Note: Descriptions are shown in the official language in which they were submitted.
0050/49042
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Substituted 6-aryl-3-thioxo-5-(thi)oxo-2,3,4,5-tetrahydro-
1,2,4-triazines
The present invention relates to novel substituted
6-aryl-3-thioxo-5-(thi)oxo-2,3,4,5-tetrahydro-1,2,4-triazines of
the formula I
RZ X
S~ / Ar I,
N-N
Ri
where:
X is oxygen or sulfur;
25
R1 is C1-C6-alkyl, C1-C6-haloalkyl or phenyl which may, if
desired, carry one to three substituents, in each case
selected from the group consisting of vitro, halogen,
C1-C6-alkyl, C1-C6-haloalkyl and C1-C6-alkoxy;
R2 is amino, C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl,
C3-C6-alkynyl, (C1-C6-alkoxy)carbonyl-C1-C6-alkyl,
C1-C6-alkoxy-C1-C6-alkyl, C1-C6-alkylthio-C1-C6-alkyl or
C3-C6-cycloalkyl;
Ar is a substituted aryl radical of the formula Arl to Ar4:
R3 R3 R3 R3
3 5 ~ ~ R4 ~ ~ Y ~ ~ R4 ~ ~ R4
\ R~~ n
R5 i / N ~ i Z / N i N\ Z
R6
RB Rs
Arl Ar2 Ar3 Ar4
R3 is hydrogen or halogen;
0050/49042
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2
R4 is cyano, halogen, -CS-NHz, hydroxyl, C1-C6-alkoxy,
C1-C6-haloalkoxy, Cz-CQ-alkenyloxy, Cz-C4-alkynyloxy,
(C1-C4-alkoxy)carbonyl-Cl-CQ-alkoxy or benzyloxy which may
be unsubstituted or may carry one to three substituents
on the phenyl ring, in each case selected from the group
consisting of halogen, C1-C6-alkyl, C1-C6-alkoxy and
C1-C6-haloalkoxy;
R5 is hydrogen, nitro, cyano, amino, hydroxylamino, halogen,
C1-C6-alkyl, C1-C6-haloalkyl, formyl, -CH=N-OR9,
/ o~
-CH (ORl~) z, -\ -~- R11, Rlz , -CO-C1, -CO-OR13,
o~
-CO-ORla-CO_OR13, -CO-N (R15) -Ris, _CO_OR14-CO-N (R15) -Ri6,
-CHz-CH (Rl~) -CO-OR13, -CH=C (Rl~) -CO-OR13, -OCH (CH3) -COOH,
-OCH (CH3) -COOCH3, -N (Rz~) -R19, -SOz-C1, -SOz-N (R15) -R16,
~ ORZl
-CO-NH-OR15, -C , -CO-N(Rzz)-OR15 or
N-OR15
together with R4 is a chain O-CHz-CHz-O which may carry a
cyano, halogen, C1-C6-alkyl, oxo, hydroxycarbonyl or
(C1-C6-alkoxy)carbonyl substituent;
R6 is hydrogen, hydroxyl, C1-C6-alkyl, C1-C6-alkoxy,
(C1-C6-alkoxy)carbonyl-C1-C6-alkyl, C1-C6-alkoxy-
(C1-C6-alkoxy)carbonyl-C1-C6-alkyl, (C1-C6-alkoxy)-
carbonyl-C1-C6-alkoxy, C3-C6-alkenyl, C3-C6-alkynyl,
C3-C6-alkenyloxy or C3-C6-alkynyloxy;
R~ is hydrogen, C1-C6-alkyl or (C1-C6-alkoxy)carbonyl;
Re is hydrogen, hydroxyl, mercapto, halogen, C1-C6-alkyl,
C1-C6-alkoxy-C1-C6-alkyl, hydroxycarbonyl, hydroxy-
carbonyl-C1-C6-alkyl, (C1-C6-alkoxy)carbonyl-C1-C6-alkyl,
(C1-C6-alkoxy)carbonyl, C1-C6-alkoxy, C1-C6-alkoxy-
C1-C6-alkoxy, C3-C6-alkenyloxy, C3-C6-alkynyloxy,
(C1-C6-alkoxy)carbonyl-C1-C6-alkoxy, C1-C6-alkylthio,
(C1-C6-alkoxy)carbonyl-Cl-C6-alkylthio, C3-C6-alkenylthio,
C3-C6-alkynylthio, -N(Rz3)-R24, -CHz-CH(Rl~)-CO-OR13 or
-CH=C (Rl~) -CO-OR13;
n is zero or 1;
Y is oxygen or sulfur:
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3
Z is oxygen, sulfur or -N(Rzs)-
R9 is hydrogen, C1-C6-alkyl or
(C1-C6-alkoxy)carbonyl-C1-C6-alkyl;
R1° is C1-C6-alkyl;
Rli,Rlz independently of one another on position 4 or 5 of the
dioxolane ring are hydrogen, C1-C6-alkyl, hydroxycarbonyl
or (C1-C6-alkoxy)carbonyl;
RI3 is hydrogen, C1-C6-alkyl, C1-C6-haloalkyl,
C1-C6-alkoxy-C1-C6-alkyl, cyano-C1-C6-alkyl,
C3-C~-cycloalkyl, 3-oxetanyl, C3-C6-alkenyl,
C3-C6-haloalkenyl or C3-C6-alkynyl;
R14 is C1-C6-alkylene;
R15 is hydrogen or C1-C6-alkyl;
R16 is hydrogen, C1-C6-alkyl, C3-C~-cycloalkyl,
(C1-C6-alkoxy)carbonyl-C1-C6-alkyl, C1-C6-alkylsulfonyl or
together with R15 is a tetramethylene or pentamethylene
chain which may be interrupted by an oxygen bridge and/or
may be substituted by a (C1-C6-alkoxy)carbonyl group;
R1~ is hydrogen, halogen or C1-C6-alkyl;
R19 is C1-C6-alkylsulfonyl;
Rz° is hydrogen, C1-C6-alkyl or C1-C6-alkylsulfonyl;
R21~Rz2 independently of one another are C1-C6-alkyl,
(C1-C6-alkoxy)carbonyl-C1-C6-alkyl, C3-C6-alkenyl,
C3-C6-alkynyl or benzyl;
Rz3 is hydrogen or C1-C6-alkyl;
Rz4 is hydrogen, C1-C6-alkyl, (C1-C6-alkoxy)carbonyl-C1-C6-
alkyl, C3-C6-alkenyl, C3-C6-alkynyl or benzyl;
and also the agriculturally useful salts of the compounds I.
Furthermore, the invention relates to
- the use of these compounds I as herbicides or for the
desiccation/defoliation of plants,
0050/49042 ~ 02332352 2000-11-17
4
- herbicidal compositions and compositions for the
desiccation/defoliation of plants which comprise the
compounds I as active ingredients,
- methods for controlling undesirable vegetation and for the
desiccation/defoliation of plants using the compounds I,
- processes for preparing herbicidal compositions and
compositions for the desiccation/defoliation of plants using
the compounds I, and also
- novel intermediates of the formula Va'.
The two 6-phenyl-3-thioxo-5-(thi)oxo-2,3,4,5-tetrahydro-
1,2,4-triazines below are already known from the following
publications, but no details about any herbicidal properties have
been given:
HsC 0
s
H3~
~ Daunis et al.; BSCFAS; Bull. Soc. Chim. Fr.; 1972;
1511, 1513, 1514, 1517;
~ Prystas; Gut; CCCCAK; Collect. Czech. Chem. Commun. ~7
(1962), 1898, 1903;
~ Mansour; Ibrahim; JPCEAO; J. Prakt. Chem. ~1~, (1973),
221, 223;
~ Ibrahim; IJSBDB; Indian J. Chem. Sect. B, ~,4 (1976),
273;
H3
S~_N
H3~
~ Prystas; Gut; CCCCAK; Collect. Czech. Chem. Commun. 27
(1962), 1898, 1903;
~ Daunis et al.; BSCFAS; Bull. Soc. Chim. Fr.; 1972;
1975, 1980-1982.
0050/49042 ~ 02332352 2000-11-17
WO 94/03454 describes herbicidally active triazinones, inter alia
of the formula II
5 Ra 0
C1-C4-alkyl
S ~ ~ Q II,
C1-C4-haloalkyl N-N
where Ra is C1-C4-alkyl, C1-C4-haloalkyl, C3-CQ-alkenyl or
C3-C4-alkynyl and Q is o-halophenyl which may carry 1 or 2 further
substituents or may have certain heterocycles fused-on.
EP-A 044 696 discloses herbicidally active trazinones, inter alia
compounds of the formula III:
O ~halogen/C1-CQ-alkyl/
C1-C4-alkoxy
C1-C4-alkoxy/N02/
C1-C4-alkylthio ~ ~ / C (halogen) 3) 0-2
di(C1-C4-alkyl)amino) i III
H2N/C1-C4-alkyl
Other herbicidally active triazinones are described in
U.S. 3,671,523, U.S. 3,966,715, U.S. 3,544,570 and also in
W. Oettmeier et al., Pestic. Sci. ~, (1991), 399-409.
Finally, JP-A 10/053 508 discloses 1,2,4-triazines of the
formula X
Rb O H/halogen
N
O~~ ~ ~ halogen
S N -N
(O/S/SO/SOz) -Rd
Rc
where Rb is C1-CQ-alkyl, C2-C4-alkenyl, C2-C4-alkynyl or
C1-C4-haloalkyl, Rc is hydrogen or Rb and Rd are, inter alia, H,
C1-C6-alkyl or -CH(C1-C4-alkyl)-COO(H/C1-C6-alkyl), and these
compounds are likewise ascribed herbicidal activity in this
publication.
0050/49042
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6
However, the herbicidal properties of the known herbicides with
regard to the harmful plants are not always entirely
satisfactory.
It is an object of the present invention to provide novel
herbicidally active compounds which allow better selective
control of undesirable plants. The object also extends to
providing novel compounds which have desiccant/defoliant action.
We have found that these objects are achieved by the subtituted
6-aryl-3-thioxo-5-(thi)oxo-2,3,4,5-tetrahydro-1,2,4-triazines of
the formula I defined at the outset and their herbicidal action.
Furthermore, we have found herbicidal compositions which comprise
the compounds I and have very good herbicidal action. Moreover,
we have found processes for preparing these compositions and
methods for controlling undesirable vegetation using the
compounds I.
Furthermore, we have found that the compounds I are also suitable
for the desiccation and/or defoliation of parts of plants,
suitable plants being crop plants such as cotton, potato, oil
seed rape, sunflower, soybean or field beans, in particular
cotton. Thus, we have found compositions for the desiccation
and/or defoliation of plants, processes for preparing these
compositions and methods for the desiccation and/or defoliation
of plants using the compounds I.
Depending on the substitution pattern, the compounds of the
formula I can contain one or more chiral centers, in which case
they exist in the form of enantiomer or diastereomer mixtures.
For compounds I having at least one olefinic radical, E/Z isomers
may also be possible. The invention relates both to the pure
enantiomers or diastereomers and to mixtures thereof.
The substituted 6-aryl-3-thioxo-5-(thi)oxo-2,3,4,5-tetra-
hydro-1,2,4-triazines may be present in the form of their
agriculturally useful salts, the kind of salt usually not being
important. In general, the salts of I with those bases and those
acid addition salts are suitable where the herbicidal action is
not negatively affected in comparison to the free compound I.
Particularly suitable basic salts are those of the alkali metals,
preferably the sodium and potassium salts, of the alkaline earth
metals, preferably calcium and magnesium salts, of the transition
metals, preferably zinc and iron salts, and also ammonium salts,
where the ammonium ion may, if desired, carry one to four
C1-C4-alkyl, hydroxy-C1-C4-alkyl substituents and/or one phenyl or
CA 02332352 2000-11-17
0050/49042
7
benzyl substituent, preferably diisopropylammonium,
tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium
and trimethyl-(2-hydroxyethyl)aammonium salts, furthermore
phosphonium salts, sulfonium salts, such as, preferably,
tri-(C1-CQ-alkyl)sulfonium salts, and sulfoxonium salts such as,
preferably, tri-(C1-C4-alkyl)sulfoxonium salts.
Anions of useful acid addition salts are primarily chloride,
bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen
phosphate, hydrogen phosphate, phosphate, nitrate, hydrogen
carbonate, carbonate, hexafluorosilicate, hexafluorophosphate,
benzoate, and also the anions of C1-CQ-alkanoic acids, preferably
formate, acetate, propionate and butyrate.
The organic moieties mentioned in the definition of R1, R2 and R9
to Rz4 are collective terms for individual listings of the
individual group members. All carbon chains, i.e. all alkyl,
haloalkyl, alkoxy, haloalkoxy, alkylthio, alkylsulfonyl,
cyanoalkyl, hydroxycarbonylalkyl, alkoxycarbonyl, alkenyl,
alkynyl, alkenyloxy, alkynyloxy, alkenylthio and alkynylthio
moieties, can be straight-chain or branched. Halogenated
substituents preferably carry one to five identical or different
halogen atoms.
The term halogen represents in each case fluorine, chlorine,
bromine or iodine, preferably fluorine or chlorine.
Examples of other meanings are:
- C1-C6-alkyl: CH3, CZHS, n-propyl, CH(CH3)2, n-butyl,
CH (CH3) -CzHS, CHz-CH (CH3) Z, C (CH3) 3, n-pentyl, 1-methylbutyl,
2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl,
1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl,
1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl,
3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl,
1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl,
2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl,
2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl,
1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl, in
particular CH3, C2H5, n-propyl, CH(CH3)z, n-butyl, C(CH3)3,
n-pentyl or n-hexyl;
- C1-C6-haloalkyl: C1-C6-alkyl as mentioned above which is
partially or fully substituted by fluorine, chlorine, bromine
and/or iodine, i.e. for example, CHzF, CHF2, CF3, CHzCl,
CH (C1) 2, C (C1) 3, CHFC1, CF (C1) 2, CFZCl, CF2Br, 1-fluoroethyl,
2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl,
v 0050/49042
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8
2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-
2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-
2-fluoroethyl, 1,2-dichloroethyl, 2,2,2-trichloroethyl, CzFs,
2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl,
2,3-difluoropropyl, 2-chloropropyl, 3-chloropropyl,
2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl,
3,3,3-trifluoropropyl, 3,3,3-trichloropropyl, CH2-CzFS,
CF2-C2F5, 1- (f luoromethyl) -2-f luoroethyl, 1- (chloro-
methyl)-2-chloroethyl, 1-(bromomethyl)-2-bromoethyl,
4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl, n-C4F9,
5-fluoropentyl, 5-chloropentyl, 5-bromopentyl, 5-iodopentyl,
5,5,5-trichloropentyl, undecafluoropentyl, 6-fluorohexyl,
6-chlorohexyl, 6-bromohexyl, 6-iodohexyl, 6,6,6-trichloro-
hexyl or dodecafluorohexyl, in particular Cl-CZ-haloalkyl such
as CH2F, CHF2, CF3, CH2C1, 2-fluoroethyl, 2-chloroethyl,
1,2-dichloroethyl, 2,2,2-trifluoroethyl or C2F5;
- C3-C~-cycloalkyl: cyclopropyl, cyclobutyl, cyclopentyl,
cyclohexyl or cycloheptyl, in particular cyclopentyl or
cyclohexyl;
hydroxycarbonyl-C1-C6-alkyl: for example CHz-COOH, 2-hydroxy-
carbonyleth-1-yl, 2-hydroxycarbonylprop-1-yl, 3-hydroxy-
carbonylprop-1-yl, 1-hydroxycarbonylprop-2-yl, 2-hydroxy-
carbonylbut-1-yl, 3-hydroxycarbonylbut-1-yl, 4-hydroxy-
carbonylbut-1-yl, 1-hydroxycarbonylbut-2-yl, 1-hydroxy-
carbonylbut-3-yl, 2-hydroxycarbonylbut-3-yl, 1-hydroxy-
carbonyl-2-methylprop-3-yl, 2-hydroxycarbonyl-2-methyl-prop-
3-yl or 2-(hydroxycarbonylmethyl)prop-2-yl, in particular
2-hydroxycarbonylethyl;
cyano-C1-C6-alkyl: for example CH2CN, 1-cyanoeth-1-yl,
2-cyanoeth-1-yl, 1-cyanoprop-1-yl, 2-cyanoprop-1-yl,
3-cyanoprop-1-yl, 1-cyanoprop-2-yl, 2-cyanoprop-2-yl,
1-cyanobut-1-yl, 2-cyanobut-1-yl, 3-cyanobut-1-yl,
4-cyanobut-1-yl, 1-cyanobut-2-yl, 2-cyanobut-2-yl,
1-cyanobut-3-yl, 2-cyanobut-3-yl, 1-cyano-2-methylprop-3-yl,
2-cyano-2-methyl-prop-3-yl, 3-cyano-2-methylprop-3-yl or
2-cyanomethyl-prop-2-yl, in particular CH2CN or 2-cyanoethyl;
- C1-C6-alkoxy: C1-C4-alkoxy as mentioned above, and also, for
example, n-pentoxy, 1-methylbutoxy, 2-methylbutoxy,
3-methylbutoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy,
2,2-dimethylpropoxy, 1-ethylpropoxy, n-hexoxy, 1-methyl-
pentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy,
1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy,
2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy,
0050/49042 ~ 02332352 2000-11-17
9
1-ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethylpropoxy,
1,2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxy and
1-ethyl-2-methylpropoxy, in particular OCH3, OC2H5 or
OCH(CH3)2%
- C1-C6-haloalkoxy: a C1-C6-alkoxy radical as mentioned above
which is partially or fully substituted by fluorine,
chlorine, bromine and/or iodine, i.e. for example OCH2F,
OCHF2, OCF3, OCH2C1, OCH(C1)2, OC(C1)3, OCHFC1, OCF2C1,
OCF(C1)2, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy,
2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy,
2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy,
2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, OC2F5,
2-fluoropropoxy, 3-fluoropropoxy, 2,2-difluoropropoxy,
2,3-difluoropropoxy, 2-chloropropoxy, 3-chloropropoxy,
2,3-dichloropropoxy, 2-bromopropoxy, 3-bromopropoxy,
3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, OCH2-C2F5,
OCF2-C2F5, 1-(fluoromethyl)-2-fluoroethoxy, 1-(chloro-
methyl)-2-chloroethoxy, 1-(bromomethyl)-2-bromoethoxy,
4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy, n-C4F9,
5-fluoro-1-pentoxy, 5-chloro-1-pentoxy, 5-bromo-1-pentoxy,
5-iodo-1-pentoxy, 5,5,5-trichloro-1-pentoxy, undecafluoro-
pentoxy, 6-fluoro-1-hexoxy, 6-chloro-1-hexoxy,
6-bromo-1-hexoxy, 6-iodo-1-hexoxy, 6,6,6-trichloro-1-hexoxy
or dodecafluorohexoxy, in particular C1-C2-haloalkoxy such as
OCH2F, OCHF2, OCF3, CH2C1, 2-fluoroethoxy, 2-chloroethoxy,
1,2-dichloroethoxy, 2,2,2-trifluoroethoxy or OC2F5;
(C1-C6-alkoxy)carbonyl: for example CO-OCH3, CO-OC2H5,
CO-OCH2-C2H5, CO-OCH(CH3)2, n-butoxycarbonyl, CO-OCH(CH3)-C2H5,
CO-OCH2-CH (CH3) 2, CO-OC (CH3) 3, n-pentoxycarbonyl, 1-methyl-
butoxycarbonyl, 2-methylbutoxycarbonyl, 3-methylbutoxy-
carbonyl, 2,2-dimethylpropoxycarbonyl, 1-ethylpropoxy-
carbonyl, n-hexoxycarbonyl, 1,1-dimethylpropoxycarbonyl,
1,2-dimethylpropoxycarbonyl, 1-methylpentoxycarbonyl,
2-methylpentoxycarbonyl, 3-methylpentoxycarbonyl,
4-methylpentoxycarbonyl, 1,1-dimethylbutoxycarbonyl,
1,2-dimethylbutoxycarbonyl, 1,3-dimethylbutoxycarbonyl,
2,2-dimethylbutoxycarbonyl, 2,3-dimethylbutoxycarbonyl,
3,3-dimethylbutoxycarbonyl, 1-ethylbutoxycarbonyl,
2-ethylbutoxycarbonyl, 1,1,2-trimethylpropoxycarbonyl,
1,2,2-trimethylpropoxycarbonyl, 1-ethyl-1-methylpropoxy-
carbonyl or 1-ethyl-2-methylpropoxycarbonyl, in particular
CO-OCH3, CO-OC2H5, CO-OCH(CH3)2 or CO-OCH2-CH(CH3)2:
0050/49042 ~ 02332352 2000-11-17
- (C1-C6-alkoxy)carbonyloxy: O-CO-OCH3, O-CO-OCZHS,
n-propoxycarbonyloxy, 1-methylethoxycarbonyloxy,
n-butoxycarbonyloxy, 1-methylpropoxycarbonyloxy,
2-methylpropoxycarbonyloxy, 1,1-dimethylethoxycarbonyloxy,
5 n-pentoxy- carbonyloxy, 1-methylbutoxycarbonyloxy,
2-methylbutoxycarbonyloxy, 3-methylbutoxycarbonyloxy,
2,2-dimethylpropoxycarbonyloxy, 1-ethylpropoxycarbonyloxy,
n-hexoxycarbonyloxy, 1,1-dimethylpropoxycarbonyloxy,
1,2-dimethylpropoxycarbonyloxy, 1-methylpentoxycarbonyloxy,
10 2-methylpentoxycarbonyloxy, 3-methylpentoxycarbonyloxy,
4-methylpentoxycarbonyloxy, 1,1-dimethylbutoxycarbonyloxy,
1,2-dimethylbutoxycarbonyloxy, 1,3-dimethylbutoxycarbonyloxy,
2,2-dimethylbutoxycarbonyloxy, 2,3-dimethylbutoxycarbonyloxy,
3,3-dimethylbutoxycarbonyloxy, 1-ethylbutoxycarbonyloxy,
2-ethylbutoxycarbonyloxy, 1,1,2-trimethylpropoxycarbonyloxy,
1,2,2-trimethylpropoxy- carbonyloxy, 1-ethyl-1-methylpropoxy-
carbonyloxy or 1-ethyl- 2-methylpropoxycarbonyloxy, in
particular methoxycarbonyloxy, ethoxycarbonyloxy or
1-methylethoxycarbonyloxy;
- (C1-C6-alkoxy)carbonylthio: methoxycarbonylthio, ethoxy-
carbonylthio, n-propoxycarbonylthio, 1-methylethoxycarbonyl-
thio, n-butoxycarbonylthio, 1-methylpropoxycarbonylthio,
2-methylpropvxycarbonylthio, 1,1-dimethylethoxycarbonylthio,
n-pentoxycarbonylthio, 1-methylbutoxycarbonylthio,
2-methylbutoxycarbonylthio, 3-methylbutoxycarbonylthio,
2,2-dimethylpropoxycarbonylthio, 1-ethylpropoxycarbonylthio,
n-hexoxy- carbonylthio, 1,1-dimethylpropoxycarbonylthio,
1,2-dimethylpropoxycarbonylthio, 1-methylpentoxycarbonylthio,
2-methylpentoxycarbonylthio, 3-methylpentoxycarbonylthio,
4-methylpentoxycarbonylthio, 1,1-dimethylbutoxycarbonylthio,
1,2-dimethylbutoxycarbonylthio, 1,3-dimethylbutoxycarbonyl-
thio, 2,2-dimethylbutoxycarbonylthio, 2,3-dimethylbutoxy-
carbonylthio, 3,3-dimethylbutoxycarbonylthio, 1-ethylbutoxy-
carbonylthio, 2-ethylbutoxycarbonylthio, 1,1,2-trimethyl-
propoxycarbonylthio, 1,2,2-trimethylpropoxycarbonylthio,
1-ethyl-1-methyl-propoxycarbonylthio or 1-ethyl-2-methyl-
propoxycarbonylthio, in particular methoxycarbonylthio,
ethoxycarbonylthio or 1-methylethoxycarbonylthio;
- C1-C6-alkylthio: SCH3, SC2H5, SCHZ-CzHS, SCH (CH3) 2,
n-butylthio, SCH(CH3)-CzH5, SCHz-CH(CH3)2, 1,1-dimethylethyl-
thio, n-pentylthio, 1-methylbutylthio, 2-methylbutylthio,
3-methylbutylthio, 2,2-dimethylpropylthio, 1-ethylpropylthio,
n-hexylthio, 1,1-dimethylpropylthio, 1,2-dimethylpropylthio,
1-methylpentylthio, 2-methylpentylthio, 3-methylpentylthio,
4-methylpentylthio, 1,1-dimethylbutylthio, 1,2-dimethylbutyl-
0050/49042 ~ 02332352 2000-11-17
11
thio, 1,3-dimethylbutylthio, 2,2-dimethylbutylthio,
2,3-dimethylbutylthio, 3,3-dimethylbutylthio, 1-ethylbutyl-
thio, 2-ethylbutylthio, 1,1,2-trimethylpropylthio, 1,2,2-tri-
methylpropylthio, 1-ethyl-1-methylpropylthio or 1-ethyl-
2-methylpropylthio, in particular SCH3 or SC2H5;
- C1-C6-alkoxy-C1-C6-alkyl: C1-C6-alkyl which is substituted by
C1-C6-alkoxy as mentioned above, i.e, for example methoxy-
methyl, ethoxymethyl, n-propoxymethyl, (1-methylethoxy)-
methyl, n-butoxymethyl, (1-methylpropoxy)methyl,
(2-methylpropoxy)methyl, (1,1-dimethylethoxy)methyl,
2-(methoxy)ethyl, 2-(ethoxy)ethyl, 2-(n-propoxy)ethyl,
2-(1-methylethoxy)ethyl, 2-(n-butoxy)ethyl, 2-(1-methyl-
propoxy)ethyl, 2-(2-methylpropoxy)ethyl, 2-(1,1-dimethyl-
ethoxy)ethyl, 2-(methoxy)propyl, 2-(ethoxy)propyl,
2-(n-propoxy)propyl, 2-(1-methylethoxy)propyl, 2-(n-butoxy)-
propyl, 2-(1-methylpropoxy)propyl, 2-(2-methylpropoxy)propyl,
2-(1,1-dimethylethoxy)propyl, 3-(methoxy)propyl, 3-(ethoxy)-
propyl, 3-(n-propoxy)propyl, 3-(1-methylethoxy)propyl,
3-(n-butoxy)propyl, 3-(1-methylpropoxy)propyl,
3-(2-methylpropoxy)propyl, 3-(1,1-dimethylethoxy)propyl,
2-(methoxy)- butyl, 2-(ethoxy)butyl, 2-(n-propoxy)butyl,
2-(1-methylethoxy)butyl, 2-(n-butoxy)butyl, 2-(1-methyl-
propoxy)butyl, 2-(2-methylpropoxy)butyl, 2-(1,1-dimethyl-
ethoxy)butyl, 3-(methoxy)butyl, 3-(ethoxy)butyl,
3-(n-propoxy)butyl, 3-(1-methylethoxy)butyl, 3-(n-butoxy)-
butyl, 3-(1-methylpropoxy)butyl, 3-(2-methylpropoxy)butyl,
3-(1,1-dimethylethoxy)butyl, 4-(methoxy)butyl, 4-(ethoxy)-
butyl, 4-(n-propoxy)butyl, 4-(1-methylethoxy)butyl,
4-(n-butoxy)- butyl, 4-(1-methylpropoxy)butyl, 4-(2-methyl-
propoxy)butyl or 4-(1,1-dimethylethoxy)butyl, in particular
methoxymethyl or 2-methoxyethyl;
- C1-C6-alkoxy-C1-C6-alkoxy: C1-C6-alkoxy which is substituted
by C1-C6-alkoxy as mentioned above, i.e. for example methoxy
methoxy, ethoxymethoxy, n-propoxymethoxy, (1-methylethoxy)-
methoxy, n-butoxymethoxy, (1-methylpropoxy)methoxy,
(2-methylpropoxy)methoxy, (1,1-dimethylethoxy)methoxy,
2- (methoxy) ethoxy, 2- (ethoxy) ethoxy, 2- (n-propoxy) ethoxy,
2-(1-methylethoxy)ethoxy, 2-(n-butoxy)ethoxy, 2-(1-methyl-
propoxy)ethoxy, 2-(2-methylpropoxy)ethoxy, 2-(1,1-dimethyl-
ethoxy)ethoxy, 2-(methoxy)propoxy, 2-(ethoxy)propoxy,
2-(n-propoxy)propoxy, 2-(1-methylethoxy)propoxy,
2-(n-butoxy)propoxy, 2-(1-methylpropoxy)propoxy,
2-(2-methylpropoxy)propoxy, 2-(1,1-dimethylethoxy)propoxy,
3-(methoxy)- propoxy, 3-(ethoxy)propoxy, 3-(n-propoxy)-
propoxy, 3-(1-methylethoxy)propoxy, 3-(n-butoxy)propoxy,
0050/49042 ~ 02332352 2000-11-17
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3-(1-methylpropoxy)propoxy, 3-(2-methylpropoxy)propoxy,
3-(1,1-dimethylethoxy)propoxy, 2-(methoxy)butoxy,
2- (ethoxy) butoxy, 2- (n-propoxy) butoxy, 2- (1-methylethoxy) -
butoxy, 2-(n-butoxy)- butoxy, 2-(1-methylpropoxy)butoxy,
2-(2-methylpropoxy)butoxy, 2-(1,1-dimethylethoxy)butoxy,
3-(methoxy)butoxy, 3-(ethoxy)- butoxy, 3-(n-propoxy)butoxy,
3-(1-methylethoxy)butoxy, 3-(n-butoxy)butoxy, 3-(1-methyl-
propoxy)butoxy, 3-(2-methylpropoxy)butoxy, 3-(1,1-dimethyl-
ethoxy)butoxy, 4-(methoxy)- butoxy, 4-(ethoxy)butoxy,
4-(n-propoxy)butoxy, 4-(1-methylethoxy)butoxy, 4-(n-butoxy)-
butoxy, 4-(1-methylpropoxy)butoxy, 4-(2-methylpropoxy)butoxy,
4-(1,1-dimethylethoxy)butoxy, 5-(methoxy)pentoxy,
5-(ethoxy)pentoxy, 5-(n-propoxy)pentoxy, 5-(1-methylethoxy)-
pentoxy, 5-(n-butoxy)pentoxy, 5-(1-methylpropoxy)pentoxy,
5-(2-methylpropoxy)pentoxy, 5-(1,1-dimethylethoxy)pentoxy,
6-(methoxy)hexoxy, 6-(ethoxy)hexoxy, 6-(n-propoxy)hexoxy,
5-(1-methylethoxy)hexoxy, 6-(n-butoxy)hexoxy, 6-(1-methyl-
propoxy)hexoxy, 6-(2-methylpropoxy)hexoxy or 6-(1,1-di-
methylethoxy)hexoxy, in particular methoxymethoxy or
ethoxymethoxy;
- (Cl-C4-alkoxy)carbonyl-Cl-C4-alkoxy: C1-C4-alkoxy, such as
OCH3, OC2Hg, OCH2-C2H5, OCH(CH3)z, OCH(CH3)-C2H5, OCH2-CH(CH3)2
or OC(CH3)3, which carries a radical CO-OCH3, CO-OCzHS,
CO-OCHZ-C2H5, CO-OCH(CH3)z, CO-O(CH2)2-C2H5, CO-OCH(CH3)-C2H5,
CO-OCHZ-CH(CH3)2 or CO-OC(CH3)3, i.e., for example,
OCH2-CO-OCH3, OCH(CH3)-CO-OCH3, OCH2-CO-OC2H5 or
OCH(CH3) -CO-OCZHS;
- (Ci-C6-alkoxy)carbonyl-Cl-C6-alkoxy: C1-C6-alkoxy which is
substituted by (C1-C6-alkoxy)carbonyl as mentioned above, i.e.
for example OCH2-CO-OCH3, OCH2-CO-OC2H5, OCH2-CO-OCHz-CZHS,
OCH2-CO-OCH(CH3)2, n-butoxycarbonylmethoxy, 1-(methoxy-
carbonyl)ethoxy, 2-(methoxycarbonyl)ethoxy, 2-(ethoxy-
carbonyl)ethoxy, 2-(n-propoxycarbonyl)ethoxy, 2-(n-butoxy-
carbonyl)ethoxy, 3-(methoxycarbonyl)propoxy, 3-(ethoxy-
carbonyl) propoxy, 3-(n-propoxycarbonyl)propoxy, 3-(n-butoxy-
carbonyl)propoxy, 4-(methoxycarbonyl)butoxy, 4-(ethoxy-
carbonyl)butoxy, 4-(n-propoxycarbonyl)butoxy, 4-(n-butoxy-
carbonyl)butoxy, 5-(methoxycarbonyl)pentoxy, 5-(ethoxy-
carbonyl)pentoxy, 5-(n-propoxycarbonyl)pentoxy, 5-(n-butoxy-
carbonyl)butoxy, 6-(methoxycarbonyl)hexoxy, 6-(ethoxy-
carbonyl)hexoxy, 6-(n-propoxycarbonyl)hexoxy or 6-(n-butoxy-
carbonyl)hexoxy, in particular OCHZ-CO-OCH3 or 1-(methoxy-
carbonyl)ethoxy;
0050/49042
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(C1-C6-alkoxy)carbonyl-C1-C6-alkyl: C1-C6-alkyl which is
substituted by (C1-C6-alkoxy)carbonyl as mentioned above,
i.e. for example methoxycarbonylmethyl, ethoxycarbonylmethyl,
1-(methoxy- carbonyl)ethyl, 2-(methoxycarbonyl)ethyl,
2-(ethoxycarbonyl)- ethyl, 3-(methoxycarbonyl)propyl,
4-(methoxycarbonyl)butyl, 5-(methoxycarbonyl)pentyl or
6-(methoxycarbonyl)hexyl;
- C1-C6-alkylthio-C1-C6-alkyl: C1-C6-alkyl which is substituted
by C1-C6-alkylthio as mentioned above, i.e. for example
CH2-SCH3, CH2-SC2H5, n-propylthiomethyl, CHz-SCH(CH3)Z,
n-butylthiomethyl, (1-methylpropylthio)methyl,
CH2-SCH2-CH(CH3)2, CH2-SC(CH3)3, 2-methylthioethyl,
2-ethylthioethyl, 2-(n-propylthio)ethyl,
2-(1-methylethylthio)ethyl, 2-(n-butylthio)ethyl,
2-(1-methylpropylthio)ethyl, 2-(2-methylpropylthio)ethyl,
2-(1,1-dimethylethylthio)ethyl, 2-(methylthio)propyl,
3-(methylthio)propyl, 2-(ethylthio)- propyl,
3-(ethylthio)propyl, 3-(propylthio)propyl, 3-(butyl-
thio)propyl, 4-(methylthio)butyl, 4-(ethylthio)butyl,
4-(n-propylthio)butyl or 4-(n-butylthio)butyl, in particular
2-(methylthio)ethyl;
- C1-C6-alkoxy-(C1-C6-alkoxy)carbonyl-C1-C6-alkyl:
(C1-C6-alkoxy)carbonyl-C1-C6-alkyl which is substituted by
C1-C6-alkoxy as mentioned above, i.e. for example
CHz-COOCH2-OCH3, CH2-COOCH2-OC2H5, CH2-COOCH2-OCH(CH3)2 or
CH2-COOCH2-OC(CH3)3;
- C3-C6-alkenyl: prop-1-en-1-yl, prop-2-en-1-yl, 1-methyl-
ethenyl, n-buten-1-yl, n-buten-2-yl, n-buten-3-yl, 1-methyl-
prop-1-en-1-yl, 2-methylprop-1-en-1-yl, 1-methylprop-2-en-
1-yl, 2-methylprop-2-en-1-yl, n-penten-1-yl, n-penten-2-yl,
n-penten-3-yl, n-penten-4-yl, 1-methylbut-1-en-1-yl,
2-methylbut-1-en-1-yl, 3-methylbut-1-en-1-yl, 1-methylbut-
2-en-1-yl, 2-methylbut-2-en-1-yl, 3-methylbut-2-en-1-yl,
1-methylbut-3-en-1-yl, 2-methylbut-3-en-1-yl, 3-methylbut-
3-en-1-yl, 1,1-dimethylprop-2-en-1-yl, 1,2-dimethylprop-
1-en-1-yl, 1,2-dimethylprop-2-en-1-yl, 1-ethylprop-1-en-2-yl,
1-ethylprop-2-en-1-yl, n-hex-1-en-1-yl, n-hex-2-en-1-yl,
n-hex-3-en-1-yl, n-hex-4-en-1-yl, n-hex-5-en-1-yl, 1-methyl-
pent-1-en-1-yl, 2-methylpent-1-en-1-yl, 3-methylpent-1-en-
1-yl, 4-methylpent-1-en-1-yl, 1-methylpent-2-en-1-yl,
2-methylpent-2-en-1-yl, 3-methylpent-2-en-1-yl, 4-methyl-
pent-2-en-1-yl, 1-methylpent-3-en-1-yl, 2-methylpent-3-en-
1-yl, 3-methylpent-3-en-1-yl, 4-methylpent-3-en-1-yl,
1-methylpent-4-en-1-yl, 2-methylpent-4-en-1-yl, 3-methylpent-
0050/49042 ~ 02332352 2000-11-17
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4-en-1-yl, 4-methylpent-4-en-1-yl, 1,1-dimethylbut-2-en-1-yl,
1,1-dimethylbut-3-en-1-yl, 1,2-dimethylbut-1-en-1-yl,
1,2-dimethylbut-2-en-1-yl, 1,2-dimethyl-but-3-en-1-yl,
1,3-dimethylbut-1-en-1-yl, 1,3-dimethylbut-2-en-1-yl,
1,3-dimethylbut-3-en-1-yl, 2,2-dimethylbut-3-en-1-yl,
2,3-dimethylbut-Z-en-1-yl, 2,3-dimethylbut-2-en-1-yl,
2,3-dimethylbut-3-en-1-yl, 3,3-dimethylbut-1-en-1-yl,
3,3-dimethylbut-2-en-1-yl, 1-ethylbut-1-en-1-yl, 1-ethyl-
but-2-en-1-yl, 1-ethylbut-3-en-1-yl, 2-ethylbut-1-en-1-yl,
2-ethylbut-2-en-1-yl, 2-ethylbut-3-en-1-yl, 1,1,2-tri-
methyl-prop-2-en-1-yl, 1-ethyl-1-methylprop-2-en-1-yl,
1-ethyl-2- methylprop-1-en-1-yl or 1-ethyl-2-methylprop-
2-en-1-yl, in particular allyl or 2-buten-1-yl;
- C2-C6-alkenyl: ethenyl or one of the radicals mentioned under
C3-C6-alkenyl, in particular ethenyl or prop-2-en-1-yl;
- C3-C6-haloalkenyl: C3-C6-alkenyl as mentioned above which is
partially or fully substituted by fluorine, chlorine, bromine
and/or iodine, i.e, for example 2-chloroallyl, 3-chloroallyl,
2,3-dichloroallyl, 3,3-dichloroallyl, 2,3,3-trichloroallyl,
2,3-dichlorobut-2-enyl, 2-bromoallyl, 3-bromoallyl,
2,3-dibromoallyl, 3,3-dibromoallyl, 2,3,3-tribromoallyl or
2,3-dibromobut-2-enyl, in particular 2-chloroallyl,
3-chloroallyl or 3,3-dichloroallyl;
- C3-C6-alkenyloxy: for example prop-1-en-1-yloxy,
prop-2-en-1-yloxy, 1-methylethenyloxy, n-buten-1-yloxy,
n-buten-2-yloxy, n-buten-3-yloxy, 1-methylprop-1-en-1-yloxy,
2-methylprop- 1-en-1-yloxy, 1-methylprop-2-en-1-yloxy,
2-methylprop- 2-en-1-yloxy, n-penten-1-yloxy, n-penten-
2-yloxy, n-penten- 3-yloxy, n-penten-4-yloxy, 1-methylbut-
1-en-1-yloxy, 2-methylbut-1-en-1-yloxy, 3-methylbut-
1-en-1-yloxy, 1-methyl-but-2-en-1-yloxy, 2-methylbut-2-en-
1-yloxy, 3-methylbut- 2-en-1-yloxy, 1-methylbut-3-en-1-yloxy,
2-methylbut-3-en- 1-yloxy, 3-methylbut-3-en-1-yloxy,
1,1-dimethylprop-2-en- 1-yloxy, 1,2-dimethylprop-1-en-
1-yloxy, 1,2-dimethylprop- 2-en-1-yloxy, 1-ethyl-prop-1-en-
2-yloxy, 1-ethylprop-2-en- 1-yloxy, n-hex-1-en-1-yloxy,
n-hex-2-en-1-yloxy, n-hex-3-en- 1-yloxy, n-hex-4-en-1-yloxy,
n-hex-5-en-1-yloxy, 1-methyl-pent-1-en-1-yloxy,
2-methyl-pent-1-en-1-yloxy, 3-methylpent- 1-en-1-yloxy,
4-methylpent-1-en-1-yloxy, 1-methylpent-2-en- 1-yloxy,
2-methylpent-2-en-1-yloxy, 3-methylpent-2-en-1-yloxy,
4-methylpent-2-en-1-yloxy, 1-methylpent-3-en-1-yloxy,
2-methylpent-3-en-1-yloxy, 3-methylpent-3-en-1-yloxy,
4-methylpent-3-en-1-yloxy, 1-methylpent-4-en-1-yloxy,
0050/49042 ~ 02332352 2000-11-17
2-methylpent-4-en-1-yloxy, 3-methylpent-4-en-1-yloxy,
4-methylpent-4-en-1-yloxy, 1,1-dimethylbut-2-en-1-yloxy,
1,1-dimethylbut-3-en-1-yloxy, 1,2-dimethylbut-1-en-1-yloxy,
1,2-dimethylbut-2-en-1-yloxy, 1,2-dimethylbut-3-en-1-yloxy,
5 1,3-dimethylbut-1-en-1-yloxy, 1,3-dimethylbut-2-en-1-yloxy,
1,3-dimethylbut-3-en-1-yloxy, 2,2-dimethylbut-3-en-1-yloxy,
2,3-dimethylbut-1-en-1-yloxy, 2,3-dimethylbut-2-en-1-yloxy,
2,3-dimethylbut-3-en-1-yloxy, 3,3-dimethylbut-1-en-1-yloxy,
3,3-dimethylbut-2-en-1-yloxy, 1-ethylbut-1-en-1-yloxy,
10 1-ethylbut-2-en-1-yloxy, 1-ethylbut-3-en-1-yloxy,
2-ethyl-but-1-en-1-yloxy, 2-ethylbut-2-en-1-yloxy,
2-ethylbut- 3-en-1-yloxy, 1,1,2-trimethyl-prop-2-en-1-yloxy,
1-ethyl- 1-methylprop-2-en-1-yloxy, 1-ethyl-2-methylprop-
1-en-1-yloxy or 1-ethyl-2-methylprop-2-en-1-yloxy, in
15 particular prop-2-en-1-yloxy;
- Cz-C4-alkenyloxy: ethenyloxy, prop-1-en-1-yloxy, prop-
2-en-1-yloxy, 1-methylethenyloxy, n-buten-1-yloxy,
n-buten-2-yloxy, n-buten-3-yloxy, 1-methylprop-1-en-1-yloxy,
2-methylprop-1-en-1-yloxy, 1-methylprop-2-en-1-yloxy or
2-methylprop-2-en-1-yloxy, in particular prop-2-en-1-yloxy;
- C3-C6-alkenylthio: for example prop-1-en-1-ylthio,
prop-2-en-1-ylthio, 1-methylethenylthio, n-buten-1-ylthio,
n-buten-2-ylthio, n-buten-3-ylthio, 1-methylprop-1-en-
1-ylthio, 2-methylprop- 1-en-1-ylthio, 1-methylprop-2-en-
1-ylthio, 2-methylprop- 2-en-1-ylthio, n-penten-1-ylthio,
n-penten-2-ylthio, n-penten-3-ylthio, n-penten-4-ylthio,
1-methylbut-1-en-1-yl- thio, 2-methylbut-1-en-1-ylthio,
3-methylbut-1-en-1-ylthio, 1-methylbut-2-en-1-ylthio,
2-methylbut-2-en-1-ylthio, 3-methylbut-2-en-1-ylthio,
1-methylbut-3-en-1-ylthio, 2-methylbut-3-en-1-ylthio,
3-methylbut-3-en-1-ylthio, 1,1-dimethylprop-2-en-1-ylthio,
1,2-dimethylprop-1-en-1-yl- thio, 1,2-dimethylprop-2-en-1-yl-
thio, 1-ethylprop-1-en-2-yl- thio, 1-ethylprop-2-en-1-ylthio,
n-hex-1-en-1-ylthio, n-hex-2-en-1-ylthio, n-hex-3-en-
1-ylthio, n-hex-4-en-1-ylthio, n-hex-5-en-1-ylthio,
1-methylpent-1-en-1-ylthio, 2-methylpent-1-en-1-ylthio,
3-methylpent-1-en-1-ylthio, 4-methylpent-1-en-1-ylthio,
1-methylpent-2-en-1-ylthio, 2-methylpent-2-en-1-ylthio,
3-methylpent-2-en-1-ylthio, 4-methylpent-2-en-1-ylthio,
1-methylpent-3-en-1-ylthio, 2-methylpent-3-en-1-ylthio,
3-methylpent-3-en-1-ylthio, 4-methylpent-3-en-1-ylthio,
1-methylpent-4-en-1-ylthio, 2-methylpent-4-en-1-ylthio,
3-methylpent-4-en-1-ylthio, 4-methylpent-4-en-1-ylthio,
1,1-dimethyl-but-2-en-1-ylthio, 1,1-dimethylbut-3-en-1-
ylthio, 1,2-dimethylbut-1-en-1-ylthio, 1,2-dimethylbut-
0050/49042
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2-en-1-ylthio, 1,2-dimethylbut-3-en- 1-ylthio,
1,3-dimethylbut-1-en-1-ylthio, 1,3-dimethylbut-2-en-
1-ylthio, 1,3-dimethylbut-3-en-1-ylthio, 2,2-dimethyl-
but-3-en-1-ylthio, 2,3-dimethylbut-1-en-1-ylthio,
2,3-dimethylbut-2-en-1-ylthio, 2,3-dimethylbut-3-en-1-ylthio,
3,3-dimethylbut-1-en-1-ylthio, 3,3-dimethylbut-2-en-1-ylthio,
1-ethylbut-1-en-1-ylthio, 1-ethylbut-2-en-1-ylthio, 1-ethyl-
but-3-en-1-ylthio, 2-ethylbut-1-en-1-ylthio, 2-ethylbut-
2-en-1-ylthio, 2-ethylbut-3-en-1-ylthio, 1,1,2-trimethylprop-
2-en-1-ylthio, 1-ethyl-1-methylprop-2-en-1-ylthio,
1-ethyl-2-methylprop-1-en-1-ylthio or 1-ethyl-2-methylprop-
2-en-1-ylthio, in particular prop-2-en-1-ylthio;
- C3-C6-alkynyl: for example prop-1-yn-1-yl, propargyl,
n-but-1-yn-1-yl, n-but-1-yn-3-yl, n-but-1-yn-4-yl,
n-but-2-yn-1-yl, n-pent- 1-yn-1-yl, n-pent-1-yn-3-yl,
n-pent-1-yn-4-yl, n-pent-1-yn- 5-yl, n-pent-2-yn-1-yl,
n-pent-2-yn-4-yl, n-pent-2-yn-5-yl, 3-methylbut-1-yn-3-yl,
3-methylbut-1-yn-4-yl, n-hex-1-yn- 1-yl, n-hex-1-yn-3-yl,
n-hex-1-yn-4-yl, n-hex-1-yn-5-yl, n-hex-1-yn-6-yl,
n-hex-2-yn-1-yl, n-hex-2-yn-4-yl, n-hex-2- yn-5-yl,
n-hex-2-yn-6-yl, n-hex-3-yn-1-yl, n-hex-3-yn-2-yl,
3-methylpent-1-yn-1-yl, 3-methylpent-1-yn-3-yl,
3-methyl-pent-1-yn-4-yl, 3-methylpent-1-yn-5-yl,
4-methylpent-1-yn- 1-yl, 4-methylpent-2-yn-4-yl or
4-methylpent-2-yn-5-yl, in particular propargyl;
- C3-C6-alkynyloxy: for example prop-1-yn-1-yloxy,
prop-2-yn-1-yloxy, n-but-1-yn-1-yloxy, n-but-1-yn-3-yloxy,
n-but-1-yn-4-yloxy, n-but-2-yn-1-yloxy, n-pent-1-yn-1-yloxy,
n-pent-1-yn-3-yloxy, n-pent-1-yn-4-yloxy, n-pent-1-yn-
5-yloxy, n-pent-2-yn-1-yloxy, n-pent-2-yn-4-yloxy,
n-pent-2-yn-5-yloxy, 3-methylbut- 1-yn-3-yloxy, 3-methylbut-
1-yn-4-yloxy, n-hex-1-yn-1-yloxy, n-hex-1-yn-3-yloxy,
n-hex-1-yn-4-yloxy, n-hex-1-yn-5-yloxy, n-hex-1-yn-6-yloxy,
n-hex-2-yn-1-yloxy, n-hex-2-yn-4-yloxy, n-hex-2-yn-5-yloxy,
n-hex-2-yn-6-yloxy, n-hex-3-yn-1-yloxy, n-hex-3-yn-2-yloxy,
3-methylpent-1-yn-1-yloxy, 3-methylpent- 1-yn-3-yloxy,
3-methyl-pent-1-yn-4-yloxy, 3-methylpent-1-yn- 5-yloxy,
4-methylpent-1-yn-1-yloxy, 4-methylpent-2-yn-4-yloxy or
4-methylpent-2-yn-5-yloxy, in particular prop-2-yn-1-yloxy;
- Cz-C4-alkynyloxy: ethynyloxy, prop-1-yn-1-yloxy or
prop-2-yn-1-yloxy, in particular prop-2-yn-1-yloxy;
0050/49042
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17
- C3-C6-alkynylthio: prop-1-yn-1-ylthio, prop-2-yn-1-ylthio,
n-but-1-yn-1-ylthio, n-but-1-yn-3-ylthio, n-but-1-yn-
4-ylthio, n-but-2-yn-1-ylthio, n-pent-1-yn-1-ylthio, n-pent-
1-yn-3-ylthio, n-pent-1-yn-4-ylthio, n-pent-1-yn-5-ylthio,
n-pent-2-yn-1-ylthio, n-pent-2-yn-4-ylthio, n-pent-2-yn-
5-ylthio, 3-methylbut-1-yn-3-ylthio, 3-methylbut-1-yn-4-yl-
thio, n-hex-1-yn-1-ylthio, n-hex-1-yn-3-ylthio, n-hex-1-yn-
4-ylthio, n-hex-1-yn-5-ylthio, n-hex-1-yn-6-ylthio,
n-hex-2-yn- 1-ylthio, n-hex-2-yn-4-ylthio, n-hex-2-yn-5-yl-
thio, n-hex- 2-yn-6-ylthio, n-hex-3-yn-1-ylthio, n-hex-3-yn-
2-ylthio, 3-methylpent-1-yn-1-ylthio, 3-methylpent-1-yn-
3-ylthio, 3-methylpent-1-yn-4-ylthio, 3-methylpent-1-yn-
5-ylthio, 4-methylpent-1-yn-1-ylthio, 4-methylpent-2-yn-
4-ylthio or 4-methylpent-2-yn-5-ylthio, in particular
prop-2-yn-1-ylthio;
- C1-C6-alkylene: for example methylene, 1,1-ethylene,
1,2-ethylene, 1,3-propylene, 2,2-propylene, 1,4-butylene,
1,5-pentylene or 1,6-hexylene, in particular methylene,
1,1-ethylene or 2,2-propylene.
With regard to the use of the substituted 6-aryl-3-thioxo-
5-(thi)oxo-2,3,4,5-tetrahydro-1,2,4-triazines I as herbicides
and/or as compounds having desiccant/defoliant action, the
variables preferably have the following meanings, in each case
either on their own or in combination:
X is oxygen;
R1 is C1-C6-alkyl, in particular methyl;
RZ is amino or C1-C6-alkyl, in particular amino or methyl;
Ar is Arl, Arz or Ar3;
R3 is halogen, in particular fluorine or chlorine;
R4 is halogen, in particular chlorine;
R5 is on the one hand hydrogen, nitro, amino, C1-C6-alkyl,
C1-C6-haloalkyl, formyl, -CH=N-OR9,
0
-CH ( OR1 ~ ) 2 , - C\ ~ R11, R12 , -CO-C 1, -CO-OR13 ,
O
-CO-OR14 -CO_OR13 , -CO-N ( R15 ) -Ri b or -N ( R2 ~ ) -Ri9 ,
CA 02332352 2000-11-17
0050/49042
18
on the other hand hydrogen, -CO-OR13, -OCH(CH3)-COOH,
-OCH (CH3) -COOCH3 or -N (R2o) _Rls;
R6 is hydrogen, hydroxyl, C1-C6-alkyl, C1-C6-alkoxy,
C3-C6-alkenyl or C3-C6-alkynyl,in particular
C3-C6-alkynyl;
R~ is hydrogen;
10Rg is hydrogen, C1-C6-alkyl or (C1-C6-alkoxy)carbonyl-
C1-C6-alkyl;
n is 1;
15Y is oxygen;
Z is oxygen or sulfur, in particular oxygen;
Rs is C1-C6-alkyl;
20
Rio Ri2 ~ Ris ~ R1s ~ R1s independently of one another
~ Rii are hydrogen or
~
C1-C6-alkyl;
R14 is methylene or 1,1-ethylene;
25
R2 ~ i s hydrogen .
Particular preference is given to the substituted
6-aryl-3-thioxo-5-oxo-2,3,4,5-tetrahydro-1,2,4-triazines of
the
30formulaIa ~= I where X = oxygen; R1, R2 = methyl; Ar = Arl;
R3 =
fluorine
and
R4
= chlorine},
in
particular
to
the
compounds
Ia.1 Ia.248 listed in Table 1 below:
to
40
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0050/49042
19
H3~ p F
S~ / / \ C1 Ia
N-N
H3C Rs
Table 1
No. -Rs m.p./1H NMR data
Ia.1 -H 6.48 (s, 1H),
7.20-7.35 (m, 2H),
8.02 (t, 1H)
Ia.2 -CHj
Ia.3 -CHz-C1
Ia.4 -CH(C1)2
Ia.S -C(C1)3
Ia . 6 -CH2-Br
Ia . 7 -CH (Br) 2
Ia.8 -CHO
Ia.9 -CH=N-OH
Ia.lO -CH=N-OCH3
Ia.l1 -CH=N-OC2Hs
Ia.l2 -CH=N-OCH2-CzHs
I a .13 -CH=N-OCH ( CH3 ) z
Ia.l4 -CH=N-OCHZ-CO-OCH3
Ia.l5 -CH=N-OCH2-CO-OC2Hs
Ia.l6 -CH=N-OCH(CH3)-CO-OCH3
Ia.l7 -CH=N-OCH(CH3)-CO-OCZHs
Ia .18 -CH (OCH3 ) 2
Ia.l9 -CH (OCzHs) 2
Ia.20 -CH(OCH2-C2HS)Z
Ia.21 1,3-dioxolan-2-yl
Ia.22 4-(CH3)-1,3-dioxolan-2-yl
Ia.23 4,5-(CH3)z-1,3-dioxolan-2-yl
Ia.24 4-(COOCH3)-1,3-dioxolan-2-yl
Ia.25 4-(COOC2H5)-1,3-dioxolan-2-yl
Ia.26 4,5-(COOCH3)2-1,3-dioxolan-2-yl
Ia.27 4,5-(COOCzHS)2-1,3-dioxolan-2-yl
Ia.28 -CN
0050/49042 ~ 02332352 2000-11-17
No. -R5 m.p./1H NMR data
Ia.29 -CO-C1
Ia.30 -COON
Ia.31 -CO-OCH3
Ia.32 -CO-OC2H5
Ia.33 -CO-OCHz-C2H5
Ia. 34 -CO-OCH (CH3) 2
Ia.35 -CO-OCH2-CH2-C2H5
Ia. 36 -CO-OCH (CH3) -C2H5
Ia.37 -CO-OCH2-CH(CH3)2
Ia.38 -CO-OC(CH3)3
Ia.39 -CO-OCHZ-CH2-CH2-CzHS
Ia.40 -CO-O(cyclopropyl)
Ia.41 -CO-O(cyclobutyl)
Ia.42 -CO-O(cyclopentyl)
Ia.43 -CO-O(cyclohexyl)
Ia.44 -CO-O(oxiran-3-yl)
Ia.45 -CO-OCHz-CH2-OCH3
Ia.46 -CO-OCH2-CHZ-OC2H5
Ia.47 -CO-OCHZ-CH2-OCH2-C2H5
Ia . 4 -CO-OCH2-CH2-OCH (CH3 ) 2
8
Ia.49 -CO-OCHz-CH=CH2
Ia.50 -CO-OCH2-CH2-CH=CHz
Ia.51 -CO-OCH(CH3)-CH=CH2
Ia . 52 -CO-OCH2-C (CH3 ) =CH2
Ia.53 -CO-OCHZ-CH=CH-CH3
Ia.54 -CO-OCH2-C-CH
I a . 5 -CO-OCH ( CH3 ) -C-CH
5
Ia.56 -CO-OCHz-C-C-CH3
Ia.57 -CO-OCHz-COOH
I a . 5 -CO-OCH (CH3 ) -COOH
8
Ia.59 -CO-OC(CH3)Z-COOH
Ia.60 -CO-OCHZ-CO-OCH3
I a . 61 -CO-OCH ( CH3 ) -CO-OCH3
Ia.62 -CO-OC(CH3)z-CO-OCH3
Ia.63 -CO-OCHz-CO-OC2H5
Ia. 64 -CO-OCH (CH3) -CO-OC2H5
Ia.65 -CO-OC(CH3)Z-CO-OCzHs
Ia.66 -CO-OCH2-CO-OCH2-CzH5
Ia.67 -CO-OCH(CH3)-CO-OCHz-C2H5
0050/49042 ~ 02332352 2000-11-17
21
No. -R5 m.p./1H NMR data
Ia.68 -CO-OC(CH3)2-CO-OCH2-C2H5
Ia.69 -CO-OCH2-CO-OCH(CH3)z
I a . 7 -CO-OCH ( CH3 ) -CO-OCH { CH3
0 ) 2
Ia.71 -CO-OC(CH3)2-CO-OCH(CH3)2
Ia.72 -CO-OCH2-CO-OCH2-CH2-C2H5
Ia.73 -CO-OCH(CH3)-CO-OCH2-CH2-C2H5
Ia.74 -CO-OC(CH3)2-CO-OCH2-CH2-C2H5
Ia.75 -CO-OCH2-CO-OCH(CH3)-C2H5
I a . 7 -CO-OCH ( CH3 ) -CO-OCH ( CH3
6 ) -C2H5
Ia.77 -CO-OC(CH3)2-CO-OCH(CH3)-C2H5
Ia.78 -CO-OCHZ-CO-OCH2-CH(CH3)2
I a . 7 -CO-OCH ( CH3 ) -CO-OCH2 -CH
9 ( CH3 ) 2
Ia.80 -CO-OC(CH3)2-CO-OCH2-CH(CH3)2
Ia.81 -CO-OCH2-CO-OC(CH3)3
Ia. 82 -CO-OCH (CH3) -CO-OC (CH3) s
Ia.83 -CO-OC(CH3)2-CO-OC(CH3)3
Ia.84 -CO-OCH2-CO-O(cyclopropyl)
Ia.85 -CO-OCH(CH3)-CO-O(cyclopropyl)
Ia.86 -CO-OC(CH3)Z-CO-0(cyclopropyl)
Ia.87 -CO-OCHz-CO-O(cyclobutyl)
Ia.88 -CO-OCH(CH3)-CO-O(cyclobutyl)
Ia.89 -CO-OC(CH3)2-CO-O(cyclobutyl)
Ia.90 -CO-OCHz-CO-O(cyclopentyl)
Ia.91 -CO-OCH(CH3)-CO-O(cyclopentyl)
Ia.92 -CO-OC(CH3)2-CO-O(cyclopentyl)
Ia.93 -CO-OCHZ-CO-O(cyclohexyl)
Ia.94 -CO-OCH(CH3)-CO-0(cyclohexyl)
Ia.95 -CO-OC(CH3)Z-CO-O(cyclohexyl)
Ia.96 -CO-OCHz-CO-O(oxetan-3-yl)
Ia.97 -CO-OCH (CH3) -CO-O (oxetan-3-yl)
Ia.98 -CO-OC(CH3)2-CO-0(oxetan-3-yl)
Ia.99 -CO-OCHz-CO-OCH2-CH2-OCH3
Ia.100 -CO-OCH(CH3)-CO-OCH2-CH2-OCH3
Ia.101 -CO-OC(CH3)z-CO-OCH2-CHz-OCH3
Ia.102 -CO-OCH2-CO-OCHz-CHZ-OC2H5
Ia.103 -CO-OCH(CH3)-CO-OCH2-CHz-OCzHs
Ia.104 -CO-OC(CH3)2-CO-OCHz-CHZ-OCzHS
Ia.105 -CO-OCH2-CO-OCH2-CH2-OCHz-CZHS
Ia.106 -CO-OCH(CH3)-CO-OCHZ-CHZ-OCHz-CZHS.
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No. -R5 m.p./1H NMR data
Ia.107 -CO-OC(CH3)z-CO-OCHz-CH2-OCHZ-C2H5
Ia.108 -CO-OCH2-CO-OCH2-CH2-OCH(CH3)2
Ia.109 -CO-OCH (CH3) -CO-OCH2-CH2-OCH
(CH3) 2
Ia.110 -CO-OC(CH3)2-CO-OCH2-CH2-OCH(CH3)2
Ia.111 -CO-OCHZ-CO-OCH2-CH=CHz
Ia . 112 -CO-OCH (CH3 ) -CO-OCH2-CH=CH2
Ia.113 -CO-OC(CH3)2-CO-OCHZ-CH=CH2
Ia.114 -CO-OCHZ-CO-OCH2-CH2-CH=CH2
Ia . 115 -CO-OCH (CH3 ) -CO-OCHZ-CHZ-CH=CH2
Ia.116 -CO-OC(CH3)2-CO-OCH2-CH2-CH=CHZ
Ia.117 -CO-OCH2-CO-OCH2-C(CH3)=CHz
Ia . 118 -CO-OCH (CH3 ) -CO-OCH2-C (CH3
) =CHZ
Ia.119 -CO-OC(CH3)2-CO-OCH2-C(CH3)=CHz
Ia.120 -CO-OCHZ-CO-OCH2-CH=CH-CH3
Ia. 121 -CO-OCH (CH3) -CO-OCHZ-CH=CH-CH3
Ia.122 -CO-OC(CH3)z-CO-OCH2-CH=CH-CH3
Ia.123 -CO-OCH2-CO-OCHz-C-CH
Ia .124 -CO-OCH (CH3 ) -CO-OCHZ-C-CH
Ia.125 -CO-OC(CH3)2-CO-OCHZ-C-CH
Ia.126 -CO-OCH2-CO-OCH2-C-C-CH3
Ia .127 -CO-OCH (CH3 ) -CO-OCH2-C-C-CH3
Ia.128 -CO-OC(CH3)2-CO-OCHz-C=C-CH3
Ia. 129 -CO-OCH2-CO-OCH (CH3) -C-CH
Ia . 13 -CO-OCH (CH3 ) -CO-OCH ( CH3
0 ) -C=CH
Ia . 131 -CO-OC (CH3 ) 2-CO-OCH (CH3 )
-C=CH
Ia.132 -CO-OCH2-COOH
Ia.133 -CO-OCH (CH3) -COON
Ia.134 -CO-OC(CH3)2-COON
Ia.135 -CO-NHz
Ia.136 -CO-NH-CH3
Ia. 137 -CO-N (CH3) 2
Ia.138 -CO-NH-CH2-CO-OCH3
Ia. 139 -CO-N (CH3) -CHZ-CO-OCH3
Ia.140 -CO-NH-CHz-CO-OC2H5
Ia.141 -CO-N (CH3) -CHz-CO-OC2H5
Ia . 14 -CO-NH-CH ( CH3 ) -CO-OCH3
2
Ia . 143 -CO-N (CH3 ) -CH ( CH3 ) -CO-OCH3
Ia. 144 -CO-NH-CH (CH3) -CO-OC2H5
I a . 14 -CO-N ( CH3 ) -CH ( CH3 ) -CO-OC2H5
I
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0050/49042
23
No. -RS m.p./1H NMR data
Ia.146 -CO-(pyrrolidin-1-yl)
Ia.147 -CO-(piperidin-1-yl)
Ia.148 -CO-(morpholin-4-yl)
Ia.149 -CO- [4- (COOCH3) pyrrolidin-1-yl)
Ia.150 -CO- [4- (COOC2H5) pyrrolidin-1-yl]
Ia . 151 -CHz-CH (CH3) -COOH
Ia. 152 -CHz-CH (C1) -COOH
Ia.153 -CHz-CH(CH3)-CO-OCH3
Ia.154 -CHZ-CH(C1)-CO-OCH3
Ia. 155 -CHz-CH (CH3) -CO-OC2H5
Ia.156 -CHZ-CH(C1)-CO-OCzHs
Ia.157 -CH=CHz-COON
Ia.158 -CH=C(C1)-COOH
Ia. 159 -CH=C (CH3) -COOH
Ia.160 -CH=CHz-CO-OCH3
Ia.161 -CH=C(C1)-CO-OCH3
Ia.162 -CH=C(CH3)-CO-OCH3
Ia.163 -CH=CH-CO-OC2H5
Ia.164 -CH=C(C1)-CO-OC2H5
Ia.165 -CH=C(CH3)-CO-OC2H5
Ia.166 -OCH(CH3)-COON 141-143C
Ia.167 -OCH(CH3)-CO-OCH3 124C
Ia.168 -NOz
Ia.169 -NH-OH
Ia.170 -NHz
Ia.171 -NH-SOz-CH3
Ia.172 -N(CH3)-SOz-CH3
Ia.173 -NH-SOz-C2H5
Ia .174 -N ( CH3 ) -SOz-CzH5
Ia.175 -NH-SOz-CHZ-C2H5
Ia.176 -N(CH3)-SOz-CHZ-CzHS
Ia.177 -NH-SOz-CH(CH3)z
Ia . 178 -N (CH3 ) -SOz-CH (CH3 ) z
Ia.179 -N(SOz-CH3)z
Ia.180 -N(SOz-CzHs)z
Ia.181 -N(SOz-CHz-CZHS)z
Ia.182 -N[SOz-CH (CH3) z) 2
Ia.183 -SOz-C1
Ia.184 -SOz-NHz
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0050/49042
24
No. -R5 m.p. /1H NMR data
Ia.185 -SOz-NH-CH3
Ia.186 -SOz-N(CH3)z
Ia.187 -SOz-NH-C2H5
Ia.188 -SOz-N(CZHS)z
Ia.189 -SOz-(pyrrolidin-1-yl)
Ia.190 -SOz-(piperidin-1-yl)
Ia. 191 -SOz- (morpholin-4-yl)
Ia.192 -SOz-NH-CHz-CO-OCH3
Ia.193 -SOz-N(CH3)-CHz-CO-OCH3
Ia.194 -SOz-NH-CHz-CO-OC2H5
Ia.195 -SOz-N(CH3)-CHz-CO-OC2H5
Ia.196 -SOz-NH-CH(CH3)-CO-OCH3
Ia.197 -SOz-N(CH3)-CH(CH3)-CO-OCH3
Ia.198 -SOz-NH-CH(CH3)-CO-OC2H5
I a . 19 -SOz-N ( CH3 ) -CH ( CH3 ) -CO-OCzH~
9
Ia. 200 -SOz- [2- (COOCH3) pyrrolidin-1-yl]
Ia.201 -SOz-[2-(COOCZHS)pyrrolidin-1-yl]
Ia.202 -CO-NH-OH
Ia.203 -CO-NH-OCH3
Ia.204 -CO-NH-OC2H5
Ia.205 -C(=N-OCH3)-OCH3
Ia.206 -C (=N-OC2H5) -OCH3
Ia.207 -C(=N-OCH3)-OCzHS
Ia.208 -C(=N-OC2H5)-OC2H5
Ia.209 -C(=N-OCH3)-OCHz-CzHS
Ia.210 -C (=N-OC2H5) -OCHz-C2H5
Ia.211 -C (=N-OCH3) -OCH (CH3) z
Ia.212 -C (=N-OC2H5) -OCH (CH3) 2
Ia.213 -C(=N-OCH3)-OCHz-CH=CHz
Ia.214 -C(=N-OCzHS)-OCHz-CH=CHz
Ia. 215 -C (=N-OCH3) -OCHz-C_--_CH
Ia. 216 -C (=N-OC2H5) -OCHz-C-CH
Ia.217 -C(=N-OCH3)-OCHZ-C6H5
Ia.218 -C(=N-OC2H5)-OCHz-C6H5
Ia.219 -C(=N-OCH3)-OCHZ-CO-OCH3
Ia.220 -C(=N-OC2H5)-OCHz-OCH3
Ia.221 -C(=N-OCH3)-OCHz-CO-OC2H5
Ia.222 -C(=N-OCzHS)-OCHz-CO-OC2H5
Ia.223 -C(=N-OCH3)-OCH(CH3)-CO-OCH3
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5.
No. -R m.p./1H NMR data
Ia.224 -C (=N-OC2H5) -OCH (CH3) -CO-OCH3
I a . 2 -C ( =N-OCH3 ) -OCH ( CH3 ) -CO-OC2H5
2 5
Ia. 226 -C (=N-OC2H5) -OCH (CH3) -CO-OC2H5
Ia.227 -CO-N(OCH3)-CH3
Ia. 228 -CO-N (OC2H5) -CH3
Ia.229 -CO-N(OCH3)-C2H5
Ia.230 -CO-N (OC2H5) -C2H5
Ia.231 -CO-N(OCH3)-CH2-C2H5
Ia.232 -CO-N(OC2H5)-CH2-C2H5
Ia.233 -CO-N(OCH3)-CH(CH3)2
Ia. 234 -CO-N (OC2H5) -CH (CH3) 2
Ia.235 -CO-N(OCH3)-CH2-CH=CH2
Ia.236 -CO-N(OC2H5)-CH2-CH=CH2
Ia . 237 -CO-N (OCH3 ) -CH2-C-CH
Ia . 2 -CO-N (OC2H5 ) -CH2-C-CH
3 8
Ia.239 -CO-N(OCH3)-CH2-C6H5
Ia.240 -CO-N(OC2H5)-CH2-C6H5
Ia.241 -CO-N(OCH3)-CH2-CO-OCH3
Ia.242 -CO-N(OC2H5)-CH2-CO-OCH3
Ia.243 -CO-N(OCH3)-CH2-CO-OC2H5
Ia.244 -CO-N(OC2H5)-CH2-CO-OC2H5
I a . 2 -CO-N ( OCH3 ) -CH ( CH3 ) -CO-OCH3
4 5
Ia . 246 -CO-N (OC2H5) -CH (CH3 ) -CO-OCH3
Ia.247 -CO-N(OCH3)-CH(CH3)-CO-OC2H5
Ia . 248 -CO-N (OC2H5) -CH (CH3 ) -CO-OC2H5
0050/49042
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26
Furthermore, particular preference is given to the substituted
6-aryl-3-thioxo-5-oxo-2,3,4,5-tetrahydro-1,2,4-triazines of the
formulae Ib to Im below, in particular to
- the compounds Ib.1 to Ib.248, which differ from the
corresponding compounds Ia.1 to Ia.248 only in that R3 is
chlorine:
H3C \ 0 C1
N _
s~ ~ ~ / Cl Ib
N-N
H3C R5
- the compounds Ic.1 to Ic.248, which differ from the
corresponding compounds Ia.1 to Ia.248 only in that R3 is
hydrogen:
H3C\ O
N _
s~ / ~ ~ 1 Ic
N-N
H3C R5
- the compounds Id.i to Id.248, which differ from the
corresponding compounds Ia.1 to Ia.248 only in that R4 is
cyano:
H3C\ O F
N
s~ ~ ~ ~ cN
- N ~ Id
H3C R5
- the compounds Ie.1 to Ie.248, which differ from the
corresponding compounds Ia.1 to Ia.248 only in that R3 is
chlorine and R4 is cyano:
0050/49042
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27
H3C\ O C1
N _
S ~ / ~ ~ C N Ie
/N - N
H3C R5
- the compounds If.1 to If.248, which differ from the
corresponding compounds Ia.1 to Ia.248 only in that R3 is
hydrogen and R4 is cyano:
H3C \ O
N -
/ ~ ~ CN If
N-N
H3C R5
- the compounds Ig.1 to Ig.248, which differ from the
corresponding compounds Ia.1 to Ia.248 only in that R2 is
amino:
H2N \ O F
N _
S~ / ~ ~ 1 Ig
N-N
H3C / R5
- the compounds Ih.1 to Ih.248, which differ from the
corresponding compounds Ia.1 to Ia.248 only in that R2 is
amino and R3 is chlorine:
HZN \ O C1
N _
S~ / ~ ~ ~ C1 Ih
N-N
H3C R5
- the compounds Ii.1 to Ii.248, which differ from the
corresponding compounds Ia.l to Ia.248 only in that Rz is
amino and R3 is hydrogen:
0050/49042
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28
HzN \ O
N _
S~ / ~ / C1
-N ~ I i
H3C R5
- the compounds Ik.l to Ik.248, which differ from the
corresponding compounds Ia.1 to Ia.248 only in that R2 is
amino and R4 is cyano:
H2 \ O F
N _
/ ~ ~ CN Ik
N-N
H3C R5
- the compounds Im.i to Im.248, which differ from the
corresponding compounds Ia.1 to Ia.248 only in that R2 is
amino, R3 is hydrogen and R4 is cyano:
H2N 0
N _
/ ~ ~ N Im
~ -N
5
H3C R
Very particular preference is given to the compounds Ia.166,
Ia.167, Ib.166, Ib.167, Ic.166, Ic.167, Id.166, Id.167, Ie.166,
Ie.167, If.166, If.167, Ig.166, Ig.167, Ih.166, Ih.167, Ik.166,
Ik.167, Im.166 and Im.167.
Moreover, particular preference is given to the substituted
6-aryl-3-thioxo-5-oxo-2,3,4,5-tetrahydro-1,2,4-triazines of the
formula In f~ I where Ar = Ar2; n = 1; X,Y = oxygen; R1,R2 =
methyl; R3 = fluorine; R~ = hydrogen}, in particular to the
compounds In.1 to In.80 listed in Table 2 below:
0050/49042
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29
Table 2
H3C 0 F
\
N -
/ ~ / O In
-N
H3C N
R6~ 0
No . -R6
In.1 -H
In.2 -CH3
In.3 -C2Hs
In.4 -CHz-C2Hs
In. S -CH (CH3) 2
In.6 -CHz-CHz-CZHs
In.7 -CHz-CH(CH3)2
In.8 -CH(CH3)-CzHs
In.9 -CHz-CHz-CHz-CzHS
In.lO -CHz-CH=CHz
In . 11 -CH (CH3 ) -CH=CHz
In.l2 -CHz-C(CH3)=CHz
In.l3 -CHz-CH=CH-CH3
In. l4 -CHz-CH=C(CH3)z
In.lS -CHz-CHz-CH=CH-CH3
In.l6 -CHz-CHz-C(CH3)=CHz
In.l7 -CHz-C=CH
In. 18 -CH (CH3) -C=CH
In.l9 -CHz-C = C-CH3
In.20 -OH
In.21 -OCH3
In.22 -OCzHs
In.23 -OCHz-CzHs
In.24 -OCH(CH3)2
In.25 -OCHz-CHz-C2Hs
In.26 -OCH(CH3)-C2Hs
In.27 -OCHz-CH(CH3)z
In. 28 -OC (CH3) 3
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No . -R6
In.29 -OCH2-CH2-CH2-C2Hs
In.30 -OCH2-CH=CH2
5 In . 31 -OCH (CH3 ) -CH=CH2
In . 3 -OCH2-C ( CH3 ) =CH2
2
In.33 -OCH2-CH=CH-CH3
In.34 -OCH2-CH=C(CH3)2
In.35 -OCH2-CH2-CH=CH-CH3
10
In.36 -OCH2-CH2-CH2-CH=CH2
In.37 -OCH2-C=CH
In.38 -OCH (CH3) -C=CH
In.39 -OCH2-C = C-CH3
15 In.40 -CH2-CO-OCH3
In.41 -CH2-CO-OC2H5
In.42 -CH2-CO-OCH2-C2Hs
In.43 -CH2-CO-OCH(CH3)2
20 In.44 -CH2-CO-OCH2-CH2-C2Hs
In . 4 -CH2-CO-OCH ( CH3 ) -C2Hs
5
In.46 -CH2-CO-OCH2-CH(CH3)2
In.47 -CH2-CO-OC(CH3)s
2 In 4 8 -CH ( CH3 ) -CO-OCH3
5
In . 4 -CH ( CH3 ) -CO-OC2Hs
9
In. 50 -CH (CH3) -CO-OCH (CH3) 2
In.51 -CH(CH3)-CO-OCH2-C2Hs
In. 52 -CH (CH3) -CO-OCH2-CH2-C2H5
30 In . 53 -CH (CH3 ) -CO-OCH (CH3 ) -C2Hs
In.54 -CH(CH3)-CO-OCH2-CH(CH3)2
In. 55 -CH (CH3) -CO-OC (CH3) 3
In.56 -OCH2-CO-OCH3
In.57 -OCH2-CO-OC2Hs
In.58 -OCH2-CO-OCH2-C2H5
In.59 -OCH2-CO-OCH(CH3)2
In.60 -OCH2-CO-OCH2-CH2-C2Hs
In.61 -OCH2-CO-OCH(CH3)-C2Hs
In.62 -OCH2-CO-OCH2-CH(CH3)2
In.63 -OCH2-CO-OC (CH3) s
In . 64 -OCH ( CH3 ) -CO-OCH3
In . 6 -OCH ( CH3 ) -CO-OC2Hs
5
In.66 -OCH(CH3)-CO-OCH2-C2H5
In . 67 -OCH ( CH3 ) -CO-OCH ( CH3 )
2
'- 0050/49042
CA 02332352 2000-11-17
31
No . -R6
In.68 -OCH(CH3)-CO-OCHz-CHZ-C2H5
In . 6 -OCH ( CH3 ) -CO-OCHz-CH ( CH3
9 ) z
In . 7 -OCH ( CH3 ) -CO-OCH ( CH3 )
0 -CZHS
In . 71 -OCH ( CH3 ) -CO-OC ( CH3 ) 3
In.72 -CHz-CO-OCHz-CHz-OCH3
In.73 -CHz-CO-OCHz-CHz-OCZHS
In.74 -CHz-CO-OCHz-CHZ-OCHz-CzHS
In.75 -CHz-CO-OCHz-CHz-OCH(CH3)z
In.76 -CH(CH3)-CO-OCHz-CHz-OCH3
In.77 -CH(CH3)-CO-OCHz-CHz-OC2H5
In.78 -CH(CH3)-CO-OCHz-CHz-OCHz-C2H5
15In . 7 -CH (CH3 ) -CO-OCHz-CHz-OCH (
9 CH3 ) z
In.80 -CH(CH3)-CO-OCHz-CHz-OCHz-CHz-C2H5
Furthermore, very particular preference is given to the
substituted 6-aryl-3-thioxo-5-oxo-2,3,4,5-tetrahydro-1,2,4-tri-
azines of the formulae Io to Is below, in particular to
- the compounds Io.1 to Io.80, which differ from the
corresponding compounds In.1 to In.80 only in that R3 is
chlorine:
H3C'
N
S~ O
N Io
H3C
R6 O
40
- the compounds Ip.l to Ip.80 which differ from the
corresponding compounds In.1 to In.80 only in that R3 is
hydrogen:
- 0050/49042
CA 02332352 2000-11-17
32
H3C\ O
S N ~ ~ 0
Ip
/N-N
H3C N
R6 O
- the compounds Iq.i to Iq.80 which differ from the
corresponding compounds In.l to In.80 only in that n is zero:
H3C\ O F
N
S~ / 0
_ Iq
~N- N
H3C N O
R6
- the compounds Ir.1 to Ir.80 which differ from the
corresponding compounds In.1 to In.80 only in that n is zero
and R3 is chlorine:
H3C\ O C1
N
0 Ir
~N-N
H3C N O
R6
- the compounds Is.1 to Is.80 which differ from the
corresponding compounds In.l to In.80 only in that n is zero
and R3 is hydrogen:
H3C' O
N
S~ ~ ~ ~ 0 Is
/N-N
H3C N O
R6
Moreover, particular preference is given to the substituted
6-aryl-3-thioxo-5-oxo-2,3,4,5-tetrahydro-1,2,4-triazines of
the formulae It f~ I where X = oxygen; R1,R2 = methyl; Ar =
0050/49042
CA 02332352 2000-11-17
33
Ar3; R3 = fluorine and R4 = chlorine}, in particular to the
compounds It.1 to It.310 listed in Table 3 below:
10
20
30
40
0050/49042
CA 02332352 2000-11-17
34
Table 3
H3C O F
S N ~ ~ 1
It
N-N
H3C z~N
R8
No. Z . _Re
It.1 O -H
It.2 S -H
I t . 3 0 -CH3
It.4 S -CH3
It.5 0 -CzHS
It.6 S -C2H5
It.7 O -CHZ-CZHs
It.8 S -CHz-CZHs
It.9 O -CH(CH3)z
It.lO S -CH(CH3)2
It. l1 O -CHz-CHz-C2H5
It. l2 S -CHz-CHZ-CzHS
It. l3 0 -CH(CH3)-C2Hs
I t . 14 S -CH ( CH3 ) -C2Hs
It.lS 0 -CHZ-CH(CH3)z
It. l6 S -CHz-CH(CH3)z
It. 17 O -C (CH3) 3
It.l8 S -C (CH3) 3
It. l9 0 -CHz-CHz-CHz-C2Hs
It.20 S -CHz-CHz-CHz-C2H5
It.21 0 -CHz-OCH3
It.22 S -CHZ-OCH3
It.23 O -CHz-OCzHs
It.24 S -CHZ-OC2Hs
It.25 0 -CHz-OCHz-C2H5
It.26 S -CHZ-OCHz-CZHs
It.27 0 -CHz-OCH(CH3)2
It.28 S -CHz-OCH(CH3)2
0050/49042
CA 02332352 2000-11-17
No . Z -RB
It.29 O -CH2-OCHz-CHZ-C2H5
It:30 S -CHz-OCH2-CH2-CZHS
I t . 31 O -CHz-OCH ( CH3 ) -C2H5
It.32 S -CHz-OCH(CH3)-C2H5
It.33 O -CH2-OCHZ-CH(CH3)Z
It.34 S -CHz-OCHZ-CH(CH3)2
It.35 0 -CHZ-OC(CH3)3
It.36 S -CHz-OC(CH3)3
It.37 O -CHz-COOH
It.38 S -CH2-COOH
It.39 O -CH2-CHz-COOH
It.40 S -CH2-CH2-COOH
It.41 O -CHz-CHZ-CH2-COON
It.42 S -CH2-CH2-CH2-COOH
It.43 O -CH2-CHZ-CHz-CH2-COOH
It.44 S -CH2-CHZ-CH2-CHz-COOH
It.45 O -CH2-CO-OCH3
It.46 S -CHz-CO-OCH3
It.47 O -CH2-CO-OCzHS
It.48 S -CH2-CO-OCzHS
It.49 O -CH2-CO-OCH2-C2H5
It.50 S -CH2-CO-OCH2-C2H5
It.51 O -CH2-CO-OCH(CH3)2
It.52 S -CHz-CO-OCH(CH3)2
It.53 O -CH2-CO-OCH2-CHZ-CzHS
It.54 S -CHZ-CO-OCH2-CH2-C2H5
It.55 O -CH2-CO-OCH(CH3)-CzHS
It.56 S -CH2-CO-OCH(CH3)-CZHS
It.57 0 -CH2-CO-OCH2-CH(CH3)2
It.58 S -CH2-CO-OCH2-CH(CH3)2
It.59 0 -CHz-CO-OC(CH3)3
It.60 S -CHZ-CO-OC(CH3)3
It.61 O -CHZ-CO-OCH2-CHz-CH2-C2H5
It.62 S -CH2-CO-OCH2-CHZ-CHZ-C2H5
It.63 O -CH2-CHz-CO-OCH3
It.64 S -CH2-CH2-CO-OCH3
It.65 O -CH2-CH2-CO-OCH2-C2H5
It.66 S -CH2-CH2-CO-OCHz-CzHS
It.67 O -CH2-CH2-CO-OCH(CH3)2
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CA 02332352 2000-11-17
36
No . Z -RB
It.68 S -CHz-CHz-CO-OCH(CH3)2
It.69 O -CHz-CHz-CHz-CO-OCH3
It.70 S -CHz-CHz-CHz-CO-OCH3
It.71 O -CHz-CHz-CHz-CO-OCZHS
It.72 S -CHz-CHz-CHZ-CO-OC2H5
It.73 0 -CHz-CHz-CHz-CHZ-CO-OCH3
It.74 S -CHZ-CHz-CHZ-CHZ-CO-OCH3
It.75 O -CHz-CHz-CHz-CHz-CO-OC2H5
It.76 S -CHz-CHz-CHz-CHZ-CO-OC2H5
It.77 0 -COOH
It.78 S -COOH
It.79 O -CO-OCH3
It.80 S -CO-OCH3
It.81 O -CO-OCzH5
It.82 S -CO-OC2H5
It.83 O -CO-OCHz-C2H5
It.84 S -CO-OCHz-CzHS
It.85 O -CO-OCH(CH3)z
It.86 S -CO-OCH(CH3)z
It.87 O -CO-OCHz-CHz-CzHS
It.88 S -CO-OCHz-CHz-CZHS
It. 89 O -CO-OCH (CH3) -CzHS
I t . 9 S -CO-OCH ( CH3 ) -CZHS
0
It.91 O -CO-OCHZ-CH(CH3)2
It.92 S -CO-OCHz-CH(CHg)z
It.93 O -CO-OCHz-CHz-CHz-C2H5
It.94 S -CO-OCHz-CHz-CHZ-C2H5
It.95 O -OH
It.96 S -OH
It.97 O -OCH3
It.98 S -OCH3
It.99 O -OC2Hg
It.100 S -OC2H5
I t .1 O -OCH ( CH3 ) 2
O 1
I t .102 S -OCH (CH3 ) 2
It.103 O -OCHz-CHz-C2H5
It.104 S -OCHz-CHZ-C2H5
It.105 O -OCH (CH3) -CZHS
I t . 106 S -OCH (CH3 ) -C2H5
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CA 02332352 2000-11-17
37
NO. Z -Ra
It.107 O -OCH2-CH(CH3)z
It.108 S -OCH2-CH(CH3)2
It.109 0 -OC (CH3) 3
I t . 110 S -OC ( CH3 ) 3
It.111 O -OCH2-CH2-CH2-C2H5
It.112 S -OCH2-CHz-CH2-C2H5
It.113 0 -OCH2-CH2-OCH3
It.114 S -OCHz-CHZ-OCH3
It.115 O -OCH2-CH2-OCZHS
It.116 S -OCH2-CHZ-OC2H5
It.117 0 -OCH2-CO-OCH3
It.118 S -OCHZ-CO-OCH3
It.119 O -OCHz-CO-OCZHS
It.120 S -OCHz-CO-OCZHS
It.121 O -OCH2-CO-OCH2-CzHS
It.122 S -OCH2-CO-OCHZ-C2H5
I t .123 O -OCH2-CO-OCH (CH3 ) 2
I t .124 S -OCHz-CO-OCH (CH3 ) 2
It.125 O -OCHZ-CO-OCH2-CH2-CZHS
It.126 S -OCH2-CO-OCH2-CH2-C2H5
It.127 O -OCHz-CO-OCH(CH3)-C2H5
It.128 S -OCH2-CO-OCH(CH3)-CzH5
It.129 0 -OCH2-CO-OCH2-CH(CH3)2
It.130 S -OCHZ-CO-OCHZ-CH(CH3)2
It.131 O -OCH2-CO-OC(CH3)3
It.132 S -OCHZ-CO-OC(CHg)3
It.133 0 -OCHz-CO-OCH2-CH2-CH2-C2H5
It.134 S -OCH2-CO-OCHZ-CH2-CHz-CzHS
I t .13 O -OCH ( CH3 ) -CO-OCH3
I t .13 S -OCH ( CH3 ) -CO-OCH3
6
It.137 O -OCH(CH3)-CO-OC2H5
It.138 S -OCH(CH3)-CO-OCZH5
It . 139 O -OCH (CH3 ) -CO-OCH2-C2H5
I t .14 S -OCH ( CH3 ) -CO-OCHz-C2H5
0
I t .141 O -OCH ( CH3 ) -CO-OCH ( CH3 )
2
I t . 14 S -OCH ( CH3 ) -CO-OCH ( CH3 )
2 2
It.143 0 -OCH(CH3)-CO-OCHZ-CH2-C2H5
It.144 S -OCH(CH3)-CO-OCHz-CH2-C2H5
I t .14 O -OCH ( CH3 ) -CO-OCH ( CH3 )
5 -CzHS
0050/49042
CA 02332352 2000-11-17
38
No . Z -R8
I t . 14 S -OCH ( CH3 ) -CO-OCH ( CH3 )
6 -C2H5
I t .14 O -OCH ( CH3 ) -CO-OCH2-CH ( CH3
7 ) 2
I t . 14 S -OCH ( CH3 ) -CO-OCH2 -CH ( CH3
8 ) 2
I t . 14 O -OCH ( CH3 ) -CO-OC ( CH3 ) 3
9
I t . 15 S -OCH ( CH3 ) -CO-OC ( CH3 ) 3
0
It.151 O -OCH(CH3)-CO-OCH2-CH2-CH2-C2H5
It.152 S -OCH(CH3)-CO-OCH2-CH2-CH2-C2H5
It.153 O -OCH2-CH=CH2
It.154 S -OCH2-CH=CH2
I t .15 O -OCH ( CH3 ) -CH=CH2
I t .15 S -OCH ( CH3 ) -CH=CH2
6
It.157 O -OCH2-C(CH3)=CH2
It.158 S -OCH2-C(CH3)=CH2
It.159 O -OCH2-CH=CH-CH3
It.160 S -OCH2-CH=CH-CH3
It.161 O -OCH2-CH2-CH=CH2
It.162 S -OCH2-CH2-CH=CH2
I t .163 0 -OCH2-CH=C (CH3 ) 2
It.164 S -OCH2-CH=C(CH3)2
I t .16 O -OCH2-C~CH
5
I t .166 S -OCH2-C=CH
I t .16 O -OCH ( CH3 ) -C-CH
7
I t .16 S -OCH ( CH3 ) -C-CH
8
It.169 O -OCH2-C-C-CH3
It.170 S -OCH2-C-C-CH3
It.171 0 -SH
It.172 S -SH
It.173 O -SCH3
It.174 S -SCH3
It.175 O -SC2H5
It.176 S -SC2H5
It.177 .O -SCH2-C2H5
It.178 S -SCH2-C2H5
It.179 O -SCH (CH3) 2
It.180 S -SCH (CH3) 2
It.181 O -SCH2-CH2-C2H5
It.182 S -SCH2-CH2-C2H5
It.183 O -SCH(CH3)-C2H5
It.184 S -SCH(CH3)-C2H5
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39
No . Z -Rs
It. 185 O .-SCH2-CH (CH3) 2
I t . 186 S -SCH2-CH (CH3 ) z
It.187 O -SC(CH3)3
It. 188 S -SC (CH3) 3
It.189 O -SCH2-CH2-CH2-C2H5
It.190 S -SCH2-CHz-CHZ-C2H5
It.191 O -5CH2-CH=CH2
It.192 S -SCH2-CH=CH2
I t . 19 O -SCH ( CH3 ) -CH=CHZ
3
I t . 194 S -SCH (CH3 ) -CH=CHZ
It. 195 O -SCHz-C (CH3) =CH2
It.196 S -SCH2-C(CH3)=CH2
It.197 O -SCH2-CH=CH-CH3
It.198 S -SCH2-CH=CH-CH3
It.199 O -SCHz-CHz-CH=CHZ
It.200 S -SCH2-CH2-CH=CH2
I t . 2 O -SCH2-CH=C (CH3 ) 2
01
It.202 S -SCH2-CH=C (CH3) 2
I t . 2 O -SCHZ-C-CH
03
I t . 2 S -SCHZ-C-CH
04
It. 205 O -SCH (CH3) -C-CH
I t . 2 S -SCH (CH3 ) -C~CH
06
It.207 O -SCH2-C-C-CH3
It.208 S -SCHZ-C-C-CH3
It.209 O -SCH2-CO-OCH3
It.210 S -SCH2-CO-OCH3
It.211 O -SCH2-CO-OCzHS
It.212 S -SCH2-CO-OCZHS
It.213 0 -SCHZ-CO-OCHZ-C2H5
It.214 S -SCH2-CO-OCHZ-C2H5
It.215 O -SCH2-CO-OCH(CH3)2
It.216 S -SCH2-CO-OCH(CH3)z
It.217 O -SCH2-CO-OCH2-CH2-CzHS
It.218 S -SCH2-CO-OCHZ-CH2-C2H5
I t . 219 O -SCHZ-CO-OCH (CH3 ) -CzHS
It.220 S -SCHz-CO-OCH(CH3)-CzHS
It.221 O -SCH2-CO-OCH2-CH(CH3)2
It.222 S -SCH2-CO-OCHZ-CH(CH3)z
It.223 O -SCHZ-CO-OC(CH3)3
0050/49042
CA 02332352 2000-11-17
No . Z -Ra
It.224 S -SCH2-CO-OC(CH3)3
It.225 0 -SCHZ-CO-OCH2-CHZ-CHZ-CzHS
It.226 S -SCHz-CO-OCHz-CH2-CH2-C2H5
It.227 O -SCH (CH3) -CO-OCHg
I t . 2 S -SCH ( CH3 ) -CO-OCH3
2 8
It.229 O -SCH(CH3)-CO-OCzHS
It.230 S -SCH(CH3)-CO-OCZH5
I t . 2 O -SCH (CH3 ) -CO-OCH2-CzHS
31
I t . 2 S -SCH (CH3 ) -CO-OCH2-C2H5
32
It . 233 O -SCH (CH3) -CO-OCH (CH3) 2
It.234 S -SCH (CH3) -CO-OCH (CH3) Z
It.235 O -SCH(CH3)-CO-OCH2-CHz-CZHS
It.236 S -SCH(CH3)-CO-OCH2-CHz-C2H5
It.237 O -SCH (CH3) -CO-OCH (CH3) -C2H5
It.238 S -SCH (CH3) -CO-OCH (CH3) -CzHS
It.239 O -SCH (CH3) -CO-OCHZ-CH (CH3)
z
It.240 S -SCH (CH3) -CO-OCH2-CH (CH3)
2
It.241 O -SCH (CHj) -CO-OC (CH3) 3
It.242 S -SCH (CH3) -CO-OC (CH3) 3
It.243 O -SCH (CH3) -CO-OCH2-CH2-CH2-CZHS
It.244 S -SCH(CH3)-CO-OCHz-CH2-CHz-C2H5
It.245 O -NHz
It.246 S -NH-CH3
It. 247 O -N (CH3) 2
It.248 S -NH-C2H5
It.249 O -N(C2H5) 2
It.250 S -NH-CH2-CH=CH2
I t . 2 O -NH-CH2 -C-CH
51
It.252 S -NH2
It.253 O -NH-CH3
It.254 S -N(CH3)2
It.255 O -NH-C2H5
It.256 S -N(CzHS)2
It.257 O -NH-CHZ-CH=CHz
I t . 2 S -NH-CH2 -C=CH
5 8
It.259 O -NH-CH2-C6H5
It.260 S -NH-CHZ-C6H5
It.261 0 -NH-CH2-CO-OCH3
It.262 S -NH-CH2-CO-OCH3
0050/49042 ~ 02332352 2000-11-17
41
No. Z -Re
It.263 O -NH-CHZ-CO-OC2H5
It.264 S -NH-CH2-CO-OC2H5
It.265 O -N(CH3)-CH2-CO-OCZHS
It.266 S -N(CH3)-CH2-CO-OC2H5
It.267 O -N(CH3)-CHz-CO-OCH3
It.268 S -N(CH3)-CH2-CO-OCH3
I t . 2 O -NH-CH (CH3 ) -CO-OCH3
6 9
I t . 2 S -NH-CH ( CH3 ) -CO-OCH3
7 0
I t . 2 O -NH-CH ( CH3 ) -CO-OC2H5
71
It.272 S -NH-CH(CH3)-CO-OC2H5
It.273 O -N (CH3) -CH (CH3) -CO-OCH3
It.274 S -N(CH3) -CH (CH3) -CO-OCH3
I t . 2 O -N ( CH3 ) -CH ( CH3 ) -CO-OC2H5
7 5
I t . 2 S -N ( CH3 ) -CH ( CH3 ) -CO-OC2H5
7 6
It.277 O -C1
It.278 S -C1
It.279 O -Br
It.280 S -Br
It.281 O -CH2-CH(CH3)-COOH
It.282 S -CHz-CH(CH3)-COOH
It.283 O -CHz-CH(CH3)-CO-OCH3
It.284 S -CH2-CH(CH3)-CO-OCH3
It.285 O -CH2-CH(CH3)-CO-OC2H5
It.286 S -CH2-CH(CH3)-CO-OC2H5
It.287 O -CHz-CH(C1)-COOH
It.288 S -CH2-CH(C1)-COOH
It.289 O -CHZ-CH(C1)-CO-OCH3
It.290 S -CHZ-CH(C1)-CO-OCH3
It.291 O -CH2-CH(Cl)-CO-OCzHS
It.292 S -CH2-CH(C1)-CO-OCzHS
It.293 O -CH=CH-COOH
It.294 S -CH=CH-COOH
It.295 O -CH=CH-CO-OCH3
It.296 S -CH=CH-CO-OCHg
It.297 O -CH=CH-CO-OC2H5
It.298 S -CH=CH-CO-OC2H5
It.299 O -CH=C(CH3)-COOH
It.300 S -CH=C(CH3)-COON
It.301 O -CH=C(CH3)-CO-OCH3
0050/49042
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42
No . Z . -Re 1
It.302 S -CH=C(CH3)-CO-OCH3
It.303 O -CH=C(CH3)-CO-OC2H5
It.304 S -CH=C(CHg)-CO-OCzHS
It.305 O -CH=C(C1)-COOH
It.306 S -CH=C(C1)-COOH
It.307 O -CH=C(C1)-CO-OCH3
It.308 S -CH=C(C1)-CO-OCH3
It.309 O -CH-C(Cl)-CO-OCZHS
It.310 S -CH-C(C1)-CO-OC2H5
'_ 0050/49042
CA 02332352 2000-11-17
43
Furthermore, very particular preference is given to the
substituted 6-aryl-3-thioxo-5-oxo-2,3,4,5-tetrahydro-1,2,4-tri-
azines of the formulae Iu to Iy, in particular to
- the compounds Iu.1 to Iu.310, which differ from the
corresponding compounds It.l to It.310 only in that R3 is
chlorine:
H3 \ O C1
g N I ~ 1
/N-N ~ Iu
H3C Z I N
R8
- the compounds Iv.l to Iv.310, which differ from the
corresponding compounds It.1 to It.310 only in that R3 is
hydrogen:
H3C O
N
C ~ ~~ 1
-N ~ Iv
H3C Z~N
R8
- the compounds Iw.1 to Iw.310, which differ from the
corresponding compounds It.1 to It.310 only in that Ar is
Ar4:
H3C\ O F
S N ~ ~ 1
N-N Iw
H3C N~ Z
R
CA 02332352 2000-11-17
0050/49042
44
- the compounds Ix.1 to Ix.310, which differ from the
corresponding compounds It.1 to It.310 only in that Ar is Ar4
and R3 is chlorine:
H3C\ O C1
N ~ ~ 1
S
/N-N ~ Ix
H3C N~ Z
Ra
- the compounds Iy.i to Iy.310, which differ from the
corresponding compounds It.1 to It.310 only in that Ar is Ar4
and R3 is hydrogen:
H3C\ O
S N / ~ ~ 1
N-N ~ IY
H3C N'\ . Z
2 5 YIa
R
The substituted 6-aryl-3-thioxo-5-(thi)oxo-2,3,4,5-tetrahydro-
1,2,4-triazines of the formula I can be obtained in various ways,
in particular by one of the following processes:
35
A~ cyclocondensation of a 2,4-disubstituted thiosemicarbazide or
2-substituted thiocarboxyhydrazide IV with an arylglyoxylic
acid or a C1-C6-alkyl ester thereof (V):
0050/49042
CA 02332352 2000-11-17
z
RZ~ 0
RZSO R~~ RzsO
S + Ar S~ 0
5 ~-NH2 0 _ H20 N"'N--
Rl R1 r
IV V
VI
RZ~ O
10 VI
- RzsOH S~- ~ Ar
a
R
15 I ~X = O~
R25 is hydrogen or C1-C6-alkyl.
The reaction is usually carried out in an inert solvent/
20 diluent, for example in acetic acid, a lower alcohol, such as
methanol, ethanol, n-propanol and isopropanol, an ether, such
as tert-butyl methyl ether, tetrahydrofuran, dioxane and
1,2-diethoxyethane, an aprotic solvent, such as dimethyl
formamide, dimethyl sulfoxide and pyridine. With the
25 exception of tert-butyl methyl ether, mixtures of the above-
mentioned solvents/diluents with water are also suitable.
The reaction is generally carried out at from 20~C to the
boiling point of the reaction mixture in question.
The condensation of IV with V is usually catalyzed by acids,
suitable acids being in particular carboxylic acids, such as
formic acid and acetic acid, sulfonic acids, such as benzene-
sulfonic acid and p-toluenesulfonic acid, or mineral acids,
such as hydrochloric acid sulfuric acid and phosphoric acid.
The ring closure reaction from IV to I is usually catalyzed
by bases. Bases which are suitable for this purpose are, for
example, alkali metal carbonates, such as sodium carbonate,
alkali metal bicarbonates, such as sodium bicarbonate, and
alkali metal hydroxides, such as sodium hydroxide, but also
nitrogen bases such as triethylamine, dicyclohexylethylamine,
pyridine and 4-dimethylaminopyridine.
Reactions of this type are generally known, for example from
CA 02332352 2000-11-17
0050/49042
46
~ H. Neunhoeffer in A.R. Katritzky, Comprehensive
Heterocyclic Chemistry, vol. 3, p. 430 ff. and the
literature cited therein;
~ J. Gut and M. Prystas, Coll. Czech. Chem. Commun.
2986 (1959);
~ M. Tisler and Z. Vrbaski, J. Org. Chem. 2~, 770
(1960);
~ V.J. Ram and M. Nath, Ind. J. Chem. Vol. 34B,
p. 423-426 (1995);
~ WO 94/03454.
The arylglyoxylic acids and their alkyl esters (V) are known
or can be prepared in a manner known per se (cf., for
example, J.S. Nimitz & H.S. Mosher, J. Org. Chem. 4~ (1981),
211-213; W.M.P. Johnson & G. Holan, Aust. J. Chem. ~ (1981),
2363 and also X. Creary, J. Org. Chem. ~ (1987), 5026).
With respect to the particularly preferred active compounds I
where A = Arl, the compounds Va
R3
O
8250
R4 Va
O
R5
are of particular interest, in particular those where
R4 = chlorine and RS = OR18', where R1s' is hydrogen, methyl or
-CH(CH3) -COOCH3.
B~ Alkylation of a 6-aryltriazine derivative VII with an alkyl
halide or dialkyl sulfate R1-L:
R2~ O RZ 0
base N
S ~ Ar + Rl_L ---~- Rl-S~ ~ Ar + I {X = 0)
_ H-L -N
H
VII VII I (byproduct )
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47
L is chloride, bromide, iodide or O-S02-OR1.
Particularly suitable solvents/diluents are aprotic solvents,
such as N,N-dimethyl formamide, dimethyl sulfoxide,
acetonitrile, acetone, tetrahydrofuran, dioxane and
1,2-diethoxyethane.
The reaction is generally carried out at from 0°C to the
boiling point of the reaction mixture in question.
Such alkylations are generally known, for example from:
~ M. Prystas and J. Gut, Coll. Czech. Chem. Commun.
1898 (1962);
~ J. Daunis et al., Bull. Soc. Chim. Fr. ~Q, 3658
(1971) and also Bull. Soc. Chim. Fr. ~>,., 1511
(1972);
~ A.K. Mansour and Y.A. Ibrahim, Journal f. prakt.
Chemie 1~5, 221 (1973) .
The 6-aryltriazine derivatives VII can be advantageously
prepared by condensation of thiocarboxyhydrazides (R2 = NH2)
or 4-monosubstituted thiosemicarbazides IX with V similarly
to process A~:
R~ O
NH R~ 50
g~ -~- Ar ~'1'~ ~ VII
O - HZO - RZSOH
H
IX V
Most of the thiosemicarbazides and thiocarboxyhydrazides Iv
and IX are known, but they can also be prepared in a manner
known per se (cf., for example, K.A. Jensen et al., Acta
Chemica Scandinavica ?~ (1968), 1 and also C.-J. Kroger et
al., Liebigs Ann. Chem. 43 (1961), 121).
Cy Thiolation of a 6-aryl-3-thioxo-5-oxo-2,3,4,5-tetrahydro-
1,2,4-triazine ~cf., for example, M. Prystas & J. Gut, Coll.
Czech. Chem. Commun. 27 (1962), 1898; J. Jonas & J. Gut,
0050/49042
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48
Coll. Czech. Chem. Commun. ~.Z (1962), 1886; C. Tzeng et al.,
J. Org. Chem. ~ (1983), 1271}:
I {X = O} sulfurization
--~ I {X = S}
The sulfurization is generally carried out in an inert
solvent/diluent, for example in an aromatic hydrocarbon, such
as toluene and the xylenes, or in an organic amine, such as
pyridine.
Particlarly suitable sulfurizing agents are phosphorus(V)
sulfide and 2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-diphos-
phetan 2,4-disulfide ("Lawesson's reagent").
Usually, 1 to 5 times the molar amount of sulfurizing agent,
based on the starting material I to be sulfurized {X = O}, is
sufficient for a virtually complete reaction.
The reaction temperature is normally at from 20~C to the
boiling point of the reaction mixture in question.
If not stated otherwise, all the processes described above are
advantageously carried out under atmospheric pressure or under
the autogenous pressure of the reaction mixture in question.
Usually, the substituted 6-aryl-3-thioxo-5-(thi)oxo-2,3,4,5-
tetrahydro-1,2,4-triazines I can be prepared by one of the above-
mentioned synthesis processes. However, for economical or
technical reasons it may be more advantageous to prepare some
compounds I from similar 6-aryl-3-thioxo-5-(thi)oxo-2,3,4,5-
tetrahydro-1,2,4-triazines which, however, differ in particular
in the meaning of one of the radicals on Ar, the preparation
being carried out in a manner known per se, for example by
nitration, sulfonation, chlorosulfonation, halogenation,
alkylation, acylation, acetal hydrolysis, acetalization,
amidation, ester hydrolysis, condensation reactions, oxidation,
Peterson olefination, reduction, etherification, esterification,
Wittig reaction or Meerwein reaction.
The starting materials given for the individual processes are
either known or they can be obtained in a manner known per se or
by the method of one of the processes described.
Work-up of the reaction mixtures is usually carried out by
methods known per se, for example
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49
by diluting the reaction solution with water and subsequently
isolating the product by filtration, crystallization or solvent
extraction, or
by removing the solvent, partitioning the residue in a mixture of
water and a suitable organic solvent and work-up of the organic
phase to afford the product.
The substituted 6-aryl-3-thioxo-5-(thi)oxo-2,3,4,5-tetrahydro-
1,2,4-triazines I can be obtained as isomer mixtures in the
preparation; however, if desired, these can be separated into
largely pure isomers using customary methods such as
crystallization or chromatography, including chromatography over
an optically active adsorbate. Pure optically active isomers can
be prepared advantageously from suitable optically active
starting materials.
Agriculturally useful salts of the compounds I can be formed by
reaction with a base of the corresponding ration, preferably an
alkali metal hydroxide or hydride, or by reaction with an acid of
the corresponding anion, preferably of hydrochloric acid,
hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
Salts of I where the metal ion is not an alkali metal ion can be
prepared by ration exchange of the corresponding alkali metal
salt in a conventional manner, similarly ammonium, phosphonium,
sulfonium and sulfoxonium salts by means of ammonia, phosphonium,
sulfonium or sulfoxonium hydroxides.
The compounds I and their agriculturally useful salts are
suitable, both in the form of isomer mixtures and in the form of
the pure isomers, as herbicides. The herbicidal compositions
comprising I control vegetation on non-crop areas very
efficiently, especially at high rates of application. They act
against broad-leaved weeds and grass weeds in crops such as
wheat, rice, maize, Soya and cotton without causing any
significant damage to the crop plants. This effect is mainly
observed at low rates of application.
Depending on the application method in question, the compounds I,
or herbicidal compositions comprising them, can additionally be
employed in a further number of crop plants for eliminating
undesirable plants. Examples of suitable crops are the following:
Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus
officinalis, Beta vulgaris spec. altissima, Beta vulgaris spec.
raga, Brassica napus var. napes, Brassica napes var.
napobrassica, Brassica rapa var. silvestris, Camellia sinensis,
Carthamus tinctorius, Carya illinoinensis, Citrus limon, Citrus
0050/49042 ~ 02332352 2000-11-17
sinensis, Coffea arabica (Coffea canephora, Coffea liberica),
Cucumis sativus, Cynodon dactylon, Daucus carota, Elaeis
guineensis, Fragaria vesca, Glycine max, Gossypium hirsutum,
(Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium),
5 Helianthus annuus, Hevea brasiliensis, Hordeum vulgare, Humulus
lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum
usitatissimum, Lycopersicon lycopersicum, Malus spec., Manihot
esculenta, Medicago sativa, Musa spec., Nicotiana tabacum
(N.rustica), Olea europaea, Oryza sativa , Phaseolus lunatus,
10 Phaseolus vulgaris, Picea abies, Pinus spec., Pisurn sativum,
Prunus avium, Prunus persica, Pyrus communis, Ribes sylvestre,
Ricinus communis, Saccharum officinarum, Secale cereale, Solanum
tuberosum, Sorghum bicolor (s. vulgare), Theobroma cacao,
Trifolium pratense, Triticum aestivum, Triticum durum, Vicia
15 faba, Vitis vinifera and Zea mays.
In addition, the compounds I may also be used in crops which
tolerate the action of herbicides owing to breeding, including
genetic engineering methods.
The compounds I, or the compositions comprising them, can be used
for example in the form of ready-to-spray aqueous solutions,
powders, suspensions, also highly-concentrated aqueous, oily or
other suspensions or dispersions, emulsions, oil dispersions,
pastes, dusts, materials for spreading, or granules, by means of
spraying, atomizing, dusting, spreading or pouring. The use forms
depend on the intended aims; in any case, they should guarantee
the finest possible distribution of the active ingredients
according to the invention.
Suitable inert auxiliaries are essentially: mineral oil fractions
of medium to high boiling point, such as kerosene and diesel oil,
furthermore coal tar oils and oils of vegetable or animal origin,
aliphatic, cyclic and aromatic hydrocarbons, e.g. paraffins,
tetrahydronaphthalene, alkylated naphthalenes and their
derivatives, alkylated benzenes and their derivatives, alcohols
such as methanol, ethanol, propanol, butanol and cyclohexanol,
ketones such as cyclohexanone, strongly polar solvents, e.g.
amines such as N-methylpyrrolidone, and water.
Aqueous use forms can be prepared from emulsion concentrates,
suspensions, pastes, wettable powders or water-dispersible
granules by adding water. To prepare emulsions, pastes or oil
dispersions, the substances, either as such or dissolved in an
oil or solvent, can be homogenized in water by means of a wetting
agent, tackifier, dispersant or emulsifier. Alternatively, it is
possible to prepare concentrates comprising active ingredient,
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51
wetting agent, tackifier, dispersant or emulsifier and, if
desired, solvent or oil, which are suitable for dilution with
water.
Suitable surfactants are the alkali metal salts, alkaline earth
metal salts and ammonium salts of aromatic sulfonic acids, e.g.
ligno-, phenol-, naphthalene- and dibutylnaphthalenesulfonic
acid, and of fatty acids, alkyl- and alkylarylsulfonates, alkyl
sulfates, lauryl ether sulfates and fatty alcohol sulfates, and
salts of sulfated hexa-, hepta- and octadecanols, and also of
fatty alcohol glycol ethers, condensates of sulfonated
naphthalene and its derivatives with formaldehyde, condensates of
naphthalene, or of the naphthalenesulfonic acids with phenol and
formaldehyde, polyoxyethylene octylphenol ether, ethoxylated
isooctyl-, octyl- or nonylphenol, alkylphenyl or tributylphenyl
polyglycol ether, alkylaryl polyether alcohols, isotridecyl
alcohol, fatty alcohol/ethylene oxide condensates, ethoxylated
castor oil, polyoxyethylene alkyl ethers or polyoxypropylene
alkyl ethers. lauryl alcohol polyglycol ether acetate, sorbitol
esters, lignin-sulfite waste liquors or methylcellulose.
Powders, materials for spreading and dusts can be prepared by
mixing or grinding the active ingredients together with a solid
carrier.
Granules, e.g. coated granules, impregnated granules and
homogeneous granules, can be prepared by binding the active
ingredients to solid carriers. Solid carriers are mineral earths,
such as silicas, silica gels, silicates, talc, kaolin, limestone,
lime, chalk, bole, loess, clay, dolomite, diatomaceous earth,
calcium sulfate, magnesium sulfate, magnesium oxide, ground
synthetic materials, fertilizers such as ammonium sulfate,
ammonium phosphate, ammonium nitrate, ureas, and products of
vegetable origin, such as cereal meal, tree bark meal, wood meal
and nutshell meal, cellulose powders, or other solid carriers.
The concentrations of the active compounds I in the ready-to-use
preparations can be varied within wide ranges. In general, the
formulations comprise approximately from 0.001 to 98% by weight,
preferably 0.01 to 95% by weight of at least one active compound.
The active compounds are employed in a purity of from 90% to
100%, preferably 95% to 100% (according to NMR spectrum).
The formulation examples which follow illustrate the preparation
of such products:
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52
I. 20 parts by weight of the compound No. Ia.167 are dissolved
in a mixture composed of 80 parts by weight of alkylated
benzene, 10 parts by weight of the adduct of 8 to 10 mol of
ethylene oxide to 1 mol of oleic acid N-monoethanolamide,
5 parts by weight of calcium dodecylbenzenesulfonate and
5 parts by weight of the adduct of 40 mol of ethylene oxide
to 1 mol of castor oil. Pouring the solution into
100,000 parts by weight of water and finely distributing it
therein gives an aqueous dispersion which comprises 0.02
by weight of the active ingredient.
II. 20 parts by weight of the compound No. Ic.1 are dissolved
in a mixture composed of 40 parts by weight of
cyclohexanone, 30 parts by weight of isobutanol, 20 parts
by weight of the adduct of 7 mol of ethylene oxide to 1 mol
of isooctylphenol and 10 parts by weight of the adduct of
40 mol of ethylene oxide to 1 mol of castor oil. Pouring
the solution into 100,000 parts by weight of water and
finely distributing it therein gives an aqueous dispersion
which comprises 0.02 by weight of the active ingredient.
III. 20 parts by weight of the active ingredient No. Ia.167 are
dissolved in a mixture composed of 25 parts by weight of
cyclohexanone, 65 parts by weight of a mineral oil fraction
of boiling point 210 to 280°C and 10 parts by weight of the
adduct of 40 mol of ethylene oxide to 1 mol of castor oil.
Pouring the solution into 100,000 parts by weight of water
and finely distributing it therein gives an aqueous
dispersion which comprises 0.02 by weight of the active
ingredient.
IV. 20 parts by weight of the active ingredient No. Ic.154 are
mixed thoroughly with 3 parts by weight of sodium
diisobutylnaphthalene-a-sulfonate, 17 parts by weight of
the sodium salt of a lignosulfonic acid from a sulfite
waste liquor and 60 parts by weight of pulverulent silica
gel, and the mixture is ground in a hammer mill. Finely
distributing the mixture in 20,000 parts by weight of water
gives a spray mixture which comprises 0.1~ by weight of the
active ingredient.
V. 3 parts by weight of the active ingredient No. Ig.167 are
mixed with 97 parts by weight of finely divided kaolin.
This gives a dust which comprises 3~ by weight of active
ingredient.
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53
VI. 20 parts by weight of the active ingredient No. Ic.172 are
mixed intimately with 2 parts by weight of calcium
dodecylbenzenesulfonate, 8 parts by weight of fatty alcohol
polyglycol ether, 2 parts by weight of the sodium salt of a
phenol/urea/formaldehyde condensate and 68 parts by weight
of a paraffinic mineral oil. This gives a stable oily
dispersion.
VII. 1 part by weight of the active ingredient No. Ig.167 is
dissolved in a mixture composed of 70 parts by weight of
cyclohexanone, 20 parts by weight of ethoxylated
isooctylphenol and 10 parts by weight of ethoxylated castor
oil. This gives a stable emulsion concentrate.
VIII. 1 part by weight of the active ingredient No. Ic.2 is
dissolved in a mixture composed of 80 parts by weight of
cyclohexanone and 20 parts by weight of Wettol~ EM 31
(= nonionic emulsifier based on ethoxylated castor oil;
BASF AG). This gives a stable emulsion concentrate.
The active compounds I or the herbicidal compositions can be
applied pre- or post-emergence. If the active ingredients are
less well tolerated by certain crop plants, application
techniques may be used in which the herbicidal compositions are
sprayed, with the aid of the spraying equipment, in such a way
that they come into as little contact as possible, if any, with
the leaves of the sensitive crop plants, while the active
ingredients reach the leaves of undesirable plants growing
underneath, or the bare soil surface (post-directed, lay-by).
The rates of application of active ingredient I are from 0.001 to
3.0, preferably 0.01 to 1.0, kg/ha of active substance (a.s.),
depending on the control target, the season, the target plants
and the growth stage.
To widen the spectrum of action and to achieve synergistic
effects, the substituted 6-aryl-3-thioxo-5-(thi)oxo-2,3,4,5-
tetrahydro-1,2,4-triazines I may be mixed with a large number of
representatives of other herbicidal or growth-regulating active
ingredients and then applied concomitantly. Suitable components
for mixtures are, for example, 1,2,4-thiadiazoles,
1,3,4-thiadiazoles, amides, aminophosphoric acid and its
derivatives, aminotriazoles, anilides, aryloxy-/hetaryl-
oxyalkanoic acids and their derivatives, benzoic acid and its
derivatives, benzothiadiazinones, 2-(hetaroyl/aroyl)-
1,3-cyclohexanediones, hetaryl aryl ketones, benzyl-
isoxazolidinones, meta-CF3-phenyl derivatives, carbamates,
0050/49042 ~ 02332352 2000-11-17
54
quinolinecarboxylic acid and its derivates, chloroacetanilides,
cyclohexane-1,3-dione derivatives, diazines, dichloropropionic
acid and its derivatives, dihydrobenzofurans, dihydrofuran-
3-ones, dinitroanilines, dinitrophenols, diphenyl ethers,
dipyridyls, halocarboxylic acids and their derivatives, ureas,
3-phenyluracils, imidazoles, imidazolinones, N-phenyl-
3,4,5,6-tetrahydrophthalimides, oxadiazoles, oxiranes, phenols,
aryloxy- and hetaryloxyphenoxypropionic esters, phenylacetic acid
and its derivatives, 2-phenylpropionic acid and its derivatives,
pyrazoles, phenylpyrazoles, pyridazines, pyridinecarboxylic acid
and its derivatives, pyrimidyl ethers, sulfonamides,
sulfonylureas, triazines, triazinones, triazolinones,
triazolecarboxamides and uracils.
It may furthermore be advantageous to apply the compounds I,
alone or in combination with other herbicides, in the form of a
mixture with other crop protection agents, for example together
with agents for controlling pests or phytopathogenic fungi or
bacteria. Also of interest is the miscibility with mineral salt
solutions, which are employed for treating nutritional and trace
element deficiencies. Non-phytotoxic oils and oil concentrates
may also be added.
Preparation Examples
1. Phenylglyoxylic acid derivatives
Example 1
Ethyl 2-(4-chloro-2-fluoro-5-methoxyphenyl)-2-oxoacetate
All operations were carried out under anhydrous conditions
and N2 protective gas.
At 20-25~C, 200 ml of a 2 molar isopropylmagnesium chloride
solution (0.4 mol) in tetrahydrofuran were added dropwise to
a solution of 95.8 g (0.4 mol) of 5-bromo-2-chloro-4-fluoro-
anisol in 350 ml of tetrahydrofuran. After the addition, the
mixture was stirred for another 20 minutes (at most!). This
solution was then added dropwise at (-50)~C to a solution of
64.2 g (0.44 mol) of diethyl oxalate in 300 ml of tetra-
hydrofuran. The cold bath was removed and the resulting
suspension was stirred overnight. With ice-bath cooling,
200 ml of water and 200 ml of 10~ strength hydrochloric acid
were then added dropwise in succession. The aqueous phase was
saturated with common salt and the organic phase was then
separated off, dried over sodium sulfate and concentrated.
The crude product was purified by silica gel chromatography
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(mobile phase cyclohexane/methyl tert-butyl ether = 100:5).
Yield: 66.2 g (white crystals); m.p.: 42-45°C.
Example 2
5 2-(4-Chloro-2-fluoro-5-methoxyphenyl)-2-oxoacetic acid
75.9 g (0.291 mol) of ethyl 2-(4-chloro-2-fluoro-5-methoxy-
phenyl)-2-oxoacetate were refluxed in 1.0 1 of 47~ strength
aqueous HBr solution for seven hours. After cooling, the
10 reaction mixture was poured into 3 1 of ice-water. The
mixture was subsequently extracted three times with 300 ml of
methyl tert-butyl ether each time. The combined organic
phases were washed twice more with a little water, dried over
sodium sulfate and then concentrated. Yield: 63.1 g (white
15 crystals); m.p.: 134-137°C.
Example 3
2-(4-Chloro-2-fluoro-5-hydroxyphenyl)-2-oxoacetic acid
20 63.1 g of 2-(4-chloro-2-fluoro-5-methoxyphenyl)-2-oxoacetic
acid were heated at reflux temperature in 1.0 1 of 47~
strength aqueous HBr solution for eight hours and then
stirred for another 3 days at room temperature. The mixture
was then poured into 3 1 of ice-water. The resulting product
25 of value was extracted with three times 300 ml of ethyl
acetate. The combined organic phases were washed twice with a
little water, dried over sodium sulfate and concentrated.
Yield: 53.5 g (white crystals); m.p.: 137-139°C.
30 Example 4
(R)-2-[4-Chloro-2-fluoro-5-(1-methoxycarbonylethoxy)phenyl]-
2-oxoacetic acid
1.8 g of an 80~ suspension of sodium hydride in mineral oil
35 were freed from mineral oil by washing with dimethyl
formamide, suspended in 20 ml of dimethyl formamide and, at
5-10°C, admixed dropwise with a solution of 6.0 g of
2-(4-chloro-2-fluoro-5-hydroxyphenyl)-2-oxoacetic acid in
30 ml of dimethyl formamide. The mixture was stirred for
40 15 minutes and 4.0 g of methyl (S)-2-chloropropionate were
added dropwise. The mixture was then stirred at 65°C for
seven hours and then at 20°C for twelve hours. The batch was
then poured into 200 ml of ice-water, acidified with dilute
hydrochloric acid and extracted three times with 50 ml of
45 ethyl acetate each time. The combined organic phases were
washed twice with 20 ml of water each time, dried over sodium
sulfate and concentrated. Yield: 7.4 g of a light yellow oil;
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56
1H NMR (270 MHz, (CD3)2S0): 8 (ppm] - 1.59 (d,3H), 3.72
(s,3H), 5.27 (q,lH), 7.43 (d,lH), 7.78 (d,lH).
Example 5
Ethyl 2-(4-chloro-3-methylphenyl)-2-oxoacetate
Using 2-chloro-5-iodotoluene, the desired product of value
was obtained by the method of Example 1. 1H NMR (270 MHz,
CDC13): 8 [ppm] - 1.42 (t,3H), 2.44 (s,3H), 4.46 (q,2H), 7.48
(d,lH), 7.80 (dd,lH), 7.90 (d,lH).
Example 6
2-(4-Chloro-3-methylphenyl)-2-oxoacetic acid
A solution of 10 g (44 mmol) of ethyl 2-(4-chloro-3-methyl-
phenyl)-2-oxoacetate in 390 ml of acetic acid and 98 ml of
2 M hydrochloric acid was heated at 80°C for 4 hours. The
mixture was then concentrated. The residue was admixed with
water and then extracted with ethyl acetate. The combined
extracts were washed with water, dried over sodium sulfate
and finally concentrated. Yield: 7.5 g; m.p.: 85-86°C.
Example 7
2-(4-Chloro-2-fluorophenyl)-2-oxoacetic acid
30
Using ethyl 2-(4-chloro-2-fluorophenyl)-2-oxoacetate, the
desired product of value was obtained by the method of
Example 2. 1H NMR (270 MHz, CDC13): 8 [ppm] - 6.48 (s,lH),
7.20-7.35 (m,2H), 8.02 (t,lH).
Example 8
Ethyl 2-(4-chloro-3-nitrophenyl)-2-oxoacetate
38.9 g (0.62 mol) of nitric acid were added dropwise to a
solution of 131.3 g (0.62 mol) of ethyl 2-(4-chlorophenyl)-
2-oxoacetate in 350 ml of conc. sulfuric acid which had been
cooled to 0°C, and the mixture was then stirred for 5 hours.
The solution was subsequently poured into ice-water. The
product of value was then extracted using methyl tert-butyl
ether. The combined extracts were washed with water, dried
over magnesium sulfate and finally concentrated. Yield:
148.6 g; MS (m/z) : 258 [M+H]'".
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57
Example 9
2-(4-Methoxy-3-nitrophenyl)-2-oxoacetic acid
With ice-cooling, a solution of 75 g (0.29 mol) of ethyl
2-(4-chloro-3-nitrophenyl)-2-oxoacetate in 150 ml of methanol
was added to a solution of 35 g (0.87 mol) of sodium
hydroxide in 250 ml of methanol. The reaction mixture was
then stirred for 16 hours, after which it was acidified with
dilute hydrochloric acid. Most of the low-boilers were
subsequently distilled off. The residue was admixed with
water. The product of value was extracted from the resulting
aqueous phase using ethyl acetate. The organic phase was
washed with water, dried over sodium sulfate and finally
concentrated. Yield: 69.5 g; MS [m/z]: 226 (M+H)+.
2. Thiosemicarbazides
Example 10:
2,4-Dimethylthiosemicarbazide
At room temperature, 9.5 g of methylhydrazine were added
dropwise to a solution of 15.0 g of methyl isothiocyanate in
200 ml of anhydrous tert-butyl methyl ether. The mixture was
stirred overnight, the solvent was removed and the residue
was recrystallized from ethanol/water (2:1). Yield: 21.5 g
(white crystals); m.p.: 139-140°C.
1H NMR (270 MHz, in (CD3)zS0): b [ppm] - 2.87 (d,3H), 3.43
(s,3H), 4.80 (s,2H), 8.13 (br.,lH).
Example 11
2-(4-Chlorophenyl)-4-methylthiosemicarbazide
A solution of 2.08 g (29 mmol) of methyl isothiocyanate in
20 ml of methyl tert-butyl ether was added to a solution of
4.08 g (29 mmol) of 4-chlorophenylhydrazine in 60 ml of
acetic acid. The mixture was stirred for 16 hours and then
concentrated. The residue was admixed with water. The product
of value was extracted from the aqueous phase using
dichloromethane. The combined organic phases were washed with
water, dried over sodium sulfate and finally concentrated.
The crude product was purified by silica gel chromatography
(mobile phase: cyclohexane/ethyl acetate). Yield: after a
first fraction of 0.6 g of 1-(4-chlorophenyl)-4-methylthio-
semicarbazide, 2.5 g of the desired product were obtained.
M.p.: 114-115°C.
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58
3. 1,2,4-Triazines
Example 12
6-(4-Chloro-2-fluoro-5-hydroxyphenyl)-2,4-dimethyl-5-oxo-
3-thioxo-2,3,4,5-tetrahydro-1,2,4-triazine
A solution of 19.7 g (90 mmol) of 2-(4-chloro-2-fluoro-
5-hydroxyphenyl)-2-oxoacetic acid and 10.7 g (90 mmol) of
2,4-dimethylthiosemicarbazide in 50 ml of acetic acid was
heated at 85-90°C for 7 hours. The reaction mixture was
subsequently diluted with water, after which the resulting
solid product of value was separated off, washed with water
and dried. Yield: 15.4 g; m.p.. 166-167°C.
Example 13
Methyl (R)-2-[2-chloro-4-fluoro-5-(2,4-dimethyl-5-oxo-
3-thioxo-2,3,4,5-tetrahydro-1,2,4-triazin-6-yl)phenoxy]-
propionate (No. Ia.167)
A suspension of 15 g (50 mmol) of 6-(4-chloro-2-fluoro-
5-hydroxyphenyl)-2,4-dimethyl-5-oxo-3-thioxo-2,3,4,5-tetra-
hydro-1,2,4-triazine and 17.2 g (124 mmol) of potassium
carbonate in 100 ml of dimethylformamide was admixed with
6.7 g (55 mmol) of methyl (S)-2-chloropropionate. The mixture
was heated at 60-65°C for 4 hours and then poured into water.
The resulting solid product of value was washed with water
and petroleum ether and then dried. Yield: 18.8 g;
m.p.: 123-124°C.
Example 14
Methyl (R)-2-(5-(4-amino-5-oxo-3-thioxo-2,3,4,5-tetrahydro-
1,2,4-triazin-6-yl)-2-chloro-4-fluorophenoxy)propionate
6.9 g (23 mmol) of (R)-2-(4-chloro-2-fluoro-5-[(1-methoxy-
carbonyl)ethoxy]phenyl)-2-oxoacetic acid and 2.4 g (23 mmol)
of thiocarbohydrazide were stirred at 85°C for 6 hours. The
mixture was subsequently concentrated and the residue was
admixed with a little ether, after which the resulting solid
product of value was filtered off and then recrystallized
from toluene. Yield: 3.9 g; m.p.: 176-178°C.
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59
Example 15
Methyl (R)-2-[5-(4-amino-2-methyl-5-oxo-3-thioxo-2,3,4,5-
tetrahydro-1,2,4-triazin-6-yl)-2-chloro-4-fluorophenoxy]-
propionate (No. Ig.167)
A suspension of 3.4 g (11 mmol) of 6.9 g of methyl
(R)-2-[5-(4-amino-5-oxo-3-thioxo-2,3,4,5-tetrahydro-
1,2,4-triazin-6-yl)-2-chloro-4-fluorophenoxy]propionate and
2.2 g (16 mmol) of potassium carbonate in 50 ml of
tetrahydrofuran was admixed with 1.5 g (11 mmol) of methyl
iodide. The reaction mixture was stirred for 3 days and then
concentrated. The residue was admixed with ethyl acetate. The
resulting organic phase was washed with water, dried over
sodium sulfate and finally concentrated. The crude product
was purified by silica gel chromatography (mobile phase:
cyclohexane/ethyl acetate = 1:1). Yield: initially, 0.6 g of
the desired product (m. p.. 89-91°C) were obtained and then,
as a second fraction, 2.3 g of methyl (R)-2-[5-(4-amino-
3-methylthio-5-oxo-4,5-dihydro-1,2,4-triazin-6-yl)-2-chloro-
4-fluorophenoxy]propionate.
Example 16
6-(4-Chloro-2-fluoro-5-hydroxyphenyl)-4-methyl-5-oxo-
2-phenyl-3-thioxo-2,3,4,5-tetrahydro-1,2,4-triazine
Using 2-(4-chloro-2-fluoro-5-hydroxyphenyl)-2-oxoacetic acid
and 4-methyl-2-phenylthiosemicarbazide, the desired product
of value was obtained by the method of Example 12.
M.p.: 168-169°C.
Example 17
6-(4-Chloro-2-fluoro-5-hydroxyphenyl)-2-(4-chlorophenyl)-
4-methyl-5-oxo-3-thioxo-2,3,4,5-tetrahydro-1,2,4-triazine
Using 2-(4-chloro-2-fluoro-5-hydroxyphenyl)-2-oxoacetic acid
and 2-(4-chlorophenyl)-4-methylthiosemicarbazide, the desired
product of value was obtained by the method of Example 12.
M.p.: 215-216°C.
45
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0050/49042
Example 18
Methyl (R)-2-(2-chloro-4-fluoro-5-(4-methyl-5-oxo-
2-phenyl-3-thioxo-2,3,4,5-tetrahydro-1,2,4-triazin-6-yl)-
phenoxy)propionate
5
Using 6-(4-chloro-2-fluoro-5-hydroxyphenyl)-4-methyl-
5-oxo-2-phenyl-3-thioxo-2,3,4,5-tetrahydro-1,2,4-triazine,
the desired product of value was obtained by the method of
Example 13. MS [m/z]: 449 (M)+.
Example 19
Methyl (R)-2-(2-chloro-5-[2-(4-chlorophenyl)-4-methyl-5-oxo-
3-thioxo-2,3,4,5-tetrahydro-1,2,4-triazin-6-yl]-4-fluoro-
phenoxy)propionate
Using 6-(4-chloro-2-fluoro-5-hydroxyphenyl)-2-(4-chloro-
phenyl)-4-methyl-5-oxo-3-thioxo-2,3,4,5-tetrahydro-
1,2,4-triazine, the desired product of value was obtained by
the method of Example 13. M.p.. 80-84°C.
Example 20
4-Amino-6-(4-chlorophenyl)-5-oxo-3-thioxo-2,3,4,5-tetra-
hydro-1,2,4-triazine
Using 2-(4-chlorophenyl)-2-oxoacetic acid, the desired
product of value was obtained by the method of Example 14.
M.p.: 273-274°C.
Example 21
4-Amino-6-(4-chlorophenyl)-2-methyl-5-oxo-3-thioxo
2,3,4,5-tetrahydro-1,2,4-triazine (No. Ii.1)
Using 4-amino-6-(4-chlorophenyl)-5-oxo-3-thioxo-2,3,4,5-
tetrahydro-1,2,4-triazine, the desired product of value was
obtained by the method of Example 15. M.p.: 157-158°C.
Example 22
6-(4-Chlorophenyl)-2,4-dimethyl-5-oxo-3-thioxo-2,3,4,5-
tetrahydro-1,2,4-triazine (No. Ic.1)
A solution of 89.4 g (0.42 mol) of ethyl 2-(4-chlorophenyl)-
2-oxoacetate, 50.1 g (0.42 mol) of 2,4-dimethylthio-
semicarbazide and 17.6 g (0.44 mol) of sodium hydroxide in
300 ml of ethanol and 800 ml of water was heated at reflux
for 7 hours. The mixture was subsequently acidified using
dilute hydrochloric acid, after which the resulting solid
crude product was filtered off and purified by silica gel
0050/49042 ~ 02332352 2000-11-17
61
chromatography (mobile phase: cyclohexane/ethyl
acetate = 9:1). Yield: 21.1 g; m.p.. 130-131°C.
Example 23
6-(4-Chloro-3-nitrophenyl)-2,4-dimethyl-5-oxo-3-thioxo-
2,3,4,5-tetrahydro-1,2,4-triazine (No. Ic.168)
Using 6-(4-chlorophenyl)-2,4-dimethyl-5-oxo-3-thioxo-
2,3,4,5-tetrahydro-1,2,4-triazine, the desired product of
value was obtained by the method of Example 8.
M.p.: 184-185°C.
Example 24
6-(3-Amino-4-chlorophenyl)-2,4-dimethyl-5-oxo-3-thioxo-
2,3,4,5-tetrahydro-1,2,4-triazine (No. Ic.170)
A suspension of 39.7 g (0.71 mol) of iron powder in 200 ml of
methanol and 870 ml of acetic acid was heated to reflux and,
a little at a time, admixed with 55.5 g (0.18 mol) of
6-(4-chloro-3-nitrophenyl)-2,4-dimethyl-5-oxo-3-thioxo-
2,3,4,5-tetrahydro-1,2,4-triazine. The mixture was
subsequently stirred for 3 hours, after which the solids were
filtered off. The filtrate was concentrated. The resulting
residue was admixed with water. The product of value was then
extracted from the aqueous phase using ethyl acetate. The
organic phase was dried over sodium sulfate and finally
concentrated. The crude product was purified by silica gel
chromatography (mobile phase: cyclohexane/ethyl
acetate = 2:1). Yield: 12.8 g; MS [m/z]: 282 (M)+.
Example 25
Methyl 2-chloro-3-[2-chloro-5-(2,4-dimethyl-5-oxo-
3-thioxo-2,3,4,5-tetrahydro-1,2,4-triazin-6-yl)phenyl]-
propionate (No. Ic.254)
A solution of 2.3 g (22 mmol) of tert-butyl nitrite in 50 ml
of acetonitrile was admixed with 12.8 g (0.15 mol) of methyl
acrylate, 2.5 g (19 mmol) of copper(II) chloride and 4.2 g
(15 mmol) of 6-(3-amino-4-chlorophenyl)-2,4-dimethyl-
5-oxo-3-thioxo-2,3,4,5-tetrahydro-1,2,4-triazine. The mixture
was stirred for 16 hours and then concentrated. The resulting
crude product was purified by silica gel chromatography
(mobile phase: cyclohexane/ethyl acetate = 10:1). Yield:
0. 6 g; MS [m/z] : 387 (M) +.
0050/49042
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62
Example 26
6-[3-Di(methylsulfonyl)amino-4-chlorophenyl]-2,4-dimethyl-
5-oxo-3-thioxo-2,3,4,5-tetrahydro-1,2,4-triazine (No. Ic.180)
A solution of 4.3 g (15 mmol) of 6-(3-amino-4-chlorophenyl)-
2,4-dimethyl-5-oxo-3-thioxo-2,3,4,5-tetrahydro-1,2,4-triazine
in 100 ml of dichloromethane was admixed with 3.4 g (35 mmol)
of triethylamine and 3.6 g (32 mmol) of methanesulfonyl
chloride, and the mixture was then stirred for 4 hours. The
reaction mixture was subsequently washed with water, dried
over sodium sulfate and then concentrated. Yield:
quantitative; m.p.: 225-235°C.
Example 27
2,4-Dimethyl-6-[3-(methylsulfonyl)amino-4-chlorophenyl]-
5-oxo-3-thioxo-2,3,4,5-tetrahydro-1,2,4-triazine (No. Ic.172)
A catalytic amount of sodium methoxide was added to a
solution of 4.5 g (10 mmol) of 6- [3-di (methylsulfonyl) -
amino-4-chlorophenyl]-2,4-dimethyl-5-oxo-3-thioxo-
2,3,4,5-tetrahydro-1,2,4-triazine in 200 ml of methanol. The
mixture was stirred for 3 hours and then concentrated. The
residue that remained was admixed with water. The product of
value was extracted from the resulting aqueous phase using
ethyl acetate. The organic phase was washed with water, dried
over sodium sulfate and finally concentrated. The crude
product was purified by recrystallization from
dichlormethane. Yield: 1.7 g; MS [m/z]: 360 (M)+.
Example 28
6-(4-Chloro-3-methylphenyl)-2,4-dimethyl-5-oxo-3-thioxo-
2,3,4,5-tetrahydro-1,2,4-triazine (No. Ic.2)
Using 2-(4-chloro-3-methylphenyl)-2-oxoacetic acid, the
desired product of value was obtained by the method of
Example 12. M.p.: 133-135°C.
Example 29
6-(4-Hydroxyphenyl)-2,4-dimethyl-5-oxo-3-thioxo-2,3,4,5-
tetrahydro-1,2,4-triazine
Using 2-(4-hydroxyphenyl)-2-oxoacetic acid, the desired
product of value was obtained by the method of Example 12.
M.p.: 214-215°C.
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63
Example 30
2,4-Dimethyl-5-oxo-3-thioxo-6-[4-(4-trifluoromethoxy-
benzyloxy)phenyl]-2,3,4,5-tetrahydro-1,2,4-triazine
A suspension of 0.62 g (18 mmol) of sodium hydride (60%) in
dimethylformamide was admixed with a solution of 4 g
(16 mmol) of 6-(4-hydroxyphenyl)-2,4-dimethyl-5-oxo-
3-thioxo-2,3,4,5-tetrahydro-1,2,4-triazine in 20 ml of
dimethylformamide. The reaction mixture was stirred for
10 minutes, and 4.5 g (18 mmol) of 4-trifluoromethoxybenzyl
bromide were then added. The mixture was subsequently stirred
for 3 days. The resulting mixture was then admixed with
ice-water. The resulting solid crude product was filtered off
and purified by silica gel chromatography (mobile phase:
cyclohexane/ethyl acetate = 3:1) Yield: 5.1 g;
m.p.: 134-135°C.
Example 31
6-[4-(4-Chlorobenzyloxy)phenyl]-2,4-dimethyl-5-oxo-
3-thioxo-2,3,4,5-tetrahydro-1,2,4-triazine
Using 4-chlorobenzyl bromide, the desired product of value
was obtained by the method of Example 30. M.p.: 162-164°C.
Example 32
6-(3-Chloro-4-hydroxyphenyl)-2,4-dimethyl-5-oxo-3-thioxo-
2,3,4,5-tetrahydro-1,2,4-triazine
Using 2-(3-chloro-4-hydroxyphenyl)-2-oxoacetic acid, the
desired product of value was obtained by the method of
Example 12. 1H NMR (270 MHz; in SO(CD3)2) : b [ppm] - 3.60
(s,3H), 3.98 (s,3H), 7.06 (d,lH), 7.85 (dd,lH), 8.03 (d,lH),
10 .84 (s, 1H) .
Example 33
Methyl (R)-2-[3-Chloro-4-(2,4-dimethyl-5-oxo-3-thioxo-
2,3,4,5-tetrahydro-1,2,4-triazin-6-yl)phenoxy]propionate
Using 6-(3-chloro-4-hydroxyphenyl)-2,4-dimethyl-5-oxo-
3-thioxo-2,3,4,5-tetrahydro-1,2,4-triazine, the desired
product of value was obtained by the method of Example 13.
M.p.. 67°C.
0050/49042 ~ 02332352 2000-11-17
64
Example 34
6-(3-Chloro-4-propargyloxyphenyl)-2,4-dimethyl-5-oxo-
3-thioxo-2,3,4,5-tetrahydro-1,2,4-triazine
Using 6-(3-chloro-4-hydroxyphenyl)-2,4-dimethyl-5-oxo-
3-thioxo-2,3,4,5-tetrahydro-1,2,4-triazine and propargyl
bromide, the desired product of value was obtained by the
method of Example 13. M.p.: 172°C.
Example 35
6-[3-Chloro-4-(2-propen-1-yloxy)phenyl]-2,4-dimethyl-
5-oxo-3-thioxo-2,3,4,5-tetrahydro-1,2,4-triazine
Using 6-(3-chloro-4-hydroxyphenyl)-2,4-dimethyl-5-oxo-
3-thioxo-2,3,4,5-tetrahydro-1,2,4-triazine and allyl bromide,
the desired product of value was obtained by the method of
Example 13. M.p.: 175°C.
Example 36
6-(3-Chloro-4-isopropoxyphenyl)-2,4-dimethyl-5-oxo-
3-thioxo-2,3,4,5-tetrahydro-1,2,4-triazine
Using 6-(3-chloro-4-hydroxyphenyl)-2,4-dimethyl-5-oxo-
3-thioxo-2,3,4,5-tetrahydro-1,2,4-triazine and isopropyl
iodide, the desired product of value was obtained by the
method of Example 13. M.p.. 81°C.
Example 37
6-(4-Methoxy-3-nitrophenyl)-2,4-dimethyl-5-oxo-3-thioxo-
2,3,4,5-tetrahydro-1,2,4-triazine
Using 2-(4-methoxy-3-nitrophenyl)-2-oxoacetic acid, the
desired product of value was obtained by the method of
Example 12. M.p.: 218-219°C.
Example 38
6-(4-Hydroxy-3-nitrophenyl)-2,4-dimethyl-5-oxo-3-thioxo
2,3,4,5-tetrahydro-1,2,4-triazine
A solution of 53 g (0.17 mol) of 6-(4-methoxy-3-nitro-
phenyl)-2,4-dimethyl-5-oxo-3-thioxo-2,3,4,5-tetrahydro-
1,2,4-triazine and 21.9 g (0.51 mol) of lithium chloride in
610 ml of dimethylformamide was heated at reflux for 7 hours.
The mixture was subsequently poured into ice-water and
acidified with dilute hydrochloric acid. The resulting solid
product of value was then filtered off, subsequently washed
0050/49042 ~ 02332352 2000-11-17
with water and ethyl acetate and finally dried. Yield:
45.5 g; m.p.: 219-221°C.
Example 39
5 6-(3-Amino-4-hydroxyphenyl)-2,4-dimethyl-5-oxo-3-thioxo-
2,3,4,5-tetrahydro-1,2,4-triazine
Using 6-(4-hydroxy-3-nitrophenyl)-2,4-dimethyl-5-oxo-
3-thioxo-2,3,4,5-tetrahydro-1,2,4-triazine, the desired
10 product of value was obtained by the method of Example 24.
M.p.. 202-208°C.
Example 40
6-(2,4-Dimethyl-5-oxo-3-thioxo-2,3,4,5-tetrahydro-
15 1,2,4-triazin-6-yl)-2H-1,4-benzoxazin-3(4H)-one (No. Ip.l)
A suspension of 8.2 g (31 mmol) of 6-(3-amino-4-hydroxy-
phenyl)-2,4-dimethyl-5-oxo-3-thioxo-2,3,4,5-tetrahydro-
1,2,4-triazine, 4.6 g (40 mmol) of chloroacetyl chloride and
20 6.5 g (47 mmol) of potassium carbonate in 70 ml of
dimethylformamide was stirred initially for 2.5 hours at room
temperature and then for 3 hours at 85°C. The reaction
mixture was subsequently admixed with ice-water. The
resulting solid crude product was filtered off and purified
25 by silica gel chromatography (mobile phase: cyclohexane/ethyl
acetate = 2:1). Yield: 4 g. 1H NMR (400 MHz; in SO(CD3)2):
b [ppm] - 3.60 (s, 3H), 3.95 (s,3H), 4.65 (s,2H), 7.03 (d,lH),
7.60 (dd,lH), 7.64 (d,lH), 10.86 (s,lH).
30 Example 41
6-(2,4-Dimethyl-5-oxo-3-thioxo-2,3,4,5-tetrahydro-
1,2,4-triazin-6-yl)-4-(2-propen-1-yl)-2H-1,4-benzoxazin-
3(4H)-one (No. Ip.lO)
35 Using 6-(4-hydroxy-3-nitrophenyl)-2,4-dimethyl-5-oxo-
3-thioxo-2,3,4,5-tetrahydro-1,2,4-triazine and allyl bromide,
the desired product of value was obtained by the method of
Example 30. M.p.: 169-170°C.
40 Example 42
5-(2,4-Dimethyl-5-oxo-3-thioxo-2,3,4,5-tetrahydro-
1,2,4-triazin-6-yl)-2(3H)-benzoxazolone (No. Is.1)
A solution of 8.2 g (31 mmol) of 6-(3-amino-4-hydroxyphenyl)-
45 2,4-dimethyl-5-oxo-3-thioxo-2,3,4,5-tetrahydro-1,2,4-triazine
and 7.6 g (46 mmol) of carbonyldiimidazole in 70 ml of
tetrahydrofuran was heated at reflux for 4 hours. The mixture
0~5~/49042 ~ 02332352 2000-11-17
66
was subsequently concentrated. The residue was stirred with
dilute hydrochloric acid and the solid crude product was then
filtered off. Yield: 5.6 g; m.p.. 242~C.
Example 43
5-(2,4-Dimethyl-5-oxo-3-thioxo-2,3,4,5-tetrahydro-
1,2,4-triazin-6-yl)-3-propargyl-2(3H)-benzoxazolone
(No. Is. l7)
Using 5-(2,4-dimethyl-5-oxo-3-thioxo-2,3,4,5-tetrahydro-
1,2,4-triazin-6-yl)-2(3H)-benzoxazolone and propargyl
bromide, the desired product of value was obtained by the
method of Example 30. 1H NMR (400 MHz; in SO (CDj) 2) : b [ppm]
- 3.50 (t,lH), 3.63 (s,3H), 4.01 (s,3H), 4.78 (d,2H), 7.51
(d, 1H) , 7 .88 (dd, 1H) , 7 .93 (d, 1H) .
Example 44
Methyl (R)-2-[5-(2,4-dimethyl-5-oxo-3-thioxo-2,3,4,5-tetra-
hydro-1,2,4-triazin-6-yl)-2(3H)-benzoxazolon-3-yl]propionate
(No. Is.64)
Using 5-(2,4-dimethyl-5-oxo-3-thioxo-2,3,4,5-tetrahydro-
1,2,4-triazin-6-yl)-2(3H)-benzoxazolone and methyl
(S)-2-chloropropionate, the desired product of value was
obtained by the method of Example 30. M.p.: 149-150~C.
Use Examples
The herbicidal activity of the substituted 6-aryl-3-thioxo-5-
(thi)oxo-2,3,4,5-tetrahydro-1,2,4-triazines I was demonstrated by
the following greenhouse experiments:
The culture containers used were plastic flowerpots containing
loamy sand with approximately 3.0% of humus as the substrate. The
seeds of the test plants were sown separately for each species.
For the pre-emergence treatment, the active ingredients, which
had been suspended or emulsified in water, were applied directly
after sowing by means of finely distributing nozzles. The
containers were irrigated gently to promote germination and
growth and subsequently covered with transparent plastic hoods
until the plants had rooted. This cover caused uniform
germination of the test plants, unless this was adversely
affected by the active ingredients.
For the post-emergence treatment, the test plants were first
grown to a plant height of 3 to 15 cm, depending on the plant
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67
habit, and only then treated with the active ingredients which
had been suspended or emulsified in water. The test plants for
this purpose were either sown directly and grown in the same
containers, or they were first grown separately as seedlings and
transplanted into the test containers a few days prior to the
treatment. The rate of application for the post-emergence
treatment was 31.2, 15.6, 7.8 and 3.9 g/ha of a.s. (active
substance) .
Depending on the species, the plants were kept at from 10-25°C or
20-35°C. The test period extended over 2 to 4 weeks. During this
time, the plants were tended, and their response to the
individual treatments was evaluated.
Evaluation was carried out using a scale from 0 to 100. 100 means
no emergence of the plants, or complete destruction of at least
the aerial parts, and 0 means no damage, or normal course of
growth.
The plants used in the greenhouse experiments belonged to the
following species:
Scientific Name Common Name
Abutilon theophrasti velvet leaf
25gchinochloa crus-galli barnyard grass
Galium aparine catchweed bedstraw
Polygonum persicaria lady's-thumb
Setaria faberii giant foxtail
3 Triticum aestivum spring wheat
0
Veronica species speedwell
The compound No. Ig.167, applied post-emergence, showed very good
activity against Galium aparine, Polygonum persicaria, Setaria
35 faberii and Veronica species at application rates of 31.2 and
15.6 g/ha a.s.
At application rates of only 7.8 and 3.9 g/ha of a.s., the
compound No. Ia.167 exhibited a highly selective herbicidal
40 action against Abutilon theophrasti, Echinochloa crus-galli and
Setaria faberii in the crop summer wheat when used by the
post-emergence method. In contrast, the comparative compound A
0050/49042
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68
H3C\ O F
S N ~ ~ 1
A (No. 29 in JP-A 10/053,508)
N IV
H3C OCH (CH3) -COOC2H5
which is known from JP-A 10/053,508 and was tested at the same
application rates was not selective.
Use Examples (desiccant/defoliant activity)
The test plants used were young cotton plants with 4 leaves
(without cotyledons) which had been grown under greenhouse
conditions (relative atmospheric humidity 50 to 70%; day/night
temperature 27/20°C).
The young cotton plants were subjected to foliar treatment to
runoff point with aqueous preparations of the active ingredients
I (with an addition of 0.15% by weight of the fatty alcohol
alkoxide Plurafac~ LF 7001>, based on the spray liquor). The
amount of water applied was 1000 1/ha (converted). After 13 days,
the number of leaves shed and the degree of defoliation in % were
determined.
No leaves were shed in the untreated control plants.
35
45 1> a low-foam nonionic surfactant, BASF AG
