrofuran. 2.60 g (0.008 mol) of 3-amino-1-(β-chloroethoxy)- 5-(2',5'-difluorophenoxy)thiatriazine are added to the resulting suspension of the sodium isopropanolate at room temperature, and a slightly exothermic reaction takes place.

Extraction of the reaction mixture with water and ethyl acetate gives 2.0 g of crude product, which is recrystallized from a mixture of ethyl acetate/hexane 3/5. Yield of desired product 1.82 g (75% of theory) of melting point 163-164°C.

Analysis: CnHι ₂ F ₂ N ₄ O ₂ S calculated. [%] found [%]

Η-NMR (300 MHz, CDCI ₃ ): 6.8-7.2 ppm (3H); 5.1-5.5 ppm (1 H); 4.4 ppm (1 H); 1.3 ppm (6H).

Example H15: Preparation of 3-dimethylamino-1-(β-chloroethoxy)-5-(2'-carbo- ethoxyphenoxy)thiatriazine (process c _$ )

(Compound No. 5.22)

2.22 g (0.0064 mol) of 3-chloro-1-(β-chloroethoxy)-5-(2'-carboethoxyphenoxy)thiatr iazine are dissolved in 30 ml of tetrahydrofuran. Dimethylamine is passed in at 0°C until the conversion is complete, the reaction mixture is extracted with water and ethyl acetate, the extract is concentrated and the crude product is purified by means of chromatography (silica gel; ethyl acetate/hexane mixture). The desired product is obtained as an oil in a yield of 1.40 g (57% of theory). The Η-NMR spectrum is in agreement with the structure of the desired compound; mass spectrum: [M ⁺ ] 386.

Example H16: Preparation of 3-amino-5-(2.5-difluorophenoxy)-1-(3-hexyloxy)thiatriazine

(Compound No. 5.340)

2.1 g of trimethylamine solution (40% in water) are added to a mixture of 3.6 g of 3-amino- 5-chloro-1 -(3-hexyloxy)thiathazine (0.014 mol), 70 ml of methylene chloride and 2.05 g of 2,5-difluorophenol (0.016 mol). The reaction mixture is stirred at 20°C until the conversion is complete, and is then evaporated. Water is added to the resulting residue and the residue is filtered off with suction. The resulting solid is stirred in diethyl ether and filtered off, the clear ether solution is concentrated and pentane is added to the residue. The desired product precipitates in the form of white crystals of melting point 171-172°C.

The compounds listed in the following Table 5 can be prepared analogously to Examples H13 to H16.

Table 5: Compounds of the formula

Comp. Process R_ R ₃

No.

-NH ₂ -N(CH ₃ )C ₄ H ₉ (n)

Comp. Process R_ No.

5.6 d ₄ -CH ₂ CH CI -N(CH ₃ ) ₂

5.11 -CH ₂ CH ₂ CI C ₆ H ₅ O- -N(CH ₃ ) ₂

5.13 d ₄ -CH ₂ CH ₂ CI C ₆ F ₅ O- -NH ₂

-145

Comp. Process R. No.

5.15 -CH ₂ CH ₂ CI -NHC(CH ₃ ) ₃

5.20 -CH ₂ CHCI -NH,

Comp. Process R_ R ₂

No.

5.22 c ₄ -CH ₂ CH,CI -N(CH ₃ ) ₂

5.23 d ₄ -CH ₂ CH ₂ CI -N(CH ₃ ) ₂

.36 -(CH ₂ )eCH ₃ C ₆ F ₅ O- -NH ₂

5.38 C ₆ F ₅ O-

-Φ> -NH,

Comp. Process R_ No.

5.46 C ₆ R ₅ O- -NH ₂

-Of: D Diiaasstttereo- mer 1

CH,

Comp. Process R _y R ₃ No.

C ₆ F ₅ O- -NH,

Comp. Process R. R ₃ No

5.59 CH ₃ C ₆ F ₅ O- -NH,

CH,

5.60 d ₄ -CH ₂ CH ₂ CI -NHCH ₂ CH ₂ CH ₃

5.62 CeFgO- -NH ₂

5.66 -CH ₂ CH ₂ COOC ₂ H ₅ C ₆ F ₅ O- -NH,

Comp. Process R. No.

-NH ₂

5.74 -NHCHa

Comp. Process R. No

5.77 -CH ₂ CH ₂ CCI ₃ C ₆ F ₅ O- -NH ₂

Comp. Process R_ R ₂ No.

5.85 -CH ₂ -Adamantyl C ₆ F ₅ O- -NH ₂

5.89 d ₄ -CH ₂ CH ₂ CI C ₆ F ₅ S- -NH ₂

5.93 C ₆ F _s O- -NH,

-CH 2 O

Comp. Process R. No.

5.101 C ₆ F ₅ O- -NH,

Comp. Process R_ No.

5.105 -(CH ₂ ) CH ₃ -NHCH ₃

Comp. Process R_ R ₃ R ₂ No.

5.118 C ₆ F ₅ O- -NH,

NCCH ₂ CH ₂

Comp. Process R. R ₃ No.

5.121 d ₄ -NHCH(CH ₃ )CHjOCH ₃

R ₂

5.135 CeFsO- -NH,

Comp. Process R_ R ₂ No.

Comp. Process R_ No.

Comp. Process R. R ₂ No.

-NH,

-NH ₂ -NH ₂ o-

Comp. Process R. No

5.164 C ₆ F ₅ O- -NH ₂

5.165 .COOCH, C ₆ F ₅ O- -NH ₂

cr 'COOCH,

5.166 C ₆ F ₅ O- -NH ₂

-NH,

-NH,

-NH ₂ -NH ₂

Comp. Process R. R ₃ No.

5.178 d ₄ -CH ₂ CH ₂ CI -NHCH ₂ CH ₂ CH ₃

5.180 d ₄ C ₆ F ₅ O- -NH,

5.182 d ₄ -CH ₂ CH ₂ CI -NHCH(CH ₃ ) ₂

Comp. Process R_ No.

5.183 d ₄ -CH ₂ CH ₂ CI -N(C ₂ H ₅ ) ₂

5.189 -CH ₂ CH ₂ CI -NH,

Comp. Process R_ R ₂ No.

5.193 -CH ₂ CH ₂ CI -N(CH ₃ ) ₂

5.197 C ₆ F ₅ O- -NH ₂

-CH -O

Comp. Process R_ No.

5.203 -CH ₂ CH ₂ CI CH(OCH ₃ ) ₂ -NH,

5.204 -CHCH-CI -NH ₂

I

C ₂ H ₅

H-C^Λ^O

Comp. Process R. R _a R ₂ No.

5.206 -CH ₂ CH ₂ CI -NH ₂

Comp. Process R _? R ₂ No.

Comp. Process R.

No.

Comp. Process R. R ₃ NO.

5.241 -CHCH-CI CH(OCH ₃ ) ₂ -NH,

I ²

C ₆ H ₅

5.252 -CH ₂ CH ₂ CI -NH,

5.259 -CH ₂ CH ₂ CI -NH,

5.267 -CH ₂ CH ₂ CI _ _N u

5.275 -CH ₂ CH ₂ CI -NH,

5.279 -CH ₂ CH ₂ CI Cl CN -NH,

// W

OC ₃ H ₇ (n)

C ₄ H ₉ (n)

5.304 CeFsO- -NH,

5.305 CβFsO- -NH,

5.307 CeFsO- -NH ₂

5.309 CeFsO- -NH,

5.311 CeFsO- -NH ₂

5.312 (CH ₃ ) ₂ C ₂ H ₅ C ₆ F ₅ O -NH,

5.313 CeFsO- -NH,

CeFsO- -NH ₂

C _β FsO- -NH ₂ C ₆ F ₅ O- -NH ₂ (CH-J ₃

-NH ₂

5.325 d ₄ CeFsO- -NH,

-NH,

-NH,

-NH ₂ -NH ₂ -NH ₂

C ₃ H ₇ (n)

5.335 q -CH ₂ CH ₂ CI CF ₃ CH ₂ O- -NH ₂

5.336 q -CH CH ₂ CI (CF ₃ ) ₂ CHO- -NH ₂

5.337 q -CH ₂ CH ₂ CI CF ₃ CCI ₂ CH ₂ O- -NH ₂

5.33g c ₅ -CH[CH ₂ CH(CH ₃ ) ₂ ] ₂ C ₆ F ₅ 0- -NH ₂

5.343 -CH ₂ Si(CH ₃ ) ₃ -NH,

5.345 d ₄ C ₆ F ₅ O- -NH,

H

5.348 C ₆ F ₅ O- -NH ₂

-O

5.354 CβFsO- -NH,

CeFsO- -NH,

CeFsO- -NH,

C ₆ F ₅ O- -NH,

C ₆ F ₅ O- -NH,

- CH,CN

5.363 d ₄ C ₆ F ₅ O- -NH ₂

5.365 C ₆ FsO- -NH,

-CH (CH

5.367 C ₆ FsO- -NH,

•CH (CH ₂ ) ₆

5.369 d ₄ CF, C ₆ F ₅ O- -NH ₂

^{■cH ~~} )

5.370 -CH ₂ CH ₂ CeFs CeFgO- -NH ₂ 5.371 C ₆ F ₅ O- -NH ₂

^■CH

CeFsO- -NH,

5.373

5.374

Physical data of compounds in Table 5:

Comp. Physical data

No.

5.1 Melting point 152- 153°C

5.2 ¹ H-NMR: 6.8-7.3 ppm (8H); 3.7-4.0 ppm (2H); 3.2-3.6 ppm (2H); 2.8-3.0 ppm (5H); 0.8-1.6 ppm (7H)

5.3 Melting point 163-164°C

5.4 Melting point 167-168°C

5.5 Melting point 141-142°C

5.6 ¹ H-NMR: 3.8-4.0 ppm (2H); 3.6 ppm (2H); 3.2 ppm (3H); 3.0 ppm (3H)

5.7 Melting point 145-146°C

5.8 Melting point 148-149°C

5.10 ¹ H-NMR: 6.8-7.3 ppm (8H); 5.3-5.5 ppm (1 H); 4.0-4.3 ppm (1 H); 3.8 ppm (2H); 2.9 ppm (2H)

5.11 'H-NMR: 7.1-7.4 ppm (5H); 3.9 ppm (2H); 3.6 ppm (2H); 3.13 ppm (3H); 3.05 ppm (3H)

5.13 Melting point 127-128°C

5.14 Melting point 140-141 °C

5.15 ¹ H-NMR: 6.5-7.2 ppm (3H); 5.3 ppm (1 H); 3.6-4.0 ppm (4H); 1.45 ppm (9H) 5.17 ¹ H-NMR: 7.1 -7.5 ppm (3H); 3.6-4.0 ppm (12H)

5.19 Melting point 179-180°C

5.22 ¹ H-NMR: 7.2-8.0 ppm (4H); 4.3 ppm (2H); 3.8-4.1 ppm (2H); 3.6 ppm (2H); 3.1 ppm (3H); 3.0 ppm (3H); 1.3 ppm (3H)

5.23 ¹ H-NMR: 6.9-7.2 ppm (3H); 3.8-4.0 ppm (2H); 3.6 ppm (2H); 3.15 ppm (3H); 3.0 ppm (3H)

Comp. Physical data No.

^" 5T28 Melting point 130-131 °C

5.30 Melting point 207-208°C

5.31 Melting point 159-160°C (decomposition)

5.35 ¹ H-NMR: 6.8-7.4 ppm (8H); 5.5 ppm (1 H); 4.7 ppm (2H); 4.2 ppm (1 H); 1.9 ppm (4H); 1.4-1.7 ppm (4H)

5.38 Melting point 163-164°C

5.42 Melting point 181 -182°C

5.45 Melting point 98-99°C

5.46 Melting point 147-148°C

5.47 Melting point 125-126°C

5.48 Melting point 161 -162°C

5.51 Melting point 87-88°C

5.52 Melting point 138-139°C

5.54 Melting point 215-216°C

5.55 ¹ H-NMR: 6.8-7.1 ppm (3H); 3.8-4.0 ppm (2H); 3.6 ppm (2H); 3.15 ppm (3H); 3.0 ppm (3H)

5.58 Melting point 202-203°C

5.59 Melting point 123-124°C

5.60 ¹ H-NMR: 6.9-7.2 ppm (3H); 3.7-4.0 ppm (2H); 3.6 ppm (2H); 3.4 ppm (2H); 1.6 ppm (2H); 0.9 ppm (3H)

5.64 Melting point 112-113°C

5.65 Melting point 103-104°C 5.67 Melting point 176-177°C

5.71 Melting point 204-206°C (decomposition)

5.72 Melting point 178-179°C

5.73 Melting point 173-174°C

5.74 ¹ H-NMR: 6.8-7.3 ppm (4H); 4.3 ppm (1 H); 4.0 ppm (1 H); 3.8 ppm (3H); 2.8-3.0 ppm (3H); 1.2-2.2 ppm (12H)

5.75 Melting point 167-168°C

Comp. Physical data

No.

5.76 Melting point 175-176°C (decomposition)

5.78 Melting point 165-166°C

5.83 Oil

5.84 Melting point 109- 110°C

5.85 Melting point 175-176°C (decomposition)

5.86 Melting point 165-166°C

5.88 Melting point 115-116°C

5.89 Melting point 91 -92°C

5.90 Melting point 179-180°C (decomposition) 5.92 Melting point 212-213°C

5.94 'H-NMR: 6.9-7.3 ppm (4H); 3.8-4.6 ppm (6H); 3.8 ppm (3H); 0.7-2.9 ppm

(22H)

5.96 Melting point 108-109°C

5.98 Melting point 138-139°C

5.101 Melting point 182-183°C

5.102 Melting point 145-146°C

5.103 Melting point 183-185°C

5.107 Melting point 190-191 °C

5.108 Melting point 204-205°C 5.110 Melting point 124-125°C

5.113 ¹ H-NMR: 6.5-7.2 ppm (3H); 5.3 ppm (1 H); 3.4 ppm (3H); 1.45 ppm (9H)

5.114 Melting point 137-138°C

5.116 Melting point 216-217°C

5.117 Melting point 161-162°C

5.119 Melting point 194-196°C (decomposition)

5.120 Melting point 156-157°C

5.121 ¹ H-NMR: 7.3 ppm (5H); 7.1 ppm (1 H); 6.9 ppm (2H); 5.6 ppm (1 H); 4.7 ppm (2H); 4.2 ppm (1 H); 3.2-3.4 ppm (5H); 1.2 ppm (3H)

5.122 Melting point 103-104°C

Co p. Physical data

No.

5.172 Melting point 148-14g°C

5.174 Melting point 125-126°C

5.176 Melting point 139-140°C

5.177 ¹ H-NMR: 8.3 ppm (1 H); 7.4 ppm (1 H); 7.2 ppm (1 H); 6.8 ppm (1 H); 6.5 ppm (1 H); 3.9 ppm (2H); 3.6 ppm (2H); 2.5 ppm (3H)

5.178 ¹ H-NMR: 7.1-7.4 ppm (3H); 3.8-4.0 ppm (2H); 3.6 ppm (2H); 3.3 ppm (2H); 1.4-1.7 ppm (2H); 0.8-1.0 ppm (3H)

5.180 Melting point 123-124°C

5.182 Melting point 138-140°C

5.183 ¹ H-NMR: 7.7 ppm (1H); 7.1-7.3 ppm (2H); 5.5 ppm (1H); 3.6-4.2 ppm (4H); 3.5 ppm (2H); 3.2 ppm (2H); 1.6 ppm (3H); 1.2 ppm (3H); 0.9 ppm (3H)

5.184 Melting point 146-147°C 5.188 Melting point 123-124°C

5.192 Melting point 182-183°C

5.193 ¹ H-NMR: 7.7 ppm (1 H); 7.2-7.3 ppm (2H); 5.5 ppm (1 H); 3.6-4.2 ppm (4H); 3.1 ppm (3H); 2.9 ppm (3H); 1.6 ppm (3H)

5.195 Melting point 167-168°C

5.197 Melting point 177-178°C

5.207 Melting point 157-158°C

5.315 Melting point 111-112°C

5.316 Melting point 145-146°C

5.317 Melting point 137-139°C

5.318 Melting point 171 -173°C

5.319 Melting point 146-147°C (decomposition)

5.320 Melting point 175-176°C (decomposition)

5.321 Melting point 179-180°C

5.322 Melting point 210-21 1 °C (decomposition)

5.323 solid

5.324 Melting point 112°C (decomposition)

5.325 Melting point 1 16°C (decomposition)

-igo-

Comp. Physical data

No.

5.364 Melting point 118-119°C

5.366 Melting point 131-132°C (decomposition)

5.369 Melting point 146-147°C

5.375 Melting point 188-189°C

5.376 Melting point >225°C

5.377 Melting point 156-157°C

Example H17: Preparation of 3-amino-1-dipropylamino-5-(2'.5'-difluoropheπoxy)thiatriazi ne

1.60 g (0.005 mol) of 3-amino-1-(β-chloroethoxy)-5-(2',5'-difluorophenoxy)thiatri azine are stirred in 20 ml of toluene with 0.53 g (0.00525 mol) of dipropylamine at 70°C for 3.5 hours. After the reaction mixture has cooled, it is extracted with ethyl acetate and water. On concentration of the reaction mixture on a rotary evaporator, the desired product crystallizes out. It is filtered off with suction, washed and dried. Yield 1.42 g (83% of theory); melting point 184-185°C.

Analysis: C ₁₄ H _1θ F ₂ N ₅ OS calculated [%] found [%]

Example H18: Preparation of 3-amino-1-decahvdroquinolinyl-5-(2'.6'-drfluorophenoxy)- thiatriazine

(Compound No. 6.3)

1.00 g (0.0027 mol) of 1-(trans-2'-chlorocyclohexanolyl)-3-amino-5-(2',6'-difluorop henoxy)- thiatriazine is heated at 80-90°C with 0.49 g (0.0035 mol of decahydroquinoline (cisΛrans mixture) in 20 ml of toluene until the conversion is complete. Thereafter, the mixture is concentrated on a rotary evaporator, the residue is dissolved in ethyl acetate, the clouding formed is filtered off with suction and the filtrate is concentrated. Recrystallization of the resulting residue from a mixture of ethyl acetate/hexane gives 0.85 g (82% of theory) of the desired product of melting point 194-195°C (decomposition). The H- and ¹³ C-NMR spectra are in agreement with the structure of the desired product.

Example H19: Preparation of 3-amino-5-pentafluorophenoxy-1-(piperidin-1-yl)thiatriazine

(Compound No. 6.53)

8.3 ml of 2N sodium hydroxide solution (0.0166 mol) and 2.2 g of trimethylamine solution (40 % in water) (0.015 mol) are added to a mixture of 3.5 g of 3-amino-5-chloro-1-(piperidin- 1-yl)thiatriazine (0.015 mol) and 3.0 g of pentafluorophenol (0.0165 mol) in 100 ml of methylene chloride. After the mixture has been stirred for 20 hours, the organic phase is dried over sodium sulfate and filtered over silica gel, with subsequent elution with a 50/50 hexane/ethyl acetate mixture. After the collected fractions have been evaporated and the residue has been stirred in pentane, the desired product is isolated as slightly yellowish crystals of melting point 104-105°C (decomposition).

The compounds listed in the following Table 6 can be prepared analogously to Examples

H17 to H19.

Table 6: Compounds of the formula II

Comp. R _T Physical data No.

6.1 -NHCH ₂ CH ₂ CH ₃ point 132-

6.2

ppm (2H)

6.3 point 194-

position)

Comp. R _T R ₂ Physical data No.

point 170-

6.6

(Diastereomer 1) 34.1 ppm; 32.2 ppm; 31.5 ppm; 24.5 ppm.

6.7 point 201 -

6.8 .CH, C ₆ F ₅ O- -NH ₂ Melting point 162-

N r O 163°C

CH,

6.9

- - CβF ₅ O- -NH ₂ Melting point 147-

CF, 148°C

(decomposition)

(Diastereomer 2) 34.4 ppm; 32.1 ppm; 31.6 ppm; 24.7 ppm

Comp. R, R ₃ R ₂ Physical data No.

point 148-

6.14 7 ^~ \ C ₆ F ₅ O- -NH ₂ Melting point 185- -N N-CH, 186°C

(decomposition)

6.15 point 102-

6.16 -N(CH ₂ CH ₂ CN) ₂ C ₆ F ₅ O- -NH ₂ ¹³ C-NMR: 165.8 ppm; 164.7 ppm; 118.5 ppm; 117.4 ppm; 48.6 ppm; 43.0 ppm; 18.6 ppm; 17.4 ppm

6.17 -NHC ₆ Hn(c) C ₆ F ₅ O- -NH, Melting point 136- 137°C

6.18 point 189-

position)

Comp. R _T R ₃ Physical data No.

6.21 -N(n-C ₃ H ₇ ) ₂ CβFsO- -NH, Melting point 111-

112°C point 137-

point 190-

point 150-

position)

Comp. R R ₂ Physical data No.

point 128-

point 161-

point 173-

point 206-

point 180-

position)

6.36 -N[CH(CH ₃ ) ₂ ] ₂ -NH ₂

Comp. R, Physical data No.

6.37 H CeFsO- -NH ₂ Melting point 183-

184°C

(decomposition)

H

6.39 -NHCH ₃

6.40 point 208-

6.41 -NH ₂ Melting point 162- 163°C ,

6.42

6.43 -N(CH ₃ ) ₂ -NHC ₃ H ₆ (n)

6.45 -NH ₂ Melting point 159-

0- 160°C

Comp. R, R ₂ Physical data No.

6.46 C ₆ F ₅ O- -NH, Melting point 203-

^■N D 204°C

6.48 point 184-

6.49 point 134-

point 104-

6.54 -NHCH ₂ CH ₂ CH ₃ -NHCH_CH ₂ CH ₃ Melting point 104- 106°C

6.55 CH, C ^X gFsO- -NH, Melting point 184-

Comp. R, R ₃ Physical data No.

(Diastereomer 1 )

6.56 point 163-

(Diastereomer 2) point 193-

6.60

105-117 ppm

6.62 -N(CH ₃ ) ₂ H ₃ C CH, -N(CH ₃ ) ₂

>=<

6.63

6.64 -N(CH ₃ ) ₂ -N(C ₂ H ₅ ) ₂

6.70 -N(CH ₃ ) ₂ -NHCH(CH ₃ )_

6.71 -N(CH ₃ ) ₂ o-°-o- ^» -NH ₂

6.72 -NH(CH ₂ ) ₃ CF ₃ g point 80-

6.73 C ₆ F ₅ O- -NH ₂ Melting point 175- 176°C

Comp. R, Physical data No.

6.77 / — \ / C ₆

^:N - = FsO- -NH ₂ Melting point 198-

199°C

(Decomposition)

6.78 -N(CH ₃ ) ₂ -NHC ₃ H ₇ (n)

6.80 -N(CH ₃ ) ₂ -NHC ₂ 2H1 15 point

Comp. R, Physical data No.

6.84

6.85

6.88 -N(CH ₃ ) ₂ CH ₃ CO -NHCH ₃

6.89 -NH ₂ Melting point 187-

^■ O 188°C

Comp. R, R ₃ Physical data No.

(Diastereomer 1)

6.93

(Diastereomer 2)

6.97 -N(C ₄ H ₉ (n)) ₂ -NH ₂

Comp. R, Physical data No.

6.99 o CβFsS -NH, Melting point 191 °C (Decomposition)

5-

Comp. R, Physical data No.

6.108 -N(C ₂ H _S ) _{2 /} COCH ₃ -NH ₂

6.109 -N(CH ₃ ) ₂ <5- point 166-

/ OCH,

Comp. R R ₃ Physical data No.

ppm; 27.9 ppm; 27.2 ppm

6.120 -

(Diastereomer 1) 58.6 ppm; 37.6 ppm; 27.8 ppm; 27.6 ppm; 25.9 ppm; 22.1 ppm; 21.1 ppm

6.121 point 174-

(Diastereomer 2)

point 201-

position)

Comp. R _T Physical data No.

CH-C-H. C ₆ F ₅ O- -NH,

6.131 CH, CeFsO- -NH ₂

-N

6.135 -NH, Melting point 195-

6.136 CβFsO- -NH ₂

point 151 ^■

Comp. R _T Physical data No.

point 140-

point 146-

point 135-

Physical data

point 167-

6.152 C ₆ F ₅ O- -NH,

6.153 point 161-

(Diastereomer 1 )

Physical data

. _N( CH ₃ )

6.158 CeFsO- -NH,

6.159 point 195-

6.160 -N(CH ₃ ) ₂ -N(CH ₃ ) ₂

point 128-

Comp. R, Physical data No.

6.171 -N(CH ₃ ) ₂

point 139-

point 1 g2-

-N(C ₂ H ₅ ) ₂

CH ₃ CO -o-

^■ Λ__

point 124-

Comp. R, Physical data No.

6.183 -NHC ₃ H ₇ (n) _/ ^SC ₂ H ₅ -NH ₂

point 173-

6.188 -N(CH ₃ ) ₂ -N(CH ₃ ) ₂

6.189 -N(C ₂ H ₅ ) ₂ -NH,

H ₃ C^ -0-

Comp. R _T R ₃ Physical data No.

6.191 -N(CH ₃ ) ₂ -NH ₂

point 171-

point 168-

6.197 H ₃ C H ₃ C -NH,

Comp. RT Physical data No.

6.199 -N(C ₄ H ₉ (n)) ₂ -N(CH ₃ ) ₂

6.200 O point 160-

(Decomposition)

6.202 -N(CH ₃ ) ₂ CH ₃ 0. -N(C ₂ H ₅ ) ₂

6.203 -NH-C ₄ H ₉ (n) fø~ -NH,

6.205 -O point 160-

6.206 -N(CH ₃ ) ₂

Comp. R _T Physical data No.

-N(C ₂ H ₅ ) ₂

.213 -N(C ₂ H ₅ ) ₂

g point 88-

Comp. R, Physical data No.

6.218 - ₂ H ₅ ) ₂ -N(CH ₃ ) ₂

6.219 -N(CH ₃ ) ₂ -NHC ₃ H ₇ (n)

point 169-

position)

6.222

6.223 point 168-

6.224 (CH ₃ ) ₂ N- -NH,

^NC - Φ∞S /λ ^"s

Comp. R, R ₂ Physical data No.

6.227 -N(CH ₃ ) ₂ CF. -N(CH ₃ ) ₂

6.228 -N(C ₄ H ₉ (n)) ₂ 2 -NH,

6.229 point 154-

(Decomposition) point 199-

point 181-

Comp. R _T Physical data

point 176-

6.239 -Q-**, point 188-

6.240 -N(CH ₃ ) ₂ -N(C ₂ H ₅ )_

6.241 -N(CH ₃ ) ₂ -NH ₂

Comp. R, Physical data No.

6.247 -N[CH(CH ₃ )2] ₂

6.250 -N(CH ₃ ) ₂ -N(CH ₃ ) ₂

Comp. R R ₃ R_ Physical data No.

point 106-

6257 C ₆ F ₅ O- -NH ₂ Melting point 160-

-N (CH ₂ ) _β 161°C

6.259 -N(CH ₃ ) ₂ "N(CH ₃ ) ₂

Comp R, R ₂ Physical data No.

point 172-

position )

-N(C ₃ H ₇ (n)) ₂

Comp. R, R ₃ R, Physical data No.

(Decomposition)

6.272 -N(CH ₃ ) ₂ -NHC ₄ H ₉ (n)

6.273 -N(CH ₃ ) ₂ -NH ₂

point 153-

6.281 1 ,

6.282 point 157-

6.283 point 133-

6.284 C ₆ F ₅ O- -NH,

R ₃ Physical data

C ₆ F ₅ O- -NH ₂ Melting point 137- 138°C

C ₆ F ₅ O- -NH ₂ MS: [M ⁺ , 50%] 449, [M ⁺ +H, 40%] 450

point 129-

(Diastereomer 1)

6.288 ,

(Diastereomer 2) 6.289 point 157-

position)

(Diastereomer 1 and 2)

Comp. R, Physical data No.

(Diastereomer 1) 6.291 point 154-

(Diastereomer 2)

6.292 point 165-

(Diastereomer 1)

6.293

24.8; 19.2

(Diastereomer 2) 6.294 point 181-

(Diastereomerengem)

6.295 C _e F _s O- -NH, Melting point 162- 163°C

Comp. R, Physical data No.

(Diastereomer 1)

6.296 point 147-

(Diastereomer 2)

6.297 point 134-

(Diastereomer 1)

6.298 point 158-

(Diastereomer 2) ⁶²⁹⁹ C ₆ FsO- -NH, Resin

(Diastereomer mixture) 6.300 point 165-

(Diastereomer mixture)

Comp. R _T R ₂ Physical data No.

6.302 point 174-

6.303 CHfCH,), -N(CH ₃ ) ₂ Melting point 125-

6.304 point 207-

6.305 — -OH -NH ₂ Melting point 178- — N S 180°C

6.306 point 176-

6.307 — -OH -NH ₂ Melting point 170-

— N 171 ^« C

6.308 point 203-

6.309 point 187-

Comp. R, R ₃ Physical data No.

6-310 O- CH-),, -N(CH ₃ ) ₂ Resin; analysis: calc. [%] found [%]

N 17.88 17.86 S 16.38 16.36

6.312 C ₆ F ₅ O- -NH, Melting point 150-

^■ c€> 151 °C

point 191 ^■

6.316 C ₆ F ₅ O- -NH,

— N O

H* "H

Comp. R, Physical data No.

6.317 C ₆ F ₅ O- -NH, H ₃

6.318 C ₆ F ₅ O- -NH ₂

6.319 cr CeFgO- -NH,

point 168-

point 174-

position)

point 171 -

C ₆ FsO- -NH ₂

Comp. R ₁ Physical data No.

6.325 point 134-

6.326 point 122-

point 179-

Comp. R, Physical data No.

6.333 point 173-

6.334 -NH-Adamant-1-yl C ₆ F ₅ O- -NH ₂

6.335 -NH-Adamant-2-yl C ₆ F ₅ O- -NH ₂

Example H20: Preparation of 3-amino-5-chloro-1-(3-hexyloxy)thiatriazine

(Compound No. 7.203)

13.6 g of a 22% methylmagnesium chloride solution in THF (0.040 mol) are added to a solution of 4.1 g of 3-hexanol (0.040 mol) in 40 ml of absolute tetrahydrofuran (THF) at a temperature of -70° to -60°C, under a nitrogen atmosphere and with vigorous stirring. After thawing to 20°C, the solution is added dropwise to a solution, cooled to -65°C, of 8.2 g of 1 ,3,5-trichlorothiatriazine (0.040 mol) in 50 ml of absolute THF, while stirring vigorously. After warming to 0°C, the resulting colourless solution is treated with ammonia, while stirring vigorously. After the intermediate (3,5-dichloro-1-(3-hexyloxy)thiatriazine) has reacted further, 1 I of water is added to the reaction mixture. The resulting suspension is filtered with suction and the residue is rinsed with water and dissolved in methylene chloride, and the solution is dried over sodium sulfate. After the solvent has been evaporated off, the residue is stirred with pentane and the desired product is isolated as white crystals of melting point 144°C by filtration with suction.

The compounds listed in the following Table 7 can be prepared analogously to Example H20.

Table 7: Compounds of the formula VIII

7.10 -NH, c ^b

Comp. Process R_ Physical data No.

7.11 -CH ₂ CH ₂ CI -NHC(CH ₃ ) ₃

7.13 -CH ₂ CH ₂ CI

— N O

7.17 -CHCH ₂ OCH ₃ -NH ₂

CH,

Comp. Process _R . _R∑ Physical data

No.

7.28 -o -NH ₂

7.30 -CH ₂ CH ₂ NO ₂ -NH ₂ 7.31 -CH ₂ CeFs -NH ₂

⁷³³ =λ -NH,

-QHCH,OOC— ά λ

I

C CrH ₃

^{734 "CH} 3 -NHCH ₂ CH ₂ CH ₃

Comp. Process R_ ^ Physical data

No.

7.37 -CH ₂ CH ₂ CI

-N \

7.39 -CH ₃ -N(CH ₃ ) ₂

7-45 -CH ₂ CH ₂ CI -NHCH ₂ CH ₂ CH ₃

Comp. Process R_ R ₂ Physical data No.

7.50 -CH ₂ CH ₂ COOC ₂ H ₅ -NH ₂

7.55 -CH ₃ -NH ₂

7.57 -NH ₂

Cl D

Comp. Process R_ Physical data No.

7.61 -CH ₂ CH ₂ CCI ₃ -NH ₂

7.64 -NH,

7.67 -CH ₂ -adamantyl -NH,

Comp. Process R_ Physical data No.

7.76 -CH ₂ CH ₂ OCH ₃ -NH,

Comp. Process R. Physical data No.

7.82 -CH ₂ CH ₂ F -NH ₂

7.84 -(CH ₂ ) CH ₃ -NHCH ₃

7.87 -CH(CH ₃ )C ₂ H ₅ -NH ₂ 7.88 -C(CH ₃ ) ₃ -NH ₂

Comp. Process R. Physical data No.

7.97 -NHCH(CH ₃ )CHj0CH ₃

7.98 -CHCH-CI -NH ₂

C ₆ H ₅

Comp. Process R_ Physical data No.

7.103 -o -NH ₂

C(CH ₃ ) _a

Comp. Process R_ Physical data No.

7.114 -NH ₂

248 -

Comp. Process R. Physical data

No.

7.123 -(CH ₂ ) ₄ CH ₃ -NH ₂

7.125 -CH ₂ CH ₂ SC ₂ H ₅ -NH ₂ 7.126 -CH ₂ CH ₂ Si(CH ₃ ) ₃ -NH ₂ 7.127 -(CH ₂ ) ₉ CH ₃ -NH ₂

Comp. Process R. Physical data No.

7.131 -NH ₂

7.138 -CH ₂ CH CI -NHCH ₂ CH ₂ CH ₃

-NHCH(CH ₃ ) ₂ -N(C ₂ H ₅ ) ₂

Comp. Process R_ Physical data

No.

Comp. Process R_ R ₂ Physical data No.

7.154 -CHCH-CI -NH ₂ I C ₂ H ₅

7.155 -CHC CI -NH ₂

I ²

C _β H ₅

7.157 -CHCH I -NH ₂

I ²

CH,

7.161 -NH ₂

Comp. Process R_ R ₂ Physical data No.

Comp. Process R_ R ₂ Physical data

No.

7.181 -NH ₂

Comp. Process R_ R ₂ Physical data

No.

7.188 -(CH ₂ ) ₃ Si(CH ₃ ) ₃ -NH ₂

7.190 CH, -NH ₂ Melting point

144°C

-O (Decomposition)

Comp. Process R. R ₂ Physical data No.

7.193 -CH ₂ Si(CH ₃ ) ₃ -NH ₂

7.200 -CH Si(CH ₃ -NH,

3)> 3

CH=CH,

ppm): 6.3 (broad s, 1 H); 5,4 (broad s, 1H); 4.25-4.35 (m, 1H); 1.9-1.3 (m,6H);1.0- 0.83 (m, 12H)

Comp. Process R_ R ₂ Physical data

No.

7.211 -NH ₂

-o

Comp. P ocess R_ R ₂ Physical data

Nc.

Diastereomer 1

7.220 CH " ^NH 2

I ³

-CH ₂ -C(CH ₂ CH ₂ CN) ₂

OCHF,

Comp. P ocess R_ R ₂ Physical data

No.

7.225

7.227

7.228

7.229

7.232

Comp. Process R_ Physical data No.

Example H21 : Preparation of 3.5-dichloro-1-(octahydroindol-1-yl)thiatriazine

(Compound No. 8.80)

A mixture of 3.1 g of octahydroindol (0.025 mol) and 2.5 g of triethylamine (0.025 mol) is added dropwise to a solution of 5.1 g of 1 ,3,5-trichlorothiatriazine (0.025 mol) in 65 ml of diethyl ether at a temperature of -70° to -60°C, under a nitrogen atmosphere and with vigorous stirring. After the reaction mixture has thawed, water is added and the organic phase is washed with water, sodium bicarbonate solution and brine, dried over sodium sulfate and evaporated. After crystallization from pentane, crystals of the desired compound of melting point 90-92°C are isolated.

The compounds listed in the following Table 8 can be prepared analogously to Example H21.

Table 8: Compounds of the the formula IX

Comp. R, Physical data No.

8.1 -NHCH ₂ CH ₂ CH ₃

8.8 CH,

/ (

-N O

CH,

Comp. R, Physical data No.

8.13 /

— N-CH,

8.15 -N(CH ₂ CH ₂ CN) ₂ 8.16 -NHCβHι,(c) 8.17 -N(n-C ₃ H ₇ ) ₂

8.21

N ( H ₂ ) ₇

Comp. R,

Physical data No.

8.31 -N[CH(CH ₃ ) ₂ ] ₂

8.32 -N(C ₂ H ₅ ) ₂

8.33 -N(C ₂ H ₅ )C ₄ H ₉ (n)

Comp. R _T Physical data No.

8.35 CH,

-N rX O

CH,

8.37 -N(CH ₃ ) ₂ 8.38

^■ o

8.40

^■N D

8.42 -N(C ₂ H ₅ ) ₂ 8.43 (not isolated)

-O

8.46

N (PH ₂ 2)> β

Comp. R _T Physical data No.

8.50 -NHCH ₃

8.53 -NH(CH ₂ ) ₃ CF ₃

8.57

-CO

Comp. R, Physical data No.

8.58

^■ 'O' ^{^} O

8.62 CH,

/

— N

CH ₂ COOC ₂ H _s

8.67

N (Wu

Comp. R _T Physical data No.

8.69 -N(C ₄ H ₉ (n)) ₂

8.75

- ^N d

Comp. R, Physical data No.

Melting point 80-g2°C

8.83 -N(CH ₃ ) ₂

8.85 -

Comp. R, Physical data No.

8.96 OH

X

Comp. R, Physical data No.

8.99 CH,

/

-N

\

CH ₂ CH ₂ CN

8.103 N(C ₄ H ₉ (n)) ₂

Comp. R, Physical data No.

Comp. R, Physical data No.

8.115 -NHC ₃ H ₇ (n)

8.121 ₃

8.122

Comp. R, Physical data No.

8.123 -NH-C ₄ H ₉ (n)

8.131

— N NCOCH,

Comp. R, Physical data No.

¹³³ -O ∞O

8.135

N

8.136 -Q-<

8.137

-N

8.139 -N[CH(CH ₃ ) ₂ } ₂

Comp. R _T Physical data

No.

8.151 Cl

-θ ⁶

Comp. R _T Physical data No.

(not isolated)

8.161

Comp. R _T Physical data No.

Comp. R _T Physical data No.

Comp. R _T Physical data No.

8.188

Example H22: Preparation of 3-amino-5-chloro-1-(piperidin-t-vDthiatriazine

(Compound No. 9.46)

15.6 ml of a 1.6 molar n-butyllithium solution in hexane (0.025 mol) are added to a solution of 2.13 g of piperidine (0.025 mol) in 10 ml of absolute tetrahydrofuran at a temperature of -70° to -60°C, under a nitrogen atmosphere and with vigorous stirring. After thawing to 20°C, the resulting white suspension is added dropwise in portions to a solution, cooled to - 60°C, of 5.11 g of 1 ,3,5-trichlorothiatriazine (0.025 mol) in 50 ml of absolute tetrahydrofuran, while stirring vigorously. After warming to -10 ^C C the reaction mixture is treated with ammonia (gas) with vigorous stirring. After all the intermediate has been used up, water and ethyl acetate are added to the reaction mixture. The organic phase is washed with water and brine, dried over sodium sulfate and evaporated. The residue is stirred with a diethyl ether/pentane mixture and filtered off with suction. The desired compound is isolated as yellowish crystals of melting point 118-120°C (decomposition).

Example H23: Preparation of 3-amino-5-chloro-1-(octahvdroindol-1-yl)thiatriazine

(Compound No. 9.93)

10.2 g of a 30% ammonia solution in water (0.180 mol) are added to a solution of 3.7 g of 3,5-dichloro-1-(octahydroindol-1-yl)thiatriazine (0.0126 mol) in 120 ml of tetrahydrofuran at 20°C and the mixture is stirred vigorously for 3 hours. After evaporation of the organic solvent, the resulting suspension is filtered off with suction and the residue is washed with water and then with diethyl ether and dried. The desired compound is isolated as slightly yellowish crystals of melting point 115°C (decomposition).

The compounds listed in the following Table 9 can be prepared analogously to Examples

H22 and H23.

Table 9: Compounds of the formula X

Comp. R _T R ₂ Physical data No.

9.5 CH, -NH ₂

-N

CH,

(Diastereomer 1)

9.8 CH, -NH ₂

— N rX O

CH,

(Diastereomer 2)

Comp. RT R ₂ Physical data No.

9.14 -NH,

— N -

9.23 -NH ₂

-N (PH ₂ ) ₇

Comp. RT Physical data No.

9.28 )',2 -NH ₂

9.33 -N[CH(CH ₃ )_] ₂ -NH ₂

9.34 -N(C ₂ H ₅ )C ₄ H ₉ (n) -NHCH ₃

9.40 -NH ₂

^•

Comp. R, Physical data No.

(Diastereomer 2)

9.60 -N(CH ₃ ) ₂ -NHCH(CH ₃ ) ₂

9.61 -NH(CH ₂ ) ₃ CF ₃ -NH ₂

Comp. R _T Physical data No.

9.66 -NH ₂

— N ^N" λ ^\ '/

9.67 -N(CH ₃ ) ₂ -NHC ₃ H ₇ (n)

9.69 -N(CH ₃ ) ₂ -NHC ₂ H ₅

9.72 CH,

/ -NH ₂

— N

\

CH ₂ COOC ₂ H ₅

Comp. R _T R ₂ Physical data No.

9.73 -NH,

-N

9.75 -N(CH ₃ ) ₂ -NHCH ₃

(Diastereomer 1)

(Diastereomer 2)

9.81 -N(C ₄ H ₉ (n)) ₂ -NH ₂

H

Comp. R _T Physical data No.

9.87 -NH ₂

-<|

Comp. R _T Physical data No.

9.93 Melting point 115°C (Decomposition)

9.94

9.98

.99 - -NH ₂

9 -NH ₂

Comp. R _T Physical data No.

Comp. R _T R ₂ Physical data No.

9.112 CH, -NH ₂

/

— N

\

CH ₂ CH ₂ CN

(Diastereomer 1)

(Diastereomer 2) 9.117 -N(C ₄ H ₉ (n)) ₂ -N(CH ₃ ) ₂

Comp. R _T Physical data No.

Comp. R _T Physical data No.

9.130 -NHC ₃ H ₇ (n) -NH ₂

Comp. R _T Physical data No.

9.143 -N(C ₂ H ₅ ) ₂ -N(CH ₃ ) ₂

9.145 -NH,

2g7 -

Comp. R _T Physical data No.

9.146 -NH ₂

— N (S)

CH ₂ OCH ₃

9.147 -N(C ₂ H ₅ ) ₂

— N NCOCH,

9.149 NH ₂

- ^N C^ ^CO O- ^F

9.152 -N(CH ₃ ) ₂

— N

9.153 -NH ₂

- ^ -CH ₃

9.154 -NH ₂

— N

9.156 -N[CH(CH ₃ ) ₂ ] ₂ -NH,

Comp. R _T Physical data No.

9.160 CHfOy. . _N H ₂

/

— N \ (CHJ-NHCyHs

9.163 -N(CH ₃ ) ₂ -N(C ₃ H ₇ (n)) ₂

9.166 -N(CH ₃ ) ₂ -NHC ₄ H ₉ (n)

Comp. R _T Physical data No.

9.169 _ _N H ₂

9.175 -NH,

(Diastereomer 1 )

Comp. R _T R ₂ Physical data No.

(Diastereomer 2)

(Diastereomer 1)

(Diastereomer 2) 9.179

(Diastereomer 1 and 2) 9.180

(Diastereomer 1)

Physical data

-NH ₂

(Diastereomer 2) 9.184

(Diastereomer mixture)

(Diastereomer 1)

Comp. R, Physical data No.

(Diastereomer 2)

(Diastereomer 1)

(Diastereomer 2)

(Diastereomer mixture)

(Diastereomer mixture)

Comp. R _T Physical data No.

9.192 -NH,

— N

X ^H '

9.193 -N(CH ₃ ) ₂

9.194 -NH ₂

^■ o

9.195 -NH ₂

-N S

Comp. R _T Physical data No.

9.206 -NH ₂

Comp. R _T Physical data No.

Formulation examples for active compounds of the formula I (% = percent by weight)

F1. Emulsion concentrates a) b) c) d)

Active compound according to Tables 4-6 5% 10% 25% 50%

Calcium dodecylbenzene- sulfonate 6% 8% 6% 8%

Castor oil polyglycol ether

(36 mol of EO) 4% - 4% 4%

Octylphenol polyglycol ether

(7-8 mol of EO) - 4% - 2%

Cyclohexanone - - 10% 20%

Aromatic hydrocarbon mixture

C ₉ -C ₁₂ 85% 78% 55% 16%

Emulsions of any desired concentration can be prepared from such concentrates by dilution with water.

F2. Solutions a) b) c) d)

Active compound according to Tables 4-6 5% 10% 50% 90% 1 -Methoxy-3-(3-methoxy- propoxy)propane 20% 20% Polyethylene glycol molecular weight 400 20% 10% N- ethyl-2-pyrrolidone 30% 10% Aromatic hydrocarbon mixture C ₉ -C ₁₂ 75% 60%

The solutions are suitable for use in the form of tiny drops.

F3. Wettable owders a b c) d)

80%

4%

6%

10%

The active compound is mixed thoroughly with the additives and the mixture is ground thoroughly in a suitable mill. Wettable powders which can be diluted with water to give suspensions of any desired concentration are obtained.

F4. Coated granules a) b) c)

Active compound according to Tables 4-6

Highly disperse silicic acid

Inorganic carrier

(0 0.1 - 1 mm), for example

CaCO ₃ or SiO ₂

The active compound is dissolved in methylene chloride, the solution is sprayed onto the carrier and the solvent is then evaporated off in vacuo.

F5. Coated granules a) b) c)

Active compound according to Tables 4-6 0.1 % 5 % 15 %

Polyethylene glycol molecular weight 200

Highly disperse silicic acid

Inorganic carrier

(0 0.1 - 1 mm), for example

CaCO ₃ or SiO ₂

The finely ground active compound is applied uniformly to the carrier, which has been moistened with polyethylene glycol, in a mixer. Dust-free coated granules are obtained in this manner.

F6. Extruded granules a) b) c) d)

Active compound according to Tables 4-6 0.1 % 3 % 5 % 15 %

Sodium lignin sulfonate 1 .5 % 2 % 3 % 4 %

The active compound is mixed with the additives and the mixture is ground and moistened with water. This mixture is extruded and the extrudate is then dried in a stream of air.

Ready-to-use dusts are obtained by mixing the active compound with the carriers and grinding the mixture on a suitable mill.

F8. Suspension concentrates a) b) c) d)

Active compound according to Tables 4-6

Ethylene glycol

Nonylphenol polyglycol ether

(15 mol of EO)

Sodium lignin sulfonate

Carboxymethyl cellulose

37% aqueous formaldehyde solution

Silicone oil emulsion

Water

The finely ground active compound is mixed intimately with the additives. A suspension concentrate from which suspensions of any desired concentration can be prepared by dilution with water is thus obtained.

Biolooical Examples

Example B1: Herbicidal action before emergence of the plants (pre-emerqent action)

Monocotyledon and dicotyledon test plants are sown in standard soil in plastic pots. Immediately after sowing, the test substances are sprayed on (500 I of water/ha) in an aqueous suspension prepared from a 25% wettable powder (Example F3, b)), corresponding to a dosage of 2000 g of active substance/ha. The test plants are then grown under optimum conditions in a greenhouse. After a test period of 3 weeks, the test is evaluated with a ratings scale of nine levels (1 = complete damage, 9 = no action). Ratings of 1 to 4 (in particular 1 to 3) mean a good to very good herbicidal action.

Test plants: Avena, Setaria, Sinapis, Stellaria

In this test, the compounds of the formula I according to the examples in Tables 4, 5 and 6 show a potent herbicidal action.

Table B1 gives examples of the good herbicidal activity of the compounds of the formula I:

Table B1: Pre-emerqent action:

Test plants: Avena Setaria Sinapis Stellaria

Compound No.

Test plants: Avena Setaria Sinapis Stellaria Compound No.

6.129 4 4 6.135 3 3 6.140 4 3 6.145 4 2 6.153 4 3 6.154 4 1 6.170 3 4 6.173 4 3 6.185 4 4 6.192 2 1 6.194 7 5 6.200 4 1 6.229 3 2 6.257 3 2 6.282 4 2 6.285 5 2 6.292 5 1 6.295 3 1 6.296 4 2 6.298 3 2 6.302 3 2 6.331 4 2

The same results are obtained when the compounds of the formula I are formulated according to Examples F1 , F2 and F4 to F8.

Example B2: Post-emeroent herbicidal action (contact herbicide)

Monocotyledon and dicotyledon test plants are grown in plastic pots with standard soil in a greenhouse and, in the 4- to 6-leaf stage, are sprayed with an aqueous suspension of the test substances of the formula 1 , prepared from a 25 % wettable power (Example F3, b)),

corresponding to a dosage of 2000 g of active substance/ha (500 I of water/ha). The test plants are then grown further in the greenhouse under optimum conditions. After a test period of about 18 days, the test is evaluated with a ratings scale of 9 levels (1 = complete damage, 9 = no action). Ratings of 1 to 4 (in particular 1 to 3) mean a good to very good herbicidal action.

Test plants: Sinapis, Stellaria

In this test also, the compounds of the formula I according to the examples in Tables 4, 5 and 6 show a good herbicidal action.

Table B2 gives examples of the good herbicidal activity of the compounds of the formula I:

Table B2: Post-emer ent action:

Stellaria

2 3 3 3 3 3 3 4 4 2 4 4 4

napis Stellaria

2 4 5 2 5 4 3 4 4 4 3 3 2 2 2 4 3 3 4 1 1 3 4 3 3 3 3 3

inapis Stellaria

2 1 3 3 3 3 2 3 1 4 4 2 3 4 2 2 5 4 3 3 3 4 4 3 2 3

The same results are obtained when the compounds of the formula I are formulated according to Examples F1 , F2 and F4 to F8.