CA2189698C - Substituted 1,2,3-triazol-3-ones - Google Patents

Abstract

This invention relates to a triazolinone of the general formula (IIa) (IIa) in which either (1) A1 represents di-(C1-C4-alkyl)-amino and A2 represents hydrogen, or represents C1-C6-alkyl which is optionally substituted by fluorine, chlorine, bromine, cyano, C1-C4-alkoxy, C1-C4-alkyl-carbonyl or C1-C4-alkoxy-carbonyl, or represents C3-C6-cycloalkyl which is optionally substituted by fluorine, chlorine, bromine and/or C1-C4-alkyl, or represents C1-C4-alkoxy;
or in which (2) A1 represents and A2 represents OCH3 CH(CH3)2 OCH2-CH=CH2 CH3 O-CH2-CH=CH2 C2H5 O-CH2-CH=CH2 C3H7 O-CH2-CH-CH-Br C3H7 ¦
Br OCH3 OCH3 OCH3 OCH3 OC2H5 C3H7 CH(CH3)2 C4H9 CH3 C2H5 C3H7 H

C2H5 -CH2CH=CH2 CH3 CH3 -CH2OC2H5 -N(CH3)2 The compounds of formula (IIa) are novel intermediates useful in the preparation of herbicidal sulphonylaminocarbonyltriazolinones of the general formula (I)

Description

Substituted 1,2,3-Triazol-3-ones.
The present divisional application is divided out of parent application Serial No. 2,027,206 filed on October 10, 1990.
The invention of the parent application relates to new sulphonylaminocarbonyl-triazolinones of the formula I, to several processes for their preparation, and to their use as herbicides.
The invention of the present divisional application relates to novel intermediates of formula IIa and processes for preparing the intermediates. Compounds of the formula IIa are useful in the preparation of compounds of formula I.
It is known that certain substituted amino-carbonylimadazolinones, such as, for example, 1-isobutyl-aminocarbonyl-2-imidazolidinone (isocarbamide), have herbicidal properties (cf. R. Wegler, Chemie der Pflanzenschutz-and Schadlingsbekampfungsmittel [Chemistry of Plant Protection Agents and PesticidesJ, Vol. 5, p. 219, Springer-Verlag, Berlin-Heidelberg-New York, 1977). However, the action of this compound is not satisfactory in all respects. The new sulphonylaminocarbonyl-triazolinones are a subgroup of the broad class of compounds of the general formula (I) O
R3 S02 NH-CO-N- _N-Ri R
in which R1 represents hydrogen, hydroxyl or amino, or represents an optionally substituted radical from the series comprising alkyl, alkenyl, alkinyl, cycloalkyl, aralkyl, aryl, alkoxy, alkenyloxy, alkylamino and dialkylamino, R2 represents hydrogen, hydroxyl, mercapto or amino, or represents an optionally substituted radical from the series comprising alkyl, cycloalkyl, cycloalkenyl, aralkyl, aryl, alkoxy, alkylamino and dialkylamino, and R3 - represents an optionally substituted radical from the series comprising alkyl, aralkyl, aryl and heteroaryl, as well as salts of compounds of the formula (I), have now been found.
The sulphonylaminocarbonyl-triazolinones of the general formula (I) are obtained when s} triazolinones of the general formula (II}
HN~N_Ri I'i~ (II) in which R1 and R2 have the abovementioned meanings, are reacted with sulphonyl isocyanates of the general formula (III}-R3 602 Ld=C ~ ( I II ) in which R3 has the abovementioned meanings, if appropriate in the presence of a diluent, or when b) triazolinone derivatives of the general formula (IV) i .i ' 21$9698 ' v ,a.~,, v Z-CO-N~N-RI (IV) N~RZ
in which Ri and RZ have the abovementioned meanings and Z represents halogen, alkoxy, aralkoxy or aryloxy, are reacted with suiphonamides of the general formula (V) R3-SOZ-NH2 (Y) in which Rg has the abovementioned meaning, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, or when c) triazolinones of the general formula (II) O
HN~N-R1 (II) ~R2 in which RI and Ra have the abovementioned meanings Le A 27 154. -3 -.

are reacted with sulphonamide derivatives of the general formula (VI) R3 B~2 NH C~ Z (VI) in which R3 has the abovementioned meaning and Z represents halogen, alkoxy, aralkoxy or aryloxy, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, and, if appropriate, salts are formed by customary methods from the compounds of the formula (I) prepared by process (a), (b) or (c).
The new sulphonylaminocarbonyl-triazolinones of the general formula (I) and their salts are distinguished by a powerful herbicidal activity. Surprisingly, the new compounds of the formula (I) show a considerably better herbicidal action than the known herbicide 1-isobutyl-aminocarbonyl-2-imidazolidinone (isocarbamide), which has a similar structure.
The new compounds of the present parent application are those compounds of the formula (I) in which R1 represents hydrogen, hydroxyl or amino, or represents C1-CS-alkyl which is optionally substituted by fluorine, chlorine, bromine, cyano, Cl-C4-alkoxy, Cl-C~-alkylcarbonyl or C1-C4-alkoxy-carbonyl, or represents C3-C6-alkenyl or C3-C6-alkinyl, each of which is _ g _ '~
optionally substituted by fluorine, chlorine and/or bromine, or represents C3-C6-cycloalkyl which is optionally substituted by fluorine, - 4a -23189-715oD

chlorine, bromine and or, C1-C~-alkyl, or represents phenyl-C1-C3-alkyl which~is optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C1-C,-alkyl, trifluoromethyl, C1-C~-alkoxy and/or C1-C~-alkoxy-carbonyl, or represents phenyl which is optionally substituted by fluorine, chlorine, bromine, cyano, nitro, Ci Ci-alkyl, trifluoromethyl, Ci C4-alkoxy, fluorine- and/or chlorine-substituted Cl-C~-alkoxy, C1-C,,-alkylthio, fluorine- and/or' chlorine-substituted C1-C~-alkylthio, C1-C4-alkylsul-phinyl, Ci Ca-alkylsuiphonyl and/or C1-C,-alkoxy-carbonyl, or represents Ci CB-alkoxy which is option-ally substituted by fluorine, chlorine, cyano, phenyl, C1-C,-alkoxy or C1-C4-alkoxy-carbonyl, or represents C3-Cw-alkenyloxy, or represents Ci C;-alkylamino which is optionally substituted by fluorine, cyano, C1-C4-alkoxy or Ci-Cw-alkoxy-car-bonyl, or represents di-(C1-C,-alkyl)-amino, R~ represents hydrogen, hydroxyl, mercapto or amino, or represents C~-CB-alkyl which is optionally substitut ed by fluorine, chlorine, bromine, cyano, C3-Cb cycloalkyl, C1-C,-alkoxy or C1-C4-alkoxy-carbonyl, or represents C3-CB-cycloalkyl which is optionally substituted by fluorine, chlorine, bromine andlor.
C1-C;,-alkyl, or represents cyclohexenyl, or repre-sents phenyl-C1-C3-alkyl which is optionally substi-tuted by fluorine, chlorine, bromine, cyano, nitro, C1-C,,-alkyl, trifluoromethyl, C1-C,-alkoxy and/or C1-C,-alkoxy-carbonyls or represents phenyl which is optionally substituted by fluorine, chlorine, T' r Le A 2T 154 _. - 5 -''.,~' ~ ~ $9698 bromine, cyano, nitro, Cl-C,-alkyl, trifluoromethyl.
C1-C,-alkoxy, fluorine- and/or chlorine-suostituted C1-C3-alkoxy, C1-C,-alkylthio, fluorine- and/or chlorine-substituted Ci C~-alkylthio, C1-C~-alkyl-sulphinyl, C1-C,-alkylsulphonyl and/or Ci-C~-alkoxy-carbonyl, or represents C1-CQ-alkoxy which is option-ally substituted by fluorine, chlorine, cyano, C1-C~-alkoxy or C1-C~-alkoxy-carbonyl, or represents C1-C,-alkylamino or di-(C1-C,-alkyl)-amino, and i0 R' represents the group ~RS , where -R-~~''~4 R" and R' are identical or different and represent hydrogen, fluorine, chlorine, bromine, iodine, nitro, C1-Ce-alkyl (which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxyl, C1-C4-alkoxycarbonyl, C1-C~-alkylamino-carbonyl, di-(C1-C4-alkyl)amino-carbonyl, hydroxyl, Ci-C,-alkoxy, formyloxy, C1-C~-alkyl-carbonyloxy, C1-C,-alkoxy-carbonyloxy, C1-C,-alkylamino-carbonyloxy, C1-C~-alkylthio, C1-Cy-alkylsulphinyl, C1-C,,-alkylsulphonyl, di-(C1-C~-alkyl)-aminosulphonyl, C3-C6-cycloalkyl or phenyl), or represent Ca-C6-alkenyl (which is option-ally substituted by fluorine, chlorine, bromine, cyano, C1-C~-alkoxy-carbonyl, carboxyl or phenyl), or represent Cs-CB-alkinyl (which is optionally substi-tuted by fluorine, chlorine, bromine, cyano, C1-C,-alkoxy-carbonyl, carboxyl or phenyl), or represent ,.
s he A 2T 154 - 5 -Ci C;-alkoxy (which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxyl, C1-C~-alkoxy-carbonyl, C~-C4-alkoxy, C1-Ch-alkylthio, Ci C,-alkylsulphinyl or Cl-C4-alkylsulphonyl), or represent Cl-C~-alkylthio (which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxyl, Ci C4-alkoxy-carbonyl, C1-C,-alkylthio, C1-C,-alkylsulphinyl or C1-C~-alkylsulphonyl), or represent C3-C°-alkenyl-oxy (which is optionally substituted by fluorine, chlorine, bromine, cyano or C1-C4-alkoxy-carbonyl), or represent C2-C°-alkenylthio (which is optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C1-C3-alkylthio or Ci C4-alkoxycarbonyl), C3-C°-alkinyloxy, C~-C°-alkinylthio, or represent the radical -S(0)p R° where p represents the numbers 1 or 2 and R° represents C1-Cw-alkyl (which is optionally substituted by fluorine, chlorine, bromine, cyano or C1-Cr,-alkoxy-carbonyl), C3-C6 alkenyl, C3-C°-alkinyl, C1-C~-alkoxy, C1-C4-aikoxy-C1-C~-alkyl-amino, C1-C4-alkylamino, di-(C1-C,-alkyl)-amino or phenyl, or represents the radical -NHOR' where R' represents C1-C~-alkyl (which is optionally substituted by fluorine, chlorine, cyano, Cz C4-alkoxy, C1-C~-alkylthio, C1-C4-alkylsul phinyl,' C1-C4-alkylsulphonyl, C1-C4-alkyl carbonyl, C1-C4-alkoxycarbonyl, Ci C,-alkyl amino-carbonyl or di-(Ci C~-alkyl)-amino carbonyl), or represents C3-C°-alkenyl (which is optionally substituted by fluorine, Le A 27 154 - 7 -~3896~8 chlorine or bromine), C3-C°-alkinyl, C3-C°-cycloalkyl, C,-C°-cycloalkyl-C1-Ca-alkyl, phenyl-C1-Ca-alkyl (which is optionally substi-tuted by fluorine, chlorine, vitro, cyano, C1-C~-alkyl, C1-C4-alkoxy or -C1-C,-alkoxy-car-bonyl), or represents benzohydryl, or repre-aents phenyl (which is optionally substituted by fluorine, chlorine, vitro, cyano, Ci C4-alkyl, trifluoromethyl, C1-C,,-alkoxy, C~ CZ-fluoroalkoxy, C1-C,-alkylthio, trifluoromethyl-thio or C,-C~-alkoxycarbonyl ) , R~ and/or Rffurthermore represent phenyl or phenoxy, or represent C1-C4-alkylcarbonylamino, C1-C4-alkoxycarbonylamino, C1-C~-alkylamino-carbonyl-amino, di-(C1-C~-alkyl}amino-carbonylamino, or represent the radical -CO-R°, where R° represents C1-CB alkyl, C1-C°-alkoxy, C3-C°-cycloalkoxy, C3-C°-alkenyloxy, C~-C, alkylthio, C1-C,-alkylamino, C~ C,-alkoxyamino, C1-C,-alkoxy-C1-C,,-alkyl-amino or di-(C1-C,-alkyl)-amino (each of which is optionally substituted by fluorine and/or chlorine), R' and/or R3 furthermore represent trimethylsilyl, thiazolinyl, C1-C,-alkylsulphonyloxy, di-(C1-C, alkyl}-aminosulphonylamino, or represent the radical -CH=N-RA, where R° represents C1-C°-alkyl which is optionally substituted by fluorine, chlorine, ~cyano, . . carboxyl, C1-C~-alkoxy, Ci C~-alkylthio, C1-C,, alkylsulphinyl or C1-Cy-alkylsulphonyl, or r Le A 27 154 - 8 -" .. ~. -..,, a.. .. . . ..

~aa~s~s represents benzyl which is optionally aubati-tuted by fluorine or chlorine, or represents Ca-C6-alkenyl or C~-C6-alkinyl, each of which is optionally substituted by fluorine or chlor-ine, or represents phenyl which is optionally substituted by fluorine, chlorine, bromine, C1-C~-alkyl, C1-C~-alkoxy, trifluoromethyl, trifluoromethoxy or trifluoromethylthio, or represents C1-CB-alkoxy, C3-C6-alkenoxy, C3-C6-alkinoxy or benzyloxy, each of which is optionally substituted by fluorine and/or chlorine, or represents amino, C1-C~-alkyl-amino, di-(C1-C~-alkyl)-amino, phenylamino, C~ C~-alkyl-carbonyl-amino, C1-Cy-alkoxy-car-bonylamino or C1-C~-alkyl-sulphonylamino, or represents phenylsulphonylamino which is optionally substituted by fluorine, chlorine, bromine or methyl, furthermore ~R12 R' represents the radical -CF1 , where R1° represents hydrogen or C1-C9-alkyl, Ril.and RIZ are identical or different and represent hydrogen, fluorine, chlorine, bromine, nitro, cyano, C1-C,-alkyl (which is optionally substitut-ed by fluorine and/or chlorine), C1-C4-alkoxy (which. is optionally substituted by fluorine andlor chlorine), carboxyl,'C1-C,-alkoxy-carbonyl, ,s be ~. 27 154 - 9 _ ' ~' 2189698 dimethylaminocarbonyl, Cl-C"-alkylsulphonyl or di-(C1-C"-alkyl)-aminosulphonyl;
furthermore R' represents the radical R13 \ ~ ~ R14, where R1' and R'" are identical or different and represent hydrogen, fluorine, chlorine, bromine, nitro, cyano, C~-C"-alkyl (which is optionally subatitut ed by fluorine and/or chlorine) or C1-c"-aixoxy (which is optionally substituted by fluorine to and/or chlorine);
furthermore R' .represents the radical i I , where R" and R'° are identical or different and represent hydrogen, fluorine, chlorine, bromine, nitro, cyano, C1-C"-alkyl (which is optionally substitut-ed by fluorine and/or chlorine), C1-C;-alkoxy (which is optionally substituted by fluorine and/or chloriney, or represent C1-C"-alkylthio, C1-Ca-alkylaulphinyl or C1-C"-alkylsulphonyl (each of which is optionall~r substituted by fluorine and/or chlorine), or represent di-(C1-C"-alkyl)-aminosulphonyl or C1-C"-alkoxy-carbonyl or di-methylaminocarbonyl;
A
Y
&e A 27 ~ 5a - to -furthermore R' represents the radical R1~ ~ ~ ~ R18 , where ~ N' R1' and R1° are identical or different and represent hydrogen, fluorine, chlorine, broraine, C,-C,-alkyl (which is optionally substituted by fluorine and/or bromine), C1-C~-alkoxy (which is optionally substi-tuted by fluorine and/or chlorine), or represent C1-C,-alkylthio, C1-C,-alkylsulphinyl or C1-C,-alkyl-sulphonyl (each of which is optionally substituted IO by fluorine and/or chlorine), or represent di-(C1-C,-alkyl)-aminoaulphonyl;
furthermore R' represents the radical , where A
R1° and RZ° are identical or different and represent hydrogen, fluorine, chlorine, bromine, cyano, nitro, C1-C~-alkyl (which is optionally aubatitut-ad by fluorine and/or chlorine), C1-C,-alkoxy (which is optionally substituted by fluorine and/or chlorine), C1-C,-alkylthio, C,-CS-alkylsul-phinyl or Ci C~-alkylsulphonyl (which is optional-ly substituted by fluorine and/or chlorine), di-(C1-C,-alkyl)-amino-sulphonyl, C1-C,-alkoxy-car-bonyl or dimethylaminocarbonyl, and A represents oxygen, sulphur or the group N-Z1, r Ire .A 2 Z 15 4 _ - l l - _ 21~9~98 where Z' represents hydrogen, C1-C,-alkyl (which is optionally substituted by fluorine, chlorine, bromine or cyano), C3-C6-cycloalkyl, benzyl, phenyl (which is optionally substituted by fluorine, chlorine, bromine or vitro), C1-C4-alkylcarbonyl, Cl-C~-alkoxy-carbonyl or di-( C,-C,-alkyl ) -aminocarbonyl;
furthermore R' represents the radical ~R22 , where ~~~SCTJ~1 Rzi and Rzz are identical or different and represent hydrogen, C1-C,-alkyl, halogen, C1-C~-alkoxy-carbonyl, C1-C;-alkoxy or C1-Ca-halogenoalkoxy, Yi represents sulphur or the group N-Rz', where I5 Rza represents hydrogen or C1-C"-alkyl;
furthermore R' represents the radical ( , where Rzi represents hydrogen, Cl-C,-alkyl, benzyl, quinolinyl or phenyl, Rz' represents hydrogen, halogen, cyano, vitro, C1-C,-alkyl (which is optionally substituted by r.e A 27 ~ Sd - I2 -fluorine and/or chlorine), C1-C4-alkoxy (which is optionally substituted by fluorine andlor chlorine), dioxolanyl or C1-C4-alkoxy-carbonyl, and R26 represents hydrogen, halogen or C1-C~-alkyl;
furthermore R3 represents one of the groups listed below, I
\ ~ SAN-C~Hy : N~

~2 The invention furthermore preferably relates to the sodium, potassium, magnesium, calcium, ammonium, C1-C4-alkylammonium, di-(C1-C4-alkyl)-ammonium, tri-(C1-C~-alkyl)-ammonium, CS- or C6-cycloalkyl-ammonium and di-(C1-C2-alkyl)-benzyl-ammonium salts of compounds of the formula (I) in which R1, R2 and R3 have the meanings mentioned_above as being preferred.
In particular, the invention of the parent application relates to compounds of the formula (I) in which R1 represents hydrogen, or represents C1-C4-alkyl which is optionally substituted by fluorine, chlorine, bromine, cyano, methoxy or ethoxy, or represents allyl, or represents C3-CS-cycloalkyl, or repre-. . 0189698 i Bents phenyl, or represents benzyl, or represents Cl-C3-elkoxy, or represents Ci-C3-alkylaroino, or represents di-(C1-CZ-alkyl)-amino, -RZ represents hydrogen, or represents C1-C,-alkyl which is optionally substituted by fluorine and/or chlor-ine or by methoxy or ethoxy, or represents C3-Cfi-cycloalkyl, or represents phenyl, or represents C1-C3-elkoxy, or represents C1-C3-alkylamino, or represents di-(Cl-C2-alkyl)-amino, and R9 represents the group 5 , where -R-('~.~.'l94 R; represents fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy, 2-chloro-ethoxy, 2-methoxy-ethoxy, C1-C3-alkylthio, Ci Cs-alkylsulphinyl, Ci C~ alkylsulphonyl, dimethylaminosulphonyl, diethylaminosulphonyl, N-methoxy-N-methylamino-sulphonyl, phenyl, phenoxy or C1-C3-alkoxy-car-bonyl, and R° represents hydrogen, fluorine, chlorine or bromine;
furthermore R3 represents the radical _CH~ , where R1° represents hydrogen, .-be A 27 154 - 14 -R11 represents fluorine, chlorine, bromine, methyl, methoxy, difluoromethoxy, trifluoromethoxy, ethoxy, methoxycarbonyl, ethoxycarbonyl, methylsulphonyl or dimethylaminosulphonyl, and R12 represents hydrogen, furthermore R3 represents the radical RO-C S ' li O
where R represents C1-C~-alkyl, or represents the radical where R represents C1-C4-alkyl.
Examples of the compounds are listed in Table 3 below - cf. also the Preparation Examples.

R3'&02-NH-CO-N~N_gl (I) R
Tatle 1: Examples of the compounds of the formula (I) gI R2 ~3 F
H
CI
N

CHa-CH=CH2 CZHS H _ ,OCHF2 0-CH2-CH=CHa S OOCH3 C2H5 CQH9-n Le A 27 154 - 16 -- continuation CH3 C3H (~,~,~-(~~
SOZNfCH3)Z
C3H ~~s(~

GH3 CZHS Cl-Z"t-B~'r CH2-CHa-C1 OC3H~ CH3 CH3 C3H~ I S ( OOCH3 N(CH3)2 CHZ""0 H2-T a h 27 154 _ 17 _ y.

Table 1 - continuation CH
NH-CH3 ~ H

CH3 C3H~
F~CHO
~F3 OC2H ~~r(5 f°~ F
CH2--(. .) CH2 CH2' C3H~
~F3 C3H7 ~N~

CH30 i CH3 C2H5 w ' ~-C4H

Le A 27 154 - 18 -~?89698 Table 1 - continuation R1 R2 ~3 CH3 C4H ' I ON(CH3)2 ON(CH31Z
C3H7 w CZHS ' C2H5 C3H7 ~
SOZ-(. ,) CZH5 C2H ~a~-(5 CH3 C3H7-n '9 2H5 C3H7-n Ls A 27 154 _ 1g _ 2~ ~~r~a Table 1 - continua~tio~

~3 CH t,/e'~~,~-3 CH3 C4H9 H2_ CH3 ~ H
~C1 C2H5 \ HZ_ C3Hy C3H~ H2_ CN
CH3 CH(CH3)2 (. ,Y-CH2-~3' ODCZHS
p ~NI

Ni I w 1~ A 27 1~4 _ 2p _ ' ' 2189698 Table 1~- continuation R

NON I
OCH3 CZHS ~ ~N
COOCH(CH3)2 ~F3 r CH3 C2H5 N\
CHg ~,N-CH 3 I ON(CH3)2 CH3 CH(CH3)2 ~1'i2-Iae A 27 154 . - 21 -Table 1 - continuation Br OCH2-CH=CH2 C2Hg CH3-t. ,J-~' ~H3 2-Nw Hr CH3 CHCCH3)2 ,SCH3 CH3 CH2-CH=CH2 ~2CH3 SCH(CH3)2 F

F
CH2-CH=CH2 H . i I ON(CH3)2 1:e A ~1 154 '189b98 . ...~.
Table 1 - continuation CHZ-CH=CH2 CH ~~-(3 r CHa-CH=CH2 CZHS

,CH3 NH-CH3 CZHg CI

NH-~H3 (~~/(~~H -~(CH3~3 i I ON(CH3)2 C2H5 Cl rae A 37 154_ _ 2g _ ..~~ ~ 21 a9~~a ~'abl~ 1 - coptinuation ~21 g2 3 R
ON(CH312 C2H5 CqH9 &

CH3 C3HT t~hS ~ CH2- F3 C H w CH ~ w ~3 C2H ((..~~~,,''~~--5 OCH3 CH(CH3)2 H

i ~ F3 r.e A 27 154 Table 1 - continuation RI R2 #;3 CH3 CZH ~s~-(S
O-SOaCH3 CH3 C3H ~~.(~
OCH3 C3H~

~2CH3 ,CH3 CH3 CaHS
Br CHZ-CH=Ckl2 CHZ-O-CH (~~(~.3 Ire A 27 154 - 25 -Tabie 1 - continuation Ri Ra R3 OCH2CHa-Cl If, for example, 2-6-difluorophenyl isocyanate and 5-ethyl-4-methoxy-2,4-dihydro-3H-1,2,4-triazol-3-one are used as starting substances, the course of the reaction in process (a) can be outlined by the following equation=
F C
H.N~N~s N-C-O +
N
C2Hs F
NH
If, for eRample, 2-methylthio-benzenesulphonamide and 2-chlorocarbonyl-4-dimethylamino-2,4-dihydro-3H-1,2,4-triazol-3-one are used as starting substances, the course of the reaction in process (b) can be outlined by the following equat ion ~3 _ '~-W ~ ~N(~3h --s N -HCl H
SCHg 1 / -SO2 ~-~'N~N'N(~~
I J~
N H
If, for example, N-methoxycarbonyl-2-methoxy-benzenesul-phonamide and 5-diethylamino-4-difluoromethyl-2,4-dihydro-3H-1,2,4-triazol-3-one are used as starting substances, the course of the reaction in process (c) can be outlined by the following equation:
~3 802 NH COOCH3 +

-HOCH~ ~ /~ ~a NH CO'N~N~CFIF2 .I
N
~N(c~sh .
Formula (II) provides a general definition of the triazo-linones to be used as starting substances in processes (a) and (c) for the preparation of compounds of the formula (I).
In formula (II), R1 and R2 preferably, or in particular, have those meanings which have already been _ 27 _ 21$9698 s mentioned above in connection with the description of the compounds of the formula (I) as being preferred, or particularly preferred, for R1 and R2.
Examples of the starting substances of the formula (II) are listed in Table 2 below.
HN~I~I-Ri N~ (II) Table 2s Examples of the starting substances of the formula (II) H H

C3H~ H
- 2e -Tabls Z2 - continuation ~2 CH(CH3)2 CHZCH(CH~)2 C(CH3)3 H CHfCH3~2 H
CQHy H CHZCH(CH3)2 H CfCH3)3 H CHaOC2H5 ~e A 27 154 _ 2g _ .. , 2189698 fable 2 - continuation ~3N7 CH3 CN(CN3)2 CH3 C~H9 CH3 CI~2C~-I I
CH3 ) 2 CH3 C(CN3)3 C2H5 CH3 , C2H~ CH3 CH ( CH3 ) 2 C)i CQHy CN3 CH2CH(CH3)2 CH

CHF2 C3H~

CF2CHF2 Cti Le A 37 159 - 30 -.. X189698 ~' Table 2 - continuation C2H5 C~H~

6H5 ~~3 ~H2 _ CH3 C~H

~H2 ~H2 CH3 (V(CH3)2 C2H5 N(CH3)2 C3H~

Le A 27 154 - 31 -~~89b98 Table 2 - continuation N(CH3)2 CH

N(CH312 C H

N(CH3)2 C H

Le A 27 154 - 32 -Table 2 - continuation ~2 OCH3 C/~~

OCH3 C~H~

OC2H5 C~13 OC2H5 C~H~

N(CH3?2 O_C3H7 C3H7 O-CH2-CH=CH2 CH3 0-CHZ-CH=CHa C2H5 O-CHZ-CH=CH2 C3H7 0-CHa-CH-CH2-8r C3H7 Br Le A 27 154 - 33 -...,,i~ ~~89698 ~ahle 2 - continuation ~2 OCH3 Ct) OCH3 N(CH~)2 O-CH2-COOCH3 C3H~
N(CH3)2 N(CH3)2 N(CH3)2 OC2H5 C3~?

I~~ A 27 154 - 34 -.....~, Table 2 - continuation Rz HH-CH3 Cj~l2-0-C1~3 CH3 CfiZ-0-C#!3 I~ ~ 27 154 - 35 -~~8~698 i The starting substances of the formula (II) are known andlor can be prepared by processes known per se (cf.
Chem. Ber. 90 (1957), 909-921 loc.cit. 98 (1965), 3025-3099; J. Heterocycl. Chem. 15 (1978), 237-240; Tetra-hedron 32 (1976), 2347-2352; Helv. Chim. Acta 63 (1980), 841-859; J. Chem. Soc. C 196?~ 746-751; EP-A 283,876;
EP-A 294,666; EP-A 301946; EP-A 298,371;
DE-P 3,839,206/LeA 26,538 dated 19.11.1988;
DE-P 3,916,207/LeA 26,849 dated 18.05.1989;
DE-P 3,916,208/LeA 26,850 dated 18.05.1989; J. Chem. Soc.
C 1970, 26-34; DE-P 3,916,930/LeA 26,886 dated 24.05.1989).
For example, the triazolinones of the formula (II) are obtained when a) oxadiazolinones of the general formula (VII) f i~N~ ( V I I ) N~Rz in which R' has the abovementioned meaning are reacted with amino pompounds of the general formula (VIII) H2N-R1 (yIII) in which R1 has the abovementioned meaning, Le A 27 154 _ 36 .. ~'189b98 at temperatures between 20°C and 120°C and, if appropriate, in the presence pf a diluent, such as, for example, watery and the hydrazine derivatives formed by this process, of the general formula (IX) H~ NCO-Nli-RI
N
(IX) ~N~
H CO-RZ
in which R1 and Ra have the abovementioned meanings, are isolated by customary methods (cf. the Preparation Examples) and - or if appropriate even without intermediate isolation - the compounds of the formula (IX) are condensed at temperatures between 20°C and 120°C and, if appropriate, in the presence of a basic condensation auxiliary, such as, for example, sodium hydroxide, and, if appropriate, in the presence of a diluent, such as, for example, water, to give the compounds of the formula (II) (cf. EP-A 301,946, DE-OS (German Published Specification) 3,743,493/LeA 25,759 and the Preparation Examples), ar when ~) amino compounds of the ~enaral formula (VIII) HaN-R1 (YIII) Le A 27 154 - 37 in which R1 has the abovementioned-meaning, are reacted with carbonic acid derivatives, such as, for example, Biphenyl carbonate, then with hydrazine or hydrazine hydrate~and eventually with a carboxylic acid derivative or carbonic acid derivative of the general formula (X) (R~)3C-R2 (X) in which R2 has the abovementioned meaning and Rrepresents-lower alkyl, -at temperature between 0°C and 150°C and, if appropriate, in the presence of a diluent, such as, for example, ethylene chloride (cf. DE-P 3,920,270lLeA-26,937 dated 21.06_1989, DE-P 3,928,662ILeA 27,137 dated 30.08.1989, and the Preparation Examplesy.
Some of the compounds of formula II are novel.
According to one aspect of the invention of the present divisional application there is provided a -triazolinone of the general formula (IIa) O
Ai HN~ ( ITa ) in which either (1) A1 represents di-(C1-C4-alkyl)-amino and A2 represents hydrogen, or represents C1-C6-alkyl which is optionally substituted by fluorine, 2189b98 chlorine, bromine, cyano, Ci-C~-alkoxy, Ci-C4-alkyl-carbonyl or C1-C~-alkoxy-carbonyl, or represents C3-C6-cycloalkyl which is optionally substituted by fluorine, chlorine, bromine and/or C1-C4-alkyl, or represents C1-C4-alkoxyf or in which ~ 2 ) Ai tepres~tsand AZ repreaeuts ~5 0~3 C3H7 ~3 ~3 ~~3)2 ~2~3 ~s C3I3~

~3 ~.'qfIg 2189b98 ~3 ~~3 ~3 ~3H7 C3~7 OCHa-CFi-CHa CH3 O-CHa-Chi-C~ia Cads O-CHa-CH-CHa C3H7 C-CH2~-CH-Ht C3H7 ~3 ~3 ~a ~a'~H3 C3H7 OCaHs C3Ii7 ~~~3~2 C,~H9 ~3 ~5 H

- 39a -~3 CHs -CH2CH-(~Ia ~3 '~2~3 '~2~3 -~a~aHs -rt(~3h.

The new triazolinones of the formula (IIa) are obtained either when oxadiazolinones of the general formula (VII8j x,~~
Aa in which A2 has the abovementioned meaning, are reacted with amino compounds of the general formula (VIIIa) H2N-A1 (VIIIa) in which Al has the abovementioned meaning, analogously to the process described above under (ay, or when amino compounds of the general formula (VIIIa) H2N-A1 (VIIIa) - 39b -~~$9~~e are reacted with carbonic acid derivatives, then with hydrazine or hydrazine hydrate and eventually with a carboxylic acid derivative or carbonic acid derivative of - 39c -. 2189b98 the general formula (Xa) (RO?gC-AZ (Xp) in which Aa and R have the aboyementioped meanings, analogously to tl~e process described above under (also see the Preparation Examples).
In the general formula (IIa), A1 preferably represents C1-C5-alkyl, C3-CS-alkenyl or C3-C6-cycloalkyl, or represents C1-C6-alkoxy which is optionally substituted by fluorine, chlo-rine, bromine, cyano, C1-C4-alkoxy or C1-C4-alk-oxy-carbonyl, in particular methyl, ethyl, allyl, cyclopropyl, methoxy, ethoxy, propoxy or isoprop-oxy, or represents di-(Cl-C4-alkyl)-amino, in par-titular dimethylamino or diethylamino, and AZ preferably represents hydrogen, or represents C1-Cfi-alkyl which is optionally substituted by fluorine, chlorine, bromine, cyano, C1-C,-alkoxy, C1-C4-alkyl-carbonyl or C1-C4-alkoxy-carbonyl, or represents C~-C6-cycloalkyl which is optionally substituted by fluorine, chlorine, bromine and/or C1-C,,-alkyl, or represents phenyl-Ci C3-alkyl which is optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C1-C~-alkyl, trifluoromethyl, C1-C,,-alkoxy and/or Ci C~ alkoxycarbonyl, or represents phenyl which is optionally substituted by fluorine, chlor-ine, bromine, cyano, nitro, Ci C4-alkyl, trifluoro-methyl, Ci C,-alkoxy, fluorine- and/or chlorine-substituted C1-C9-alkoxy, C1-C,,-alkylthio, fluorine-and/or chlorine-substituted C1-C3-alkylthio, C1-C4-alkylsulphinyl, C1-C,-alkylsulphonyl and/or C1-C,-1,e A 27 154 - 40-alkoxy-carbonyl, or represents C1-C4-alkoxy, in particular hydrogen, C1-C4-alkyl which is optionally substituted by fluorine and/or chlorine, methoxy or ethoxy, or represents C3-C6-cycloalkyl, or represents methoxy or ethoxy, provided that both A1 and A2 do not simultaneously represent C1-C6-alkyl.
The compounds of the formulae (VII), (VIIa), (VIII), (VIIIa) and (X) or (Xa) which are to be used as starting substances for the preparation of the triazolinonea of the formulae (II) or (IIa) are known (cf. xelv. Chim. Acts 55(1972), 1174; EP-A 301,946; DE-OS (German Published Specification) 3,743,493).
Formula (III) provides a general definition of the aulphonyl isocyanates further to be used as starting substances in process (a) for the preparation of compounds of the formula (I).
In formula (III),-R3 preferably, or in particular, has the meaning which has already been mentioned above in connection with the description of the compounds of the formula (I) as being preferred, or particularly preferred, for R3.
Examples of the starting substances of the formula (III) which may be mentioned area 2-fluoro-, Z-chlorb-, 2-bromo-, 2-methyl-, Z-methoxy-, 2-trifluoromethyl-, 2-difluoro-methoxy-, 2-trifluoromethoxy-, 2-methylthio-, 2-ethylthio-, 2-propylthio-, 2-methyl-aulphinyl-, Z-methylsuiphonyl-, 2-dimethylaminosulphonyl-, 21896°8 2-diethylaminosulphonyl-, 2-(N-methoxy-N-methyi)-aminosulphonyl-, 2-phenyl-, Z-phenoxy-, 2-methoxycarbonyl-, 2-ethoxycarbonyl, 2-propoxycarbonyl- and 2-isopropoxy-carbonyl-phenylsulphonyl isocyanate, Z-fluoro-, 2-chloro-, 2-difluoromethoxy-, 2-trifluorometh-2-methoxycarbonyl- and 2-ethoxycarbonyl-benzylsulphonyl isocyanate, 2-methoxy-carbonyl-3-thienyl-sulphonyl isocyanate, 4-methoxycarbonyl-and 4-ethoxycarbonyl-1-methylpyrazol-5-yl-sulphonyl isocyanate.
The sulphonyl isocyanates of the formula (III) are known andlor can be prepared by processes known per se (cf.
US-P 4,127,405, 4,169,719, 4,371,391; EP-A 7,687, 13,480, 21,641, 23,141, 23,422, 30,139, 35,893, 44,808, 44,809, 48,143, 51,466, 64,322, 70,041, 173,3I2).
Process (a) for the preparation of the new compounds of the formula (I) is preferably carried ovt using diluents. Suitable diluents in this context are virtually all inert organic solvents. These preferably include aliphatic and aromatic, optionally halogenated hydrocarbons, ZO such as pentane, hexane, heptane, cyclohexane, petroleum ether, benzine, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dicf~lorobenzene, ethers, such as diethyl ether and dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, tatrahydrofuran and dioxane, ketones, such as acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone, esters, such as methyl acetate and ethyl acetate, nitriles, such as, _ 42 _ for example, acetonitrile and propionitrile, -amides, such as, for example, dimethylformamide, dimethylacetamide and N-methyl-pyrrolidone, and also dimethyl sulphoxide, tetra-methylQne sulphone and hexamethylphosphoric triamide.
In process (a}, the reaction temperatures can be varied within a substantial range. In general, the process is carried out at temperatures between 0°C and 150°C, preferably at temperatures between 10°C and 80°C.
Process (a) is generally carried out under atmospheric pressure.
For carrying out process (a}, between 1 and 3 moles, preferably between l and 2 moles, of sulphonyl isocyanate of the formula (III) are generally employed per mole of triazollnone of the formula (II).
The reactants can be combined in any desired sequence. The reaction mixture is stirred until the reaction ie complete and concentrated, and the crude product which remains in the residue is crystallized using a suitable solvent, such as, for example, diethyl ether. The product of the formula (I) which has been obtained in crystalline form' is isolated by filtration with suction.
Formula (IU) provides a general definition of the triazolinone derivatives to be used as starting substances in process (b) for the preparation of compounds o~f the formula (I).
In formula (IV), R1 and R2, preferably, or in particular, have those meanings which have already been mentioned above in connection with the description of the 2I$~698 compounds of the formula (Ij as being preferred, or particularly preferred, for Rl and R2, and Z preferably represents chlorine, Cl-C4-alkoxy, benzyloxy or phenoxy, in particular methoxy or - 43a -., ~~i phenoxy.
Examples of the starting substances of the formula (IVj which are possible are the compounds of the formula (IV) to be prepared from the compounds of the formula (II) listed in Table 2 'and phosgene, methyl chloroformate, benzyl chloroformate, phenyl chloroformate or diphenyl carbonate.
The starting substances of the formula (IV) are known and/or can be prepared by processes known per se (cf. EP-A 283,876; EP-A 294,666; EP-A 298,371.
The triazolinone derivatives of the formula (IV) are obtained for e~ampla When triazolinones of the general formula (II) o Hj~NiRl (II) ~R2 in which R1 and RZ have the abovementioned meanings, are reacted With carbonic acid derivatives of the general formula (XI) Z-CO-Z1 (XI) in which 8 has the abovementioned meaning and he A 27 154 - 44 -'189698 Z1 represents a leaving group, such as chlorine, methoxy, benzyloxy or phenoxy, at temperatures between -20°C and +100°C, if appropriate in the presence of a diluent, such as, for example, tetrahydrofuran, and, if appropriate, in the presence of an acid acceptor, such as, for example, sodium hydride or potassium tert-butylate (cf. the Preparation Examples). -Formula (U) provides a general definition of the sulphonamides further to be used as starting substances in process (b) for the preparation of compounds of the formula (1).
In formula (V), R3 preferably, or in particular, has the meaning which has already been mentioned above in connection with the description of tYie compounds of the formula (I) as being preferred, or particularly preferred, for R3.
Examples of the starting substances of the formula (U) which may be mentioned are:
2-fluoro-, 2-chloro-, 2-bromo-, 2-methyl-, 2-methoxy-, 2-trifluoromethyl-, 2-difluoro-methoxy-, 2-trifluoromethoxy-, 2-methylthiv--, Z--ethylthio-, Z=propylthio-, -2-methylsulphinyl-, 2-methylsulphonyl-, 2=dime~thylamino-sulphonyl-, Z-die~hylaminosulphonyl-, 2-(N=methoxy-ft-methyl)-aminoaulphonyl-, 2-phenyl-, 2-phenoXy-, 2-methoxycarbonyl-, 2-ethoxycarbonyl-, 2-propvxycarbonyl- and 2-isopropoxy-carbonyl-benzenesulphonamide, 2-fluoro-, 2-chloro-Y
2-difluoromethoxy-, 2-trifluoromethoxy-, 2-methoxycarbonyl-.
and 2-ethoxycarbonyl-phenylmethanesulphonamide, 2-methoxy-carbonyl-3-thiophenesulphonamide, 4-methoxycarbonyl- and 4-ethoxycarbonyl-1-methyl-pyrazol-5-sulphonamide.
The sulphonamides of the formula (U) are known and/or can be prepared by processes known per se (cf. US-P
4,127,405, 4,169,719, 4,371,391; EP-A 7,687, 13,480, 21,641, 23,141, 23,422,-30,42Z~--30,139; 35,893, 44,808, 44,809, 4$,143, 51,466, 64,322, 70,041, 173,312}.
Process (b) for the preparation of the new compounds of the formula (I} is preferably carried out using diluents. Suitable diluents in this context are virtually all inert organic solvents, for example those which have been indicated above in the case of process (a}.
klcid acceptors which can be employed in process (b}
are all acid-binding agents which can customarily be used for reactions of this type. The following are preferably suitable= alkali metal hydroxides, such as, for example, sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides, such as, for example, calcfum hydroxide, alkali metal carbonates and alkali metal alcohoiates, such as sodium carbonate, potassium carbonate, sodium tent-butylate and potassium tent-butylate, furthermore aliphatic, aromatic or heterocyclic amines, for example triethylamine, trimethylamine, dimethylaniline, dimethylbenzylamine, pyridine, 1-5-diazabicyclo-[4.3.0]-non-5-ene (DBN), 1-8-diazabicyclo-[5.4.0]-undec-7-ene (DBU) and 1,4-diazabicyclo-[2,2,2]-octane (DABCO).
When carrying out process (b), the reaction ~~89~~~
temperatures can be varied within a substantial range. In general, the process is carried out at temperatures between 0°C and 100°C, preferably at temperatures between 10°C
and 60°C.
In general, process (b) is carried out under atmospheric pressure. However, it is also possible to carry out the process under increased or reduced pressure.
For carrying out process (b), the specifically required starting substances are generally employed in approximately equimolar amounts. However, it is also possible to use one of the two specifically employed components in a substantial excess. In general, the reactions are carried out in a suitable diluent in the presence of an acid acceptor, and the reaction mixture is stirred for several hours at the specifically required temperature. Working-up in process (b) is carried out in each case by customary methods.
The triazolinones of the formula (II) which are to be used as starting substances in process (c) for the preparation of compounds of the formula (I) have already been described as starting substances for process (a).
Formula (VI) provides a general definition of the sulphonamide derivatives further to be used as starting substances in process (c) for the preparation of compounds of the formula (I).
In formula (VI), R3 and Z preferably, or in particular, have those meanings which have already been mentioned above in connection with the description of the -~ ~ s9s~s compounds of the formula (I) or (IV) as being preferred, or particularly preferred, for R3 and Z.
Process (c) is preferably carried out using diluents. Suitable diluents in this context are the same organic solvents as have been mentioned above in connection with the description of process (a).
If appropriate, process (c) is carried out in the presence of an acid acceptor. Suitable acid-binding agents in this context are the same as have been mentioned above in connection with the description of process (b).
When carrying out process (c) the reaction temperatures can be varied within a substantial range. In general, the process is carried out at temperatures between 0°C and 100°C, preferably at temperatures between 10°C
and 60°C.
In general, process (c) is carried out under atmospheric pressure. However, it is also possible to carry out the process under increased or reduced pressure.
For carrying out process (c), the specifically required starting substances are generally employed in approximately equimolar amounts. However, it is also possible to use one of the two specifically employed components in a substantial excess. In general, the reactions are carried out in a suitable diluent in the presence of an acid acceptor, and the reaction mixture is stirred for several hours at the specifically required temperature. Working-up in process (c) is carried out in each case by customary methods.

To convert the compounds of the formula (I) into salts, they are stirred with suitable salt formers, such as, for example, sodium hydroxide, sodium methylate, sodium ethylate, potassium hydroxide, potassium methylate or potassium ethylate, ammonia, isopropyl8mine, dibutylamine or triethylamine, using suitable diluents, such as, for example, water, methanol or ethanol. The salts can be isolated as crystalline products - then if appropriate after concentrating the mixture.
The active compounds can be used as defoliants, desiccants, agents for destroying broad-leaved plants and, especially, as weed-killers. By weeds; in the broadest sense, there are to be understood all plants which grow in locations where they are undesired. Whether the substances act as total or selective herbicides depends essentially on the amount used.
The active compounds can be used, for example, in connection with the following plants' Dicotvledon weeds of the ~tenera~ __$inapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Hanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Ciraium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus and Taraxacum.
Dicotvledon cultures of he ae~ r~.~ Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, 9 _ Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cubumis and Cucurbita.
Monocotyledon weeds of the ~lebera~ Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Branchiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and Apera.
Monoc tvledon cut urea Qf the g era Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and Allium.
However, the use of the active compounds is in no way restricted to these genera, but also extends in the same manner to other plants.
The compounds are suitable, depending on the concentration, for the total combating af- weeds, for example on industrial terrain and rail tracks, and on paths and squares with or without tree plantings. Equally, the compounds can be employed for combating weeds in perennial cultures, far example afforestations, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft-fruit plantings and hopfields, in lawns, turf, meadows and pastures, and for the selective combating of weeds in annual cultures.
The compounds of the formula (I} are suitable for combating monocotyledon and dicotyledon weeds both in the ~189bg8 pre-emergence and the post-emergence method. They are markedly more effective than, for example, isocarbamide.
To a certain extent, the compounds also show a fungicidal action, for example against powdery mildews and against apple scab, and also against Pyricularia oryzae on rice. -The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspension-emulsion concentrates, natural and synthetic materials impregnated with active compound, and very fine capsules in polymeric substances.
These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that-is liquid solvents andlor solid carriers, optionally with the use of surface-active agents, that is emulsifying agents and/or dispersing agents and/or forming agents.
In the case of the use of water-as an extender, ZO organic solvents can, for example, also be used as auxiliary solvents. As liquid solvents, there are suitable in the maim aromatics, such se xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such ae cyclohexane or paraffina, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, as well as water.
As solid carriers there pre suitable: for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly disperse silica, alumina and silicates, as solid carriers for granules there are suitable: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; as emulsifying andlor foam-forming agents there are suitable: for example non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates as well as albumen hydrolysis products; as dispersing agents there are suitable: for example lignin-sulphite waste liquors and methylcellulose.
l~dhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, ae well as natural phospholipids, such as cephali~s and lecithins, and 1.e A 27 154 - 52 -synthetic phospholipids, can be used in the formulations.
Further additives can be mineral and vegetable oils.
It-is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of ion, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90~.
For combating weeds, the active compounds as such or in the form of their formulations, can also be used as mixtures with known herbicides, finished formulations or tank mixes being possible.
Suitable herbicides for the mixtures are known herbicides, such as, for example, 1-amino-6-ethylthio-3-(2,2-dimethylpropyl)-1,3,5-triazine-2,4(1H,3H)-dione (AMETHYDIONE) or N-(2-benzothiazolyl)-N, N'-dimethylurea (METABENZTHIAZURON) for combating weeds in cereals; 4-amino-3-methyl-6-phenyl-1,2,4-triazin-5(4H)-one (METAMITRON) for combating weeds in sugar beet and 4-amino-6-(1,l-dimethylethyl)-3-methylthio-1,2,4-triazin-5(4H)-one (METRIBUZIN) for combating weeds in soya beans; furthermore also mixtures with 2,4-dichlorophenoxyacetic acid (2,4-D);
4-(2,4-dichlorophenoxy)-butric acid (2,4-DB); 2,4-dichlorophenoxypropionic acid (2,4-DP); 5-(2-chloro-4-trifluoromethyl-phenoxy)-2-nitrobenzoic acid (ACIFLUORFEN);
2-chloro-2',6'-diethyl-N-methoxy-methyl-- 53a -v'~ ' ' 2189698 i' acetanilide (ALACHLOR); 2-chloro-4-ethylamino-6-iso-propylamino-1,3,5-triazine {ATRAZINE); methyl 2-[[[[[(4,6-dimethoxypyrimidin-2-yl)-amino]carbonyl]-amino]-sulphonyl]-methyl]-benzoate (BENSULFURON); 3-isopropyl-2,1,3-benzothiadiazin-4-one 2,2-dioxide {BENTAZONE); methyl 5-(2,4-dichlorophenoxy)-2-nitro-benzoate (BIFENOX); 3,5-dibromo-4-hydroxy-benzonitrile;
(BROMOxYNIL); N-(butoxymethyl)-2-chloro-N-(2,6-diethyl-phenyl)-acetamide (BUTACHLOR); ethyl 2-{[(4-chloro-6-methoxy-2-pyrimidinyl)-aminocarbonyl]-aminosulphonyl}-benzoate(CHLORIMURON);2-chloro-N-{[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino]-carbonyl}-benzenesulphonamide (CHLORSULFURON); N,N-dimethyl-N'-(3-chloro-4-methyl-phenyl)-urea(CHLORTOLURONj; 2-chloro-4-ethylamino-6-(3-cyanopropylamino)-1,3,5-triazine(CYANAZINE);2,6-dichlo-robenzonitrile(DICHLOBENIL);2-[4-(2,4-dichlorophenoxy)-phenoxy]-propionic acid, its methyl eater or its ethyl ester (DICLOFOP); 2-[(2-chlorophenyl)-methyl]-4,4-di-methylisoxazolidin-3-one (DIMETHAZONE); 4-amino-6-t-butyl-3-ethylthio-1,2,4-triazin-5(4H)-one (ETHIOZIN); 2-{4-[6-chloro-2-benzoxazolyl)-oxy]-phenoxy}-propanoic acid, its methyl ester or its ethyl ester (FENOXAPROP);
2-[4-(5-trifluoromethyl-2-pyridyloxy)-phenoxy]-propanoic acid or its butyl ester (FLUAZIFOP); N,N-dimethyl-N'-(3-trifluoromethylphenyl)-urea (FLUOMETURON); 1-methyl-3-phenyl-5-(3-trifluoromethylphenyl)-4-pyridone (FLURIDONE); 5-(2-chloro-4-trifluoromethyl-phenoxy)-N-methylsulphonyl-2-nitrobenzamide (FOMESAFEN); N-phos-phonomethyl-glycine (GLYPHOSATE);
methyl 2-[4,5-dihydro-4-methyl-4-~1-methylethyl)-5-oxo-Le A 27 154 - 54 -iH-imidazol-2-yl]-4(5)-methylbenzoate (IMAZAMETHABENZ);
2-(4,5-dihydro-4-methyl-4-isopropyl-5-oxo-1H-imidazol-2-yl)-pyridine-3-carboxylic acid (IMA7,APYR); 2-[5-methyl-5-(1-methylethyl)-4-oxo-2-imidazolin-2-yl]-3-quinolin-carboxylic acid (IMAZAQUIN); 2-[4,5-dihydro-4-methyl-4-isopropyl-5-oxo-(1H)-imidazol-2-yl]-5-ethylpyridin-3-carboxylic acid (IMAZETHAPYR); 3,5-diiodo-4-hydroxy-benzonitrile (IOXYNIL); N,N-dimethyl-N'-(4-ieo-propylphenyl)-urea (ISOPROTURON); {2-methyl-4-chloro-phenoxy)-acetic acid (MCPA}; (4-chloro-2-methylphenoxy)-propionic acid {MCPP); N-methyl-2-(1,3-benzothiazol-2-yloxy)-acetanilide(MEFENACET);2-chloro-N-(2,6-dimethyl-phenyl)-N-[(1H)-pyrazol-1-yl-methyl]-acetamide (METAZACHLOR); 2-ethyl-6-methyl-N-(1-methyl-2-metho-xyethyl)-chloroacetanilide (METOLACHLOR); 2-{[j((4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino)-carbonyl]-amino]-sulphonyl}-benzoic aicd or its methyl ester (METSULFURON); 1-{3-trifluoromethyl-phenyl)-4-methyl-amino-5-chloro-6-pyridazone (NORFLURAZON); N-(1-ethyl-propyl)-3,4-dimethyl-2,6-dinitroaniline (PENDIMETHALIN);
0-(6-chloro-3-phenyl-pyridazin-4-yl) S-octyl thio-carbamate (PYRIDATE); ethyl 2-[4-(6-chloro-quinoxalin-2-yl-oxy)-phenoxy]-propionate (QUIZALOFOP-ETHYL); 2-jl-{ethoxamino)-butylidene]-5-(2-ethylthiopropyl)-1,3-cyclohexadione (SETHORYDIM); methyl 2-{[(4,6-dimethyl-2-pyrimidinyl)-aminocarbonyl]-aminosulphonyl}-benzoate (SULFOMETURON); 4-ethylamino-2-t-butylamino-6-methylthio-s-triazine {TERBUTRYNE); methyl 3-[[[j(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino]-carbonyl]-amino]-sulphonyl]-thiophene-2-carboxylate (THIAMETURON); S-I~ A 2Z 154 - 55 -(2,3,3-trichloroallyl)-N,N-diisopropylthiocarbamate (TRI
ALLATE), 2,6-dinitro-4-trifluoromethyl-N,N-dipropylaniline (TRIFLURALINa. Surprisingly, some mixtures also show a synergistic effect.
Mixtures with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellants, plant nutrients and agents which improve soil structure, are also possible.
The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are used in the customary manner, for example by watering, spraying, atomizing or scattering.
The active compounds can be applied either before or after emergence of the plants.
They can also be incorporated into the soil before sowing.
The amount of active compound used can vary within a substantial range. It depends essentially on the nature of the desired effect. In general, the amounts used are between 0.01 and 15 kg of active compound per hectare of soil surface, preferably between 0.05 and 10 kg per ha.
The preparation and use of the active compounds can be seen from the following examples.

COOCI~i3 O
'-S02-Nh/-CON
'"H3 (Process (a)) 3.0 g (17.95 mmol) of 4-cyclopentyl-5-methyl-2,4 dihydro-3H-1,2,4-triazol-3-one are dissolved in 60 ml of acetonitrile, and 6.9 g (28.6 mmol) of 2-methoxycarbonyl phenylsulphonyl isocyanate, dissolved in 20 ml of aceto nitrile, are added to this solution with stirring. The reaction mixture is stirred for 6 hours at 20°C and then concentrated. The residue which remains is stirred with diethyl ether, and the product which has been obtained in crystalline form is isolated by filtration with suction.
This gives 6.6 g (90 % of theory) of 4-cyclo pentyl-5-methyl-2-(2-methoxycarbonyl-phenylsulphonyl aminocarbonyl)-2~4-dihydro-3~-).,2,4-triazol-3-one of melting point 146°C.
Le A 27 ~ 54 _ 57 _ Example 2 NH
(Process (b}}
1.8 g (11.8 mmol} of 1,8-diazabicyclo-[5,4,0]-undec-7-ene (DBU} are added to a stirred mixture of 3.0 g (12.1 mmol} of 5-ethyl-4-methyl-2-phenoxycarbonyl-2,4-dihydro-3H-1,2,4-triazol-3-one, 2.5 g (12.2 mmoI} of 2-chloro-6-methyl-benzenesulphonamide and 60 ml of acetonitrile. The reaction mixture is stirred for 2 hours at 20°C, then poured into about twice the volume of ice-water, and a pH of about 2 is established by dropwise addition of concentrated hydrochloric acid. The product which has been obtained during this process in crystalline form is isolated by filtration with suction.
This gives 3.2 g 973.5 ~ of theory} of 5-ethyl-4-methyl-2-(2-chloro-6-methyl-phenylsulphonyl-aminocarbonyly-2,4-dihydro-3H-1,2,4-triazol-3-one of melting point 176°C.
For example the compounds of the formula (I) listed in Table 3 below can also be prepared analogously to Examples 1 and 2 and following the general instructions of the preparation processes R3-S02-NH-CO~N~N~#il ( I ) ~H2 Table 3a Preparation Examples of the compounds of the formula (1) (m. p. = melting point):
EX. RI Ra R' m.p. ('C) No.

~Fa 4 CH3 CZHS ~

l~9 6 CH3 C3H~ 143 Cl CZHS C2H5 ~ 139 Le A 27 154 _ 5g _ 2~ a969a Table 3: - continuation Ex. R1 Ra R$ m.p. ( °C) No.

8 CH3. C3H7 141 CpOCH3 9 OCH3 CH3 ,~~-( 121 ~2N(CH3)2 OCH3 Cli3 ~ 180 1l OCH3 CH3 149 12 OCH3 C2H5 '/,.,~~.(/~~ 144 $02N(CH3)2 L~ ~ 27 154 - 60 -Table 3: - continuation EX. R1 RZ R~ m.p. (°C) No.
T;O~N(CH3)2 16 C2H5 ~ 154 17 0CH3 CH(CH3)~ 137 802N(CH3)2 18 C2H5 ~' 174 H
20 CH3 N(CH3)2 168 2i OCHaC6l~[S CH3 179 Le A 27 154 - 61 -'. '' ~ 21~969~
Table 3: - continuation EX. R1 R2 R9 m.p. ( C) No.

23 N(Cyi3)2 C2H5 '~~l 139 24 N(CH3)2 H ~ 197 ~

25 N(CH3)2 CH(CH3)2 148 26 OC2H5 C2HS ~ 153 ~

28 CtlfCH3)2 186 ~

29 C3H? 146 30 N(CH3)2 C3H7 110 I~ A 27 154 - 62 -. , ~ .~~ 2189698 Tak~le 3s - continuation Ex. RI R~ ~3 m~P~ I~C) No.

3I N(CH3>2 32 C2H5 C4l-!~ 9 33 CH3 C4H9 (,-~~('~ 113 3T CH3 ~ (~~o~('~ 141 38 C2H5 ~ 130 Le A 27 154 - 63 -. . '-,y 2189698 Table 3s - continuation EX. R1 RZ ~3 a No. m~P~ C

39 C3H~ 139 42 CH(CH3)2 NHCI-7(CH3)2 (~.~~('~ 135 43 N(CH3)2 N(CH3)2 171 ~F3 44 CH3 C3H~ ~/~--~~,~- 168 C2H5 N(CH3)Z 134 ~F3 46 CH3 C ~'/s~~~,,JJ------H

r Ire A 27 ~ 54 - 64 -Table 3: - continuation EX. R1 Ra R3 m.p. ( °C) No.
~F3 4 H~2 C3H~ '/°~~~ 120 48 ~ NH~

4 9 ~ ~,~~'H

50 -CH2CH=CH2 C2H5 108 51 -CH2CH~CH2 H (~~s.~~('~ 158 ~F3 52 OCH3 C3H~ ~~'' 110 - 111 j'~ COpCF(3 53 CH2--(. J H 212 - 214 54 C3H~ H
168 - 1b9 ~e A 27 154 - 65 -Table 3: - continuation EX. R1 RZ Rs m.p. ('C) NO.

~

56 C2H5 12?

57 OCH3 C2H5 ~ 111 - 113 / ~~\

59 -IaHCH3 C3H7-n ~ 196 F

60 CH3 C3H7-n 178 61 ~ H 177 --Le A 2T 154 - 6fi -~'abl~ 3: - continuation EX. R1 Rz R~ m.p. ('C) No.

b2-CH2CHfCH3 )2JC2H8 ~ 123 63-CH2-CH-CH2 C3H7-n ~ (amorphous) 64CH2~ C2H5 157 65~ C2H5 117 COOCli3 66-C(CH3)3 C2H5 182 67~ C2H5 133 68~ C2H5 162 69-CH2-CH=CH2 CH3 120 ~e ,A 27 154 - 67 -Tabl e 3: - continuation EX. R1 Rz R~ m.p. (Cj No.

COOCI-~3 70 ~ C2H5 183 71 C2H~ H 196 72 ~ CH3 153 73 -OCH3 ~ 138 79 CH(CH3)2 H ~~ 191 75 H ~ 191 77 -C(CH3)3 H ~ 211 Le A 27 154 - fig -Table 3; - continuation EX. R1 R$ Rj m.p. (°C) No.

78 -CH2-iH-CH2Br CH3 110 Hr 79 CH3 -CH20CH3 ~-- 152 F

81 CH3 -CH20C2H5 ~ 123 82 -OCH3 C3H7-n (amorphous) CON(CH3)2 83 C2H5 \ ~ 124 ~

84 -CH20CH3 ~ 102 COOC#~3 ~

85 -CH20CH3 ~ 155 1,e A 27 1~4_ , - 69 -21.89 698 Table3: - continuation Ex. R1 Ra R$ m.p. ('CJ

No.

86 -CH~OC2H5 123 ocF3 87 -CH20C2H5 ~ 99 ~

88 -N(CH3)2 ~ 189 CI

GI
~

CI

91 -OCH3 C3H7-n ~ 125 ~

92 C2H$ ~ 138 ~

Le 1~ 27 154 - 70 -Table 3: - continuation Ex. R' Ra R9 m.p. (C) No.

94 -OC2H5 C3H7-n ~ 107 95 -OCH3 CH(CH3)2 ~ 128 oCF3 , 96 OCH3 CH3 ~~ 119 ~

97 C3H7-n ~ 100 ~

s 98 ~ 140 ~

99 -N(CH3)2 ~ 163 ~ , i00 . -N(CH3)Z ~~ 182 1.e A 27 154 _ _ 71 _ Table 3: - continuation EX. R' R2 R' m.p. (°C) No.
C

101 CH3 -N(CH3)2 ~ 181 --102 CH3 -OCH3 ~ 150 ~
~-~

103 C2H~ 197 104 -CH2-CH=CH2 CH3 132 105 -CH2-CH=CH2 C2Hr~ ~ 109 106 -CH2-CH=CH2 C3H7-n ~ 104 T.e ~ 27 154 - 72 -2? 8969$
i Table3: - continuation EX. R1 Ra Ids m.p. (C) No.

108 -DC2H5 C3H7-n ~ 136 C~3 109 -OCH3 CHtCH3)2 126 112 CH3 CH(CH3)2 124 Le A ~7 154 . _ 73 _ =.. ~, 2189b98 Table 3~ - continuation Ex. R1 Ra R3 m.p. (°C) No.

i13 CH3 ~ 171 114 C~1(CH3)2 132 115 ~ 167 ~3 116 CH3 CH3 ~ 155 ,CH3 117 CH3 C2H5 ~~ 147 i18 CH3 C3H7-n ~~ 169 ~e A 2~q - 7g Table 3s -_continuation _.. _ Ex. R1 Rz R3 m.p. ('C) No.
119 OCH3 CZH5 ~
~ODCH3 C ~ CH3 lzo -cHZ c2H5 laz ,r~ , r, &e A 27 1~4 . - 7g _ ' 21$969$
Startigg substances of the formula 1171:
Exam~~~-11 H11 ~~~OC2H5 ~a~s H-i-CO-NH-OC2H5 (IX-1) A mixture of 68.5 g (0.60 mol) of 5-methyl-1,3,4-oxadiazolin-2-one, 45.8 g (0.75 mol) of 0-ethyl-hydroxyl-amine and 400 ml of water is refluxed for 12 hours and then concentrated. The residue is taken up in ethanol and reconcentrated. The residue which is obtained in this process is stirred With diethyl ether, and the product which has been obtained in crystalline form is isolated by filtration with suction.
This,gipes 77.5 g (74 % of theory) of 1-ethoxy-afiinocarbonyl-2-propionyl-hydrazine of melting point 122'C.
Le A 27 154_ - 76 -fiteg Z:

/ii~N~pC2H5 tII-1) ~2H5 A mixture of 75.5 g (0.43 mol) of 1-ethoxyamino-carbonyl-2-propionyl-hydrazfne~ 17.5 g (0.44 mol) of sodium hydroxide and 300 ml of water is refluxed for 12 hours. When the mixture is cold, a ph of between 3 and 4 is established by adding concentrated hydrochloric acid, and the mixture is concentrated. The residue is stirred with ethyl acetate, and the sodium chloride which has remained undissolved is separated off by filtration with suction. The filtrate is concentrated, the residue is stirred with diethyl ether, and the product which has been obtained in crystalline form is isolated by filtra-tion with suction.
This gives 37 g (55 % of theory) of 4-ethoxy-5 ethyl-2,4-dihydro-3H-1,24-triazol-3-one of melting point 93'C.
Ea~amnle f IZ-21 Hi~N~CH3 (II-2) "3H7 A mixture of 40 g (0.31 mol) of 5-propyl-1,3,4-Le A 27 154 - 77 -, 2189698 oxadiazolin-2-one, 109 g of aqueous methylamine solution (32 % strength, 1.125 mol of CH3NHa) and 500 ml of water is refluxed for 12 hours and then concentrated. The residue is taken up in ethanol and~reconcentrated. The residue obtained in this process is stirred with diethyl ether, and the product which has been obtained in crys-talline form is isolated by filtration tvith suction.
This gives 31.7 g (72 % of theory) of 4-methyl 5-propyl-2,4-dihydro-3H-12,4-triazol-3-one of melting point 86°C.
R=xampl-9 (7_T-3~
O
Hi~N~(CH3)2 N~H
856 g (4.0 mol) of diphenyl carbonate are dis-solved in 588 g of ethylene chloride. 245 g (4.0 mol) of dimethylhydraaine (98 % pure) are added dropwise with i5 water-cooling, and the mixture is heated slowly and, for 4 hours, stirred at 60°C.
After the mixture has cooled to 20°C, 200 q (4.0 mol) of hydrazine hydrate are added dropwise, and the mixture is then stirred for 12 hours. It is warmed to 70-80°C and, for about 1 hour, stirring is continued.
When cold, the solution is distilled in vacuo, during which process ethylene chloride and water are removed (final bottom temperature 100°C). The above phenolic r~e A 27 154. _ 7g _ .. . .~. ~~ ag~9a dimethyl carbodihydrazide solution is added dropwise in the course of 90 minutes at reflux temperature (about 102°C) to ø24 g (4.0 mol) of trimethyl orthoformate.
After the methanol which has formed is removed by distil-s lation, phenol is distilled off in vacuo, after which 282 g of product mixture are obtained at a head temper-ature of 85-105°C. This mixture is boiled with fi00 ml of acetone, and filtered at boiling point, and the filtrate is then cooled. The product which has been obtained fn this process in crystalline form is isolated by filtra-tion with suction.
This gives 71 g (14 8 of theory) of 4-dimethyl-amino-2,4-d3hydro-3H-1, Z,4-triazol-3-one of melting point 127°C.
For example the compounds of the formulae (II) and (IIa) listed in Table ø below can also be prepared analogously to Examples (II-1) to (II-3).

HN~N~R1 (II) N~RZ
he A 27 154 - 79 -Table Preparation examples of the compounds of the 4s formula (II) Ex. R1 RZ m.p. (C) No.

II-4 C3NT CH3 . 48 , II-5 CH(CH3)~ CH3 118 II-? C2H5 C2H5 117 ~

IZ-9 CH(CH3)~ C~HS 102 II-ii C3H7 C3H' (amorphous) II-12 CH(CH3)2 C3H7 91 II-13 CH3 Cti(CH3)2 92 II-I4 C2H5 CH(CH3)2 (amorphous) II-15 C3H7 CH(CH3)2 (amorphous) II-16 CH(CH3)2 CH(Crl3)~ 168 1.e A 27 154 - 80 -Table - continuation Ex. R! Rz m.p. ( C) No.

II-22 OCH3 ~1~[(~(~~)~ 130 II-23 pCIj2C6Hc~ CHI 106 I I-27 C)~ ( C~13 ) 121 II-30 C3H7 CQH9 (amorphous) II-33 CH3 ~ 68 II-34 C2H5 ~ 130 II-35 C3H7 ~ 68 II-36 ~ ~ 154 ~e A 27 154 - 81 -218969$
T~le 4 - continuation Ex. R1 A2 m.g. (C) No.

II-37 N(CH3)2 CH3 153 II-38 N(CH3)2 C2H5 114 II-39 N(CH3)2 C3H7 108 II-40 N(CH3)2 CH(CH3)2 100 II-41 CH3 N(CH3)2 80 ti-4a N(CH312 134 II-43 CH(CH3)2 NHCI~(CH3)2 205 II-44 N(CH3)a IV(CH3)2 93 II-45 C2H5 N(CH3)2 50 II-46 ~ CH3 145 II-47 ~ C1-l3 163 II-49 OCH3 ~ 136 - 137 II-50 CH3 CbHS

II-53 ' NH2 CF3 163 I~e A 27 154 - 82 _ . .:. y,;.
218969$
Table 4 - continuation Ex. R1 R~ m.p. ( C) No.

II-54 NHCtJ3 CH(CH3)2 1D5 II-55 NHCH3 ~ 95 II-57 NH2 C3H7 i47 II-60 NHCl~3 H 133 II-61 NHCH3 N(CH3)2 129 NH2 -iHC2H5 176 CHI

II-65 NH2 ~. 183 II-68 NH2 N(C2H5)2 196 be A 27 1S4 - 83 -'2189698 1e - continuation Es. R1 Vita m.p. ( °C?
No.

II-70 NH2 CH(CH3)2 172 II-T1 NH2 C(CH3)3 261 II-72 NH2 CH2CH20CH3 9g 3I-73 NH2 G(CH~)2C~H5 213 II-75 NH2 OCH3 (amorphous) II-76 NH2 C#(~OCH3 134 .

II-78 N(CH3)2 CH3 153 II-79 -CH2~C1 C2H8 103 Cl II-80 -CH2CH(CH3)2 C2H5 105 II-82 N(CH3)2 , CH(CH3)2 (amorphous]

II-84 NH2 CH2CbH5 168 II-85 NH2 N(CH3)2 207 II-86 NH2 CaHS 230 3~e ~ 27 ~ 54 _ gq _ zt s9b9s Ta>?le 4 - cpnt.inua~ion Es. Itf Rz m~P~ ~~C) Ho.

II-88 NH2 NHCH(CH3)2 152 II-89 NHCH3 NHCH(CH3)2 120 II-90 ~ NH 254 II-91 N(C/~13)2 II-95 C(CH3)3 C2H5 158 II-99 -CH2CH=CH2 II-100 CbHS CH3 150 II-101 ~ CH3 1i6 II-102 ~ C2H5 146 II-104 CH(CH3)2 H 105 Le A Z7 154 _ g5 _ ,2189698 Table - continuation EX. R' R~ mP

No.

II-105 ~ H 79 II-106 ~ H 162 II-107 C(CH3)3 H 194 II-108 -CH2-iH-CH28r CH3 11i BF

, II-111 -a -CH20CH3 102 II-112 ~ -CH20C2H5 119 II-lI3 -~ -N(CH3)2 ~CH3 \C2H5 ~CH3 ~C3H7-n ~2H5 ~C3H7-n V

yP a ~~ i ice - 86 -The compound of Example (II-118) disclosed in Table 4 (above) can be prepared as follows;
O
H~~N~CH3 (II-118) ~CH3 5D.2 g (0.33 mol) of hydrazino-formic acid phenyl ester (a 1-phenoxycarbonyl-hydrazine) and 36.6 g (0.33 mol;
90 ~ purity) of O,O,N-trimethyl-iminocarbonate sre mixed at 40 °C with 100 ml of 1,2-dichlorobenzene, and this mixture is then stirred for two hours at 60 °C. There-after the mixture is heated further up to 120 °C, while methanol (formed during the reaction) is being distilled off. Then the reaction mixture is cooled and heated again in vacuo (0.01 mbar) to ,a temperature of 120 °C in order to remove any remaining volatile com-pounds (methanol, phenol and 1,2-dichlorobenzene) from the reaction mixture. At a temperature above 12D °C the reaction product is distilled roughly and then crystal-lized from toluene.
This gives 7.5 g (18 x of theory) of 5-methoxy-4-methyl-2,4-dihydro-3H-1,2,4-triazol-one as colorless crystals of melting point 144-°C.
I,e A 27 154 _ g7 _ y n ' a~' a 2189b98 Examples of hydrazine the derivatives of formula (I%) obtained analogously to Ex-Which can be ample (II-1), step 1~ are Table 5 below, listed in ( IX) Table 5s Examples of the hxdra~inederivatives of the formula (i%) EX. R1 Ra m.p. (' C) No.

IX-3 OCH3 C3H? 125 IX-4 OCH3 CH(CH3)2 127 C2H5 17q IX-?

IX-9 CH(Cl-l3)2150 IX-10 OCH3 CqHq 134 IX-II
C4tly 159 Le A ~7 154 _ gg _ . ,: r :, Table - continuation Ex. R1 R2 No.

IX-12 ~ ~

IX-13 OCH3 ~ 140 IX-14 CH2-CH=CH2 C3HT 134 iX-15 -CHZOC2H5 9T

Le A 27 15a_ _ $9 . ' '~ ~' 2189698 &tartina substances of the f~~~m p (IV1=
Examx~le (,IV-11 ~O-CO~N~N~CH3 "2H5 6.4 g (0.05 mol) of 5-ethyl-4-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one are dissolved in 80 ml of tetra-s hydrofuran, and 1.8 g (0.06 mot) of sodium hydride (80 %
of substance) are added under nitrogen. After the mixture has been stirred for one hour at 20°C, 7.9 g (0.05 mol) of phenyl chloroformate are added dropwise, and the reaction mixture is stirred at 20°C for a further ZO
hours. After the mixture has been concentrated, the residue is taken up in methylene chloride, and the mixture is washed with water, dried with sodium sulphate and filtered. The filtrate is concentrated, the residue is triturated.with diethyl ether, and the product which has been obtained in crystalline form is isolated by filtration with suction.
This gives 4.5 g (36 % of theory) of 5-ethyl-4-methyl-2-phenoxycarbonyl-2,4-dihydro-3H-1,2,4-triazol-3-one of melting point 141°C.
For example the compounds of the formula (IV) listed in Table 6 below can also be prepared analogously to Example (IV-1).
Le A 2T 154 - g0 -2~$9~9$

z-co~N~.-R1 mo N~R2 Examples of the compounds of the formula (IV) Ex. R1 R2 Z
m~p~ ('C) No.

IY-2 C3N7 C3H~ . CbHS 88 IY-9 OCH2CH=CH2 CH3 C6H5 IY-10 ~ C4H9 C6H5 ~

IV-11 CH3 CbH

IV-12 NHCH3 C2H5 CbHS

Le ~! 27 ~ 54 - 91 -. 2189698 Table - continuation Ea. R1 R2 Z m.p. ("C) No.

IY-13 CH3 CH~C6H5 C6H5 IV-14 CH3 NHCH(CH3)Z C~[-!5 IY-15 N(Ck~~)2 N(C1~3)2 C6H5 IV-17 OC2H5 ~ C H

IY-18 OC3H7 C2H5 C~HS

IV-19 C2Hr~ C,~Hy C6H5 IV-20 CH(CH3)2 CH(CH3)2 C6H5 IY-22 C3H7-n C6H5 104 .

be n 27 i54, . g2 .!
Use Examples:
In the following use examples, the known herbicide isocarbamide, of formula (A) below, is used as comparison substance:
HN N-CO-NH-CHaCH(CHsyy ( A ) O
The formulae of the compounds used in the Use Examples are listed individually below in conjunction with the number of the Preparation Examples:
~2 SO2 NH CO~N~N~CH3 (4) I
N
~CaHs ~2 SOZ NH CO~N~N~Ca~s ( 5 ) I _ N
~~s NH-CO~N~N~CH3 ( 2 ) N
~~s ,. - 93 -23189-1150D ..

CI 0'' (, ,r-S02-NH-CO~N~N~C2H5 (7) ~--~CH3 N~C2H5 502-NH-CO~~~N~CH3 (8) ~--~CH3 3H7 502-NH-CO~i~N~OCH3 (12) e~r " "2H5 COOCH3 0I' S, r-S02-NH-CO~N~N~OCH3 (13) "3H7 ,~./S02N(CH3)2 0~~
t 7-S02-NH-CO~N~N~CH3 (14) !~' 2H5 802N(CH3)2 0 502-NH-CO~N~N~CH3 (15) e~' N~C 3H 7 ~fi02-NH-CO~N~~ (1b) 502-NH-CO~~~N~OCH3 (17) '~H(CH3)2 &e A 27 154 ~ - 9q -,y 802N(CH3)2 O
~SO
-NH-CO~
~
~

Z N (1g) N
~

,~( COOCH~ p'I
S
r-S0 -NH-CO~
~~

" N (19) 2 ~

SO (2 -NH-CO~N~N~CH

~ 3 0) N~

N(CH3)a COOCH3 p ~--so (2 -NH-CO~N~N~OC
H

2 2 6) ~

50 ( -NH-CO~N~N~OC
H

2 2 27) "3H7 --S0 ~
-NH-C ~
~

2 N (2g) O N
~H

(CH3)2 C1 p SO
-NH-CO~N~~

Z (29) ~-~(CH

-SO (30) -NH-CO~
~N-~N(CH
) Z ; a H

"3 Y
Ie P~ 21 ~ 54 .. - 95 -~~~._ . ~ 189698 -NH-CO~N~N~G
H

5 (32) ~N9 ~S0 CO~
-NH- ~NiCH

2 ~
3 (33) 1~

-S0 CO~
-NH- ~N
iC
H

2 [ 3 ~ ~ (34) ~

(i ,rS02-NH-CO~N~~ (35) "4H9 ~SD2-NH-CO~N~N~CH3 (37) i N
,~( CODCH3 O(f 502-NH-CO~N~N~C3H~ (39) v i N' ~SOZ-NH-CO~N~~ (40) i ~.e R ~7 154 - 96 -2189b98 COOCIi3 0 ~~-502-NH-CO~i~N~OC~J3 ('9) ~SOZ-NH-CO~N~N~iCH3)2 (31) -SOZ-NH-CO~i~N~DCH3 (36) ~4H9 LP n ~~ ~ s° _ __ . - 97 -t r, 2~s9~9a Pre-emergence test Solvents 5 parts by Weight of acetone Emulsifier; 1 part by weight of alkylaryl polyglycol ether To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added, and the concentrate is diluted with water to the desired concentration.
Seeds of the test plants are sown in normal soil and, after 24 hours, watered With the preparation of active compound. It is expedient here to keep constant the amount of water per unit area. The concentration of active compound in the preparation is of no importance, only the amount of active compound applied per unit area being decisive. After three weeks, the degree of damage of the plants is rated fn % damage in comparison with the development of the untreated control. The figures denotes 0 % = no action (like untreated control) 100 % = total destruction In this test a clearly superior activity com pared with the prior art is shown, for example, by the compounds of Preparation Examples 2, 6, 8, 12, 13, 16, 17, 18, 19, 20, 26, 27, 28, 29, 34, 37, 39 and 40.
he A 27 154 _ gg _ z.
~~89698 Example B
Post-emergence test Solvent: 5 parts by weight of acetone Emulsifiers 1 part by weight of alkylaryl polyglycol ether To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added, and the concentrate is diluted with water to the desired concentration.
Test plants having a height of 5 - 15 cm are sprayed with the preparation of active compound in such a way that the specifically desired amounts of active compound per unit area are applied. The concentration of the spray liguor is chosen in such a way that the speci fically desired amounts of active substance are applied in 1000 1 of water/ha. After three weeks, the degree of damage of the plants is rated in % damage in comparison with the development of the untreated control. The figures denote:
0 % = no action (like untreated control) 100 % ~ total destruction In this test a clearly superior activity com-pared with the prior art is shown, for example, by the compounds of Preparation Examples 2, 4, 5, 6, 7, 8, 12, 13, 14, 15, 16, 17, 18, 19, 20, 26, 27, 28, 29, 30, 32, 33, 34, 35, 37, 39 and 40.
Le A 27 154 - 99 2189b98 Example Pyricularia test (rice) / protective Solvent: 12,5 parts by weight of acetone Emulsifier: 0,3 parts by weight of alkyla,rylpolyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, and~the concentrate is diluted with water and the stated amount of emulsifier to the desired concentration.
To test for protective activity, young rice plants are sprayed with the preparation of active compound until dripping wet. After the spray coating has dried off, the plants are inoculated With an aqueous spore suspension of Pyricularia orycae. The plants are then placed in a greenhouse at 100 ~ relative atmospheric humidity and 2s°c.
Evaluation of the disease infestation is carried out 4 days after the inoculation.
In this test, a very good activity is shokn, for example, by the compounds according to the following preparation examples:
9, 12, 13, 20, 30, 31, 32, 33, 34, 35, 36, 37.
Ire A 27 154 - 100 -~xample D
Pyricularia Test (rice? / systemic Solvent . 12,5 parts by weight of acetone Emulsifier: D,3 parts by weight of alkylaryl-poly-glycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, and the concentrate is diluted with water and the stated amount of emulsifier, to the desired concentration.
To test for systemic properties, standard soil in which young plants have been grown is watered with 40 m1 of the preparation of active compound. 7 days after the treatment, the plants are inoculated with an aqueous spore suspension of Pyricularia oryzae.
Thereafter, the plants remain in a greenhouse at a temperature of 25° and a relative atmospheric humidity of 1009c until they are evaluated, Evaluation of the disease infestation is carried out 4 days after the inoculation.
In this test, an excellent activity is shown, for example, by the compounds according to the following preparation examples:
9, 12, 13, 20, 30, 31, 32, 33, 34, 35, 36, 37.
T.e l~ 27 154 - ioi

Claims (5)

1. A triazolinone of the general formula (IIa) in which A1 and A2 represent groups selected from the following pairs of groups:

2. A triazolinone according to claim 1, wherein

3. A triazolinone according to claim 1, wherein

4. A triazolinone according to claim 1, wherein

5. A process for preparing a compound of formula IIa as defined in claim 1 wherein A1 and A2 are as defined in claim 1, which process comprises a) reacting a compound of formula VII

in which A2 is as defined above, with a compound of formula VIII

H2N-A1 (VIII) in which A1 is as defined above at a temperature between 20°C and 120°C and condensing the hydrazine derivative of formula IX so obtained or, b) reacting a compound of formula VIII

H2N-A1 (VIII) in which A1 is as defined above, with a carbonic acid derivative, and reacting the product so obtained with hydrazine or hydrazine hydrate, and then reacting the product so obtained with a compound of the formula (X) (RO)3C-A2 (X) in which A2 is as defined above and R is lower alkyl, at a temperature of from 0°C to 150°C.