KUNZ WALTER (CH)
STOLLER ANDRE (FR)
KUNZ WALTER (CH)
| WO1996001814A1 | 1996-01-25 |
| EP0075117A2 | 1983-03-30 |
| 1. | A compound of the formula in which Ri is a group R2 and R3 independently of one another are hydrogen, CιC6alkyl, dC6alkyl which is substituted by S(O)nRe, halogen, cyano, nitro, CrCβalkoxy, C3C6trialkylsilyl, hydroxyl, amino, ammonium, tridC4alkylammonium, COOH, COOR∞, COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or by CsCβcycloalkyl, dCsalkylcarbonyloxy, phenylcarbonyloxy, naphthylcarbonyloxy, CιC6alkylamino, dCsalkoxycarbonyl, C2Cι2dialkylamino, phenyl, naphthyl, phenoxy, naphthoxy, biphenyl, biphenyloxy, phenthio or naphthio, it being possible for the abovementioned aromatic rings to be substituted by halogen, cyano, nitro, OR5, NRι0Rn, C C4alkyl, formyl, dC alkylcarbonyl, COOR7, CιC4alkylthio, dC4alkylsulfonyl or CONRβRg, or R2 and R3 independently of one another are C2Cealkenyl, C2C6alkenyl which is substituted by halogen, cyano, nitro, dC8alkoxy, C3C6trialkylsilyl, hydroxyl, amino, ammonium, triCιC4alkylammonium, COOH, COOR∞, COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or QrCβcycloalkyl, CrCsalkylcarbonyloxy, phenylcarbonyloxy, naphthylcarbonyloxy, CιC6alkylamino, C2C alkoxycarbonyl, C2Cι2dialkylamino, phenyl, naphthyl, phenoxy, naphthoxy, biphenyl, biphenyloxy, phenthio or naphthio, it being possible for the abovementioned aromatic rings to be substituted by halogen, cyano, nitro, OR5, NRι0Rn, CιC4alkyl, formyl, CιC4alkylcarbonyl, COOR7, dC4alkylthio, dC4alkylsulfonyl or CONR8R9, or R2 and R3 independently of one another are C3Cβalkynyi, C3C6alkynyl which is substituted by halogen, cyano, nitro, CιC8alkoxy, C3Cβtriaf kylsilyl , hydroxyl, amino, ammonium, triddalkylammonium, COOH, COOR∞, COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or C3C8cycloalkyl, dC5alkylcarbonyloxy, phenylcarbonyloxy, naphthylcarbonyloxy, CιC6alkylamino, CrC5alkoxycarbonyl, C2C12dialkylamino, phenyl, naphthyl, phenoxy, naphthoxy, biphenyl, biphenyloxy, phenthio or naphthio, it being possible for the abovementioned aromatic rings to be substituted by halogen, cyano, nitro, OR5, NR10Rn, CιC alkyl, formyl, CιC alkylcarbonyl, COOR7, dC4alkylthio, CιC4alkylsulfonyl or CONR8R9, or R2 and R3 independently of one another are formyl, dC15alkylcarbonyl, C2Cι5alkenylcarbonyl, C C9cycloalkylcarbonyl, CβCgcycloalkenylcarbonyl or C3 C8cycloalkylC Cβalkylcarbonyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, hydroxyl, amino, dC6alkylamino, C2Cι2dialkylamino, COOH, COOR∞, COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or by dCβalkoxycarbonyl, C4Cι0cycloalkoxycarbonyl, CιC8alkylaminocarbonyl or C2C12dialkylaminocarbonyl, or R2 and R3 independently of one another are heterocyclyl, heterocyclylcarbonyl, heterocyclyl which is substituted by halogen, cyano, nitro, CιC3alkyl, dC5alkoxy, dC5alkylcarbonyl, dCsalkylcarbonyloxy, CιC6alkoxycarbonyl, aminocarbonyl, dC6alkylaminocarbonyl or C^Cndialkylaminocarbonyl, or are heterocyclylcarbonyl which is substituted by halogen, cyano, nitro, dC5alkyl, Crdalkoxy, CιC3alkylcarbonyl, CιCβalkoxycarbonyl, aminocarbonyl, CiCβalkylamino or CιC5alkylcarbonyloxy, or R2 and R3 independently of one another are phenylcarbonyl, biphenylcarbonyl, naphthylcarbonyl, phenyldCβalkylcarbonyl, biphenyldC6alkylcarbonyl, naphthyl CιC6alkylcarbonyl, phenylC2C6alkenylcarbonyl, biphenylCrCβalkenylcarbonyl, naphthyl C2C6alkenylcarbonyl, phenylCaCβalkynylcarbonyl, biphenylC3C6alkynylcarbonyl or naphthylC3C6alkynylcarbonyl, it being possible for these substituents to be substituted by CiCsalkyl, CrCsalkoxy, dCsalkylthio, dC5haloalkyl, dC5alkylcarbonyl, halogen, cyano, amino, nitro, COOR7, CiCβalkoxycarbonyl, hydroxyl, CιC5alkylsurfinyl, dC5alkylsulfonyl, CrC8alkylaminocarbonyl or C2d2dialkylaminocarbonyl, or R2 and R3 independently of one another are phenyl or naphthyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, dC5aikyl, CιC5alkoxy, CιC5alkylthio, COOH, CONH2, dCβalkylaminocarbonyl, C2Cιodialkylaminocarbonyl, C C5alkylcarbonyl or CιC5alkoxycarbonyl, or R2 and R3 together with the nitrogen atom to which they are bonded form a heterocyclic ring which can be substituted by CιC5alkyl, CιC5alkoxy, halogen, cyano or nitro, or R2 and R3 independently of one another are amino, CιC6alkylamino, C2C8dialkylamino, phenylamino, naphthylamino, dCβalkylcarbonylamino, ddoalkoxycarbonylamino, hydroxyl, dCβalkoxy, CiCealkylcarbonyloxy, phenoxy, biphenyloxy or naphthoxy, X is O or S(O)x, in which x is 0, 1 or 2, and R is C C8alkyl, C2Cβalkenyl, C3C8alkynyl, C3Cβcycloalkyl, CsCβcycloalkenyl, C3C8cycloalkylCιC alkyl or CιC4alkylC3C8cycloalkyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, =O or OR5, or R4 is phenyl, biphenyl, naphthyl, heterocyclyl, dC4alkylphenyl, ddalkylnaphthyl, phenyl CιC alkyl or naphthyldC4alkyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, amino, COOH, hydroxyl, dC10alkyl, Crdoalkyloxy, C C6alkylamino, diC2Cβalkylamino, dC10alkylthio, CιC10haloalkyl, CιCιohaloalkoxy, d Ciohaloalkylthio, C2C10alkoxycarbonylalkoxy, CrCealkylsulfinyl, dC6alkylsulfonyl, C C6alkyloxycarbonyl, CiCβalkylcarbonyl, CONH2, formyl, CιC7alkylaminocarbonyl, C2 ddialkylaminocarbonyl, C3C6trialkylsilyl, CιCιoalkylcarbonylamino, C C10alkylcarbonyloxy, phenoxy, halophenoxy, pyridyloxy or pyridyloxy which is substituted by halogen, CιC alkyl, CιC4alkoxy, cyano, nitro or amino, or. |
| 2. | adjacent substituents on the phenyl or naphthyl ring R4 form a carbocyclic or heterocyclic ring which can be substituted by halogen, cyano, nitro, amino, COOH, =O, CιC10alkyl. CιCιoalkoxy, dC10alkylthioP d dohaloalkyl, hydroxyl, C3C10alkoxycarbonylalkoxy, dC6alkylsulfinyl, dCealkylsulfonyl, C2C6alkyloxycarbonyl, C2C6alkylcarbonyl, CONH2, formyl, C2Cτalkylaminocarbonyl, C3 Cndialkylaminocarbonyl, C3C6trialkylsilyl, C2C10alkylcarbonylamino, d Cioalkylcarbonyloxy, phenoxy, pyridyloxy or pyridyloxy which is substituted by halogen, Ci C alkyl, CιC4alkoxy, cyano, nitro or amino, R5 is hydrogen, dC6alkyl, CιC6haloalkyl, 02Csalkoxyalkyl, CiCecyanoalkyl, phenyl, phenyldC4alkyl, formyl, C2C7alkylcarboπyl, C2C7alkoxycarbonyl, CiCβalkyl¬ aminocarbonyl, dCβdialkylaminocarbonyl, benzoyl, halobeπzoyl, CiCβalkylamino, C2Cβdialkylamino, N=CH2, N=CHdC alkyl, N=C(CιC alkyl)2l tri(dC4alkyl)silyl, C3C7cycloalkyl, C2C7alkenyl or C3C7alkynyl, heterocyclyl, n is 0, 1 or 2, R6 is hydrogen or cyano when n is 0 or R6 is CιC5alkyl, CrC5alkenyl, C3C5alkynyl, CrCβalkoxyalkyl, CiCshaioalkyl, dCδhydroxyalkyl, phenyl, phenylC C alkyl, heterocyclyl, heterocyclylCιC4alkyl or dC^ycloalkyl, R7 is hydrogen, dC12alkyl, dCι2haloalkyl, dCenitroalkyl, CιCβcyanoalkyl, phenyl, C2Cιoalkoxyalkyl, C2Cιoalkylcarbonylalkyl, C2Cιoalkoxycarbonyialkyl, heterocyclyl, CsCTcycloalkyl, C3dhalocycloalkyl, N=CH2, N=CHCιC4alkyl, N=C(dC alkyl)2 or C2C6dialkylamino, Re and R9 independently of one another are hydrogen, phenyl, CiCβalkyl, CιC8haloalkyl, dC8alkoxy, phenoxy, C2C7cyanoalkyl, C3C7alkenyl, CaCralkynyl, C2C8alkoxyalkyl, CιC6alkylamino or C2C6dialkylamino, or R8 and R9 together with the nitrogen atom to which they are bonded form a three to seven membered heterocycle which can contain one or two further hetero atoms and, in turn can be substituted by d^alkyl groups or halogen, R10 and Rn independently of one another are hydrogen, phenyl, CιC8alkyl, CrCβhaloalkyl, CrCsalkoxy, phenoxy, C2C7cyanoalkyl, C3C7alkenyl, C3C7alkynyl, C2C8alkoxyalkyl, CιC6alkylamino, (CιCβalkylamino)carbonyl, C2C6dialkylamino, (C2 C6dialkylamino)carbonyl, formyl, (CιCτalkyl)carbonyl, (dCβalkoxy)carbonyl, phenylcarbonyl, phenoxycarbonyl, benzyloxycarbonyl, heterocyclylcarbonyl, heterocyclyloxycarbonyl, or R10 and Rn together with the nitrogen atom to which they are bonded form a three to sevenmembered heterocycle which can contain one or two further hetero atoms and, in turn, can be substituted by C16alkyl groups or halogen, Rι2 is dCβalkyl, CιC8alkoxy, dCβalkenyloxy, CιC8alkynyloxy, CιC8haloalkyl, phenyl, phenyloxy, R13 and Rι4 independently of one another are hydrogen, dC6alkyl, C2Cβalkylcarbonyl or phenyl, and Ris, Riβ, R17, Riβ and R19 independently of one another are CιC10alkyl, C3Cβcycloalkyl, dCβalkyldCβcycloalkyl, C2C10alkenyl, dCβcycloalkyl C2C4alkenyl, C2C6alkenylC3Cβcycloalkyl, C2Cιoalkynyl, C3C6cycloalkylC2C alkynyl, C2C6alkynyldC6cycloalkyl, CsCβcycloalkenyl, CsC6cycloalkenylCιC4alkyl, dC6alkyl C5Cecycloalkenyl, CsCβcycloalkenylCgC^lkenyl, CrCealkenylCsCβcycloalkenyl, C5C6cycloalkenylC2C alkynyl, C2CealkynylC5Cecycloalkenyl, C3C6cycloalkyl C3C6cycloalkyl, CsCβcycloalkenylCsCβcycloalkenyl, CaCβcycloalkylCsCβcycloalkenyl, C5CβcycloalkenylC3C6cycloalkyl, dCβalkynyldCβalkenyl or C2CβalkenylC2C8alkynyl, phenyl, phenylCιC alkyl, phenylC2C4alkenyl, phenylC2C4alkynyl, heterocyclyl, heterocyclylCιC4alkyl, heterocyclyldC^lkenyl or heterocyclyldC4alkynyl, it being possible for the substituents R15, Riβ. R17, Ris and Rig independently of one another to be substituted by halogen, cyano, azido, nitro, OR5, =O, S(O)nRβ, COOR7, CONR8RB, NR10Rιι, =NRι2 or =NNR13Rι , or R15, R16, Ri7, Riβ and R19 independently of one another are halogen, cyano, azido, nitro, OR5, S(O)nR6, COOR7, CONRβR9, NR10R11, tri(dC4alkyl)silyl, di(dC4alkyl) (C C4alkoxy)silyl, B(OH)2 , B(dC4alkoxy)2 , tri(C1C4alkyl)silyl, tri(CιC4alkyl)silyl dC6alkyl, tri(C C4alkyl)silylC2Cealkenyl, tri(CιC alkyl)silylC2C8alkynyl, tri(dC alkyl) stannyl, tr ddalky stannylCiCealkyl, tri(dC alkyl)stannylC2Cβalkenyl, tri(CιC4alkyl) stannylC2C8alkynyl, and R∞ is CιC12alkyl, CιC6nitroalkyl, CiCβcyanoalkyI, phenyl, C^doalkoxyalkyl, C2Cιoalkylcarbonylalkyl, CrCioalkoxycarbonylalkyl, heterocyclyl, 03Cτcycloalkyl, C3C7halocycloalkyl, N=CH2, N=CHCιC4alkyl, N=C(dC4alkyl)2 or C2C6dialkylamino, and the salts of the compounds of the formula I, with the exception of the compounds 1 (4hydroxyphenyl)3amino5(2,5difluorophenoxy)thiatriazine, 1 (4methylpheπyl)3 amino5phenoxythiatriazine, 1(4methoxyphenyl)3amino5(2,3,4,5,6pentafluoro phenoxy)thiatriazine, 1(4methoxyphenyl)3amino5(2,3,4trichlorophenoxy)thiatriazine, 1 (4chlorophenyl)3amino5(2,3,4,5,6pentafluorophenoxy)thiatriazine, 1 (4chlorophenyl) 3amino5(2,3dichlorophenoxy)thiatriazine, 1(2hydroxy5tertbutylphenyl)3amino5 (2,5difluorophenoxy)thiatriazine, 1 (4hydroxy3methylphenyl)3amino5(2,5 difluorophenoxy)thiatriazine, 1(4hydroxy3methoxyphenyl)3amino5(2,5 difluorophenoxy)thiatriazine, 1(3,5dimethyl4hydroxyphenyl)3amino5(2,5 difluorophenyloxy)thiatriazine, 1(3,5dimethoxy4hydroxyphenyl)3amino5(2,5 difluorophenyloxy)thiatriazine, 1(3,5dimethyl2hydroxyphenyl)3amino5(2,5 difluorophenyloxy)thiatriazine, 1(3,5dimethyl4hydroxyphenyl)3dimethylamino5(2,5 difluorophenyloxy)thiatriazine, 3amino1(4amino2,3,5,6tetrafluorophenyl)5(2,3,4,5,6 pentafluorophenoxy)thiatriazine, 3amino1 (4amino2,3,5,6tetrafluorophenyl)5(2, 4, 6 trichlorophenoxy)thiatriazine, 3amino1(4amino2,3,5I6tetrafluorophenyl)5(2,5 difluorophenoxy)thiatriazine, 3amino5(2,5difluorophenoxy)1 (2,3,4,5,6 pentafluorophenyl)thiatriazine and 3amino5(2,3,4I5I6pentafluorophenoxy)1 (2,3,4,5,6 pentafluorophenyl)thiatriazine. |
| 3. | 2 A compound according to Claim 1 , wherein R2 and R3 independently of one another are hydrogen, dCealkyl, CiCsalkyl which is substituted by S(O)nRe, halogen, cyano, nitro, CiCβalkoxy, C3C6trialkylsilyl, hydroxyl, amino, ammonium, tridC4alkylammonium, COOH, COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or by C3C8cycloalkyl, dCsalkylcarbonyloxy, phenylcarbonyloxy, naphthylcarbonyloxy, CιC6alkylamino, dC5alkoxycarbonyl, C2C 2dialkylamino, phenyl, naphthyl, phenoxy, naphthoxy, biphenyl, biphenyloxy, phenthio or naphthio, it being possible for the abovementioned aromatic rings to be substituted by halogen, cyano, nitro, OR5, NR10Rπ, dC4alkyl, formyl, dC4alkylcarbonyl, COOR7, dC alkylthio, dC4alkylsulfonyl or CONRβRg, or R2 and R3 independently of one another are C2Cealkenyl, C2C6alkenyl which is substituted by halogen, cyano, nitro, dC8alkoxy, C3Cβtriaikylsilyl, hydroxyl, amino, ammonium, triCι dalkylammonium, COOH, COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or by dC8cycloalkyl, C2C5alkylcarbonyloxy, phenylcarbonyloxy, naphthylcarbonyloxy, CιCβalkylamino, C2C5alkoxycarbonyl, C2C12dialkylamino, phenyl, naphthyl, phenoxy, naphthoxy, biphenyl, biphenyloxy, phenthio or naphthio, it being possible for the abovementioned aromatic rings to be substituted by halogen, cyano, nitro, ORs, NR10R11, dC4alkyl, formyl, CιC4alkylcarbonyl, COOR7, dC4alkylthio, Cι dalkylsulfonyl or CONRβRg, or R2 and R3 independently of one another are C3C6alkynyl, C3C6alkynyl which is substituted by halogen, cyano, nitro, dC8alkoxy, C3Cβthalkylsilyl, hydroxyl, amino, ammonium, triC dalkylammonium, COOH, COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or by C3C8cycloalkyl, CιC5alkylcarbonyloxy, phenylcarbonyloxy, naphthylcarbonyloxy, dC6alkylamino, dCsalkoxycarbonyl, C2Cι2dialkylamino, phenyl, naphthyl, phenoxy, naphthoxy, biphenyl, biphenyloxy, phenthio or naphthio, it being possible for the abovementioned aromatic rings to be substituted by halogen, cyano, nitro, ORs, NR10R11, CιC4alkyl, formyl, dC4alkylcarbonyl, COOR7, dC4alkylthio, d C alkylsulfonyl or CONRβRg, or R2 and R3 independently of one another are formyl, CιCi5alkyicarbonyl, C2dsalkenyl carbonyl, C4C9cycloalkylcarbonyl, C6C9cycloalkenylcarbonyl or CaCβcycloalkyldCealkyl carbonyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, hydroxyl, amino, CιCβalkylamino, C2Cι2dialkylamino, COOH, COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or by dCβalkoxycarbonyl, C4C10cycloalkoxycarbonyl, dCθalkylaminocarbonyl or C2C12dialkylaminocarbonyl, or R2 and R3 independently of one another are heterocyclyl, heterocyclylcarbonyl, heterocyclyl which is substituted by halogen, cyano, nitro, CιC5alkyl, dC5alkoxy, CιC5alkylcarbonyl, dC3alkylcarbonyloxy, CιC6alkoxycarbonyl, aminocarbonyl, CiCβalkylaminocarbonyl or CrCπdialkylaminocarbonyl, or are heterocyclylcarbonyl which is substituted by halogen, cyano, nitro, CiCsalkyl, CrCsalkoxy, dC5alkylcarbonyl, CιC6alkoxycarbonyl, aminocarbonyl, CιC6alkylamino or dC5alkylcarbonyloxy, or R2 and R3 independently of one another are phenylcarbonyl, biphenylcarbonyl, naphthylcarbonyl, phenylCiCβalkylcarbonyl, biphenylCiCβalkylcarbonyl, naphthylCr C6alkylcarbonyl, phenylC2C6alkenylcarbonyl, biphenylCϋCβalkenylcarbonyl, naphthylC2 C6alkenylcarbonyl, phenylC3C6aikynylcarbonyl, biphenylC3Cβalkynylcarbonyl or naphthyl C3C6alkynylcarbonyl, it being possible for these substituents to be substituted by C Csalkyl, dC5alkoxy, CrC5alkylthio, CιC5haloalkyl, dGsalkylcarbonyl, halogen, cyano, amino, nitro, COOR7, CιC8alkoxycarbonyl, hydroxyl, CιC5alkylsulfinyl, CrC5alkylsulfonyl, dC6alkylaminocarbonyl or C2Cι2dialkylaminocarbonyl, or R2 and R3 independently of one another are phenyl or naphthyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, dC5alkyl, CrCsalkoxy, CrC5alkylthio, COOH, CONH2, CrC6alkylaminocarbonyl, C2Cιodialkylaminocarbonyl, CrC5alkylcarbonyl or dC5alkoxycarbonyl, or R2 and R3 together with the nitrogen atom to which they are bonded form a heterocyclic ring which can be substituted by CiCsalkyl, CrC5alkoxy, halogen, cyano or nitro, or R2 and R3 independently of one another are amino, CrC6alkylamino, C2C8dialkylamino, phenylamino, naphthylamino, dCβalkylcarbonylamino, CrC10alkoxycarbonylamino, hydroxyl, CrC6alkoxy, CrC6alkylcarbonyloxy, phenoxy, biphenyloxy or naphthoxy, and is, R16, Ri7, Riβ and R19 independently of one another are dCioalkyl, C3Cβcycloalkyl, C3C6cycloalkylCrC alkyl, dCβalkyldCβcycloalkyl, C2Cιoalkenyl, dCβcycloalkyld C alkenyl, C2C6alkenylC3C6cycloalkyl, dCι0alkynyl, C3CecycloalkylC2C4alkynyl, C2C6alkynylC3C6cycloalkyl, C3C6cycloalkenyl, C5C6cycloalkenylCiC4alkyl, dCβalkylCs Cβcycloalkenyl, CsCβcycloalkenylddalkenyl, C2CealkenylC5Cecycloalkenyl, C5C6cycloalkenyldC4alkynyl , C2C6alkynylC5Cβcycloalkenyl, C3C6cycloalkylC3 C6cycloalkyl, CsCβcycloalkenylCsCβcycloalkenyl, CsCβcycloalkylCsCβcycloalkenyl, C5C6cycloalkenylC3C6cycloalkyl, C2C8alkynylC2Cβalkenyl or C2C8alkenylC2C8alkynyl, phenyl, phenylCrC4alkyl, phenyldC alkenyl, phenyldC4alkynyl, heterocyclyl, heterocyclylCrC4alkyl, heterocyclylC2C alkenyl or heterocyclylCrC4alkynyl, it being possible for the substituents Rι5, R16, R17, Riβ and R19 to be substituted by halogen, cyano, azido, nitro, OR5, =O, S(O)nR6l COOR7, CONR8R9, NR10R11, =NRι2 or =NNRι3R14, or Ris, Riβ, R17, R18 and R g independently of one another are halogen, cyano, azido, nitro, ORs, S(O)nR6, COOR7, CONRβR9, NRι0Rn, tri(dC4alkyl)silyl, di(dC4alkyl)(Cr C4alkoxy)silyl, B(OH)2 or B(dC4alkoxy)2. |
| 4. | A compound according to Claim 1 , wherein Ris, Riβ, R17, Riβ and Rι9 independently of one another are CιCιoalkyl, C3Cecycloalkyl, C2Cιoalkenyl, C2Cιoalkynyl, C5 Cβcycloalkenyl, C2C8alkynyldC8alkenyl or dCβalkenylC2C8alkynyl, phenyl, phenyld C4alkyl, phenylC2C4alkenyl, heterocyclyl, heterocyclylC C alkyl or heterocyclyl C2 C4alkenyl, it being possible for Rι5, Rι6, Rι7, Rι8 and Rι9 independently of one another to be substituted by halogen, cyano, OR5, =O, S(O)nR6, COOR7, CONR8R9 or NRioRn, or is, Riβ, Ri7, RIB and Rι9 independently of one another are halogen, cyano, OR5, S(O)nRe, COOR7, CONRβR9 or NR10Rn, R5 is hydrogen, dCβalkyl, C Cβhaloalkyl, C2C5alkoxyalkyl, phenyl, phenylCrC4alkyl, C2dalkylcarbonyl, CrCβalkylaminocarbonyl, C2C8dialkylaminocarbonyl, tri(CrC4alkyl)silyl, C2Cτalkenyl or C3C alkynyl or heterocyclyl, Re is hydrogen when n is 0, or R6 is CiCsalkyl, phenyl, phenylC C alkyl or heterocyclyl, R7 is hydrogen, dCβalkyl, CrC6haloalkyl, CrC6cyanoalkyl, C2Cioalkoxycarbonylalkyl, heterocyclyl, C3C6cycloalkyl or C2C6dialkylamino, R8 and R9 independently of one another are hydrogen or CrC8alkyl, or R8 and R9 together with the nitrogen atom to which they are bonded form a three to seven membered heterocycle which may contain one or two further hetero atoms and which may be substituted by dβalkyl groups, R10 and Rn independently of one another are hydrogen, phenyl, CrCβalkyl, C3C7alkenyl, (dCealkylaminoJcarbonyl, (C2C6dialky!amino)carbonyl, (dC7alkyl)carbonyl, (CrC6alkoxy)carbonyl or heterocyclylcarbonyl, or R10 and R together with the nitrogen atom to which they are bonded form a three to sevenmembered heterocycle which may contain one or two further hetero atoms and which may be substituted by C16 alkyl groups. |
| 5. | A compound according to Claim 1 , wherein R2 and R3 independently of one another are hydrogen, CrCβalkyl, dC6alkyl which is substituted by halogen, cyano, nitro, CrC4alkoxy, dCβtrialkylsilyl, hydroxyl, amino, ammonium, triCrC4alkylammonium, COOH, COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or by dC8cycloalkyl, CιC5alkylcarbonyloxy, phenylcarbonyloxy, naphthylcarbonyloxy, ddalkylamino, C C5alkoxycarbonyl, C2C6dialkylamino or phenyl, it being possible for the phenyl ring to be substituted by halogen, cyano, nitro, OR5, NRι0Rn, dC alkyl, formyl, ddalkylcarbonyl, COOR7, CrC alkylthio, dC4alkylsulfonyl or CONR8Rg, or R2 and R3 independently of one another are C2C6alkenyl, C2C6alkenyl which is substituted by halogen, cyano, nitro, dC4alkoxy, C3C6trialkylsilyl, hydroxyl, amino, ammonium, trid C4alkylammonium, COOH, COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or by CrCβalkylamino, CrCsalkoxycarbonyl, dCβdialkylamino or phenyl, it being possible for the phenyl ring to be substituted by halogen, cyano, nitro, OR5, NR10Rιι, dC4alkyl, formyl, dC4alkylcarbonyl, COOR , dC alkylthio, dC4alkylsulfonyl or CONR8R9, or R2 and R3 independently of one another are C3Cβalkynyl, C3Cβalkynyl which is substituted by halogen, cyano, nitro, CιC8alkoxy, C3C6trialkylsilyl, hydroxyl, amino, ammonium, trid C alkylammonium, COOH, COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or by dCβalkylamino, C2C5alkoxycarbonyl, C2C6dialkylamino or phenyl, it being possible for the phenyl ring to be substituted by halogen, cyano, nitro, OR5, NR10R11, ddalkyl, formyl, CιC alkylcarbonyl, COOR7, dC4alkylthio, dC4alkylsulfonyl or CONRaRg, or R2 and R3 independently of one another are formyl, C C8alkylcarbonyl, C2C8alkenyl carbonyl, C C9cycloalkylcarbonyl, C6C9cycloalkenylcarbonyl or C3C8cycloalkylCr C6alkyicarbonyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, hydroxyl, amino, CrC6alkylamino, dC^ialkylamino, COOH, COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or by C2C8alkoxycarbonyl, C Cιocycloalkoxycarbonyl, dC8alkylaminocarbonyl or C2C8dialkylaminocarbonyl, or R2 and R3 independently of one another are heterocyclyl, heterocyclylcarbonyl, heterocyclyl which is substituted by halogen, cyano, nitro, CrC5alkyl, CιC5alkoxy, dCsalkylcarbonyl, CrC5alkylcarbonyloxy, CrC6alkoxycarbonylr aminocarbonyl, C C6alkylaminocarbonyl or C2C8dialkylaminocarbonyl, or heterocyclylcarbonyl which is substituted by halogen, cyano, nitro, CrC alkyl, CrC4alkoxy, CrC4alkylcarbonyl, CrC4alkoxycarbonyl, aminocarbonyl, CrC6alkylamino or CrCsalkylcarbonyloxy, or R2 and R3 independently of one another are phenylcarbonyl, biphenylcarbonyl, naphthylcarbonyl, phenylCiCβalkylcarbonyl, biphenylCrC6alkylcarbonyl, naphthyld C6alkylcarbonyl, phenylC2C6alkenylcarbonyl, biphenylC2C6alkenylcarbonyl or naphthyl C2C6alkenylcarbonyl, it being possible for these substituents to be substituted by C C4alkyl, CrC4alkoxy, ddalkylthio, dC4haloalkyl, dC4alkylcarbonyl, halogen, cyano, amino, nitro, COOR7, dCsalkoxycarbonyl, hydroxyl, CιC4alkylsulfonyl, d C5alkylaminocarbonyl or drCβdialkylaminocarbonyl, or R2 and R3 independently of one another are phenyl, naphthyl or heterocyclyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, CrC4alkyl, Crdalkoxy, dC4alkylthio, COOH, CONH2, CrC5alkylaminocarbonyl, C2ddialkyl aminocarbonyl, ddalkylcarbonyl or CrC5alkoxycarbonyl, or R2 and R3 together with the nitrogen atom to which they are bonded form a heterocyclic ring which can be substituted by ddalkyl, ddalkoxy, halogen, cyano or nitro, or R2 and R3 independently of one another are amino, ddalkylamino, C2C6dialkylamino, phenylamino, CrC5alkyicarbonylamino, CrC5alkoxycarbonylamino, hydroxyl, dC4alkoxy, CrC5alkylcarbonyloxy or phenoxy, R5 is hydrogen, CrC6alkyl, dCβhaloalkyl, CrC6alkoxyalkyl, dCβcyanoalkyl, phenyl, haiophenyl, CrC alkoxyphenyl, phenyldC alkyl, CrC alkylcarbonyl, benzoyl, halobenzoyl, CιC4alkylamino, C2Cedialkylamino, C3C6trialkylsilyl, C3C6cycloalkyl, C2 C4alkenyl or C3C alkynyl, R7 is hydrogen, CrC alkyl, C C haloalkyl, CrC cyanoalkyl, phenyl, haiophenyl, C2C4alkoxyalkyl, heterocyclyl or haloheterocyclyl, R8 and R9 independently of one another are hydrogen, phenyl, haiophenyl, CrC alkyl, ddhaloalkyl, dC4cyanoalkyl, C3C alkenyl, C3C4alkynyl or C2C alkoxyalkyl, or R8 and R9 together with the nitrogen atom to which they are bonded form a heterocycle which can be substituted by dC alkyl, R10 and Rn independently of one another are hydrogen, phenyl, haiophenyl, dC4alkyl, Crdhaloalkyl, dC cyanoalkyl, C3C alkenyl, 03dalkynyl, C2C alkoxyalkyl, formyl, dC4alkylcarbonyl or phenylcarbonyl, it being possible for the phenyl moiety therein to be substituted by ddalkyl, halogen, dC4alkoxy, hydroxyl, cyano, nitro or C C alkoxy carbonyl, or R10 and Rn together with the nitrogen atom to which they are bonded form a heterocycle which can be substituted by CrC alkyl. |
| 6. | A compound according to Claim 4, wherein R2 and R3 independently of one another are hydrogen, CrC6alkyl, dC6alkyl which is substituted by halogen, hydroxyl, amino, ammonium, triCrC4alkylammonium, COOH, COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or by CrC5alkylcarbonyloxy, phenylcarbonyloxy, CrC6alkylamino, CrC5alkoxycarbonyl or dCβdialkylamino, or R2 and R3 independently of one another are formyl, CrC8alkylcarbonyl, C2C8alkenyl carbonyl, C4C9cycloalkylcarbonyl, CβCgcycloalkenylcarbonyl or C3C8cycloalkylCrCβalkyl carbonyl, it being possible for these substituents to be substituted by halogen, cyano, hydroxyl, amino, COOH or COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or R2 and R3 independently of one another are heterocyclyl, heterocyclylcarbonyl, heterocyclyl which is substituted by halogen, cyano, nitro, dC5alkyl, CrC alkoxy or CrC6alkoxy carbonyl, or are heterocyclylcarbonyl which is substituted by halogen, cyano, nitro, dC4alkyl, CrC4alkoxy or dC4alkoxycarbonyl, or R2 and R3 independently of one another are phenylcarbonyl, biphenylcarbonyl, naphthylcarbonyl, phenylCrC6alkylcarbonyl, biphenyldCβalkyicarbonyl, naphthyld Cβalkylcarbonyl, phenylC2C6alkenylcarbonyl, biphenylC2C6alkenylcarbonyl or naphthyl C2C6alkenylcarbonyl, it being possible for these substituents to be substituted by d C alkyl, dC4alkoxy, dC4alkylthio, CrC4haloalkyl, Crdalkylcarbonyl, halogen, cyano, amino, nitro, COOH, CrC5alkoxycarbonyl, hydroxyl or dC4alkylsulfonyl, or R2 and R3 independently of one another are phenyl, naphthyl or heterocyclyl, it being possible for these substituents to be substituted by halogen, cyano, dC alkyl, dC4alkoxy, CrC4alkylthio, COOH or CrC5alkoxycarboπyl, or R2 and R3 together with the nitrogen atom to which they are bonded form a heterocyclic ring which can be substituted by CιC alkyl, dC alkoxy, halogen or cyano. |
| 7. | A compound according to Claim 5, wherein R2 and R3 are hydrogen, or R2 and R3 independently of one another are formyl, dC8alkylcarbonyl, C2C8alkenyl carbonyl, C C9cycloalkylcarbonyl, CβCgcycloalkenylcarbonyl or C3CBcycloalkylCr C6alkylcarbonyl, it being possible for these substituents to be substituted by halogen, cyano, hydroxyl or amino, or R2 and R3 are phenylcarbonyl, it being possible for the phenyl ring to be substituted by dC alkyl, C C4alkoxy, ddalkylthio, CrC4haloalkyl, halogen, cyano, nitro, COOH, dCsalkoxycarbonyl, hydroxyl or dC4alkylsulfonyl. |
| 8. | A compound according to Claim 1 , wherein X is O or S(O)x where x is 0, 1 or 2, and R4 is methyl which is substituted by halogen, cyano, nitro or OR5, or R* is CsrCβalkyl, C2C8alkenyl, C3C8alkynyl, C3C8cycloalkyl, C5C8cycloalkenyl, C3C8cycloalkylCrC4alkyl or CrC4alkylC3C8cycloalkyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, =O or OR5 , or R« is phenyl which is substituted by halogen, cyano, nitro, amino, COOH, hydroxyl, CrC4alkyl, CrC alkyloxy, CrC4alkylthio, dC+haloalkyl, C C4haloalkoxy, d C4haloalkylthio, C2C6alkoxycarbonylalkoxy, Crdalkylsulfinyl, C C alkylsulfonyl, Cr C6alkyloxycarbonyl, CiCβalkylcarbonyl, CONH2, formyl, CrC5alkylaminocarbonyl, C2 ddialkyiaminocarbonyl, dC4alkylamino, CrC6dialkylamino, C3Cetrialkylsilyl, CiCβalkylcarbonylamino, dCβalkylcarbonyloxy, phenoxy, halophenoxy or Pyridyloxy, or FU is biphenyl, naphthyl, heterocyclyl, dC4alkylphenyl, ddalkylnaphthyl, phenyld C4alkyl or naphthyldC alkyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, amino, COOH, hydroxyl, CrC4alkyl, dC4alkyloxy, CrC4alkylthio, dC4haloalkyl, CrC haloalkoxy, CιC4haloalkylthio, C2C6alkoxycarbonylalkoxy, dC4alkylsulfinyl, CrC alkylsulfonyl, CrCealkyloxycarbonyl, CrC6alkylcarbonyl, CONH2, formyl, CrC5alkylaminocarbonyl, dC^ialkylaminocarbonyl, C3Cβtrialkylsilyl, CrC6alkylcarbonylamino, CrC6alkylcarbonyloxy, phenoxy, halophenoxy or pyridyloxy, and R5 is hydrogen, CrC8alkyl, dCβhaloalkyl, C2C6alkoxyalkyl, CrC6cyanoalkyl, phenyl, haiophenyl, CiC4alkoxyphenyl, phenylCrC alkyl, dC4alkylcarbonyl, benzoyl, halobenzoyl, dC4alkylamino, C2C6dialkylamino, dCetrialkylsilyl, CaCβcycloalkyl, C2 Ctalkenyl or C3C4alkynyl. |
| 9. | A compound according to Claim 7, wherein X is O or S, and R is methyl which is substituted by halogen or cyano, or R» is dCβalkyl, CrCβalkenyl, C3Cβalkynyl, C3CβCycloalkyl, C5C8cycloalkenyl, C3Cβ cycloalkylCιC alkyl or CιC4alkylC3C8cycloaikyl, it being possible for these substituents to be substituted by halogen or cyano, or R is phenyl which is substituted by halogen, cyano, nitro, amino, CιC alkyl, CιC alkyloxy, dC alkylthio, dC4haloalkyl, dC4haloalkoxy, C2C6alkoxycarbonylalkoxy, CrC4alkylsulfonyl, CrC6alkyloxycarbonyl, CrCβalkylcarbonyl, formyl, dC4alkylamino, C2C6dialkylamino, C3C6trialkylsilyl or C2C6alkylcarbonyloxy, or R4 is biphenyl, naphthyl, heterocyclyl, dC4alkylphenyl, CrC4alkylnaphthyl, phenyld C4alkyl or naphthylCi04alkyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, amino, dC alkyl, CrC4alkyloxy, CrC alkylthio, CιC haloalkyl, dC4haloalkoxy, C2C6alkoxycarbonylalkoxy, dC4alkylsulfonyl, CrC6alkyloxycarbonyl, CrCβalkylcarbonyl, C3Cβtrialkylsilyl or CrC6alkylcarbonyloxy. |
| 10. | A compound according to Claim 8, wherein X is O and R4 is phenyl which is substituted by halogen, cyano, nitro, amino, dC alkyl, dC alkyloxy, CιC4alkylthio, dC4haloalkyl, halomethoxy, CrC4alkylsulfoπyl, dC4alkylamino or C2C6dialkylamino. |
| 11. | A compound according to Claim 1 , wherein R15, R16, R17, Ri8 and Rι9 independently of one another are CrC4alkyl, C2C4alkenyl, CιC4alkoxy, fluorine, chlorine, bromine, phenyl, CrC alkoxyCrC4alkoxy, trimethylsilyl, diCrC alkylamino, diCrC alkylaminoCrC4alkyl, morpholinylCrC4alkyl, CrC alkylthio, CιC alkylsulfinyl, CιC4alkylsulfonyl, dC4alkyl carbonyl, CrC4alkoxyCιC4alkyl, 1 (CιC4alkyl)dioxolanyl, 1phenyldioxolanyl, trifluoromethyl, hydroxyl, phenoxy, phenoxycarbonyl, CsCβcycloalkyl, Crdalkyl perhydroazinyl, R2 is hydrogen, R3 is hydrogen or methylcarbonyl, X is O or S and R4 is phenyl, naphthyl, pyridyl, CrC7haloalkoxy, CrCθalkoxy, dC4alkylthio, cyclohexyl, thienyl or the group , or is phenyl, naphthyl, pyridyl or thienyl, each of which is substituted by C C4alkyl, dC4alkoxy, fluorine, chlorine, nitro, cyano, C3C6cyclo alkyloxycarbonyl, CrC6alkylthio, dC4hydroxycarbonyl, alkylsulfonyl, didC alkylamino, CιC4alkylsulfonyl or trifluoromethyl. |
| 12. | A compound according to Claim 1 , wherein Ri is a group A1 , A2, A3, B1 , B2, B3, B4, B5, B6, C1 , C2, 03, 04, C5, 06, D1 , D2 or D3. |
| 13. | A compound according to Claim 1 , wherein Ri is a group A1 , A2, A3, B1 , B2, B3, B4, B5, B6, C1 , 02, C3, 04, 05 or 06. |
| 14. | A compound according to Claim 1 , wherein R15, R16, Rι7, Rm and Rig independently of one another are halogen, CrC6alkyl or dC6alkoxy. |
| 15. | A compound according to Claim 1 , wherein Rι5, Rι6, Rι7, Riβ and R19 independently of one another are fluorine, chlorine, dC alkyl or C C alkoxy. |
| 16. | A compound according to Claim 1 , wherein Rι5 is fluorine when Ri is A1 , B1 , B2, B3, C1 , 02 or C6. |
| 17. | A process for the preparation of a compound according to Claim 1 , which comprises (1 ) reacting a compound of the formula II in which Hal radicals independently of one another are fluorine, bromine or chlorine with an organometallic compound of the formula III RrM (III), in which Ri has the meaning given in Claim 1 and M is a mono or polyvalent metal atom, (2a) reacting the resulting compound of the formula IV in which Ri has the meaning given in Claim 1 and Hal radicals independently of one another are fluorine, chlorine or bromine with the compound of the formula V HXR4 (V), in which X and R4 have the abovementioned meaning to give the compounds of the formula VI and (3a) then converting this product with the compounds of the formula VII M NR2R3 (VII), in which R2 and R3 have the abovementioned meanings and Mi is hydrogen or a metal atom into the end product of the formula I; or (2b) reacting the compounds of the formula IV with the compounds of the formula VII to give the compounds of the formula VIII in which R^ R2 and R3 have the meanings given in Claim 1 and Hal is fluorine, chlorine or bromine, and (3b) then converting this product with the compounds of the formula V into the end products of the formula I. |
| 18. | A herbicidal and plant growthinhibiting composition which contains one or more compounds of the formula according to claim 1. |
| 19. | A composition according to Claim 17, which comprises between 0.1% and 95% of active ingredient of the formula I. |
| 20. | A method of controlling undesirable vegetation, which comprises applying an active ingredient of the formula I according to Claim 1 , or a composition comprising this active ingredient, in an effective amount to the plants or their environment. |
| 21. | A method according to Claim 19, wherein an amount of between 0.001 and 5 kg, in particular between 0.005 and 2 kg, of active ingredient is applied per hectare. |
| 22. | A method of inhibiting plant growth, which comprises applying an active ingredient of the formula I according to Claim 1 , or a composition comprising this active ingredient, in an effective amount to the plants or their environment. |
| 23. | A method according to Claim 19 for the selective pre or postemergence control of weeds and crops of useful plants. |
| 24. | The use of a composition according to Claim 17 for the selective pre or post emergence control of weeds in crops of useful plants. |
| 25. | A compound of the formula IV in which Ri has the meaning given in Claim 1 and Hal radicals independently of one another are fluorine, chlorine or bromine, with the exception of the compounds 1(4 methylphenyl)3,5dichlorothiatriazine, 1 (4hydroxyphenyl) 3,5dichlorothiatriazine, 1 (4 methoxyphenyl)3,5dichlorothiatriazine, 1 (4chlorophenyl)3,5dichlorothiatriazine, 1 (2 hydroxy5tertbutylphenyl)3,5dichlorothiatriazine, 1(4hydroxy3methylphenyl)3,5 dichlorothiatriazine and 1 (4hydroxy3methoxyphenyl)3,5dichlorothiatriazine, 1 (3,5 dimethyl4hydroxy phenyl)3,5dichlorothiatriazine, 1 (3,5dimethoxy4hydroxyphenyl) 3,5dichlorothiatriazine, 1 (2hydroxy3,5dimethylphenyl)3,5dichlorothiatriazine and 3,5dichloro1 (2,3,4,5,6 pentafluorophenyl)thiatriazine. |
| 26. | A compound of the formula VI in which R1 ( R4 and X have the meanings given in Claim 1 and Hal is fluorine, chlorine or bromine, with the exception of the compounds 1(4methylphenyl)3phenoxy5chloro thiatriazine, 1 (4methoxyphenyl)3(2,3,4,5,6pentafluorophenoxy)5chlorothιatriazine, 1 (4chlorophenyl)3(2,3,4,5,6pentafluorophenoxy)5chlorothiatriazine, 1(4 methoxyphenyl)3(2,3,4trichlorophenoxy)5chlorothiatriazine, 1(4chlorophenyl)3(2,3 dichlorophenoxy)5chlorothiatriazine, 1(3,5dimethyl4hydroxyphenyl)3(2,5 difluorophenoxy)5chlorothiatriazine, 3chloro5(2,5difluorophenoxy)1(2,3,4,5,6penta fluorophenyl)thiatriazine and 3chloro5(2,3,4,5,6pentafluorophenoxy)1 (2,3,4,5,6 pentafluorophenyl)thiatriazine. |
| 27. | A compound of the formula VIII in which R1 t R2 and R3 have the meanings given in Claim 1 and Hal is fluorine, chlorine or bromine, with the exception of the compounds 1(4methylphenyl)3amino5chloro thiatriazine, 1 (4chlorophenyl)3amino5chlorothiatriazine, 1 (4methoxyphenyl)3amino 5chlorothiatriazine, 1 (4hydroxyphenyl)3amino5chlorothiatriazine, 1 (2hydroxy5tert butylphenyl)3amino5chlorothiatriazine, 1 (4hydroxy3methylphenyl)3amino5 chlorothiatriazine, 1 (4hydroxy3methoxyphenyl)3amino5chlorothiatriazine, 1 (3,5 dimethyl4hydroxyphenyl)3amino5chlorothiatriazine, 1 (3,5dimethoxy4hydroxyphenyl) 3amino5chlorothiatriazine, 1(2hydroxy3,5dimethylphenyl)3amino5chlorothiatriazine, 1 (3,5dimethyl4hydroxyphenyl)3dimethylamino5chlorothiatriazine, 3amino5chloro1 (4amino2,3,5,6tetrafluorophenyl)thiatriazine and 3amino5chloro1 (2,3,4,5,6penta fluorophenyl)thiatriazine. Abstract: Compounds of the formula I in which Ri is a group and R2, R3, X, R« and R 5 have the meanings given in Claim 1 are well suited for use as herbicides. |
Novel herbicides
The present invention relates to novel herbicidally active thiatriazine derivatives, to processes for their preparation, to compositions comprising these compounds, and to their use for controlling weeds, mainly in crops of useful plants, or for inhibiting plant growth.
Thiatriazine compounds are described, for example, in Chem. Ber. 121 , 383-386 (1988), Z. Naturforsch. 43, 763-768 (1988), Chem. Ber. 126, 2601-2607 (1993), J. Am. Chem. Soc. 1989, 11 1 , 1 180-1185 and DD 113 006. There have now been found novel thiatriazine derivatives having herbicidal and growth-inhibitory properties.
The present invention thus relates to compounds of the formula I
in which Ri is a group
A2 or A3 ,
R 2 and R 3 independently of one another are hydrogen, d-C 6 alkyl, d-C 3 alkyl which is substituted by S(O) n R6, halogen, cyano, nitro, d-C 8 alkoxy, C 3 -C 6 trialkylsilyl, hydroxyl, amino, ammonium, tri-Cι-C 4 alkylammonium, -COOH, -COOR 20 , -COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or by C- 3 -C 8 cycloalkyl, d-C 3 alkylcarbonyloxy, phenylcarbonyloxy, naphthylcarbonyloxy, d-Cβalkylamino, d-C 3 alkoxycarbonyl, C 2 - C 12 dialkylamino, phenyl, naphthyl, phenoxy, naphthoxy, biphenyl, biphenyloxy, phenthio or naphthio, it being possible for the abovementioned aromatic rings to be substituted by halogen, cyano, nitro, -OR 5 , -NR 10 Rn, C C alkyl, formyl, d-C alkylcarbonyl, COOR 7 , d-C 4 alkylthio, Cι-C 4 alkylsulfonyl or -CONR β R 9) or
R 2 and R 3 independently of one another are C 2 -Cealkenyl, C 2 -C 6 alkenyl which is substituted by halogen, cyano, nitro, d-C 8 alkoxy, C 3 -C 6 trialkylsilyl, hydroxyl, amino, ammonium, tri-Cι-C alkylammonium, -COOH, -COOR 2 0, -COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or C 3 -C β cycloalkyl, CrCsalkylcarbonyloxy, phenylcarbonyloxy, naphthylcarbonyloxy, d-Cealkylamino, C 2 -C 5 alkoxycarbonyl, C 2 -Ci2dialkylamino, phenyl, naphthyl, phenoxy, naphthoxy, biphenyl, biphenyloxy, phenthio or naphthio, it being possible for the abovementioned aromatic rings to be substituted by halogen, cyano, nitro, -OR 5 , -NRι 0 Rn, Cι-C 4 alkyl, formyl, Cι-C 4 alkylcarbonyl, -COOR 7 , Cι-C 4 alkylthio, Cι-C alkylsulfonyl or -CONR 8 R 9l or
R 2 and R 3 independently of one another are C 3 -C 6 alkynyl, C 3 -C 6 alkynyl which is substituted by halogen, cyano, nitro, d-C 8 alkoxy, C 3 -C 6 trialkylsilyl, hydroxyl, amino, ammonium, tri-Cι-C alkylammonium, -COOH, -COOR∞, -COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or C 3 -C 8 cycloalkyl, d-C 5 alkylcarbonyloxy, phenylcarbonyloxy, naphthylcarbonyloxy, d-C 6 alkylamino, d-C 5 alkoxycarbonyl, C 2 -Cι 2 dialkylamino, phenyl, naphthyl, phenoxy, naphthoxy, biphenyl, biphenyloxy, phenthio or naphthio, it being possible for the abovementioned aromatic rings to be substituted by
halogen, cyano, nitro, -OR 5 , -NR 10 Rn, d-C 4 alkyl, formyl, d-C 4 alkylcarbonyl, -COOR 7 ,
C,-C 4 alkylthio, d-C 4 alkylsulfonyl or -CONR 8 R 9 , or
R 2 and R 3 independently of one another are formyl, d-dsalkylcarbonyl,
C 2 -C 15 alkenylcarbonyl, d-Cgcycloalkylcarbonyl, C 8 -C 9 cycloalkenylcarbonyl or
C 3 -C β cycloalkyl-Cι-Cealkylcarbonyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, hydroxyl, amino, d-Cealkylamino, C 2 -C 12 dialkylamino, -COOH,
-COOR20, -COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or by CrC 8 alkoxycarbonyl, C -Cι 0 cycloalkoxycarbonyl, Ci-Cβalkylaminocarbonyl or
C 2 -Ci 2 dialkylaminocarbonyl, or
R 2 and R 3 independently of one another are heterocyclyl, heterocyclylcarbonyl, heterocyclyl which is substituted by halogen, cyano, nitro, C -Csalkyl, d-C 5 alkoxy, Cι-C 5 alkylcarbonyl, d-C 5 alkylcarbonyloxy, d-C 6 alkoxycarbonyl, aminocarbonyl, Ci-Cβalkylaminocarbonyl or
C 2 -Cιιdialkylaminocarbonyl, or are heterocyclylcarbonyl which is substituted by halogen, cyano, nitro, Cι-C 5 alkyl, d-C 5 alkoxy, d-C 3 alkylcarbonyl, C T Cβalkoxycarbonyl, aminocarbonyl, d-Cβalkylamino or d-C 3 alkylcarbonyloxy, or
R 2 and R 3 independently of one another are phenylcarbonyl, biphenylcarbonyl, naphthylcarbonyl, phenyl-d-C 6 alkylcarbonyl, biphenyl-d-C 6 alkylcarbonyl, naphthyl-
CrCβalkylcarbonyl, phenyl-C 2 -C e aikenylcarbonyl, biphenyl-C 2 -C e alkenylcarbonyl, naphthyl-
C 2 -C 6 alkenylcarbonyl, phenyl-d-Cealkynylcarbonyl, biphenyl-C 3 -Cβalkynylcarbonyl or naphthyl-C 3 -C β alkynylcarbonyl, it being possible for these substituents to be substituted by d-C 5 alkyl, d-C 5 alkoxy, d-C 5 alkylthio, C C 5 haloalkyl, Ci-Csalkylcarbonyl, halogen, cyano, amino, nitro, -COOR 7 , d-C 8 alkoxycarbonyl, hydroxyl, Cι-C 5 alkylsulfinyl, d-C 5 alkylsulfonyl,
CrCβalkylaminocarbonyl or C 2 -C 12 dialkylaminocarbonyl, or
R 2 and R 3 independently of one another are phenyl or naphthyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, Ci-Csalkyl, Ci-Csalkoxy,
Cι-C 5 alkylthio, -COOH, -CONH 2 , d-C 6 alkylaminocarbonyl, C 2 -Cιodialkylaminocarbonyl, d-Csalkylcarbonyl or Ci-Csalkoxycarbonyl, or
R 2 and R 3 together with the nitrogen atom to which they are bonded form a heterocyclic ring which can be substituted by d-C 5 alkyl, Cι-C 3 alkoxy, halogen, cyano or nitro, or
R 2 and R 3 independently of one another are amino, CrC 6 alkylamino, C 2 -Cβdialkylamino, phenylamino, naphthylamino, Cι-C 6 alkylcarbonylamino, Cι-Cιoalkoxycarbonylamino, hydroxyl, d-C 6 alkoxy, d-C 6 alkylcarbonyloxy, phenoxy, biphenyloxy or naphthoxy,
X is O or S(O) Xl in which x is 0, 1 or 2, and
R 4 is d-C 8 alkyl, C 2 -C 8 alkenyl, d-Cβalkynyl, C 3 -C 8 cycloalkyl, C 5 -C 8 cycloalkenyl, C 3 -
C B cycloalkyl-CrC alkyl or Cι-C 4 alkyl-C 3 -Cβcycloalkyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, =O or -OR 5 , or
R 4 is phenyl, biphenyl, naphthyl, heterocyclyl, d-C 4 alkylphenyl, d-C alkylnaphthyl, phenyl-
Cι-C alkyl or naphthyl-Cι-C alkyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, amino, -COOH, hydroxyl, Cι-d 0 alkyl, d-C 10 alkyloxy, d-
C 6 alkylamino, di-C 2 -C 8 alkylamino, d-Cioalkylthio, Cι-Cιohaloalkyl, Ci-dohaloalkoxy, d- dohaloalkylthio, C 2 -Cιoalkoxycarbonylalkoxy, Cι-C 6 alkylsulfinyl, d-C e alkylsulfonyl, d-
C 6 alkyloxycarbonyl, d-C 6 alkylcarbonyl, -CONH 2 , formyl, d-dalkylaminocarbonyl, C 2 -
Cndialkylaminocarbonyl, d-Cβtrialkylsilyl, d-doalkylcarbonylamino, d-
Cioalkylcarbonyloxy, phenoxy, halophenoxy, pyridyloxy or pyridyloxy which is substituted by halogen, Cι-C alkyl, d-C 4 alkoxy, cyano, nitro or amino, or 2 adjacent substituents on the phenyl or naphthyl ring R 4 form a carbocyclic or heterocyclic ring which can be substituted by halogen, cyano, nitro, amino, -COOH, =O, C Cιoalkyl, d-Cioalkoxy, Cι-Cιoalkylthio, d-
Ciohaloalkyl, hydroxyl, C 3 -C 10 alkoxy-carbonylalkoxy, d-C 6 alkylsulfinyl, Cι-C 6 alkylsulfonyl,
C 2 -C 6 alkyloxycarbonyl, C 2 -C 6 alkyl-carbonyl, -CONH 2 , formyl, C 2 -C 7 alkylaminocarbonyl, d-
Cndialkylaminocarbonyl, d-C 6 trialkylsilyl, d-Cioalkylcarbonylamino, C 2 -
C 10 alkylcarbonyloxy, phenoxy, pyridyloxy or pyridyloxy which is substituted by halogen, Cι- dalkyl, d-C alkoxy, cyano, nitro or amino,
R 5 is hydrogen, Ci-CβalkyI, d-Cβhaloalkyl, C 2 -C 5 alkoxyalkyl, d-C 6 cyanoalkyl, phenyl, phenyl-Cι-C alkyl, formyl, C 2 -dalkylcarbonyl, CrCτalkoxycarbonyl, d-C 6 alkyl- aminocarbonyl, C 2 -C 8 dialkylaminocarbonyl, benzoyl, halobenzoyl, Cι-C 6 alkylamino,
C 2 -C 8 dialkylamino, -N=CH 2 , -N^H-d-dalkyl, -N=C(d-C 4 alkyl) 2 , tri(Cι-C 4 alkyl)silyl,
C 3 -Cτcycloalkyl, C 2 -C 7 alkenyl or C 3 -Cτalkynyl, heterocyclyl, n is 0, 1 or 2,
R 6 is hydrogen or cyano when n is 0 or
Re is d-Csalkyl, C 2 -C 5 alkenyl, d-dalkynyl, d-Cealkoxyalkyl, d-C 5 haloalkyl, d-C 5 hydroxyalkyl, phenyl, phenyl-d-C 4 alkyl, heterocyclyl, heterocyclyl-C -C alkyl or
C 3 -Cτcycloalkyl,
R 7 is hydrogen, Cι-C 12 alkyl, d-C 12 haloalkyl, d-C 6 nitroalkyl, C C 6 cyanoalkyl, phenyl,
C 2 -Cιoalkoxyalkyl, C 2 -doalkylcarbonylalkyl, C 2 -C 10 alkoxycarbonylalkyl, heterocyclyl,
C 3 -Cτcycloalkyl, C 3 -C 7 haiocycloalkyl, -N=CH 2 , -N=CH-Cι-C 4 alkyl, -N=C(Cι-C 4 alkyl) 2 or
C 2 -C 6 dialkylamino,
R θ and R 9 independently of one another are hydrogen, phenyl, d-C 8 alkyl, C C 8 haloalkyl,
Cι-C β alkoxy, phenoxy, C 2 -Cτcyanoalkyl, C 3 -Cτalkenyl, d-C 7 alkynyl, C 2 -C β alkoxyalkyl, d-C 6 alkylamino or C 2 -C 6 dialkylamino, or
R β and R 9 together with the nitrogen atom to which they are bonded form a three- to seven- membered heterocycle which can contain one or two further hetero atoms and, in turn can be substituted by ^alkyl groups or halogen,
R 10 and Rn independently of one another are hydrogen, phenyl, d-C 8 alkyl, Cι-C 8 haloalkyl, d-C 8 alkoxy, phenoxy, C 2 -Cτcyanoalkyl, Crdalkenyl, C 3 -dalkynyl, C 2 -C 8 alkoxyalkyl,
Cι-C 6 alkylamino, (d-C 6 alkylamino)carbonyl, d-Cedialkylamino, (C 2 -
C 6 dialkylamino)carbonyl, formyl, (d-C 7 alkyl)carbonyl, (d-C 6 alkoxy)carbonyl, phenylcarbonyl, phenoxycarbonyl, benzyloxycarbonyl, heterocyclylcarbonyl, heterocyclyloxycarbonyl, or
R 10 and Rn together with the nitrogen atom to which they are bonded form a three- to seven-membered heterocycle which can contain one or two further hetero atoms and, in turn, can be substituted by C h alky! groups or halogen,
R 12 is Cι-C 8 alkyl, d-dalkoxy, d-Cβalkenyloxy, d-C B alkynyloxy, d-C 8 haloalkyl, phenyl, phenyloxy,
R 13 and R independently of one another are hydrogen, d-C 6 alkyl, C 2 -Cβalkylcarbonyl or phenyl, and
Ri5, R 1 6, Ru, iβ and R 19 independently of one another are d-Cι 0 alkyl, C 3 -C 6 cycloalkyl,
C 3 -C 6 cycloalkyl-Cι-C alkyl, d-Cβalkyl-d-dcycloalkyl, C 2 -C 10 alkenyl, C 3 -C 6 cycloalkyl-
C 2 -C alkenyl, C 2 -C 6 alkenyl-C 3 -C 6 cycloalkyl, d-C 10 alkynyl, C 3 -C β cycloalkyl-C 2 -C 4 alkynyl, C 5 -C 6 cycloalkenyl, C 3 -C 6 cycloalkenyl-Cι-C 4 alkyl, d-C β alkyl-
C 5 -C 6 cycloalkenyl, C 5 -C 6 cycloalkenyl-C 2 -C 4 alkenyl, C 2 -C 8 alkenyl-C 5 -C 6 cycloalkenyl,
C 5 -C 6 cycloalkenyl-C 2 -C 4 alkynyl, C 2 -C 6 alkynyl-C 5 -C 6 cycloalkenyl, C 3 -C 6 cycloalkyl-
C 3 -C 6 cycloalkyl, C 5 -C 6 cycloalkenyl-C 5 -Cecycloalkenyl, C 3 -C 6 cycloalkyl-C 5 -C β cycloalkenyl,
Cs-Cβcycloalkenyl-Cs-Cβcycloalkyl, C 2 -C 8 alkynyl-C 2 -C 8 alkenyl or C 2 -C 8 alkenyl-C 2 -C 8 alkynyl, phenyl, phenyl-Cι-C alkyl, phenyl-C 2 -C alkenyl, phenyl-C 2 -C 4 alkynyl, heterocyclyl, heterocyclyl-d-C 4 alkyl, heterocyclyl-C 2 -C 4 alkenyl or heterocyclyl-d-C 4 alkynyl, it being possible for the substituents R 15 , R 16 , R 17 , R 1β and R 19 independently of one another to be substituted by halogen, cyano, azido, nitro, -OR s , =O, -S(O)„R6, -COOR 7 , -CONR 8 R 9 ,
-NR 10 Rn, =NR 12 or =N-NR 13 R 14) or
R 15 , Riβ. i7, Riβ and Rig independently of one another are halogen, cyano, azido, nitro,
-ORs, -S(O) n R 6 , -COOR 7 , -CONR 8 R 9 , -NR 10 Rn, tri(d-C 4 alkyl)silyl, di(C,-C 4 alkyl)-
(d-C 4 alkoxy)silyl, -B(OH) 2 , -B(C,-C 4 alkoxy) 2 , tri(d-C 4 alkyl)silyl, tri(d-C 4 alkyl)silyl- Cι-C 3 alkyl, ^(d-C^lky silyl-CrCealkenyl, tri(d-C 4 alkyl)silyl-C 2 -C 6 alkynyl, tri(d-C 4 alkyl)stannyl, tri(Cι-C 4 alkyl)stannyl-C 2 -C 6 alkenyl, tri(d-C 4 alkyl)stannyl-d-C 6 alkynyl, and
R 20 is d-Ci 2 alkyl, C Cι 2 haloalkyl, d-C 6 nitroalkyl, d-C 6 cyanoalkyl, phenyl, C 2 -Cιoalkoxyalkyl, C 2 -Cιoalkylcarbonylalkyl, d-Cioalkoxycarbonylalkyl, heterocyclyl, C 3 -C 7 cycloalkyl, C 3 -C 7 halocycloalkyl, -N=CH 2 , -N=CH-C C 4 alkyl, -N=C(d-C 4 alkyl) 2 or C -C 6 dialkylamino, and to the salts of the compounds of the formula I, with the exception of the compounds 1 -(4-hydroxyphenyl)-3-amino-5-(2,5-difluorophenoxy)thiatriazi ne, 1 -(4-methylphenyl)-3- amino-5-phenoxythiatriazine, 1-(4-methoxyphenyl)-3-amino-5-(2,3,4,5,6-pentafluoro- phenoxy)thiatriazine, 1-(4-methoxypheπyl)-3-amino-5-(2,3,4-trichlorophenoxy)thiat riazine, 1 -(4-chlorophenyl)-3-amino-5-(2,3,4,5,6-pentafluorophenoxy)th iatriazine, 1 -(4-chlorophenyl)- 3-amino-5-(2,3-dichlorophenoxy)thiatriazine, 1-(2-hydroxy-5-tert-butylphenyl)-3-amino-5- (2,5-difluorophenoxy)thiatriazine, 1-(4-hydroxy-3-methylphenyl)-3-amino-5-(2,5- difluorophenoxy)thiatriazine, 1-(4-hydroxy-3-methoxyphenyl)-3-amino-5-(2,5- difluorophenoxy)thiatriazine, 1-(3,5-dimethyl-4-hydroxyphenyl)-3-amino-5-(2,5- difluorophenyloxy)thiatriazine, 1-(3,5-dimethoxy-4-hydroxyphenyl)-3-amino-5-(2,5- difluorophenyloxy)thiatriazine, 1-(3,5-dimethyl-2-hydroxyphenyl)-3-amino-5-(2,5- difluorophenyloxy)thiatriazine, 1 -(3,5-dimethyl-4-hydroxyphenyl)-3-dimethylamino-5-(2,5- difluorophenyloxy)thiatriazine, 3-amino-1-(4-amino-2,3,5,6-tetrafluorophenyl)-5-(2,3,4,5,6- pentafluorophenoxy)thiatriazine, 3-amino-1-(4-amino-2,3,5,6-tetrafluorophenyl)-5-(2,4,6- trichlorophenoxy)thiatriazine, 3-amino-1-(4-amino-2,3,5,6-tetrafluorophenyl)-5-(2,5- difluorophenoxy)thiatriazine, 3-amino-5-(2,5-difluorophenoxy)-1 -(2,3,4,5,6- pentafluorophenyl)thiatriazine and 3-amino-5-(2,3,4,5,6-pentafluorophenoxy)- 1 -(2,3,4,5,6-pentafluorophenyl)thiatriazine.
The alkyl groups in the definitions of the substituents can be straight-chain or branched and mono- or polysubstituted; they are, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl and their branched isomers. Alkoxy, alkenyl and alkynyl radicals are derived from the abovementioned alkyl radicals. The alkenyl and alkynyl groups can be mono- or polyuπsaturated.
Suitable cycloalkyl substituents contain 3 to 8 carbon atoms and are, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl. Corresponding cycloalkenyl substituents can be mono- or polysubstituted and mono- or else polyunsaturated, for example cyclopentadienyl or cyclooctatetraenyl.
When alkyl, alkenyl or alkynyl are substituents on a cycloalkyl, cycloalkenyl, phenyl, biphenyl, naphthyl or heterocyclyl, these ring systems may also be mono- or polysubstituted by alkyl, alkenyl or alkynyl.
As a rule, halogen is fluorine, chlorine, bromine or iodine. The same applies analogously to halogen in conjunction with other meanings such as haloalkyl or halophenyi.
Phenyl may be unsubstituted or mono- or polysubstituted by halogen, cyano, nitro, -OR 5 , -NR10R11, d-C 4 alkyl, formyl, d-C 4 alkylcarbonyl, -COOR 7 , d-C 4 alkylthio, d-C alkylsulfonyl or -CONR 8 R 9 .
Heterocyclyl radicals are to be understood as meaning ring systems which, besides carbon atoms, contain at least one hetero atom such as nitrogen, oxygen and/or sulfur. They may be saturated or unsaturated. Such ring systems preferably contain 3 to 8 ring atoms. This also applies to those heterocycles which are formed by 2 substituents bonded to a nitrogen atom, as is the case in groups such as -NR 10 Rn.
Heterocyclyl ring systems within the scope of the present invention may also be mono- or polysubstituted. Examples of suitable substituents are C C alkyl, d-C 4 haloalkyl, Cι-C alkoxy, cyano, nitro or C 3 -Cβcycloalkyl.
Heterocyclyl as a substituent of a group Ri can be, for example, epoxidyl, dioxolanyl, pyrrolidyl, piperidinyl, morpholinyl, pyridyl, imidazolyl, tetrahydrofuryl, tetrahydropyranyl, dihydrofuryl, dihydropyranyl, isoxazolyl, oxazolyl, thiazolyl, oxazolinyl (for
example: ), oxazolidinyl, imidazolinyl, imidazolidinyl, dioxanyl or
phthalimidyl.
Preferred heterocycles R 6 are, inter alia, pyridyl, pyrimidinyl and triazinyl.
Preferred heterocycles R 7 are, for example, oxetanyl, pyridyl, thiophenyl and furyl.
R 8 and R 9 preferably form rings such as piperidinyl, morpholinyl and pyrrolidinyl.
Preferred examples of heterocycles formed by R 1 0 and R , or R 2 and R 3 , with the nitrogen atom to which these radicals are bonded are piperidinyl, morpholinyl, pyrrolidyl, triazolyl, tetrazolyl and imidazolyl.
Preferred heterocycles R 9 are thiophenyl, furyl, pyridyl and oxetanyl.
Phenyl and naphthyl rings R 4 can be substituted by carbo- or heterocyclic radicals which are formed on these phenyl or naphthyl rings by 2 adjacent substituents. The carbocycles preferably contain 4 to 6 carbon atoms, such as cyclobutyl, cyclopentyl and cyclohexyl. Especially suitable as heterocyclic groups are dioxolanyl and tetrahydrofuryl.
Heterocycles R 4 , such as succinimidyl, pyridyl, thiophenyl or furyl, may contain fused carbocycles, such as phenyl or cyclohexenyl.
Preferred heterocycles R 2 and R 3 are pyridyl, pyrrolidyl and pyrimidinyl.
Heterocycles formed by -NR 2 R 3 include, for example, succinimidyl, imidazolyl and triazolyl, it being possible for such groups to contain fused carbocycles, such as phenyl or cyclohexenyl.
Heterocyclylcarbonyl R 2 or R 3 is, for example, pyridyl, pyrrolidyl, triazolyl, thiophenyl, furyl or isoxazolyl.
The alkyl radicals in substituents such as -N=C(Cι-C alkyl) 2 can be identical or different. They preferably have the same meaning. The same applies analogously to the alkyl radicals in dialkylamino, dialkylaminocarbonyl, trialkylammonium and trialkylsilyl substituents.
C 2 -C 7 alkylcarbonyl within the scope of the present invention is, for example, methylcarbonyl, ethylcarbonyl, propylcarbonyl, i-propylcarbonyl, butylcarbonyl, pentylcarbonyl and hexylcarbonyl and also the branched isomers of these.
Suitable examples of alkali metals and alkaline earth metals are lithium, sodium, potassium, magnesium, calcium or barium.
The invention equally includes the salts which the compounds of the formula I can form, in particular with amines, alkali metal and alkaline earth metal bases or quaternary ammonium bases.
Salt formers which must be emphasized among the alkali metal and alkaline earth metal hydroxides are the hydroxides of lithium, sodium, potassium, magnesium or calcium, but in particular those of sodium or potassium.
Possible examples of amides which are suitable for ammonium salt formation are not only ammonia, but also primary, secondary and tertiary d-Cι 8 alkylamines, d-C 4 hydroxy- alkylamines and C 2 -C 4 alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropylamine, the four isomeric butylamines, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, hβptadecylamine, octadecylamine, methylethylamine, methylisopropylamine, methylhexylamine, methyl nonylamine, methylpeπtadecylamine, methyloctadecylamine, ethylbutylamine, ethylheptylamine, ethyloctylamine, hexylheptylamine, hexyloctylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-n-amylamine, di-isoamylamine, dihβxylamine, diheptylamine, dioctylamine, ethanolamine, n-propanolamine, isopropanolamine, N,N-diethanolamine, N-ethylpropanolamine, N-butylethanolamine, allylamine, n-butenyl-2- amine, n-pentenyl-2-amine, 2,3-dimethylbutenyl-2-amine, di-butenyl-2-amine, n-hexenyl-2- amine, propylenediamine, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tri-n-amylamine, methoxyethylamine and ethoxyethylamine; heterocyclic amines, for example pyridine, quinoline, isoquinoline, morpholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine; primary arylamines, for example aniline, methoxyaniline, ethoxyaniline, o,m,p-
toluidine, phenylenediamine, benzidine, naphthylamine and o,m,p-chloroaniline; but, in particular, triethylamine, isopropylamine and diisopropylamine.
The compounds of the formula I have an asymmetric centre in the sulfur atom of the thiatriazine ring. This is why, upon preparation of these compounds, racemates are obtained which can be separated into the corresponding enantiomers by customary separation methods. If further asymmetric centres exist in the substituents of the thiatriazine ring, the corresponding diastereoisomers may also be separated in the customary manner. The present invention also includes such diastereoisomers and enantiomers.
Preferred amongst the compounds of the formula I are those in which R 2 and R 3 independently of one another are hydrogen, d-C 6 alkyl, d-C 6 aikyl which is substituted by S(O) n R 6ι halogen, cyano, nitro, d-C θ alkoxy, C 3 -C 6 trialkylsilyl, hydroxyl, amino, ammonium, tri-Cι-C 4 alkylammonium, -COOH, -COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or by C 3 -C 8 cycloalkyl, d-C 5 alkylcarbonyloxy, phenylcarbonyloxy, naphthylcarbonyloxy, d-C 6 alkylamino, d-dalkoxycarbonyl, C 2 -C 12 dia!kylamino, phenyl, naphthyl, phenoxy, naphthoxy, biphenyl, biphenyloxy, phenthio or naphthio, it being possible for the abovementioned aromatic rings to be substituted by halogen, cyano, nitro, -ORs, -NR10R 11 , d-C alkyl, formyl, d-C alkylcarbonyl, -COOR 7 , C C 4 alkylthio, d- dalkyisulfonyl or -CONRβR 9 , or
R 2 and R 3 independently of one another are C 2 -C β alkenyl, C 2 -C 6 alkenyl which is substituted by halogen, cyano, nitro, Cι-C 8 alkoxy, C 3 -C 6 trialkylsilyl, hydroxyl, amino, ammonium, tri-d- dalkylammonium, -COOH, -COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or by d-C 8 cycloalkyl, Crdalkylcarbonyloxy, phenylcarbonyloxy, naphthylcarbonyloxy, d-Cβalkylamino, C 2 -C 3 alkoxycarbonyl, C 2 -Cι 2 dialkylamino, phenyl, naphthyl, phenoxy, naphthoxy, biphenyl, biphenyloxy, phenthio or naphthio, it being possible for the abovementioned aromatic rings to be substituted by halogen, cyano, nitro, -ORs, -NR 10 Rn, d-C alkyl, formyl, Cι-C alkylcarbonyl, -COOR 7 , d-C 4 alkylthio, d- C 4 alkylsulfonyl or -CONR 8 R 9 , or
R 2 and R 3 independently of one another are C 3 -C 6 alkynyl, d-dalkynyl which is substituted by halogen, cyano, nitro, Cι-C 8 alkoxy, d-C 6 trialkylsilyl, hydroxyl, amino, ammonium, tri-Cι- C 4 alkyiammonium, -COOH, -COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or by C 3 -C 8 cycloalkyl, d-C 3 alkylcarbonyloxy, phenylcarbonyloxy, naphthylcarbonyloxy, d-C 6 alkyiamino, d-C 5 alkoxycarbonyl, C 2 -C 12 dialkylamino, phenyl,
naphthyl, phenoxy, naphthoxy, biphenyl, biphenyloxy, phenthio or naphthio, it being possible for the abovementioned aromatic rings to be substituted by halogen, cyano, nitro, -OR 5 , -NR 10 Rιι, C,-C 4 alkyl, formyl, d-C 4 alkylcarbonyl, -COOR 7 , C,-C 4 alkylthio, Ci- dalkylsulfonyl or -CONR 8 R 9 , or
R 2 and R 3 independently of one another are formyl, Cι-C 15 alkylcarbonyl, d-d 5 alkenyl- carbonyl, C -C 9 cycloalkylcarbonyl, C 6 -C 9 cycloalkenylcarbonyl or C 3 -C 8 cycloalkyl- Cι-C 6 alkylcarbonyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, hydroxyl, amino, Ci-Cβalkylamino, C 2 -C 12 dialkylamino, -COOH, -COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or by d-C 8 alkoxy- carbonyl, C -Cιocycloalkoxycarbonyl, d-C 8 alkylaminocarbonyl or C 2 -Cι;>dialkyl- aminocarbonyl, or
R 2 and R 3 independently of one another are heterocyclyl, heterocyclylcarbonyl, heterocyclyl which is substituted by halogen, cyano, nitro, d-C 5 alkyl, Cι-C 5 alkoxy, d-Csalkylcarbonyl, Cι-C 3 alkylcarbonyloxy, d-C 6 alkoxycarbonyl, aminocarbonyl, d-C 6 alkylaminocarbonyl or C 2 -C 1 dialkylaminocarbonyl, or are heterocyclylcarbonyl which is substituted by halogen, cyano, nitro, d-C 5 alkyl, d-dalkoxy, d-C 5 alkylcarbonyl, d-C 6 alkoxycarbonyl, aminocarbonyl, d-C 6 alkylamino or d-C 5 alkylcarbonyloxy, or R 2 and R 3 independently of one another are phenylcarbonyl, biphenylcarbonyl, naphthylcarbonyl, phenyl-CrC 6 alkylcarbonyl, biphenyl-d-C 6 alkylcarbonyl, naphthyl-Cι- C 6 alkylcarbonyl, phenyl-C 2 -Cβalkenylcarbonyl, biphenyl-C 2 -C 6 alkenylcarbonyl, naphthyl-C 2 - C 6 alkenylcarbonyl, phenyl-C 3 -C 6 alkynylcarbonyl, biphenyl-C 3 -C 6 alkynylcarbonyl or naphthyl- C 3 -C β alkynylcarbonyl, it being possible for these substituents to be substituted by Ci- Csalkyl, d-dalkoxy, Cι-C 5 alkylthio, Cι-C 5 haloalkyl, Cι-C 3 alkylcarbonyl, halogen, cyano, amino, nitro, -COOR , Ci-Cβalkoxycarbonyl, hydroxyl, Ci-Csalkylsulfinyl, Cι-C 5 alkylsulfonyl, Cι-C 6 alkyl-aminocarbonyl or C 2 -C 12 dialkylaminocarbonyl, or
R 2 and R 3 independently of one another are phenyl or naphthyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, d-C 5 alkyl, Cι-C 5 alkoxy, Cι-C 3 alkylthio, -COOH, -CONH 2 , d-C 6 alkylaminocarbonyl, C 2 -Cιodialkylaminocarbonyl, C C s alkylcarbonyl or d-C 5 alkoxycarbonyl, or
R 2 and R 3 together with the nitrogen atom to which they are bonded form a heterocyclic ring which can be substituted by d-C 5 alkyl, d-C 5 alkoxy, halogen, cyano or nitro, or R 2 and R 3 independently of one another are amino, d-C 6 alkylamino, d-C 8 dialkylamino, phenylamino, naphthylamino, Cι-C 6 alkylcarboπylamino, d-doalkoxycarbonylamino, hydroxyl, Ci-Cβalkoxy, d-C 6 alkylcarbonyloxy, phenoxy, biphenyloxy or naphthoxy, and
i 5 , Ri 6 , Ri7, ιβ and Rι 9 independently of one another are Cι-C oalkyl, d-C 6 cycloalkyl, C 3 -C 6 cycloalkyl-Cι-C alkyl, d-C 6 alkyl-C 3 -C 6 cycloalkyl, d-Cioalkenyl, C 3 -C 6 cycloalkyl- C 2 -C alkenyl, C 2 -C 6 alkenyl-C 3 -C 6 cycloalkyl, d-Cι 0 alkynyl, C 3 -C 6 cycloalkyl-C 2 -C 4 alkynyl, C 2 -C 6 alkynyl-C 3 -C 6 cycloalkyl, Cs-Cecycloalkenyl, C5-C 6 cycloalkenyl-CrC 4 alkyl, d -Cealkyl-Cs-Cβcycloalkenyl, C 5 -C 6 cycloalkenyl-C 2 -C alkenyl , d-Cealkenyl-Cs-Cβcydo- alkenyl, C 5 -C 6 cycloalkenyl-C 2 -C alkynyl, C 2 -Cealkynyl-C 5 -C 6 cycloalkenyl, C 3 -Cecycloalkyl- C 3 -C 6 cycloalkyl, C 3 -Cβcycloalkenyl-C5-C 6 cycloalkenyl, C 3 -C 6 cycloalkyl-C5-C 6 cycloalkenyl, C 5 -C 6 cycioalkenyl-C 3 -C 6 cycloalkyl, C 2 -C 8 alkynyl-C 2 -C 8 alkenyi or C 2 -C 8 alkenyl-C 2 -Cβalkynyl, phenyl, phenyl-Cι-C alkyl, phenyl-C 2 -C alkenyl, phenyl-C 2 -C 4 alkynyl, heterocyclyl, heterocyclyl-C C alkyl, heterocyclyl-C 2 -C 4 alkenyl or heterocyclyl-d-C 4 alkynyl, it being possible for the substituents R 15 , R 16 , R 17 , Riβ and R 19 to be substituted by halogen, cyano, azido, nitro, -OR 5 , =O, -S(O) n R 6 , -COOR 7 , -CONR 8 R 9 , -NR 10 Rn, =NR 12 or =N-NRι 3 Rι 4 , or Ri5 > Rιe, R17, Riβ and Rι 9 independently of one another are halogen, cyano, azido, nitro, -OR5, -S(O) n R 6 , -COOR7, -CONRβRg, -NR10R11, tri(Cι-C 4 alkyl)silyl, di(Cι-C 4 alkyl)-(Cι- C 4 alkoxy)silyl, -B(OH) 2 or -B(Cι-C 4 alkoxy) 2 .
Especially preferred compounds of the formula I are distinguished by the fact that R 15 , R β.
R 1 l Riβ and R 19 independently of one another are Cι-Cιoalkyl, C 3 -C 6 cycloalkyl,
C 2 -C 10 alkenyl, C 2 -Cιoalkynyl, Cs-Cβcycloalkenyl, C 2 -C 8 alkynyl-C 2 -C 8 alkenyl or C 2 -Cβalkenyl-
C 2 -C 8 alkynyl, phenyl, pheπyl-Cι-C alkyl, phenyl-C 2 -C alkenyl, heterocyclyl, heterocyclyl-
Cι-C alkyl or heterocyclyl-QrC 4 alkenyl, it being possible for Rι 5 , Rι 6 , R 1 7. iβ and Rι 9 independently of one another to be substituted by halogen, cyano, -OR 5 , =O, -S(O) n Re,
-COOR7, -CONRβRg or -NR 10 Rn, or
R15 R16. R17, Riβ and R 19 independently of one another are halogen, cyano, -OR s , -S(O)nRβ,
-COOR 7 , -CONR 8 R 9 or -NR 10 Rn,
R 5 is hydrogen, d-C 8 alkyl, d-C 6 haloalkyl, C 2 -C 3 alkoxyalkyl, phenyl, phenyl-Cι-C 4 alkyl,
C 2 -Cτalkylcarbonyl, d-C 6 alkylaminocarbonyl, d-C 8 dialkylaminocarbonyl, tri(Cι-C alkyl)silyl,
C 2 -C 7 alkenyl or d-dalkynyl or heterocyclyl,
R 8 is hydrogen when n is 0, or
R 6 is Cι-C 5 alkyl, phenyl, phenyl-Cι-C 4 alkyl or heterocyclyl,
R 7 is hydrogen, Cι-C 6 alkyl, d-C e haloalkyl, C C 6 cyanoalkyl, C 2 -C 10 alkoxycarbonylalkyl, heterocyclyl, C 3 -C 6 cycloalkyl or C 2 -C 6 dialkylamino,
R 8 and R 9 independently of one another are hydrogen or d-C 8 alkyl, or
R 8 and R 9 together with the nitrogen atom to which they are bonded form a three to seven- membered heterocycle which may contain one or two further hetero atoms and which may be substituted by C h alky! groups,
R 10 and Rn independently of one another are hydrogen, phenyl, Cι-C 8 alkyl, Ordalkenyl, (d-CealkylaminoJcarbonyl, (C 2 -C 6 dialkylamino)carbonyl, (Cι-C 7 alkyl)carbonyl, (Cι-C 6 alkoxy)carbonyl or heterocyclylcarbonyl, or
R 10 and Rn together with the nitrogen atom to which they are bonded form a three- to seven-membered heterocycle which may contain one or two further hetero atoms and which may be substituted by C,. 6 alkyl groups.
Very specially preferred are those compounds of the formula I in which R 2 and R 3 independently of one another are hydrogen, d-C 6 alkyl, d-C 6 alkyl which is substituted by halogen, cyano, nitro, d-C 4 alkoxy, C 3 -C 6 trialkylsilyl, hydroxyl, amino, ammonium, tri-Ci- C 4 alkylammonium, -COOH, -COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or by C 3 -Cβcycloalkyl, Ci-Csalkylcarbonyloxy, phenylcarbonyloxy, naphthylcarbonyloxy, d-Cβalkylamino, Cι-C 5 alkoxycarbonyl, C 2 -C β dialkylamino or phenyl, it being possible for the phenyl ring to be substituted by halogen, cyano, nitro, -OR 5 , -NR10R11, Cι-C 4 alkyl, formyl, C -C 4 alkylcarbonyl, -COOR 7 , d-C alkylthio, d-C 4 alkylsulfonyl or -CONRβRg , or
R 2 and R 3 independently of one another are C^Cealkenyl, C 2 -C 6 alkenyl which is substituted by halogen, cyano, nitro, Cι-C 4 alkoxy, C 3 -C 6 -trialkylsilyl, hydroxyl, amino, ammonium, tri-d- C 4 alkylammonium, -COOH, -COOM, in which M is ammonium or ah alkali metal or alkaline earth metal atom, or by Cι-C e alkylamino, C 2 -dalkoxycarbonyl, C 2 -C 6 dialkylamino or phenyl, it being possible for the phenyl ring to be substituted by halogen, cyano, nitro, -OR 5 , -NR 10 Rn, Cι-C alkyl, formyl, Cι-C 4 alkylcarbonyl, -COOR 7 , d-C alkylthio, d-C 4 alkylsulfonyl or -CONRβRg, or
R 2 and R 3 independently of one another are C 3 -Cβalkynyl, C 3 -C 6 alkynyl which is substituted by halogen, cyano, nitro, Ci-Cβalkoxy, C 3 -C 6 trialkylsilyl, hydroxyl, amino, ammonium, tri-d- C 4 alkylammonium, -COOH, -COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or by d-C 6 alkylamino, C 2 -C 5 alkoxycarbonyl, Crdsdialkylamino or phenyl, it being possible for the phenyl ring to be substituted by halogen, cyano, nitro, -OR 5 , -NR 10 R 11 , d-C alkyl, formyl, d-C 4 alkylcarbonyl, COOR 7 , Cι-C 4 alkylthio, d-C 4 alkylsulfonyl or -CONRβRg, or
R 2 and R 3 independently of one another are formyl, d-C 8 alkylcarbonyl, C 2 -C 8 alkenyl- carbonyl, C 4 -C 9 cycloalkylcarbonyl, C 6 -Cgcycloalkenyicarbonyl or C 3 -C β cycloalkyl-Cι-
C 6 alkylcarbonyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, hydroxyl, amino, Cι-C 8 alkylamino, C 2 -Cτdialky!amino, -COOH, -COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or by C 2 -C B alkoxycarbonyl,
C -Cιocycloalkoxycarbonyl, d-C 8 alkylaminocarbonyl or C 2 -C 8 dialkylaminocarbonyl, or
R 2 and R 3 independently of one another are heterocyclyl, heterocyclylcarbonyl, heterocyclyl which is substituted by halogen, cyano, nitro, Ci-Csalkyl, CrC 5 alkoxy, Ci-Csalkylcarbonyl, d-Csalkylcarbonyloxy, d-C 6 alkoxycarbonyl, aminocarbonyl, d-Cealkylaminocarbonyl or
C 2 -C 8 dialkyiaminocarbonyl, or heterocyclylcarbonyl which is substituted by halogen, cyano, nitro, d-C 4 alkyl, d-C 4 alkoxy, d-C 4 alkylcarbonyl, Cι-C alkoxycarbonyl, aminocarbonyl,
Cι-C 6 alkylamino or d-C 5 alkylcarboπyloxy, or
R 2 and R 3 independently of one another are phenylcarbonyl, biphenylcarbonyl, naphthylcarbonyl, phenyl-Ci-Cealkylcarbonyl, biphenyl-d-C 6 alkylcarbonyl, naphthyl-d-
C 6 alkylcarbonyl, phenyl-C^Cβalkenylcarbonyl, biphenyl-C 2 -C 6 alkenylcarbonyl or naphthyl-
C 2 -C 6 alkenylcarbonyl, it being possible for these substituents to be substituted by d-
C 4 alkyl, d-C alkoxy, Cι-C 4 alkylthio, C -C haloalkyl, Cι-C 4 alkylcarbonyl, halogen, cyano, amino, nitro, -COOR 7 , CrC s alkoxycarbonyl, hydroxyl, d-C 4 alkylsulfonyl, d-
C 5 alkylaminocarbonyl or C 2 -C 6 dialkylaminocarbonyl, or
R 2 and R 3 independently of one another are phenyl, naphthyl or heterocyclyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, d-C alkyl,
Cι-C 4 alkoxy, d-C 4 alkylthio, -COOH, -CONH 2l Cι-C 5 alkylaminocarbonyl, C 2 -Cτdialkyl- aminocarbonyl, d-C 4 alkylcarbonyl or d-C 5 alkoxycarbonyl, or
R 2 and R 3 together with the nitrogen atom to which they are bonded form a heterocyclic ring which can be substituted by d-C 4 alkyl, d-C alkoxy, halogen, cyano or nitro, or
R 2 and R 3 independently of one another are amino, Cι-C 4 alkylamino, C 2 -Cβdialkylamino, phenylamino, d-Csalkylcarbonylamino, Cι-C 5 alkoxycarbonylamino, hydroxyl, d-C 4 alkoxy,
Cι-C 5 alkylcarbonyloxy or phenoxy,
R 5 is hydrogen, C -C β alkyl, Cι-C 6 haloalkyl, C 2 -C 6 alkoxyalkyl, Cι-C 6 cyanoalkyl, phenyl, haiophenyl, Ci-C 4 alkoxyphenyl, phenyl-d-C 4 alkyl, Cι-C 4 alkylcarbonyl, benzoyl, halobenzoyl, d-C alkylamino, C 2 -C6dialkylamino, C 3 -C 6 trialkylsilyl, C 3 -C β cycloalkyl, C 2 -
C 4 alkenyl or C 3 -C 4 alkynyl,
R 7 is hydrogen, d-C alkyl, Cι-C 4 haloalkyl r d-C 4 cyanoalkyl, phenyl, haiophenyl,
C 2 -C 4 alkoxyalkyl, heterocyclyl or haloheterocyclyl,
R θ and R 9 independently of one another are hydrogen, phenyl, haiophenyl, Cι-C 4 alkyl, d-C 4 haloalkyl, d-C 4 cyanoalkyl, d-dalkenyl, C 3 -C 4 alkynyl or C 2 -C 4 alkoxyalkyl, or
R 8 and R 9 together with the nitrogen atom to which they are bonded form a heterocycle which can be substituted by Cι-C alkyl,
R10 and R independently of one another are hydrogen, phenyl, haiophenyl, d-dalkyl, d-C 4 haloalkyl, Cι-C cyanoalkyl, C 3 -C 4 alkenyl, C 3 -C 4 alkynyl, C 2 -C 4 alkoxyalkyl, formyl, d-C alkylcarbonyl or phenylcarbonyl, it being possible for the phenyl moiety therein to be substituted by Cι-C 4 alkyl, halogen, Cι-C alkoxy, hydroxyl, cyano, nitro or Cι-C alkoxy- carbonyl, or
R10 and Rn together with the nitrogen atom to which they are bonded form a heterocycle which can be substituted by d-C 4 alkyl.
Preferred amongst this group of compounds of the formula I are those in which R 2 and R 3 independently of one another are hydrogen, d-C 6 alkyl, Cι-C 6 alkyl which is substituted by halogen, hydroxyl, amino, ammonium, tri-Cι-C 4 alkylammonium, -COOH, -COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or by Ci-Csalkylcarbonyloxy, phenylcarbonyloxy, d-C 6 alkylamino, Cι-C 5 alkoxycarbonyl or C 2 -C 6 dialkylamino, or R 2 and R 3 independently of one another are formyl, Cι-C 8 alkylcarbonyl, d-dalkenyl- carbonyl, C 4 -C 9 cycloalkylcarbonyl, Ce-Cgcycloalkenylcarbonyl or C 3 -dcycloalkyl-Cι- C 6 aikylcarbonyl, it being possible for these substituents to be substituted by halogen, cyano, hydroxyl, amino, -COOH or -COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or
R 2 and R 3 independently of one another are heterocyclyl, heterocyclylcarbonyl, heterocyclyl which is substituted by halogen, cyano, nitro, d-C 5 alkyl, d-C 5 alkoxy or d-C β alkoxy- carbonyl, or are heterocyclylcarbonyl which is substituted by halogen, cyano, nitro, CrC 4 alkyl, d-C alkoxy or CrC 4 alkoxycarbonyl, or
R 2 and R 3 independently of one another are phenylcarbonyl, biphenylcarbonyl, naphthylcarbonyl, phenyl-Cι-C 6 alkylcarbonyl, biphenyl-d-C 6 alkylcarbonyl, naphthyl-Cι- C 6 alkylcarbonyl, phenyl-C 2 -C 6 alkenylcarbonyl, biphenyl-C 2 -C 6 alkenylcarbonyl or naphthyl- C 2 -C 6 alkenylcarbonyl, it being possible for these substituents to be substituted by d- dalkyl, d-C alkoxy, Cι-C 4 alkylthio, Cι-C 4 haloalkyl, Cι-C 4 alkylcarbonyl, halogen, cyano, amino, nitro, -COOH, Ci-Csalkoxycarbonyl, hydroxyl or Cι-C 4 alkylsulfonyl, or
R 2 and R 3 independently of one another are phenyl, naphthyl or heterocyclyl, it being possible for these substituents to be substituted by halogen, cyano, Cι-C 4 alkyl, d-dalkoxy, d-dalkylthio, -COOH or d-C 5 alkoxycarbonyl, or
R 2 and R 3 together with the nitrogen atom to which they are bonded form a heterocyclic ring which can be substituted by Cι-C 4 alkyl, Cι-C alkoxy, halogen or cyano.
Compounds amongst this group which are of particular interest are those in which R 2 and
R 3 are hydrogen, or
R 2 and R 3 independently of one another are formyl, d-C 8 alkylcarbonyl, C 2 -
C 8 alkenylcarbonyl, d-Cgcycloalkylcarbonyl, C 6 -C 9 cycloalkenylcarbonyl or C 3 -C 8 cycloalkyl- d-C 6 alkylcarbonyl, it being possible for these substituents to be substituted by halogen, cyano, hydroxyl or amino, or
R 2 and R 3 are phenylcarbonyl, it being possible for the phenyl ring to be substituted by C dalkyl, Cι-C 4 alkoxy, C C 4 alkylthio, d-C 4 haloalkyl, halogen, cyano, nitro, -COOH, Cι-
C 5 akoxycarbonyl, hydroxyl or Cι-C alkylsulfonyl.
A further preferred group of compounds of the formula I is the group in which X is O or
S(O) x where x is 0, 1 or 2, and
R is methyl which is substituted by halogen, cyano, nitro or OR 5 , or
R 4 is C 2 -C 8 alkyl, C 2 -C 8 alkenyl, C 3 -C 8 alkynyl, C 3 -C 8 cycloalkyl, C 5 -C 8 cycloalkenyl,
C 3 -C 8 cycloalkyl-Cι-C 4 alkyl or d-C 4 alkyl-C 3 -C 8 cycloalkyl, it being possible for these substituents herein to be substituted by halogen, cyano, nitro, =O or -OR 5 , or
R 4 is phenyl which is substituted by halogen, cyano, nitro, amino, -COOH, hydroxyl,
Cι-C alkyl, Cι-C 4 alkyloxy, Cι-C 4 alkylthio, d-C 4 haloalkyl, d-C 4 haloalkoxy, d-
C 4 haloalkylthio, C 2 -C 6 alkoxycarbonylalkoxy, Cι-C 4 alkylsulfιnyl, Cι-C 4 alkylsulfonyl, d-
Cealkyloxycarbonyl, Cι-C 6 alkyicarbonyl, -CONH 2 , formyl, Cι-C 5 alkylaminocarbonyl, C 2 - ddialkylaminocarbonyl, Cι-C alkylamino, C 2 -C 6 dialkylamino,
C 3 -C 6 trialkylsilyl, d-C 6 alkylcarbonylamino, d-C 6 alkylcarbonyloxy, phenoxy, halophenoxy or
Pyridyloxy, or
R 4 is biphenyl, naphthyl, heterocyclyl, Cι-C 4 alkylphenyl, C C 4 alkylnaphthyl, phenyl-d-
C 4 alkyl or naphthyl-Cι-C alkyl, it being possible for the substituents to be substituted by halogen, cyano, nitro, amino, -COOH, hydroxyl, Cι-C alkyl, Cι-C 4 alkyloxy, d-C alkylthio, d-C 4 haloalkyl, Cι-C 4 haloalkoxy, d-C haloalkylthio, C 2 -C 6 alkoxycarbonylalkoxy, d-C 4 alkyl-
sulfinyl, Cι-C 4 alkylsulfonyl, Cι-C 6 alkyloxycarbonyl, d-C 6 alkylcarbonyl, -CONH 2 , formyl, C
C 5 alkylaminocarbonyl, C 2 -Cτdialkylaminocarbonyl,
C 3 -C 6 trialkylsilyl, Cι-C 6 alkylcarbonylamino, d-Cβalkylcarbonyloxy, phenoxy, halophenoxy or pyridyloxy, and
R 5 is hydrogen, d-C 6 alkyl, Cι-C 6 haloalkyl, C 2 -C e alkoxyalkyl, d-Cecyanoalkyl, phenyl, haiophenyl, Cι-C 4 alkoxyphenyl, phenyl-d-C alkyl, Cι-C alkylcarbonyl, benzoyl, halobenzoyl, d-C 4 alkylamino, C 2 -C 6 dialkylamino, C 3 -C e trialkylsilyl, C 3 -C 6 cycloalkyl, C 2 -
C 4 alkenyl or C 3 -C alkynyl.
Outstanding compounds of the formula I amongst this group are those in which X is O or S, and
R is methyl which is substituted by halogen or cyano, or
R 4 is C 2 -C 8 alkyl, C 2 -C 8 alkenyl, C 3 -C 8 alkynyl, C 3 -Cβcycloalkyl, Cs-Cβcycloalkenyl, C 3 -C β - cycloalkyl-Cι-C 4 alkyl or Ci-dalkyl-drCβcycloalkyI, it being possible for the substituents herein to be substituted by halogen or cyano, or
RJ 4 is phenyl which is substituted by halogen, cyano, nitro, amino, Cι-C 4 alkyl, Cι-C 4 alkyloxy, d-C alkylthio, C 1 -C 4 haloalkyl, Cι-C haloalkoxy, C 2 -C 6 alkoxycarbonylalkoxy, Cι-C 4 alkyl- sulfonyl, Cι-C β alkyloxycarbonyl, d-C 6 alkylcarbonyl, formyl, Cι-C alkyiamino,
C 2 -C 6 dialkylamino,
C 3 -C 6 trialkylsilyl or C 2 -C 6 alkylcarbonyloxy, or
R 4 is biphenyl, naphthyl, heterocyclyl, d-dalkylphenyl, Cι-C 4 alkylnaphthyl, phenyl-d-
C 4 alkyl or naphthyl-d-C 4 alkyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, amino, d-dalkyl, Cι-C 4 alkyloxy, d-C alkylthio, d-C haloalkyl, d-C 4 haloalkoxy, C 2 -C β alkoxycarbonylalkoxy, Cι-C 4 alkylsulfonyl, d-C 8 alkyloxycarbonyl, d-C 6 alkylcarbonyl, C 3 -C 6 trialkylsilyl or Cι-C 6 alkylcarbonyloxy, very preferably X being O and R being phenyl which is substituted by halogen, cyano, nitro, amino, Cι-C 4 alkyl, d-C 4 alkyloxy, Cι-C 4 alkylthio, Cι-C haloalkyl, halomethoxy, Ci-
C 4 alkyl-sulfonyl, Cι-C alkylamino or d-ddialkylamino.
Other compounds of the formula I which must be emphasized are those in which R 1S , Rι 6 , R 17 , Riβ and Rι 9 independently of one another are Cι-C alkyl, C 2 -C 4 alkenyl, Cι-C 4 alkoxy, fluorine, chlorine, bromine, phenyl, d-C alkoxy-Cι-C alkoxy, trimethylsilyl, di-Cι-C 4 alkyl- amino, di-Ci-dalkylamino-d-dalkyl, morpholinyl-d-C 4 alkyl, d-C 4 alkylthio, d-C 4 - alkylsulfinyl, Cι-C 4 alkyl.sulfonyl, d-C 4 alkylcarbonyl, d-C 4 alkoxy-C,-C 4 alkyl, 1 -(Cι-C 4 alkyl)-
dioxolanyl, 1-phenyldioxolanyl, trifluoromethyl, hydroxyl, phenoxy, phenoxycarbonyl, C 3 - Cβcycloalkyl, Cι-C alkylperhydroazinyl, R 2 is hydrogen, R 3 is hydrogen or methylcarbonyl, X is O or S and R 4 is phenyl, naphthyl, pyridyl, Ci-dhaloalkoxy, d-C 8 alkoxy, Cι-C 4 -alkylthio,
cyclohexyl, thienyl or the group , or is phenyl, naphthyl, pyridyl or thienyl, each of which is substituted by d-C 4 alkyl, Cι-C alkoxy, fluorine, chlorine, nitro, cyano, C 3 - C 6 cycloalkyloxycarbonyl, d-C 6 alkylthio, Cι-C 4 hydroxycarbonyl, alkylsulfonyl, di-d-C alkylamino, d-C alkylsulfonyl or trifluormethyl.
An outstanding group of compounds of the formula I is the group in which R is the groups A1 , A2, A3, B1 , B2, B3, B4, B5, B6, C1 , C2, C3, C4, C5, C6, D1 , D2 or D3, but preferably the groups A1 , A2, A3, B1 , B2, B3, B4, B5, B6, C1, C2, C3, C4, C5 or C6.
Other compounds of the formula I which are especially preferred are those in which Rι 5 , R 16 , R 17 , R 18 and Rι 9 independently of one another are halogen, d-Cβalkyl or d-Cealkoxy, preferably fluorine, chlorine, d-C 4 alkyl or d-C 4 alkoxy.
Compounds of the formula I which are of particular interest are those in which Rι 5 is fluorine when R, is A1 , B1 , B2, B3, C1 , C2 or C6.
The compounds of the formula I can be prepared in various ways via process steps known per se using known starting materials.
For example, compounds of the formula I can be prepared by reacting an S,S- diorganosulfodiimide with an O.O'-diaryl N-cyanoimidocarbonate and subsequently subjecting the product to cyclization under acidic conditions:
ln the above diagram, Ri has the abovementioned meaning, R is R or another group which is suitable for the reaction, for example methyl or benzyl, and Ar is an aryl group, for example phenyl. Such processes are described, for example, in Winfried Jϋrgler's Ph.D. thesis, 1988, Philipps-Universitat, Marburg/L, Germany.
Compounds of the formula I can furthermore be prepared by starting from a trihalogenated thiatriazine of the formula II
in which Hal radicals independently of one another are fluorine, bromine or, in particular, chlorine, and reacting this trihalogenated thiatriazine with the corresponding organometallic compound of the formula III
RrM (III)
in which Ri has the abovementioned meanings and M is a mono- or polyvalent metal atom, which, depending on the valence, can have attached to it an appropriate number of Ri groups, in order to introduce the phenyl ring.
Compounds of the formula II and their preparation are described, for example, in Chem. Ber. (1991) 124 1347-1352 and Z. Chem. (1976) 16358-359.
Examples of suitable metals are, in particular, lithium, magnesium, zinc, aluminium, silicon, tin, and furthermore also manganese and titanium. Besides one or more Ri groups, the polyvalent metal atoms can also have attached to them further substituents such as halogen, cyano, d-C 4 alkyl, tetrafluoroborate or halogenated or unhalogenated alkanesulfonates. The organometallic compound of the formula III can furthermore be used in combination with salts such as aluminium chloride, zinc chloride, tin chloride, cerium
chloride, aluminium bromide and/or copper bromide, aluminium chloride, aluminium bromide and zinc chloride being preferred.
The compounds of the formula III can be prepared by customary methods, for example
• by reacting the corresponding halide Ri-halogen with the metal M,
• by halogen/metal exchange reaction of the corresponding halide Rrhalogen, halogen preferably being bromine or iodine, with a reactive organometallic compound, such as an alkyllithium compound, for example n-butyl-, s-butyl- or t-butyllithium,
• by treating the corresponding aromatic Ri-H with a strong base, for example lithium diisopropylamide, lithium bis(trimethylsilyl)amide, lithium tetramethylpiperidide, n-butyl-, s-butyl- or t-butyllithium, and the like. Aromatics of the formula Ri-H which are especially suitable for this reaction are those which carry a function which facilitates deprotonation and/or which influence orientation (see, for example, Snieckus V. Chem. Rev. (1990) 90, 879-933),
• by subjecting an organometallic compound prepared as described above to a transmetalation with a derivative of another metal, for example a halide,
• some of the compounds of the formula III and their solutions are commercially available. As a rule, the organometallic compound is not isolated but is reacted directly with the thiatriazine halide, in the presence or absence of a metal salt.
The group R, may be introduced in an aprotic solvent such as a hydrocarbon, for example hexane, heptane or toluene, or an ether such as dioxane, diethyl ether or, in particular, tetrahydrofuran, at temperatures from -100 C C to 150°C, in particular -80°C to 50°C (depending on the solvent).
Alternatively, the group Ri may be introduced by means of a Friedel-Crafts reaction between the aromatic R H and a compound of the formula It in the presence or absence of a catalyst such as a Lewis acid (for example AICI 3 , SnCI 4 and the like) or activated clay (for example montmorillonite). This reaction can be carried out in an aprotic solvent such as a hydrocarbon, for example nitrobezene, benzene, carbon tetrachloride and the like, or an ether, such as diethyl ether or tetrahydrofuran at temperatures from -50°C to 120°C, in particular -10°C to 60°C (depending on the solvent).
Compounds of the formula IV
(IV),
in which RT has the abovementioned meaning and Hal radicals independently of one another are fluorine, chlorine or bromine, with the exception of the compounds 1-(4- methylphenyl)-3,5-dichlorothiatriazine, 1 -(4-hydroxyphenyl)-3,5-dichlorothiatriazine, 1 -(4- methoxyphenyl)-3,5-dichlorothiatriazine, 1 -(4-chlorophenyl)-3,5-dichlorothiatriazine, 1 -(2- hydroxy-5-tert-butylphenyl)-3,5-dichlorothiatriazine, 1-(4-hydroxy-3-methylphenyl)-3,5- dichlorothiatriazine and 1 -(4-hydroxy-3-methoxyphenyl)-3,5-dichlorothiatriazine, 1 -(3,5- dimethyl-4-hydroxyphenyl)-3,5-dichlorothiatriazine, 1-(3,5-dimethoxy-4-hydroxyphenyl)-3,5- dichlorothiatriazine, 1-(2-hydroxy-3,5-dimethylphenyl)-3,5-dichlorothiatriazine and 3,5- dichloro-1-(2,3,4,5,6-pentafluorophenyl)thiatriazine, which have been obtained by reacting the compounds of the formula II with the compounds of the formula III, are novel and thus also subject-matter of the invention.
The substituents -NR 2 R 3 - and -XR 4 - can subsequently be introduced into the compound of the formula IV in any sequence in order to obtain the compounds of the formula I.
The reaction of the compounds of the formula IV with the compounds of the formula V
H-XR 4 (V),
in which X and R have the abovementioned meaning to give the compounds of the formula VI
is advantageously carried out in such a way that, prior to the reaction with the compounds of the formula IV, the compounds of the formula V are pretreated with a base such as metal hydride, for example lithium hydride, sodium hydride or potassium hydride, a metal hydroxide such as sodium hydroxide or potassium hydroxide, or a basic salt such as sodium carbonate or potassium carbonate, preferably in equivalent amounts. Alternatively, the reaction mixture of the compounds of the formulae IV and V may also be treated with the abovementioned bases. Solvents which are suitable for this step are hydrocarbons such as hexane or toluene, halogenated hydrocarbons such as chlorobenzene, ethers such as tetrahydrofuran, dioxane or diethyl ether, and also tertiary amides such as dimethylformamide. It is also possible to employ a mixture of these solvents with water, in which case it is advantageous to use a phase transfer catalyst. As a rule, the reaction temperatures are between -50°C and 100°C, preferably between 0°C and 40°C.
The compounds of the formula V are known and can be prepared in a manner known to those skilled in the art.
With the exception of the compounds 1 -(4-methylphenyl)-3-phenoxy-5-chlorothiatriazine, 1-(4-methoxyphenyl)-3-(2,3,4,5,6-pentafluorophenoxy)-5-chlor othiatriazine, 1-(4-chlorophenyl)-3-(2,3,4,5,6-pentafiuorophenoxy)-5-chloro thiatriazine, 1 -(4-methoxyphenyl)-3-(2,3,4-trichlorophenoxy)-5-chlorothiatr iazine, 1 -(4-chlorophenyl)- 3-(2,3-dichlorophenoxy)-5-chlorothiatriazine, 1-(3,5-dimethyl-4-hydroxyphenyl)-3-(2,5- difluorophenoxy)-5-chlorothiatriazine, 3-chloro-5-(2,5-difluorophenoxy)-1 -(2,3,4,5,6- pentafluorophenyl)-thiatriazine and 3-chloro-5-(2,3,4,5,6-pentafluorophenoxy)-1 -(2,3,4,5,6- pentafluorophenyl) -thiatriazine , the compounds of the formula VI are novel and also subject-matter of the present invention.
They can be converted into the end products of the formula I by conversion with a compound of the formula VII
Mι-NR 2 R 3 (VII)
in which R 2 and R 3 have the abovementioned meanings and M is hydrogen or a metal atom such as lithium, sodium, potassium or calcium, the process advantageously being carried out in the presence of a base. If R 2 and/or R 3 are hydrogen, M 1 is preferably hydrogen. If R 2 or R 3 is an acyl group, Mi is preferably lithium, sodium or potassium.
Solvents which are suitable for this reaction are hydrocarbons such as hexane or toluene, halogenated hydrocarbons such as chlorobenzene or dichloromethane, ethers such as diethyl ether, dioxane or tetrahydrofuran, alcohols such as ethanol or isopropanol, esters such as ethyl acetate, nitriles such as acetonitrile, or water. The reaction temperatures are in the range of from -70°C to 100°C, in particular 0°C to 40°C.
If Mi has the meaning of hydrogen, an acid binder is preferably used in order to scavenge the Hal acid. This may be, for example, a second equivalent of the compound of the formula VII, or a tert-amine such as triethylamine, pyridine, or an inorganic base such as sodium carbonate, potassium carbonate or sodium hydrogen carbonate. In the event that R 2 , R 3 and Mi are hydrogen, an excess of base may be used. If required, the process may be carried out under pressure.
The compounds of the formula VII and their preparation are described in the literature.
If the compound of the formula IV is to be reacted first with the base of the formula VII, then, again, the reaction conditions to be followed for the reaction of compound VI with compound VII must be maintained. The resulting compounds of the formula VIII
in which R^ R 2 and R 3 have the abovementioned meanings and Hal is fluorine, chlorine or bromine, with the exception of the compounds 1-(4-methylphenyl)-3-amino-5-chloro- thiatriazine, 1 -(4-chlorophenyl)-3-amino-5-chlorothiatriazine, 1 -(4-methoxyphenyl)-3-amino- 5-chlorothiatriazine, 1 -(4-hydroxyphenyl)-3-amino-5-chlorothiatriazine, 1 -(2-hydroxy-5-tert- butylphenyl)-3-amino-5-chlorothiatriazine, 1-(4-hydroxy-3-methylphenyl)-3-amino-5- chlorothiatriazine, 1 -(4-hydroxy-3-methoxyphenyl)-3-amino-5-chlorothiatriazine, 1 -(3,5- dimethyl-4-hydroxyphenyl)-3-amino-5-chlorothiatriazine, 1-(3,5-dimethoxy-4-hydroxyphenyl)- 3-amino-5-chlorothiatriazine, 1-(2-hydroxy-3,5-dimethylphenyl)-3-amino-5-chlorothiatriazin e, 1 -(3,5-dimethyl-4-hydroxyphenyl)-3-dimethylamino-5-chlorothia triazine, 3-amino-5-chloro-1 - (4-amino-2,3,5,6-tetrafluorophenyl)thiatriazine and 3-amino-5-chloro-1 -(2,3,4,5,6- pentafluorophenyl)thiatriazine, are also novel and subject-matter of the present invention.
The further reaction of the compounds of the formula (VIII) with the compounds of the formula (V) is carried out analogously to the procedure in the reaction of the compounds of the formulae (IV) and (V). However, a catalytic amount up to an excess of an amine such as trimethylamine is additionally added to the reaction mixture.
The end products of the formula I can be isolated in the customary manner by concentrating and/or evaporating the solvent and purified by recrystaiiization or trituration of the solid residue in solvents in which they are not readily soluble, such as ethers, aromatic hydrocarbons or chlorinated hydrocarbons, or by chromatographic methods.
Other compounds of the formula I may be prepared by customary derivatization of compounds of the formula I. The same applies to the intermediates of the formula IV, VI and VIII.
All application methods conventionally used in agriculture, for example pre-emergence application, post-emergence application and seed dressing, and a variety of methods and techniques, for example controlled release of active ingredient, are suitable for the use according to the invention of the compounds of the formula I or of compositions comprising them. To this end, a solution of the active ingredient is applied to mineral carriers for granules or to polymerized granules (urea/formaldehyde), and these are dried. If required, an additional coating may be applied (coated granules) which allows the active ingredient to be released in a controlled manner over a specific period.
The compounds of the formula I can be employed as pure active ingredients, i.e. as obtained upon synthesis, but they are preferably processed in the customary manner with the auxiliaries conventionally used in the art of formulation to give, for example, emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules. The application methods, such as spraying, atomizing, dusting, wetting, scattering or pouring, and the type of composition, are selected to suit the intended aims and the prevailing circumstances.
The formulations, i.e. the compositions, preparations or combinations comprising the active ingredient of the formula I, or at least one active ingredient of the formula I and, as a rule, one or more solid or liquid formulation auxiliaries, are prepared in a known manner, for example by intimately mixing and/or grinding the active ingredients with the formulation auxiliaries, for example solvents or solid carriers. Surface-active compounds (surfactants) may furthermore additionally be used in the preparation of the formulations.
The following are examples of suitable solvents: aromatic hydrocarbons, preferably the fractions C 8 to d 2 , for example xylene mixtures or substituted naphthalenes, phthalate esters such as di butyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters such as ethanol, ethylene glycol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or N,N-dimethyiformamide, or epoxidized and unepoxidized vegetable oils such as epoxidized coconut oil or soya oil; or water.
Solid carriers which are used for example for dust and dispersible powders are, as a rule, ground natural minerals such as calcite, talc, kaolin, montmorillonite or attapulgite. To improve the physical properties of the formulation, it is also possible to add highly disperse silica or highly disperse absorptive polymers. Suitable paniculate, absorptive carriers for granules are porous types, for example pumice, crushed bricks, sepiolite or bentonite, and non-sorptive carrier materials, for example, calcite or sand. Moreover, a large number of pregranulatθd materials of inorganic or organic nature can be used, in particular dolomite or comminuted plant residues.
Suitable surface-active compounds are non-ionic, cation ic and/or anionic surfactants and surfactant mixtures which have good emulsifying, dispersing and wetting properties, depending on the nature of the active ingredient of the formula I to be formulated.
Suitable anionic surfactants can be either so-called water-soluble soaps or water-soluble synthetic surface-active compounds.
Soaps which are suitable are the alkali metal salts, alkaline earth metal salts or substituted or unsubstituted ammonium salts of higher fatty acids (do-da), for example the sodium or potassium salts of oleic or stearic acid, or of natural mixtures of fatty acids which can be obtained from, for example, coconut oil or tallow oil. Furthermore mention must also be made of the fatty acid methyltaurine salts.
However, so-called synthetic surfactants are used more frequently, in particular fatty alcohol sulfonates, fatty alcohol sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.
As a rule, the fatty alcohol sulfonates or fatty alcohol sulfates are present in the form of alkali metal salts, alkaline earth metal salts or substituted or unsubstituted ammonium salts and have an alkyl radical of 8 to 22 C atoms, alkyl also including the alkyl moiety of acyl radicals, for example the sodium or calcium salt of ligninsulfonic acid, of dodecyl sulfuric ester or of a fatty alcohol sulfate mixture prepared from natural fatty acids. This group also includes the salts of the sulfuric esters and sulfonic acids of fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives have preferably 2 sulfonyl groups and a fatty acid radical of 8 to 22 C atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfuric acid, of dibutylnaphthalenesuffonic acid, or of a naphthalenesulfonic acid/formaldehyde condensate.
Furthermore phosphates, for example salts of the phosphoric ester of p-nonylphenol-(4-14)- ethylene oxide adducts, or phospholipids, are also suitable.
Non-ionic surfactants which are suitable are mainly polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, of saturated or unsaturated fatty acids and of 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 alkyl phenols.
Other non-ionic surfactants which are suitable are the water-soluble polyethylene oxide adducts with polypropylene glycol, ethylene diaminopolypropylene glycol and alkyl polypropylene glycol which have 1 to 10 carbon atoms in the alkyl chain and contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. The abovementioned compounds normally have 1 to 5 ethylene glycol units per polypropylene glycol unit.
Examples of non-ionic surfactants which may be mentioned are nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.
Other substances which are also suitable are fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate.
The cationic surfactants are mainly quaternary ammonium salts which have, as N-substituents, at least one alkyl radical having 8 to 22 C atoms and, as further substituents, lower halogenated or unhalogenated alkyl, benzyl or lower hydroxyalkyl radicals. The salts are preferably in the form of haiides, methylsulfates or ethylsulfates, examples being stearyltrimethylammonium chloride or benzyldi(2- chloroethyl)ethylammonium bromide.
The surfactants conventionally used in the art of formulations 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 [Surfactants Guide]", Carl Hanser Veriag, MunichVienna, 1981 , and M. and J. Ash, "Encyclopedia of Surfactants", Vol I— 111, Chemical Publishing Co., New York, 1980-81.
As a rule, the herbicidal formulations 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 now preferred as commercial products, the end consumer uses, as a rule, dilute compositions.
The compositions may also comprise further additives such as stabilizers, for example free or epoxidized vegetable oils (epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders, adhesives and fertilizers or other active ingredients.
Preferred formulations have, in particular, the following compositions: (% = percent by weight)
Emulsifiable concentrates: Active ingredient: 1 to 90%, preferably 5 to 50% Surfactant: 5 to 30%, preferably 10 to 20% Solvent 15 to 94%, preferably 70 to 85%
Dusts:
Active ingredient: 0.1 to 50%, preferably 0.1 to 1%
Solid carrier: 99.9 to 90%, preferably 99.9 to 99%
Suspension concentrates: Active ingredient: 5 to 75%, preferably 10 to 50% Water: 94 to 24%, preferably 88 to 30% Surfactant: 1 to 40%, preferably 2 to 30%
Wettable powders:
Active ingredient: 0.5 to 90%, preferably 1 to 80%
Surfactant: 0.5 to 20%, preferably 1 to 15%
Solid carrier: 5 to 95%, preferably 15 to 90%
Granules:
Active ingredient: 0.1 to 30%, preferably 0.1 to 15%
Solid carrier: 99.5 to 70%, preferably 97 to 85%
As a rule, the active ingredients of the formula I are successfully applied to the plant or its environment at rates of application of from 0.001 to 5 kg, in particular between 0.005 and 2 kg. The dosage required for the desired activity can be determined by experiments. It depends on the type of activity, the development stage of the crop plant and of the weed, and on the application (location, timing, method) and can, due to these parameters, vary within wide ranges.
The compounds of the formula I are distinguished by herbicidal and growth-inhibiting properties, which allow them to be used in crops of useful plants, in particular in cereals, cotton, soya beans, sugar beet, sugar cane, plantations, oil seed rape, maize and rice.
Crops are also to be understood as meaning those which have been made tolerant to herbicides, or classes of herbicides, by conventional breeding or genetic engineering methods. The weeds to be controlled can be both mono- 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 Examples which follow illustrate the invention in greater detail without imposing any limitation thereon.
The nomenclature used in the following text is based on the numbering shown below:
6
N N - λ
S N 4
N
Preparation Examples:
Example H1 : Preparation of 3.5-dichloro-1- 2-methylphenyl)thiatriazine: A 2 M solution of o-tolylmagnesium bromide in tetrahydrofuran (150 ml) is added dropwise with intensive stirring and cooling at a temperature of -20°C to a solution of 40.9 g of ZnCI 2 (0.3 mol) in 500 ml of absolute tetrahydrofuran. The resulting mixture is stirred for 45 minutes at a temperature of -20°C and subsequently cooled to a temperature of -70°C. A solution of 61.3 g of trichlorothiatriazine (0.3 mol) in 50 ml of tetrahydrofuran is subsequently added to this reaction mixture dropwise with stirring and cooling at a temperature held between -70 C C and -60°C. The reaction mixture is subsequently slowly warmed to room temperature. After 500 ml of water has been added and the reaction mixture has been poured into 1.5 I of water, the resulting suspension is placed on a suction filter. The residue obtained is washed with water and dried. After further washing with cold diethyl ether and drying, 3,5-dichloro-1-(2-methylphenyl)thiatriazine is obtained in the form of yellow crystals of melting point 140-142°C.
Example H2: Preparation of 3-amino-5-chloro-1-(2-methylphenyl)thiatriazine: Ammonia is passed into a vigorously stirred solution of 3,5-dichloro- 1 -(2-methylphenyl)thiatriazine (39.0 g, 0.150 mol) in 700 ml of tetrahydrofuran at a temperature of 0°C. When passing-in is complete, the reaction mixture is concentrated by half in vacuo, diluted with water to 1 I and stirred. The resulting suspension is filtered with suction, until the filter residue is washed with water and dried. This gives 3-amino-5-chloro- 1 -(2-methylphenyl)thiatriazine in the form of white crystals of melting point 196°C (decomposition).
Example H3: Preparation of 3-amino-1-(2-methylphenyl)-5-(4-(3-oxobutvD- phenoxy)thiatriazine::
A mixture of 2.4 g of 3-amino-5-chloro-1-(2-methylphenyl)thiatriazine (0.010 mol), 1.8 g of 4-hydroxyphenyl)-2-butanone (0.011 mol) and 70 ml of dichloromethane is treated with 6.0 ml of 2 N sodium hydroxide solution (0.012 mol) and 1.5 g of trimethylamine solution (40% in water). The reaction mixture is subsequently stirred for 2 days at a temperature of 20°C. The organic phase is subsequently dried over sodium sulfate and evaporated. After chromatographic pre-purification on silica with a hexane/ethyl acetate mixture (1 :1) and recrystallization from this mixture, 3-amino-1-(2-methylphenyl)-5-(4-(3-oxobutyl)- phenoxy)thiatriazine is obtained in the form of white crystals of melting point 186-188°C.
Example H4: Preparation of 3.5-dichloro-1- 2.5-dichlorophenyl)thiatriazine: A solution of 43.7 g of 1 ,4-dichloro-2-iodobenzene (0.16 mol) in 200 ml of absolute tetrahydrofuran is treated at a temperature of from -70°C to -65°C with a solution of 0.16 mol of n-butyllithium in 100 ml of hexane. Then, a solution of 21.8 g of ZnCI 2 in 150 ml of absolute tetrahydrofuran is added dropwise. After the mixture has been stirred for 5 minutes, a solution of 32.7 g of trichlorothiatriazine in 50 ml of absolute tetrahydrofuran is added dropwise at this temperature. After the reaction mixture has come to room temperature, it is placed on a suction filter and the residue obtained is washed with diethyl ether and ethyl acetate. The filtrate is washed in succession with water, sodium bicarbonate solution, water and saturated NaCI solution, dried over sodium sulfate and evaporated. The resulting residue is stirred with pentane, during which process crystals form. After filtration with suction, washing with pentane and drying, 3,5-dichloro-1-(2,5-dichlorophenyl)- thiatriazine crystals are obtained which have a melting point of 200-203°C (decomposition).
Example H5: Preparation of 3-amino-5-chloro-1-(2.5-dichlorophenvDthiatriazine: Ammonia is passed into a vigorously stirred solution of 2.2 g of 3,5-dichloro-1 -(2,5- dichlorophenyl)thiatriazine (0.007 mol) in 80 ml of tetrahydrofuran at a temperature of 0 C C. When the starting material has reacted completely, the reaction mixture is treated with ethyl acetate and water. The organic phase is washed with water and subsequently with saturated NaCI solution and dried over sodium sulfate. When the liquid is reduced, crystals precipitate. The suspension is placed on a suction filter and the residue obtained is washed with a small amount of diethyl ether and with pentane and dried. White crystals of 3-amino- 5-chloro-1-(2,5-dichlorophenyl)thiatriazine of melting point 225-227°C (decomposition) are isolated.
Example H6: Preparation of 3-amino-5-(3.5-bistrifluoromethylphenoxy)-1 -(3.5- dimethylphenvDthiatriazine.
A mixture of 2.54 g of 3-amino-5-chloro-1-(3,5-dimethylphenyl)thiatriazine (0.010 mol) and 2.53 g of 3,5-bistrifluoromethylphenol (0.011 mol) in 70 ml of dichloromethane is added with 5.5 ml of 2 N sodium hydroxide solution (0.011 mol) and 1.5 g of trimethylamine solution (40% in water). The mixture is stirred for 18 hours at a temperature of 20°C. The dichloromethane is distilled off and the residue obtained is stirred with water. The suspension is placed on a suction filter and the residue obtained is washed with water and subsequently dried. This gives 3-amino-5-(3,5-bistrifluoromethylphenoxy)- 1-(3,5-dimethylphenyl)thiatriazine in the form of white crystals of melting point 222-223 c C (decomposition).
Example H7: Preparation of 3.5-dichloro-1-(2.4.6-trimethylphenylUhiatriazine: A 1 M solution of 2-mesitylmagnesium bromide in diethyl ether (100 ml) is added dropwise with vigorous stirring and cooling at a temperature of 20°C to a solution of 13.6 g of ZnCI 2 (0.1 mol) in 200 ml of absolute tetrahydrofuran. The mixture obtained is subsequently stirred for 45 minutes at a temperature of 20°C and then cooled to a temperature of -70°C. A solution of 20.4 g of trichlorothiatriazine (0.1 mol) in 20 ml of tetrahydrofuran is added dropwise to this reaction mixture with stirring and cooling at a temperature kept between -70°C and -60°C. After the reaction mixture has been heated slowly, it is filtered with suction. The residue is washed with diethyl ether and the filtrate is extracted with water, sodium bicarbonate solution and saturated NaCI solution. The organic phase is dried over sodium sulfate and concentrated. Trituration of the residue with pentane results in the formation of yellow crystals of 3,5-dichloro-1 -(2,4,6-trimethyiphenyl)thiatriazine which, after washing with pentane and subsequent drying, have a melting point of 98-100°C.
Example H8: Preparation of 3-amino-5-chloro-1-(2.4.6-trimethylphenyl)thiatriazine: Ammonia is passed into a vigorously stirred solution of 3,5-dichloro-1 -(2,4,6-trimethyl- phenyl)thiatriazine (10.1 g, 0.035 mol) in 200 ml of tetrahydrofuran at a temperature of 0°C. When the addition is complete, the reaction mixture is treated with ethyl acetate and water. After extraction, the organic phase is washed with water and subsequently with saturated NaCI solution and dried over sodium sulfate. The solution is then concentrated until a
viscous suspension is formed which is filtered with suction. After the residue has been washed with cold ethyl acetate and subsequently with diethyl ether and dried, pale yellow crystals of 3-amino-5-chloro-1-(2,4,6-trimethylphenyl)thiatriazine which have a melting point of 167°C (decomposition) are isolated.
Example H9: Preparation of 3-amino-1-(2.4.6-trimethylphenyl)-5-(2.3.5.6-tetrafluoro- 4-trifluoromethylphenoxy)thiatriazine:
A mixture of 1.07 g of 3-amino-5-chloro-1-(2,4,6-trimethylphenyl)thiatriazine (0.004 mol), 40 ml of dichloromethane and 1 g of 2,3,5,6-tetrafluoro-4-trifiuoromethylphenol (0.0043 mol) is treated with 2 N sodium hydroxide solution (0.0044 mol) and 0.6 g of trimethylamine solution (40% in water). The mixture is subsequently stirred for 4 days at a temperature of 20°C. The organic phase is separated off and dried over sodium sulfate. After evaporation, chromatographic pre-purification on silica with a hexane/ethyl acetate mixture (3:1) and recrystallization from this mixture, 3-amino-1-(2,4,6-trimethylphenyl)-5-(2,3,5 I 6-tetrafluoro- 4-trifluoromethylphenoxy)thiatriazine crystals of melting point 206-208°C are obtained.
Example H10: Preparation of 3.5-dichloro-1-(2.3.5.6-tetramethylphenylUhiatriazine: A solution of 13.6 g of ZnCI 2 (0.100 mol) in 200 ml of absolute tetrahydrofuran is treated with a solution of 2,3,5,6-tetramethylphenylmagnesium bromide (prepared with 21.3 g of 1-bromo-2,3,5,6-tetramethylbenzene (0.100 mol) and 2.64 g of magnesium (0.110 mol) in 100 ml of absolute tetrahydrofuran) at a temperature of -20°C. The mixture is subsequently stirred for 1 hour at a temperature of 20°C and then cooled to a temperature of -70°C. A solution of 20.4 g of trichlorothiatriazine in 10 ml of absolute tetrahydrofuran is subsequently added dropwise to the mixture at a temperature of from -70°C to -65°C. The reaction mixture is subsequently allowed to come to room temperature and then transferred into 1 litre of water. The suspension is placed on a suction filter, and the residue obtained is washed with water, dried with suction and then washed with pentane and dried. This gives 3,5-dichloro-1-(2,3,5,6-tetramethylphenyl)thiatriazine in the form of yellow crystals of melting point 138-140°C.
Example H11 : Preparation of 3-amino-5-chloro-1-(2.3.5.6-tetramethylphenylHhiatriazine. Ammonia is passed into a vigorously stirred solution of 15.2 g of 3,5-dichloro- 1-(2,3,5,6-tetramethylphenyl)thiatriazine (0.0503 mol) in 300 ml of tetrahydrofuran at a
temperature of 0°C. After the starting material has reacted completely, the reaction mixture is treated with water. The suspension is placed on a suction filter, and the residue is washed with water, dried with suction, washed with diethyl ether and dried. This gives 3- amino-5-chloro-1 -(2,3,5,6-tetramethylphenyl)thiatriazine in the form of white crystals of melting point 185°C (decomposition).
Example H12: Preparation of 3-amino-5-(2-bromophenoxy)-1-(2.3.5,6-tetramethylphenyl)- thiatriazine:
A mixture of 2.1 g of 3-amino-5-chloro-1-(2,3,5,6-tetramethylphenyl)thiatriazine (0.0075 mol) and 1.43 g of 2-bromophenol (0.0082 mol) in 70 ml of dichloromethane is treated with 4.5 ml of 2 N sodium hydroxide solution (0.009 mol) and 1.1 g of trimethylamine solution (40% in water). The mixture is subsequently stirred for 70 hours at a temperature of 20°C. The dichloromethane is subsequently distilled off and the residue is stirred with water. The resulting suspension is placed on a suction filter, and the residue is washed with water, dried with suction, washed with pentane and dried. This gives 3-amino-5-(2- bromophenoxy)-1-(2,3,5,6-tetramethylphenyl)thiatriazine in the form of white crystals of melting point 212-214°C.
Example H13: Preparation of 3.5-dichloro-1-(2.3.4.5.6-pentamethylphenyl)thiatriazine: A solution of 13.6 g of ZnCI 2 (0.100 mol) in 200 ml of absolute tetrahydrofuran is treated with a solution of 2,3,4,5,6-pentamethylphenylmagnesium bromide (prepared with 22.7 g of 1-bromo-2,3,4,5,6-pentamethylbenzene (0.100 mol) and 2.64 g of magnesium (0.110 mol) in 130 ml of absolute tetrahydrofuran) at a temperature of -20°C. The mixture is stirred for 30 minutes at a temperature of 20°C and subsequently cooled to a temperature of -70°C. A solution of 20.4 g of trichlorothiatriazine in 10 ml of absolute tetrahydrofuran is then added dropwise to the mixture at a temperature of from -70°C to -65 C C. The reaction mixture is allowed to come to room temperature, with stirring, and is subsequently transferred into 1 litre of water. The suspension is then placed on a suction filter and the residue obtained is washed with water, dried with suction, washed with pentane and dried. This gives 3,5-dichloro-1 -(2,3,4,5,6-pentamethylphenyl)thiatriazine in the form of yellow crystals of melting point 140-142 C C.
Example H14: Preparation of 3-amino-5-chloro-1-(2.3.4.5.6-pentamethylphenyl)thiatriazine : Ammonia is passed into a vigorously stirred solution of 14.0 g of 3,5-dichloro- 1-(2,3,4,5,6-pentamethylphenyl)thiatriazine (0.0443 mol) in 300 ml of tetrahydrofuran at a temperature of 0°C. After the starting material has reacted completely, the reaction mixture is evaporated and the residue obtained is treated with water. The suspension is placed on a suction filter and the residue obtained is washed with water, dried with suction and then washed with diethyl ether and dried. This gives 3-amino-5-chloro-1 -(2,3,4,5,6- pentamethylphenyl)thiatriazine in the form of yellowish crystals of melting point 189°C (decomposition).
Example H15: Preparation of 3-amino-5-(2.3.4.5.6-pentafluorophenoxy)-1 -(2,3.4.5.6- pentamethylphenyDthiatriazine:
A mixture of 2.2 g of 3-amino-5-chloro-1-(2,3,4,5,6-pentamethylphenyl)thiatriazine (0.0075 mol) and 1.5 g of 2,3,4,5,6-pentafluorophenol (0.0082 mol) in 70 ml of dichloromethane is treated with 4.5 ml of 2 N sodium hydroxide solution (0.009 mol) and 1.1 g of trimethylamine solution (40% in water). The mixture is subsequently stirred for 70 hours at a temperature of 20°C. The suspension is filtered and the residue obtained is washed with water. The organic phase is separated from the filtrate and dried over sodium sulfate. After evaporation of the solution, chromatographic pre-purification of the crude product on silica with a hexane/ethyl acetate mixture (3:1) and recrystallization from the abovementioned mixture, 3-amino-5-(2,3,4,5,6-pentafluorophenoxy)- 1-(2,3,4,5,6-pentamethylphenyl)thiatriazine is obtained in the form of white crystals of melting point 210-211°C.
Example H16: Preparation of methyl 2-ri-(3.5-difluorophθnyl)-5-chloro-1λ 4 -(1.2.4.6)- thiatriazin-3-ylamino1-3-methyl-pentanoate (Example B5.052): A cooled suspension of 1.27 g of L-isoleucine methyl ester hydrochloride in 15 ml of tetrahydrofuran is treated with 14 ml of propylene oxide and 2.1 g of 3,5-dichloro- 1-(3,5-difluorophenyl)1 4 -(1 ,2,4,6)thiatriazine in 3 ml of tetrahydrofuran and 0.68 ml of 1 ,8-diazabicyclo[5.4.0]undec-7-ene(1 ,5-5) (DBU). The resulting solution is held at a temperature of 20°C until the reaction is complete. The mixture is subsequently evaporated, and the residue is taken up in ethyl acetate, washed with water, dried and filtered through silica gel. This gives methyl 2-[1-(3,5-difluorophenyl)-5-chloro-1λ 4 -(1,2,4,6)thiatriazin-
3-ylamino]-3-methylpentanoate (diastereomer mixture) in the form of a colourless resin of n D 50 1.5005.
Example H17: Preparation of methyl 2-ri-(3.5-difluorophenyl)-5-pentafluorophenoxy-1λ 4 - (1.2.4.6)thiatriazin-3-ylamino1-3-methylpentanoate (Compound B6.009): 1.6 g of the product obtained in Example H16 are dissolved in 35 ml of dichloromethane, and the solution is treated with 0.65 ml of trimethylamine solution (45%, aqueous) and 27.3 ml of a 0.145 molar solution of pentafluorophenol in dichloromethane. 2 ml of 2 N sodium hydroxide solution are subsequently added dropwise with stirring and cooling, and the mixture is stirred at a temperature of 20°C until the reaction is complete. It is then treated with dichloromethane and ice-water, and extracted with dichloromethane, and the extracts are washed with water, dried and evaporated. After purification under silica gel (hexane/ethyl acetate 8:2), the residue yields methyl 2-[1 -(3,5,-difluorophenyl)-5- pentafluorophenoxy-1λ 4 -(1 ,2,4,6)thiatriazin-3-ylamino]-3-methylpentanoate (diastereomer mixture) in the form of a colourless resin of no 50 1.5139.
Example H19: Preparation of 2.2.2-trichloro-1-ri-(4-bromophenyl)-5-pentafluorophen- oxy-1λ -(1.2.4.6)-thiatriazin-3-ylaminoethanol (Compound A6.034)
A suspension of 262 mg of 1-(4-bromophenyl)-5-pentafluorophenoxy-3-amino-1λ
-(1 ,2,4,6)thiatriazine in 12 ml of dichloromethane is treated with 0.3 ml of anhydrous chloral and refluxed with stirring until the reaction is complete. The mixture is then evaporated in vacuo and the residue is filtered through silica gel (hexane/ethyl acetate 8:2). This gives
2,2,2-trichloro-1 -[1 -(4-bromophenyl)-5-pentafluorophenoxy-1 λ 4 -(1 ,2,4,6)thiatriazin-3- ylaminoethanol (diastereomer mixture) in the form of a white solid of melting point 187-
188°C.
Example H20: Preparation of 2.6-dichloro-N-f1-(3-chloro-4-methvtphenyl)- pentafluorophenoxy-1λ 4 -(1.2.4.6)thiatriazin-3-yηisonicotinamide (Compound B6.033): A solution of 1.5 g 2,6-dichloroisonicotinoyl chloride in 6 ml of acetonitrile is added dropwise to a stirred solution of 2.5 g of 1-(3-chloro-4-methylphenyl)-5-pentafluorophenoxy-3-amino- 1 λ 4 -(1 ,2,4,6)thiatriazine in 16 ml of pyridine under a nitrogen atmosphere at a temperature
of from -5 to 0°C , and the resulting solution is stirred for 30 hours at a temperature of 0°C. The reaction mixture is then diluted with ethyl acetate, transferred into ice-water and is extracted rapidly with ethyl acetate while adding saturated sodium chloride solution. The extracts are dried over sodium sulfate and evaporated, and the residue is purified on silica gel (hexane/ethyl acetate 7:3). This gives 2,6,-dichloro-N-[1-(3-chloro-4-methylphenyl)- pentafluorophenoxy-1λ 4 -(1,2,4,6)-thiatriazin-3-yl]isonicotinamide of melting point 196- 198°C.
Other compounds which can be prepared analogously are those listed in the Tables which follow.
Table A1 : Compounds of the formula la:
R«
A1.002 A2 CH 3
A1.005 A2 CH 3 F 203
0~ y (decomp.)
F A1.006 A3 CH 3 /=\ 239-241
A1.007 A1 CH 3 . =\ ... 186-188
O^H(CH 2 ) 2 COCH 3
Comp. Ri Rl5 No.
A1.008 A2 CH 3
A1.009 A3 CH 3
A1.011 A3 SCH 3
A1.012 A3 n-C 4 H 9
A1.013 A3 i-C 3 H 7
A1.016 A3 n-C 4 H 9
A1.017 A3 SO 2 CH 3
115
i-C 3 H 7
A1.020 A3 i-C 3 H 7 192-194
A1.021 A3 n-C 4 H s 159-160
A1.022 A3 n-C 3 H 7 220-225
A1.023 A3 C 2 H 5 222-223
A1.025 A3 n-C 3 H 7 193-195
A1.026 A3 SOCH 3 F
F
R 15 XR Physical data M.p. °C
A1.035 A3 CH=CH 2 188-191
A1.037 A3 SO 2 CH 3
H5 XR 4 Physical data M.p. °C
XR 4 Physical data M.p. °C
OCH(CF 3 ) 2 F F
F F
A1.067 A2 O-t-C 4 H 9 OCH 2 C7F 15
A1.070 A3 Br F F 182-183
°- F& F F
A1.071 A3 OC 6 H 5 S-i-C 3 H 7 A1.072 A3 OC 2 H 5 OCH(CF 3 ) 2
0-(
CH,
A1.073 A3 OC 2 H 5 OCH 2 C 6 F 5 A1.075 A3 COC 6 H 5
° " ~Ci=3
XR 4 Physical data
M.p. °C
OCH 2 C 3 F 7
°^ COOCH,CCH
A1.084 A3 C(CH 3 )=CH 2 F F
F F
A1.086 A3 Si(CH 3 ) 3
0-^ N0 2
R15 XR 4 Physical data M.p. °C CF 3 196-198
A1 .098 A3 CβH 5 F F 250-252
°-β- ■ 'F
A1.099 A3 C « 6 Hns 250-252
A1 .102 A3 CH 2 -O-CH 2 -CH=CH 2 149-151
A1 .105 A3 CH 2 OCH 2 CH=CH(CH 3 ) 128-130
R 15
f-C 4 Hg
A1 .126 A2 — C≡C— H
> /=<
F
A1.127 A3 — C≡C— Si(CH 3 ),
Table A2: Compounds of the formula lb:
Comp. RT R 1S XR 4 Physical
No. data
M.p. °C
A2.002 A2 CH 3 F F
°- - F&F F'
A2.006 A3 CH 3
0- ^)-t-C 4 H 9
A2.007 A1 CH 3 0-< -(CH 2 ) 2 COCH 3
R15 XR 4 Physical data
M.p. °C
n-C 4 H 9
>
F
n-CaH ? F F
O -O- - Ϊ F F F
Comp. R, R 1S XR 4 Physical
No. data
M.p. °C
A2.031 A3 SOCH 3 -
C β H 13 /
Comp. R, R 15 XR 4 Physical
No. data
M.p. °C
A2.051 A1 COCH
S-
A2.060 A2 v O
C '2' H '5 5 O N-'
,
Comp. Ri Rιs XR 4 Physical
No. data
M.p. °C
A2.081 A3 CH 2 -N^ 0-<^-COOCH 2 CCH
A2.082 A2 SO-i-C 3 H 7 F F
F F A2.083 A3 F F F
° F F ~F
A2.086 A3 Si(CH 3 ) 3
Comp. RT R 15 XR 4 Physical
No. data
M.p. °C
A2.093 A1 C-C 3 3Hrl5 o CP 3
CF,
A2.095 A3 C(CH 3 )=CH 2 0^\^
A2.096 A2 CH 3 F
° F
Table A3: Compounds of the formula IVa
Table A4: Compounds of the formula Via
Comp. R t R 15 XR 4 Physical
No. data
M.p. °C
A4.031 A3 SOCHa
A4.032 A3 SO 2 CH 3
A4.061 A2 °-
CaHs ^
Comp. R 1 R 1S XR 4 Physical
No. data
M.p. °C
A4.064 A2 CF 3 OCH(CF 3 ) 2
A4.067 A2 O-t-C 4 H 9 OCH 2 C7F 15
A4.071 A3 OC 6 H 5 S-i-C 3 H 7
A4.072 A3 OC 2 H 5 OCH(CF 3 ) 2
CH 3
A4.073 A3 OC 2 H 5 OCH 2 C 6 F 5
A4.074 A3 C 6 H 5 OC 6 H 5
A4.075 A3 COC 6 H 5
° ~ 0 ~CF3
XFU Physical data
M.p. °C
A4.094 A2 SOC 2 H 5 F F
O^ F
F F
Table A5: Compounds of the formula Villa
(Villa)
NR 22 Rn 3 Physical data M.p. °C
NH 2 NH 2
NH 2 NH 2 NH 2 NH 2 NH 2 196-197 NH 2 NH 2 NH 2 NH 2 NH 2
NH 2 NH 2 NH 2
NH 2 NH 2 NH 2 NH 2 NH 2 NH 2 NH 2 NH 2
NH 2
115 NR ι 22 Rπ 3 Physical data M.p. °C
A5.067 A3 CH 2 OCH 3 NH 2 160 A5.068 A3 CH 2 OCH 3 NHCH(OH)CCI 3
A5.070 A3 O-CH 2 -CH=CH 2 NH 2 150
A5.071 A2 — C≡C— H NH 2
A5.072 A2 — C≡C— H NHCH(OH)CCI 3
A5.073 A2 O-CH 2 -CH=CH 2 NH 2 127-129
A5.074 A3 CF(CH 3 ) 2 NH 2
A5.075 A3 CF(CH 3 ) 2 NHCH(OH)CCI 3
A5.076 A3 CβHs NHCH(OH)CCI 3
A5.077 A3 — C≡C— n-C 3 H 7 NH 2
A5.078 A3 — C≡C— t-C 4 H 9 NH 2
p.)
Table A6: Compounds of the formula Ic:
NR 2 R 3
N=
R; N (IC)
* //
OR 4
Comp. RT RIS R 4 NR 2 R 3 Physical data
M.p.
A6.005 A2 F C 'βFr,s NHCH(OH)CCI 3
A6.006 A3 F C 6F' , 5 172-173°C
A6.007 A1 CH 3 C 6 H 4 (CF 3 -3)
A6.008 A2 CH 3 C 6 F 5 NHCOCCI 3
A6.009 A3 CH 3 C 6 H 3 F 2 (2,5-) NHCH(OH)CCI 3
A6.010 A2 C 2 H 5 C 6 H 4 (NO 2 -4) NHCOCCI 3
A6.01 1 A3 C 2 H 5 C 6 H 4 F(2-)
A6.012 A2 CF 3 C 6 H 3 CI 3 (2,3,6-)
Comp. R T R 15 R 4
A6.013 A3 CF 3 C 6 H 4 (CH 3 -4)
A6.014 A2 t-butyl C β F 5
A6.015 A3 t-butyl C β F s NHCH(OH)CCI 3 61-62°C
A6.017 A2 OCH 3 C 6 HF 4 (2,3,5,6-)
A6.018 A3 OCH3 CH 4 Br (4-) NHCH(OH)CCI 3
A6.019 A2 Br C e H 3 F 2 (2,5-)
A6.020 A3 F NHCH(OH)CCI 3
A6.021 A3 , CH 3 C 6 F S NHCH(OH)CCI 3
A6.025 A3 NHCOCI 3
A6.026 A3 C 6 H 5 C •»6F' , 5 NHCH(OH)CCI 3 95-103°C
A6.028 A3 Br C 6 H 2 CI 2 (2,6-) NHCH(OH)CCI 3
A6.030 A3 t-butyl
Comp. R, R 15 R 4 NR 2 R 3 Physical data
M.p.
A6.032 A3 CH 3 CH 4 (CH 3 -4)
A6.033 A2 t-butyl C 6 H 4 (Si(CH 3 ) 3 (-4)) NHCH(OH)CCI 3
A6.034 A3 Br C 6 F 5 NHCH(OH)CCI 3 187-189°C
Table B1 : Compounds of the formula la:
Comp. R, R 15 Riβ XR 4 Physical
No. data
M.p. °C
B1.004 B3 Cl Cl
**$
B1 .005 B6 CH 3 CH 3 OCH 2 CH(CF 3 ) 2
B1.006 B2 CH 3 CH 3 O , r
B1.007 B5 Cl Cl F F 195-197
OHghF
F F B1.008 B6 CH 3 CH 3 F 233
0 ~ (\ // (decomp.)
F
Rιs R16 XR 4 Physical data
M.p. °C
B1.037 B3 o^>
H 3 C0 2 C
Comp. R, R 15 R 16 XR 4 Physical
No. data
M.p. °C
B1 .047 B3 OCH 3 CH 3 OC 8 H 17
B1 .052 B1 CON(C 2 H 5 ) 2 OCH,SI(CH&
Comp. R, 115 116 XR 4 Physical No. data M.p. °C
B1.054 B1 NHCOCH 3
°-©- NO,
B1.055 B1 CON(C 2 H 5 ) 2 OCH 3
B1.056 B1 -CN OCH 3 oP S0 2 -C 2 H 5
B1.059 B1 -CN Cl c- _
B1.061 B1 -CN OCH 3 o SCH,
B1.062 B2 CH 3 CH 3 >-0 ~oc < H *
B1.063 B1 -CN OC 2 H 5
N-
B1.065 B2 CF 3 NHCH 3
\ιs R 16 XR 4 Physical data
M.p. °C
B1.071 B3 CF 3 OCH 2 C 6 F 5
B1.072 B4 CF 3 CF 3 SCβHs
B1.073 B3 NHCOCH 3 Cl
230
Comp. R T R, 5 Rl6
No.
B1.080 B1 Cl Cl
B1.081 B4 Cl Cl
B1.083 B5 OCH 3 Cl
B1.084 B6 F
B1.085 B2 OCH 3 OCH 3
B1.086 B5 Cl CH 3
B1.087 B4 F
Comp. R, R 15 R 16 XR 4 Physical
No. data
M.p. °C
Table B2: Compounds of the formula lb:
Comp. R, R 15 R16 XR 4 Physical
No. data
M.p. °C
B2.012 B3 CH 3 CH 3
OH^-CF 3
B2.018 B5 F 0-(^)-(CH 2 ) 2 COOH
R15 R16 XR 4 Physical data
M.p. °C
B2.020 B2
Cl
Comp. R T R 15 R 16 XR,, Physical
No- data
M.p. °C
B2.042 B3 OCH 3 CH 3
°& F F F
B2.046 B2 CH 3 OCH 3 F F
°- -F
F& F'
B2.047 B3 OCH 3 CH 3 OC 8 H, 7
B2.052 B1 CON(C 2 H 5 ) 2 0CH 2 si(CH,) 3 C 2 H 5 oP
Comp. Ri R 15 R 1 6 XR Physical
No. data
M.p. °C
B2.054 B1 NHCOCH 3 F
B2.055 B1 CON(C 2 H 5 ) 2 OCH 3
B2.061 B1 -CN OCH 3 ° P SCH.
B2.063 B1 -CN OC 2 H 5 s=\
N- 7
Comp. RT R, 5 R 16 XR 4 Physical
No. data
M.p. °C
B2.065 B2 CF 3 NHCH 3
^N
B2.066 B6 Cl Cl i -Q
S-t-C 4 H 9
B2.067 B1 -CN CF 3 S-i-C 3 H 7 B2.068 B4 F CF 3 OCH 2 CN
B2.069 B4 CF 3 NHCOCH 3
°^ t-C„H Q
B2.071 B3 F CF 3 OCH 2 C 6 F 5
B2.072 B4 CF 3 CF 3 SC 6 H 5
B2.073 B3 NHCOCH 3 Cl
B2.075 B3 CF 3 CH 2 OC 4 H 9 OCF, o J
B2.076 B4 OCH 3 OCH 3 S-c-CHn
-99
Table B3: Compounds of the formula IVa
Comp. Ri R 15 R 16 Physical
No. data
M.p. °C
B3.048 B3 NHCOCH 3 Cl
B3.049 B4 Cl OCH 3
B3.050 B3 CF 3 CH 2 OC 4 H 9
B3.051 B4 OCH 3 OCH 3
B3.052 B6 F F resin
B3.053 B4 F F resin
B3.054 B2 F Cl resin
B3.055 B5 OCH 3 Cl resin
B3.056 B5 CH 3 Cl resin
B3.057 B5 CF 3 F
B3.058 B5 C≡CH Cl
B3.059 B6 C 2 H 5 CH 3
B3.060 B6 CH 3 F
B3.061 B1 F F
B3.062 B5 Br Br
B3.063 B6 Br Cl
B3.064 B5 C=CCH 3 βr
B3.065 B6 Cl O C 3 H 7
Table B4: Compounds of the formula Via
Comp. Ri R 1S Rie XR 4 Physical
No. data
M.p. °C
B4.005 B6 CH 3 CH 3 OCH 2 CH(CF 3 ) 2
B4.007 B5 Cl Cl F F
F F
B4.009 B6 CH 3 CH 3 O, y
Comp. R, R 15 R 16 XR 4 Physical
No - data
M.p. °C
B4.015 B6 CH 3 CH 3 CF,
0 - CF 3
Comp. Ri R 15 R 16 XR Physical
No. data
M.p. °C
B4.052 B1 CON(C 2 H s ) 2 ocH,si<t»w. C 2 H S
Comp. R, R 15 R1 6 XR 4 Physical
No. data
M.p. °C
B4.066 B6 Cl Cl
°-Q S-t-C 4 H g
B4.075 B3 CF 3 CH 2 OC 4 H 9 OCF 3 o-&
B4.076 B4 OCH 3 OCH 3 S-C-CHn
Table B5: Compounds of the formula Villa
(Villa)
Comp. Ri R15 R 16
No.
B5.001 B2 OCH 3 OCH 3
NH 2 NH 2 NH 2 NH 2 NH 2
NH 2 192-193 (decomp.)
NH 2 NH 2 NH 2 196-198 NH 2 275 NH 2 NH 2 NH 2
Comp. RT R 15 *16 NR 22 Rπ 3 Physical
No. data M.p. °C
50
NH 1.5005)
B5.054 B5 CH 3 Cl NHCH(OH)CCI 3
N
e NR 2 2R" : 3 Physical data M.p. °C
Cl NHCH(OH)CCI 3
F NHCH(OH)CCI 3
B5.068 B6 F F NHCH(OH)CCI 3
B5.070 B6 NH, 179-180 (decomp.)
B5.071 B4 NH 2 167 (decomp.)
B5.072 B2 Cl NH 2 193 (decomp.)
B5.074 B6 CH 3 NHCH(OH)CCI 3
115 r R»ii6
B5.076 B2
B5.077 B5 OCH 3 Cl
Table B6: Compounds of the formula Ic
NR 2 R 3
,"=<
N (Ic)
OR.
Comp. RT R 15 116 a. NR 2 R 3 Physical data M.p.
B6.001 B2 OCH3 OCH3 CH 3 CI 2 (2,5-)
B6.002 B5 Cl Cl C 6 H 3 CI 2 (2,4-) NHCH(OH)CCI 3 resin
resin
B6.005 B3 CH 3 Cl C '6F' ,5 NHCH(OH)CCI 3
B6.006 B5 F C 6 H 3 F 2 (2,5-)
B6.007 B6 F C 6F~5 NHCH(OH)CCI 3 resin
Comp. Ri. R 15 " R1i6 NR 22 Rπ 3 . Physical data M.p.
B6.009 B6 F C βFδ no 50 1.5139
B6.015 B5 Cl CH 3 Cβ 6Fr,5 n D S0 1.5295
B6.016 B5 Cl CH 3 C 6 6F1 5 n D 50 1.5302
B6.017 B5 CH 3 Cl CH 3 (CI-2,NO 2 -5) NHCH(OH)CCI 3 B6.018 B5 Cl CH 3 CF 5 NHCH(OH)CCI 3 no 50 ! .5320
Comp. Ri R 15 ^16
B6.020 B5 F CH 3
B6.021 B6 C 2H« I5 CH a
B6.022 B5 CH 3 F CH 4 (OCH 3 -2) NHCH(OH)CCI 3 B6.023 B6 F F CF 5 NHCH(OH)CCI 3 n D S0 1.5262
B6.024 B4 CF 3 CF 3 C 6 H 2 F 3 (3,4,5-) NHCH(OH)CCI 3
B6.025 B5 CF 3 CF 3 CβH 2 CI 3 (3,4,5-)
B6.026 B5 Br Br CβH 2 Cl3(3,4,5-) NHCH(OH)CCI 3
B6.027 B6 F C 'β6F~,5 no 50 ! .5295
Cl
B6.028 B6 Br Br CeH 2 CI 3 (3,4,5-) NH- N
Cl
B6.029 B6 Br Cl CH 2 F 3 (3,4,5-) NHCH(OH)CCI 3
B6.031 B6 Br Cl C 6 HF 4 (2,3,5,6-) NHCH(OH)CCI 3
Comp. Ri R 15 e R4 NR 2 2R» l ; 3 Physical data M.p.
B6.032 B6 Br Cl CHF 4 (2,3,5,6-)
B6.033 B5 Cl CH 3 C 6 6F' ,5 196-198° C
B6.035 B6 Br Cl CH 2 F 3 (2,3,4-) NHCH(OH)CCI 3
B6.036 B5 H Br C 6 H 3 F 2 (2,5-) NHCH(OH)CCI 3
///
B6.037 B6 F C 6 H 3 F 2 (2,5-)
B6.038 B5 F CH 3 C 6 H 3 F 2 (2,5-)
B6.039 B5 Cl CH 3 C 6 HF 4 (2,3,5,6-)
B6.040 B6 Cl O-iPropyl C 6 H 3 F 2 (2,6-) NHCH(OH)CCI 3
Table C1: Compounds of the formula la:
OH
XR Physical data
183-185
NC o^ ^N>
0-^ N
0-n-C 4 H g op
16 117 XFI 4 Physical data
CH 3 CH 2 OH
SC(CH 3 ) 3 CH 3
CHa oO> n-C 4 H
CH, CH 3
F F
Cl Cl 141 -143
F F
C 2 He OC 2 2H^5 °Pt CH,
C1.032 C2 NHCO 2 -t-C 4 H 9 n-C 3 H 7 n-C 3 H 7
C1.033 03 OCHa CH, CF 3 o F,PC - NO,
01.04603 -CN
Comp. i R 16 Rl7 XR4 Physical No. data
C1.047 C3 CON(C 2 H 5 ) 2 Cl Cl
Comp. Ri R15
No.
C1.060 C6 NHCOC 2 H s
C1.062 03
C1.065 03
C1.066 C1 Cl
C1.067 03 CH,
C1.071 01 OCH a
Comp. i R15 Ri6
No.
01.074 C5 CH 3 OC 3 H 7
C1.076 C1 Cl
O - 1
C1.08304 CHa oco-t.-C4.H9 CHa Cl
Cl
C1.085C6 OC 3 H 7 OC 3 H 7 COOH s SC 5 H 11 o ^
* . 16 R 17 XR 4 Physical data
M.p. °C CH 3 CH 3 0 _^>_ CF
3
C1.089C1 -NHCOO-t-CH 9
o
C1.110C3 -NHCOO-t-C 4 H 9 CH 3 Cl
F F
C1.11103 NHCON(CH 3 ) 2 Cl CF 3
F F
01.112 C3 Cl F -NHCOO-t-C 4 t-
RlE *16
Cl OC 2 H 5
OCH, OCH 3 OCH 3 o ^N
OCH, OCH 3 OCHa
01.124 C6 Cl O-i-C 3 H 7 172-173
Comp. Ri R^ R16 Rι XR 4 Physical
No. data
M.p. °C
ci
Table C2: Compounds of the formula lb:
Comp. i R15 Ri6 R17 XR4 Physical
No. data
M.p. °C
Cl
C2.001 C1 CH 3 CH 3 CH a op Cl
C2.003C3 CH 3 CH 3 CH, o -Q
C2.005C5 CH 3 CH 3 CH 3
OCH 3
02.006 C6 CH 3 CH 3 CH 3 o CH 3
C2.007C1 CH 3 CH 3 CH 3 o- -a
Cl
XR 4 Physical data
F F
F F
02.025 C1 SO 2 -f-C 4 Hc OCH 3 CH 3
C2.026C2 CONfCuHste CH 3 CH 3
C2.029 C5 N(CH 3 ) 2 CH 3 F
C2.031 C1 OCON(CH 3 ) 2 C 2 H 5 OC 2 H 5 °-Q- -'CH,
-N
C2.032 C2 NHco 2 -t-c 4 H 9 n-C 3 H 7 n-C 3 H 7 T s S
C2.033 C3 OCH, CH, CF 3
Comp. Ri *15 "16 *17 XR 4 Physical No. data M.p. °C
02.034 C4 CH 3 CH 3 (CH 2 0) 2 CH 3 oO
C2.038C4 OC(CH 3 ) 3 OCH 3 OCH 3 F F
OH^CI
F F
C2.039C1 F F F 0-^-C0 2 C 2 H 5
C2.042C1 OCH 2 CH 3 CH 3 CH 3 C 3
02.04603 -CN CHa CH, SCβHs
Comp. Ri R 15 R 16 *17 XR 4 Physical No. data
C2.047 C3 CON(C 2 H 5 ) 2 Cl Cl
Physical data M.p. °C
Comp. Ri Ru R« 17 XR 4 Physical No. data M.p. °C
C2.088 C2 NHCON(CH 3 ) 2 CH 3 CH,
»^ CF,
C2.089C1 -NHCOO-t-CHg
F F
C2.09004
O^-F
F F
SC 5 H„
C2.100C4 CON(C 2 H 5 ) 2 CF 3 CF, o
Comp. Ri R15 R16 R17 XR 4 Physical
No. data
M.p. °C
C2.101C4 Cl Cl OCH,
0 p~?
F F
C2.104C3 Cl CH 3 NHCON(CH 3 ) 2
C2.105 C2 NHCOC6H5 F F J ^ s S
C2.110C3 -NHcoo-t-c 4 H S CH 3 Cl
C2.111C3 NHCON(CH 3 ) 2 Cl CF 3
02.112 C3 Cl F -NHcoo.t-c 4 H 9
Comp. i R15 Riβ R1 XR 4 Physical
No- data
Table C3: Compounds of the formula IVa
*15 '16 Rl Physical data
M.p. °C
Cl OC 2 H 5 CH 3 resin F F F resin F F Cl F F OCH 3 F F F resin OCH 3 OCH 3 OCH 3 resin F Cl O-i-C 3 H 7 resin
Table C4: Compounds of the formula Via
Cl
Rr— S N (Via)
N
XR.
Comp. i R15 Riβ R17 XR Physical
No. data
M.p.°C
Cl
C4.00101 CHa CHa CHa op Cl
04.003 C3 CHa CHa CH 3 o >
C4.004C4 CH 3 CH 3 CH 3
C4.005C5 CH 3 CH 3 CH 2
OCH 3
C4.007C1 CH 3 CH 3 CH 3 0^ . -Cl
Cl l
Comp. Ri Ri. *16 Ri; XR 4 Physical No. data
C4.023 C5 CH 3 SC(CH 3 ) 3 CH 3 o
C4.02501 SO r C(CHJ, OCHa CHa
C4.02602 CON(C 2 H 5 ) 2 CH 3 CHa
C4.031 01 OCON(CH 3 ) 2 C 2 H 5 OC 2 H 5
°-Q- CH,
04.032 C2 NHCO^t^H n-C 3 H 7 n-C 3 H 7 s-
04.03303 OCH 3 CHa CF 3 o NO,
F,C
Comp. i Ris "16 "17 XR 4 Physical No. data
M.p.°C
04.034 C4 CHa CH 3 (CH 2 0) 2 CH 3
04.03505 CH 3 CH 3 F F
F F
C4.038C4 OC(CH 3 ) 3 OCH 3 OCH 2
C4.03901 F
°- - C0 2 C 2 H 5
C4.040 C1 -CN OCHa OCH 3
C4.04201 OCH 2 CH 3 CHa CH 0- >-N0 2 C 3
C4.04306 NH 2 CHa CHa
C0 2 C 2 H 5
C4.044C2 CON(CH 3 ) 2 F
C4.046C3 -CN CH 3 CH 3 SC 6 H 5
Comp. Ri s *ιe 11 No.
C4.047 C3 CON(C 2 H 5 ) 2 Cl
04.051 01
C4.05301 -NHCO-t-C4Hg CH 3 Cl o -Q
CN
04.056 C3 Cl CHa -CN SCH,
04.05701 OCH 3 C0N(CH3) 2 OCH 3 OCH 2 CF 3
04.05901 OCH 3 CON(CH 2 ). OCH 3
Comp. Ri R15 Rιβ R1 XR 4 Physical
No- data
M.p.°C
C4.060C6 NHCOC 2 H 5 CH 3 Cl H 3
F F
C4.061 C3 Cl CF 3
F F C4.062C3 F OCH 3 CON(C 2 H 5 ) 2
04.065 C3 F OCH 3 CON(C 2 H 5 ) 2 C l
04.066 C1 Cl Cl OCH 2 CH-CH 2
C4.067C3 CH 3 NHCH 2 OCH; CH 3
C4.070C3 Cl CH 3 Cl
C4.071C1 OCH 3 iJC -@ OCH 3 0 - -CH 2 -t-C 4 H 6
Comp. Ri R15 R16 R17 X Physical
No. data
M.p.°C
04.07405 CHa OC 3 H 7 Cl 0"^-t-C 4 H,
C4.07503 OCHa OC 2 H 5 >-<Q>-(CH 2 ) 2 COCH 3
0 J
C4.077 C1 OCH 2 CF 3 -CN OCH 2 CF 3 OCH 2 CF 3
C4.078 C2 OC 5 Hn Br CH 3 SCH 2 C 6 H 5
C4.079 C5 Br C 6 H 5 Br OC 6 H 5
C4.080 C2 OCH 3 OCH 3 CH 2 0-t-C 4 Hg OCH 2 C 7 F 15
C4.081 C5 CH 3 O-t-C 4 H 9 CH 3 N(C 2 H 5 ) 2
04.082 C4 -CN CF 3 CF 3 '^Tf^Y^
C4.083 C4 CH 3 OCO-t-C 4 H CH 3
04.08406 Cl Br Cl
C4.085 C6 OC3H 7 OC 3 H 7 COOH
Comp. i R 15 R 16 R 17 XR 4 Physical No. data
M.p.°C
C4.088 C2 NHCON(CH ) 2 CH 3 CHa "O- CF,
C4.089 C1 -NHCoo-t-C t Hg
C4.09004 F F
F F
C4.09304 -NHC00-t-C4Hg CF 3 OCH a
C4.09704 t-C 4 H 9 CH 3 CH 3 OC 6 H
04.10004 CON(C 2 H 5 ) 2 CF 3 CFa
Comp. i 5 6 Rll XR 4 Physical No. data
M.p.°C
C4.101C4 F F
Cl Cl OCHa O-^F
C4.103C4 C 2 H δ C 2 H 5 C 2 H 5 o-Q
S0 2 -C 2 H s
C4.104C3 Cl CH 3 NHCON(CH 3 ) 2
C o,H
C4.105C2 NHCOC 6 H 5 F F
C4.106C1 OCH 2 CF 3 -CN OCH 2 CF 3
C4.110 C3 -NHC00-t-C4Hg CH 3 Cl -
C 6 H 13 /
C4.111 C3 NHCON(CH 3 ) 2 Cl CF,
C4.112C3 Cl -NHCOO-t-C 4 Hg
Comp. Ri R15 R16 R17 XR 4 Physical
No. data
M.p.°C
Table C5: Compounds of the formula Villa
(Villa)
Comp. Ri R15 Riβ R17 NR 2 R 3 Physical No. data
M.p. °C
C5.023 C4 OCH 3 OCH 3 OCH 3 NH 2
05.024 C4 F F F NH 2
C5.025 04 OC(CH 3 ) 3 OCH 3 OCH 3 NH 2
05.026 01 F F F NH 2
05.027 01 -CN OCH 3 OCH 3 NH 2
C5.028 C2 NH 2 CH 3 Cl NH 2
C5.029 01 OCH 2 CH 3 CH 3 CH 3 NH 2
C5.030 C6 NH 2 CH 3 CH 3 NH 2
C5.031 02 CON(CH 3 ) 2 F F NH 2
C5.032 C3 F F F NH 2
C5.033 C3 -CN CH 3 CH 3 NH 2
05.034 03 CON(C 2 H 5 ) 2 Cl Cl NH 2
C5.035 C3 CF 3 Cl Cl NH 2
C5.036 C3 OCH 3 OCH 3 -CN NH 2
C5.037 03 -CN F F NH 2
C5.038 01 -NHCO-t-C 4 Hg CH 3 Cl NH 2
C5.039 02 -CN OCH 3 OCH 3 NH 2
C5.040 03 Cl Cl CF 3 NH 2
C5.041 C3 Cl CH 3 -CN NH 2
C5.042 C1 OCH 3 CON(CH 3 ) OCH 3 NH 2
C5.043 03 OCH 3 OH -CN NH 2
C5.044 01 OCH 3 CON(CH 2 ) OCH 3 NH 2
05.045 06 NHCOCzHs CH 3 Cl NH 2
C5.046 C3 F Cl CF 3 NH 2
05.047 03 F OCH 3 CON(C 2 H 5 ) 2 NH 2
C5.048 C3 Cl Cl Cl NH 2
C5.049 03 OCH 3 OC 2 H 5 _< 0 NH 2
0
C5.050 C1 Cl Cl OCH 2 CH=CH 2 NH 2
05.051 C3 CH 3 NHCH 2 OCH CH 3 NH 2
C5.052 03 OCH 2 C 6 H 5 OCH 3 -CHO NH 2
05.053 05 CH 3 OC 3 H 7 Cl NH 2
C5.054 03 Cl CH 3 Cl NH 2
157 -
Table C6: Compounds of the formula (Ic):
NR 2 R 3
, N =<
R; N (Ic)
N— ^
OR.
C6.007 03 F C e H 4 (CN-3)
06.008 C5 F C 6 H 4 (CF3-3)
C6.009 05 F C ' 6 6R~5
Comp. R, R 15 H6 Rl7 FU NR 22 Rπ 3 Physical data
M.p.
C6.011 05 F Cl O-i-propyl C β F 5
06.012 05 F CH 3 Br C6H 4 (CF 3 -4)
C6.013 C5 F Cl O-i-propyl OC 6 H 3 F 2 (2,5-)
Table D1 : Compounds of the formula la:
R« 1 16 "1
-CN OCH 3 OCH 3
D1.002 D1 CH 3 CH 3 OH
D1.003 D1 -CN Cl OCH 3
D1.004 D1 CON(C 2 H 5 ) 2 OCH 3 OCH 3
D1.006 D1
D1.008 D1 OCON(C 2 H 5 ) 2 CH 3 CH 3
Comp. RT R 15 He 117
No.
D1 .010 D2 CON(C 2 H 5 ) 2 OCH 3 OCH 3
D1.011 D3 OC 2 H s OC 2 2H« I;5 OC 2 H s
D1.013 D1 CH 3 CH 3 CH 3
D1 .014 D2 OCON(C 2 H s )2 j-C 3 H 7 Cl
D1.015 D3 NHCOO1-C4H9 F NCH 3 COt-C«H β
D1.016 D1 OCH 2 OCH 3
D1.018 D1 NHCOOt-C«H 9 OCH 3 OCH 3
D1.019 D1 Cl F F
Comp. R, R 15 R 16 Rl7 R 18 XR 4 Physical
No. data M.p.°C
D1.020 D1 CH 3 CH 3 N(CH 3 ) 2 N(CH 3 ) 2
D1 .023 D1 CH 3 CH 2 N(C 2 H S ) 2 OC 3 H 7 CH 3 oP
C 2 H 5
D1.024 D2 NHSO 2 C 6 H s CH 3 CH 3 CH 3
D1.025 D1 CH 3 OC 2 H 5 OC 2 H 5 t-C 4 H 9
D1.028 D1 OCH 3 CH a CH 3 OCH 3 F F
F F
D1.029 D1 CH 3 CH 3 OCH 3 OCH 3 0 p F F
F F
Comp. R, R 15 Riβ R Riβ XR 4 Physical
No. data
M.p.°C D 1.030 D2 CH 3 CH 3 CH 3 175-178
D1.031 D2
D1.032 D1 NH,
D1.033 D1 CH 3 CH 3 OCH 2 2 C«βHπs
D1.034 D3 CH 3 CH 3 CH 3
D1.035 D3 CH 3 Br CH 3
D1.036 D3 CH 3 CH 2 OCH 3 CH 3 CH 3
D1.037 D3
D1.038 D1 OCH 3 COoC- OCH 3 OCH 3
D1.039 D3 CH 3 NHCOt- CH 3 CH 3
D1.040 D1 -CN OCH3 OCH3 OCH 3
Comp. R, R 15 R16 R Riβ XR 4 Physical
No. data
M.p.°C
D1.041 D2 CH 3 CH 3 CH 3 212-214
D1.042 D1 CH 3 CH 3 OH
D1.043 D1 -CN Cl OCH 3
D1.046 D1 CON(i- CH 3 D1.047 D3 F
D1.048 D1 OCON(C2H 5 ) 2 CH 3 CH a
D1.050 D2 CON(C 2 H 5 ) 2 OCH 3 OCH 3
D1.051 D3 OC 2 H 6 OC 2 H 5 OC 2 H 5
Comp. Ri R 15 Ri6 R17 Riβ XR 4 Physical
No. data
M.p.°C
D1.053 D2 CH 3 CH 3 CH 3 CH 3 o 215-216
Br D1.054 D1 CH 3 CH 3 CH 3 CH 3
D1.055 D2 OCON(C2H 5 ) 2 j-CgH Cl CH 3 oP
F 3 C
D1.056 D3 NHCOOt-C 4 H 9 F
D1.058 D3 OCH 3 OCH3 OCH3 r~ F F
F F D1.059 D1 NHCOOt-C 4 H 9 OCH 3 OCH 3 OCH 3 OC 8 H 17
D1.061 D1 CH 3 CH 3 N(CH 3 ) 2 N(CH 3 ) 2
D1.062 D1 -CN F F F O^ o 0
Comp. R R 15 »16 '17 118 XR 4 Physical
No. data M.p.°C
D1.064 D1 CH 3 CH 2 N(CaH 5 ) 2 0C 3 H 7 CHa
D1.065 D2 NHSOaCβHs CH 3 CH 3 CHa
Cl Cl
D1.066 D1 CH 3 OC 2 H 5 OC 2 H 5 t-C 4 H 9
D1.068 D2 Cl Cl Cl Cl
S0 2 -C 2 H 5
D1 .069 D1 OCHa CH 3 CHa OCHa
D1 .070 D1 CH 3 CH 3 OCH 3 OCHa
D1.071 D2 CH 3 CH 3 CHa CH 3 s
D1.072 D2 F F F F OCH 2 CH(CF 3 ) 2
D1.073 D1 NH 2 F F F 0.
D1 .074 D1 CHa CH 3 OCH 2 CeHs CH 3 F F
°P F F F
Comp. R T 115 H Rl7 No.
D 1.076 D3 CH 3 Br CH 3
D1.077 D3 CH 3 CH 2 OCH 3 CH 3 CH oP
D1.078 D3
D1.079 D1 OCH 3 CO 2 c- OCH 3
D1.080 D3 CH 3 NHCOt- CH 3
Table D2: Compounds of the formula lb:
Comp. R R 15 6
No.
D2.001 D1 -CN OCH 3
D2.003 D1 -CN Cl
D2.004 D1 CON(C 2 Hs) 2 OCH 3
D2.006 D1
Comp. Ri R 15 ie 117 118 XR 4 Physical
No. data M.p. °C
D2.018 D1 NHCOOt-C 4 H 9 OCH 3 OCH 3 OCH 3 o^)>
D2.019 D1 Cl »-o- NO,
D2.020 D1 CH 3 CH 3 N(CH 3 ) 2 N(CH 3 ) 2
D2.023 D1 CHa CH 2 N(C 2 H 5 )2 OC 3 H 7 CH 3
D2.024 D2 NHSO 2 C 6 H 5 CH 3 CH 3 CH a
D2.025 D1 CH 3 OCaHg OCaHs t-C H 9
D2.027 D2 Cl Cl Cl Cl
Comp. Ri R15
No.
D2.028 D1 OCH 3
D2.029 D1 CHa
D2.030 D2 CH 3
D2.032 D1 NH 2
D2.033 D1 CH 3
D2.034 D3 CH 3
D2.035 D3 CH 3
0 ~?
F F D2.036 D3 CH 3 CH 2 OCH 3 CH 3 CH 3
D2.037 D3 F F F F Cl op Cl
Comp. RT R 15 R 16 R 17
No.
D2.038 D1 OCH 3 CO 2 c-C 6 H 1 1 OCH 3
D2.039 D3 CH 3 NHCOt-C 4 H 9 CH 3
D2.040 D1 -CN OCH 3 OCH 3 OCH 3
D2.043 D1 -CN Cl
D2.044 D1 CON(C 2 H 5 ) 2 OCH 3
D2.046 D1 CON(i- CH 3
C 3 H ) 2
D2.048 D1 OCON(C 2 H 5 )2 CH 3 CH 3 OCH 3
Comp. Rt R 15 R16 R17 Riβ XR 4 Physical
No. data
M.p.
°C
D2.050 D2 CON(C 2 H 5 ) 2 OCH 3 OCH 3 OCH 3 Cl
O-c^-α Cl D2.051 D3 OC2H5 OC2H5 OC 2 H 5
D2.052 D3 Cl CF o ^
D2.053 D2 CH 3 CH 3 CH 3 CH 3 0 - ^
Br D2.054 D1 CH 3 CH 3 CH 3 CH 3
D2.055 D2 OCON(C2H 5 )2 j-C 3 H 7 Cl CH 3
F3C
D2.056 D3 NHCOOt-C 4 H 9 f NCH 3 C0t-C 4 H 9 CF 3
D2.058 D3 OCH 3 OCH 3 OCH 3
D2.059 D1 NHCOOt-C4H 9 OCH 3 OCH 3 OCH 3 OC 8 H 17
Comp. Ri R15 R 16 R17 Riβ XR Physical
No. data
M.p.
°C
D2.061 D1 CH 3 CH 3 N(CH 3 ) 2 N(CH 3 ) 2
D2.064 D1 CH 3 CH 2 N(C 2 H 5 ) 2 OC 3 H 7 CH 3
D2.065 D2 NHSO 2 C 6 H 5 CH 3 CH 3 CH 3
D2.066 D1 CH 3 OC 2 H 5 OC 2 H 5 ' c ^ oP NO,
D2.069 D1 OCH 3 CH 3 CH 3 OCH 3 0 p F F
F F
D2.074 D1 CH 3 CH 3 OCH 2 C 6 H 5 CH 3
D2.076 D3 CH 3 Br CH 3 CH 3 O^^
^ ^
D2.077 D3 CH 3 CH 2 OCH 3 CH 3 CH o
CH 3
D2.079 D1 OCH3 COjC-CeHu OCH 3 OCH 3
°^ F 3
D2.080 D3 CH 3 NHCOt-C 4 H β CH 3 CH 3 CH 3 op Cl
Table D3: Compounds of the formula IVa
Comp. Ri R 15 R 16 Physical
No. data
M.p. °C D3.050 B3 CF 3 CH 2 OC 4 H 9
D3.051 B4 OCH 3 OCH3
D4: Com ounds of the formula Via
D4.005 D2 CH 3 CH 3 CH 3 o^>
OCH,
D4.007 D1 CH 3 CH 3 CH 3 OH^-CI
Cl
R15 R16 R17 Ria XR 4 Physical data M.p. °C
CH 3 CH 3 CH 3 F F o-Q
D4.012 D3 CH 3 CH 3 CH 3 CH 3
O -Q
D4.017 D2 CH 3 CH 3 CHa o N0 2
D4.018 D3 Cl Cl Cl
N
D4.019 D1 OCH 2 OCH 3 Si(CH 3 ) 3 OCH 2 OCH 3 oO- NO,
R 16 Rι 7 Rιβ XR 4 Physical data M.p. °C CH 3 CH(CH 3 ) 2
Cl
O
Cl
D4.022 D1 OC(CH 3 ) 3 OCH 3 OCH 3
D4.023 D2 CH 3 SC(CH 3 ) 3 CH 3
D4.024 D3 Cl Cl CH 3 F F
F F
D4.025 D1 S0 2 -C(CH 3 ) 3 OCH 3 CH 3
D4.026 D2 CON(C 2 Hs) 2 CH 3 CH 3
R15 R16 R17 Riβ XR 4 Physical data CH 3 Cl CHa F F
F F
D4.031 D1 OCON(CH 3 ) 2 c 2 H 5 OC 2 H 5 °P CH
D4.032 D2 OCH 3 OCH 3 OCH 3
D4.033 D3 OCH 3 CH 3 CF 3
0-^-NO 2 3 C
Table D5: Compounds of the formula Villa
Table E1 : Compounds of the formula la:
XFU Physical data
M.p. "C
CH 3 CH 3
E1.004 CH 3 CH 2 θC 4 H 9 CH 3 CH 2 OC4H 9 CH 3
E1.005 CH 3 CH 2 N(CH 3 )2 CH 3 CH 2 (C2H 6 )2 CH 3 o OCH 3
E 1.006 C2H 5 CHzOCsH CaHs CH2OC3H7 C2H5 oP
CH 3
E1.007 CON(CH 3 ) 2 Cl Cl OC3H7 OCH 3 o^ ~cι
Cl
R 16 R 1 Riβ R19 R 4 Physical data
M.p. °C CH 3 OCH 3 CHa OCH3 l
E1.009 F F F F F F F
°
E1.010 NH 2 Cl Cl Cl Cl
E1.01 1 CH 3 CH 3 Br CH 3 CH 3 CH 3
0 -
CH 3
E1.013 OCH3 COCH3 0-t-C 4 H 9 CH 3 OCH3
E1.016 F F CH 3 F F F F
0 p~?
F F
E1.018 Cl
^-N
N0 2
R 19 XRA Physical data M.p. °C i-CaH 7
E1.022 Cl Cl OCH 3 Cl Cl
E1.025 OCH2CβH 5 Cl CaHs Cl CH 3
E1.028 CH 3 CHO OCHa 0CH 3 0CH 3
E1.029 COOH F F
F F
1i9 XFU Physical data
M.p. °C SCH 3 SCH 3 SCH 3 SCH 3
E1.031 CH 3 CH 3 CH 3 CH 3 CH 3
E1.038 OCO-t-C 4 H 9 Cl CH 3 Cl C 2 H 5
E1.039 OCH 3 CH 3 CH 3
Riβ Ru Riβ Rn
CH 3 CH 3 CH 3 CH 3
E1.043 OCOCH 3 CH 3 CH 3 Cl CH 3 θ }-t-C 4 H 9
E1.044 OCHa OCH 3 OSi(CH 3 ) 2 -t- CH , 3 , 0O -^, O UCCHH33 /=\
E1.046 Cl OCH 3 CONHC 4 H 9 OCH 3 Cl
E1.049 OCH 3 CH 3 CH 3 S0 N(C 2 H 5 ) 2 CH 3 o -O F Cl
Table E2: Compounds of the formula lb:
XR 4
E2.004 CH 3 CH 2 OC 4 H9 CH 3 CH 2 OC 4 Hg CH 3
E2.005 CH 3 CH 2 N(CH 3 ) 2 CH 3 CH a N(C2Hβ) 2 CH 3 op OCH 3
E2.006 C 2 H 5 CH 2 OC 3 H 7 C 2 H 5 CH 2 0C 3 H 7 C 2 H 5 o CH 3
E2.007 CON(CH3) 2 ci Cl OC 3 H 7 OCH 3 o-^-α
Cl
E2.008 OCH 3 CH 3 OCH 3 CH 3 OCH 3
E2.009 F F F F F F F
° F E2.010 NH 2 Cl Cl Cl Cl 0-n-C 4 H 9 oP
Comp. '15 R 16 Rl7 R 18 V9 XR 4
No. E2.01 1 CH 3 CH 3 Br CH 3
E2.013 OCH 3 COCH 3 O-t-C 4 H 9 CH 3
E2.018 F F Cl
E2.019 OH CH 3 CH 3 OH
E2.020 i-C 3 H 7 N(CH 3 )CO- i-C 3 H 7 N(CH 3 )CO- i
E2.021 F F OH F o
Comp. Ri. R 16 Rl7 1β "19 XR 4
No. E2.022 Cl Cl OCH 3 Cl Cl
E2.025 OCH 2 2 C-. 6 βHπ5 Cl C 2 2 Hri5 Cl CH 3
E2.026 NHCON(CH 3 ) 2
E2.028 CH 3 CHO OCH 3 OCH 3 OCH 3 F F
F F
E2.030 SCH 3 SCH 3 SCH 3 SCH 3 SCH 3 F F
0 p ?
F F
E2.031 CH 3 CH 3 CH 3 CH 3 CH 3
Comp. R15 Ri6 Rι Riβ R19 Λ *
No. E2.032 OH Cl CH 3 Cl CH 3 °P CH,
E2.033 NH, s^
E2.034 OCH 3 CHO OCH 3 CH 3 OCH 3 o^ NO,
F 3 C
E2.035 C 2 H 5 N
E2.036
E2.037 F F Si(CH 3 ) 3 F F F o -
F E2.038
E2.039 OCH 3 CH 3 CH 3
E2.041 CH 3 CH 3 CH 3 CH 3 CH 3
E2.042 F F F F F F F
F F op F
Comp. R 15 R 16 R 17 Riβ R19 XR
No. E2.054 Cl OCH 3 CON(CaH 5 ) 2 OCH 3 Cl
E2.055 CH 3 C 2 H 5 CH 3 CH 3 CH 3
E2.057 OCO (C 2 H 5 ) 2 CH 3 CH 3 oco fCsHs), CH 3
Table E3: Compounds of the formula la:
Cl
E.— S N (IVa) x — /
Cl
Comp. R 6 ^17 118 H9 Physical No. data M.p. °C
E3.001 CH 3 CH 3 CH, CH, CH 3 CH 3
(CH r.
Riβ R19 XR 4
Cl Cl F op F
Comp. Rιs R16 u Riβ R19 XR4
No.
E4.004 CH 3 CH 2 OC 4 H 9 CH 3 CH 2 OC 4 H 9 CH 3
E4.005 CH 3 CH 2 N(CH 3 ) 2 CH 3 CH 2 N(C2H5)2 CH 3
E4.006 C 2 2H1 15 CH 2 OCaH 7 C 2 Hs CH 2 OC 3 H 7 C 2 2 Hri5 0-
CH 3
E4.007 CON(CH 3 ) 2 Cl Cl OC 3 H 7 OCH 3 o- -ci
Cl
E4.008 OCHa CH 3 OCH 3 CH, OCH 3
E4.010 NH 2 Cl Cl Cl Cl
E4.011 CH 3 CH 3 Br CH 3 CH 3
E4.013 OCHa COCHa O-t-C 4 H 9 CH 3 OCH 3
Riβ R19 XR 4
E4.016 F F CH 3 F F F F
F F
E4.018 Cl °P
E4.020 i-C 3 H 7 N(
E4.022 Cl Cl OCH 3 Cl Cl
E4.024 Cl Cl SCH 3 Cl Cl F F
0- }-F
F F
t18 nig XR 4
Cl CH 3
E4.028 CH 3 CHO OCH 3 OCH 3 OCH 3
E4.030 SCH 3 SCH 3 SCH 3 SCH 3 SCH 3 F F
°V F T F
E4.031 CH 3 CH 3 CH 3 CH 3 CH 3
E4.032 OH Cl CHa Cl CH 3 -CH,
E4.033 NH 2 s^
E4.034 OCH 3 CHO OCH 3 CH 3 OCH 3
E4.035 C 2 H 5 N(CH 3 )COO- c 2 H 5 N(CH 3 )COO- C 2 H 5 l"C4H9 t-C 4 H 9 o -Q
19 XR 4
ci CH 3 Cl C ■ 22 Hns
CH 3 CH 3 CH 3 CH 3
E4.043 OCOCHa CH 3 CH 3 Cl CH 3
E4.044 OCH 3 OCH 3 OSi(CH 3 ) 2 CH 3 O ^ , OCH 3 =\
X J 0-( N VfCH COC
-t-C 4 H 9 '0-* v- 22
E4.045 F F Br
O F P,C
Comp. R 15 R16 R17 Riβ R19 XR
NO. E4.046 Cl OCH 3 CONHC 4 H 9 0CH 3 Cl F F
°p F F- F
E4.049 OCH 3 CH 3 CH 3 S0 2 N(C2H 5 )2 CH 3 o - F Cl
E4.051 F F CF 3 F F
E4.052 CO N(C 2 H 5 )2 CH 3 CH 3 CH 3 CH 3
E4.053 CH 3 CH 3 CH 3 CH 3 CH 3
NC
E4.054 Cl OCH 3 C0N(C 2 H 5 ) 2 QCH 3 Cl
E4.055 CH 3 C 2 2 Hπ5 CH 3 CH 3 CH 3
E4.056 CF 3 CF a OC 2 H 5 0- ^CH 2 -t-C 4 H g
Comp. R 15 R 16 R 17 t18 119 XR 4
No. E4.057 oco N(C 2 H 5 ) 2 CH a CH 3 OCO N(C 2 H S ) 2 CHa
Table E5: Compounds of the formula Villa
(Villa)
Comp. 15 R 16 Rl7 *1β NR 2 Rs Physic,
V|8 data No. .p. °C
Comp. Ru *16 Rl7 ie R 19 NR2R3 Physic. data No. M.p. °C
E5.040 OCOCHa CH 3 CH 3 Cl CH 3 NH 2 E5.041 OCH 3 OCH3 OSi(CH 3 ) 2 -t- CH 3 O OCH 3 NH 2
E5.042 F F Br F F NH 2 E5.043 Cl OCH3 CONHC 4 H 9 OCHa Cl NH 2 E5.044 -CN F F F F NH 2 E5.045 Cl Cl CβHs Cl Cl NH 2 E5.046 OCHa CH 3 CH 3 Sθ2N(C2H 5 )2 CH 3 NH 2
E5.048 F F CF 3 F F NH 2
E5.049 CO N(C2H 5 )2 CH 3 CH 3 CH 3 CH 3 NH 2 E5.050 Cl OCH 3 CO N(C2H 5 )2 OCHa Cl NH 2
E5.051 CH 3 C 2 Hs CH 3 CH 3 CHa NH 2
E5.052 CF 3 F CF 3 OC 2 H 5 F NH 2
E5.053 oco N(C 2 H 5 ) 2 CH 3 CH 3 OCO N(C 2 H 5 ) 2 CH 3 NH 2
F rmulation Exam l ive in redients the formula I % = ercent b wei ht
Emulsions of any desired concentration can be prepared from such concentrates by diluting them with water.
F2. Solutions a) b) c) d)
Active ingredient in accordance with Tables 5 %
1 -Methoxy-3-(3-methoxy- propoxy)propane
Polyethylene glycol MW 400 20 %
N-Methyl-2-pyrrolidone
Aromatic hydrocarbon 75 % 60 % mixture C 8 -C 12
The solutions are suitable for use in the form of microdrops.
F3. Wettable powders a) b) c) d)
Active ingredient in accordance with Tables 5 % 25 % 50 % 80 %
Sodium lignosulfonate 4 % - 3 %
Sodium lauryl sulfate 2 % 3 % - 4 %
Sodium diisobutylnaphthalenesulfonate - 6 % 5 % 6 %
Octylphenol polyglycol ether - 1 % 2 %
(7-8 mol of EO)
Highly disperse silica 1 % 3 % 5 % 10 %
Kaolin 88 % 62 % 35 %
The active ingredient is mixed thoroughly with the additives and the mixture is ground thoroughly in a suitable mill. This gives wettable powders which can be diluted with water to give suspensions of any desired concentration.
F4. Coated granules a) b) c)
Active ingredient in accordance with Tables 0.1 % Highly disperse silica 0.9 %
Inorganic carrier 99.0 %
(0 0.1 - 1 mm), for example CaCO 3 or SiO 2
The active ingredient is dissolved in methylene chloride, the solution is sprayed onto the carrier, and the solvent is subsequently evaporated in vacuo.
F5. Coated granules a) b) c)
Active ingredient in accordance with Tables 0.1 %
Polyethylene glycol MW 200 1.0 %
Highly disperse silica 0.9 %
Inorganic carrier 98.0 % (0 0.1 - 1 mm), for example CaCO 3 or SiO 2
In a mixer, the finely ground active ingredient is applied uniformly to the carrier which has been moistened with polyethylene glycol. This gives dust-free coated granules.
F6. Extruder granules a) b) c) d)
Active ingredient in accordance with Tables 0.1 %
Sodium lignosulfonate 1.5 %
Carboxymethylcellulose 1.4 %
Kaolin 97.0 %
The active ingredient is mixed with the additives, and the mixture is ground and moistened with water. This mixture is extruded and subsequently dried in a stream of air.
F7. Dusts a) b) c)
Active ingredient in accordance with Tables 0.1 % Talc 39.9 %
Kaolin 60.0 %
The ready-to-use dusts are obtained by mixing the active ingredient with the carriers and grinding the mixture in a suitable mill.
F8. Suspension concentrates a) b) c) d)
Active ingredient in accordance with Tables
Ethylene glycol
Nonyl phenol polyglycol ether
(15 mol of EO)
Sodium lignosulfonate
Carboxymethylcellulose
37% aqueous formaldehyde solution
Silicone oil emulsion
Water
The finely ground active ingredient is mixed intimately with the additives. This gives a suspension concentrate from which suspensions of any desired concentration can be prepared by diluting it with water.
Biological Examples
Example B1 : Herbicidal action before emergence of the plants (pre-emergence action) Monocotyledon and dicotyledon test plants are sown in standard soil in plastic pots. Immediately after sowing, the test substances are sprayed on in the form of an aqueous suspension (25% wettable powder, Example F3, b)), corresponding to a dosage of 2 kg of a.i./ha (500 I of water/ha). The test plants are subsequently grown in the greenhouse under optimal conditions. After a test period of 3 weeks, the experiment is evaluated using a nine- point scale (1 = complete damage, 9 = no action). Scores of 1 to 4 (in particular 1 to 3) mean a good to very good herbicidal activity. In this experiment, the compounds of the formula I show a good to very good herbicidal action. Examples of the herbicidal activity of the compounds of the formula I are given in the Table which follows:
Table B1 : Pre-emergence action:
Table Example Avena Setaria Sinapis Stellaria
A 1 4 5 A 2 2 1 A 3 2 5 A 5 3 3 A 9 1 1 A 10 2 6 A 11 4 2 A 13 4 2 A 15 3 9 2 A 16 6 4 2 A 19 2 3 1 A 20 4 7 2
Table Example Avena Setaria Sinapis Stellaria
Table Example Avena Setaria Sinapis Stellaria
The same results are obtained when the compounds of the formula I are formulated in accordance with Examples F1 to F2 and F4 to F8.
Example B2: Post-emergence herbicidal action
Monocotyledon and dicotyledon test plants are grown in the greenhouse in plastic pots containing standard soil and, in the 4- to 6-leaf stage, sprayed with an aqueous suspension of the test substances of the formula I, prepared with a 25% wettable powder (Example F3, b)), which corresponds to a dosage of 2 kg of a.i./ha (500 1 of water/ha). The test plants are subsequently grown on in the greenhouse under optimal conditions. After a test period of approximately 18 days, the experiment is evaluated using a nine-point scale (1 = complete damage, 9 = no action). Scores of 1 to 4 (in particular 1 to 3) mean a good to very good herbicidal action. In this experiment, a good to very good herbicidal activity is shown by the compounds of the formula I. Examples of the herbicidal activity of the compounds of the formula I are given in the Table which follows:
Table B2: Post-emergence action:
Table Example Avena Setaria Sinapis Sellaria
A1 1 1 5 2 3
A1 2 1 2 1 2
A1 5 2 5 2 3
Table Example Avena Setaria Sinapis Sellaria
The same results are obtained when the compounds of the formula I are formulated in accordance with Examples F1 to F2 and F4 to F8.
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