TETRFTZPLINQNRS Field of the Invention The present invention relates to new tetrazolinones, to processes for their preparation and to their use as herbicides, also relating to new intermediate compounds for their preparation. Description of the State of the Art It is already known that certain tetrazolinon derivatives have herbicidal activity (see: EP-A-146 279 (»US Patents 4,618,365, 4,826,529, 4,830,661, 4,956,469,
. 003,075 and 5,019,152); Japanese Patent Publications
Hei 5-331153, Hei 5-331154, Hei 5-339249, Hei 6-199818 and Hei
6-30601). Summary of the Invention New compounds and mixtures of geometric isomers of formula (I) have now been found:
wherein R1 and R2 are independently C ^ alkyl, C1.6 haloalkyl, C3.β cycloalkyl, C2.6 alkenyl, C2.6 haloalkenyl, C3.6 alkynyl or optionally substituted phenyl; or REF: 25170 R1 and R2 together with the nitrogen atom to which they are linked, can form a 5- or 6-membered heterocyclic ring which can be benzo-fused or can be substituted by halogen or C ^ alkyl; R3 is hydrogen or C ^ alkyl; R * is hydrogen or Cx_6 alkyl; or R3 and R4, together with the carbon atoms to which they are attached, form cyclopentylidene or cyclohexylidene; R5 is C ^ alkyl, C3.6 alkenyl or benzyl; and ^ is a simple link of the Anti form or the Sin form. The compounds of formula (I), according to the invention, can be obtained, for example, by processes wherein: (a) compounds of formula (II) are reacted:
wherein R3, R4 and R5 are defined as above, with compounds of formula (III):
wherein R1 and R2 are defined as above and hal is a leaving group such as a chlorine or bromine atom, in the presence of inert solvents and, if appropriate, in the presence of an acid acceptor; or (b) compounds of formula (IV) are reacted:
(IV)
wherein R1, R2, R3 and R4 are defined as above, with compounds of formula (V):
R-O-NH. (V)
wherein Rs is defined as above, in the presence of inert solvents and, if appropriate, in the presence of an acid acceptor. The compounds of formula (I) according to the invention have strong herbicidal activity. Surprisingly, the compounds of the formula (I) exhibit an excellent and superior herbicidal activity compared to that exhibited by the compounds of the state of the art, for example, of the aforementioned references EP-A-146 279 (= Patents US 4,618,365, 4,826,529, 4,830,661, 4,956,469, 5,003,075 and 5,019,152);
Japanese Patent Publications Hei 5-331153, Hei 5-331154, Hei 5-339249, Hei 6-199818 and Hei 6-30601. Description of the Invention In each of the formulas relating to the compounds of formula (I) and intermediates for their preparation according to the invention, the term "halogen" in halogen, haloalkyl and haloalkoxy represents fluorine, chlorine, bromine or iodine , preferably chlorine or fluorine. "Alkyl" may be straight or branched chain and represents, for example, methyl, ethyl, propyl, isopripolar, n-, iso-, sec- or tere-butyl, n-, iso-, sec-, tere- or neo-pentyl or n-, iso-, sec-, tere- or neo-hexyl. "Haloalkyl" represents the aforementioned alkyl which is substituted by one or more halogens and, if substituted by a plurality of halogens, these halogens may be the same or different. For example, "haloalkyl" is trifluoromethyl, 2-chloroethyl or 2,2,2-trifluoroethyl. "Cycloalkyl" is, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl. "Alkenyl" is straight or branched chain, for example, vinyl, allyl, isopropenyl, l-methyl-2-propenyl, 2-or 3-butenyl or 2-, 3- or 4-pentenyl. "Haloalkenyl" represents the aforementioned alkenyl which is substituted by one or more halogens and, if substituted by a plurality of halogens, these halogens may be the same or different. For example, "haloalkenyl" is 2-chloro-2-propenyl. "Alkynyl" includes, for example, propargyl. "Phenyl" may be optionally substituted.
Examples of substituents thereof include halogen such as chlorine, fluorine and bromine; cyano; nitro; alkyl such methyl, ethyl, propyl and isopropyl; haloalkyl such as trifluoromethyl; alkoxy such as methoxy and ethoxy; haloalkoxy such as trifluoromethoxy; and alkylthio such as methylthio. The "5- or 6-membered heterocyclic ring" contains at least one nitrogen atom as a heteroatom and may also contain one or more heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom. Said heterocyclic ring may be optionally substituted by halogen such as fluorine, chlorine and bromine, or by C 1 alkyl such as methyl, ethyl, propyl and isopropyl, or it may be benzo-fused.
Examples of said 5- or 6-membered heterocyclic rings include: pyrrolidinyl, 2,5-dimethylpyrrolidinyl, pyrrolinyl, 2,5-dimethylpyrrolinyl, imidazolidinyl, pyrazolidinyl, pyrazolinyl, piperidyl, 2-methylpiperidyl, 2,6-dimethyl-piperidyl, piperazinyl, indolinyl, morpholinyl, 1,2,3,4-tetrahydroquinolyl, 2-methyl-l, 2,3,4-tetrahydroquinolyl, 2,2-dimethyl-l, 2,3,4-tetrahydroquinolyl, 2, 2- dimethyl-l, 2-dihydroquinolyl and 6-fluoro-2,2-dimethyl-1,2-dihydroquinolyl. "Alkoxy" can be straight or branched chain and represents, for example, methoxy, ethoxy, propoxy, isopropoxy, n-, iso-, sec- or tert-butoxy, n-, iso-, sec-, tere- or neo -pentoxy, n-, iso-, sec-, tere- or neo-hexoxy. Preferred Modalities of the Invention Among the compounds and mixtures of geometric isomers of formula (I), preferred compounds are those wherein: R1 and R2 independently are C3-4 alkyl, C2 haloalkyl, cyclopropyl, cyclopentyl, cyclohexyl, C2_4 alkenyl, C2 haloalkenyl. 4 or C3.4 alkynyl or represent phenyl which may be substituted by halogen or C1.4alkyl; or R1 and R2 together with the nitrogen atom to which they are d, form pyrrolidin-1-yl, 2,5-dimethylpyrrolidin-1-yl, 3-pyrrolin-1-yl, 2, 5-dimethyl-3- pyrrolin-1-yl, piperidino, 2-methylpiperidino, 2,6-dimethylpi- peridino, piperazin-1-yl, morpholino, 1,2,3,4-tetrahydroquinolin-1-yl, 2-methyl- 1, 2,3,4-tetrahydroquinolin-1-yl, 2,2-dimethyl-1, 2, 3, 4-tetrahydroquinolyl, 2,2-dimethyl-1,2-dihydroquinolyl or 6-fluoro-2, 2- dimethyl-l, 2- dihydroquinolyl; R3 is hydrogen or alkyl R4 is hydrogen or Cx alkyl; or R3 and R4, together with the carbon atoms to which they are attached, form cyclopentylidene or cyclohexylidene; R5 is C1 alkyl, C2.4 alkenyl or benzyl; and / ^ is a simple link of the Anti form or the Sin form. Among the compounds and mixtures of geometric isomers of formula (I) according to the invention, more preferred compounds are those wherein: R 1 and R 2 independently are C 1 alkyl, C 4 haloalkyl, cyclopropyl, cyclopentyl, cyclohexyl, C 2-4 alkenyl , C2.4 haloalkenyl or C3.4 alkynyl or represent phenyl which may be substituted by methyl, fluoro, chloro or bromo; or R1 and R2 together with the nitrogen atom to which they are d, form pyrrolidin-1-yl, 2,5-dimethylpyrrolidin-1-yl, 3-pyrrolin-1-yl, 2, 5-dimethyl-3- pyrrolin-1-yl, piperidino, 2-methylpiperidino, 2,6-dimethylpi- peridino, piperazin-1-yl, morpholino, 1,2,3,4-tetrahydroquinolin-1-yl, 2-methyl- 1, 2, 3, 4-tetrahydroquinolin-1-yl, 2,2-dimethyl-1,2,3,4-tetrahydroquinolyl, 2,2-dimethyl-1,2-dihydroquinolyl or 6-fluoro-2, 2- dimethyl-l, 2- dihydroquinolyl; R3 represents hydrogen or methyl; R 4 represents hydrogen, methyl or ethyl; or R3 and R4, together with the carbon atoms to which they are attached form cyclopentylidene or cyclohexylidene; R 5 represents methyl, ethyl, allyl or benzyl; Y *? represents a simple link of the Anti form or the Sin form. Examples of the compounds of formula (I) according to the invention include, in addition to those mentioned in the Examples described below, those shown in the following Tables 1, 2 and 3. Table 1 shows the compounds according to the invention wherein R1, R2, R3 and R4 independently represent a group. Table 2 shows the compounds according to the invention wherein R1 and R2 independently represent a group and wherein R3 and R4, together with the carbon atoms to which they are attached, represent cyclopentylidene or cyclohexylidene. Table 3 shows the compounds according to the invention wherein R1 and R2, together with the nitrogen atom to which they are attached, represent a heterocyclic ring.
lal-Jül IahlaLÍ: (continued)
Iahlü_l: (continuation)
Ia2la_l: (continued)
IaJ2la. :( continuation)
R5 * R2
CH2CH3 CH2CH3 CH2CH3 Anti CH (CH V3) i C6H3
C i2 ii5 CH2CH3 CH2CH3 Without CH (CH3) 2 CSH3
CH2CH3 CH2CH3 CH2CH3 Anti CH (CH3) 2 4-F-C6H4
CH2CH3 Cri Cri? Without CH (CH3) 2 4-F-CéH4
Ta a IaJ2la_2: (continued)
Ial2li? _2: (continued)
Table 3 Table 3: (continuation)
Table 3: (continuation)
Iaj2la_3 (continued)
Table 3: (continuation)
Table 3: (continued)
Table 3: (continued)
When in process (a) above, for example, l- (2-methoxyiminopropyl) -5 (4H) -tetrazolinone and N- (4-fluorophenyl) -N-isopropylcarbamoyl chloride are used as starting materials, the course of the reaction can be represented by the following equation:
When in process (b), for example, 1- (acetonyl) -4- (N-isopropyl-N-phenyl-carbamoyl) -5 (4H) -etrazo-linone and O-methylhydroxylamine are used as starting materials, the course of the reaction can be represented by the following equation:
In process (a) according to the invention, the compounds of formula (II) mean those based on the above definitions of R3, R4 and R5, and preferably those based on the above preferred definitions of R3, R4 and R5. In process (a), examples of compounds of formula (II) used as starting materials, include the following compounds: 1- (2-methoxyiminoethyl) -5 (4H) -tetrazolinone, 1- (2-ethoxyiminoethyl) -5 (4H) -tetrazolinone, l- (2-aliloxiiminoetil) -5 (4H) -tetrazolinone, 1- (2-Benzyloxyimino-ethyl) -5 (4H) -tetrazolinone, l- (2-metoxiiminopropil) -5 (4H) -tetrazolinone , l- (2-etoxiiminopropil) -5 (4H) -tetrazolinone, 1- (2-aliloxiiminopropil) -5 (4H) -tetrazolinone, l- (2-benciloxiiminopropil) -5 (4H) -tetrazolinone, l- (2 -metoxiiminobutil) -5 (4H) -tetrazolinone, l- (2-etoxiiminobutil) -5 (4H) -tetrazolinone, l- (l-methyl-2-metoxiiminopropil) -5 (4H) -tetrazolinone, l- (2- ethoxyimino-l-methylpropyl) -5 (H) -tetrazolinone, l- (l-ethyl-2-metoxiiminopropil) -5 (4H) -tetrazolinone, l- (l-ethyl-2-etoxiiminopropil) -5 (4H) - tetrazolinone, l- (l-methyl-2-metoxiiminobutil) -5 (4H) -tetrazolinone, l- (l-ethyl-2-etoxiiminobutil) -5 (4H) -tetrazolinone, l- (2-metoxiiminociclopentil) -5 ( 4H) -tetrazolinone, l- (2-methoxyiminocyclohexyl) - 5 (4H) -tetrazolinone, 1- (2-ethoxyiminocyclopentyl) -5 (4H) -tetrazolinone, 1- (2-ethoxyiminocyclohexyl) -5 (4H) -tetrazolinone, and others. The compounds of formula (II) are new and such compounds can be obtained by the following process: (c) compounds of formula (VI) are reacted:
wherein R3 and R4 are defined as above, with compounds of the formula (V) above, in the presence of inert solvents and, if appropriate, in the presence of an acid acceptor. The process (c) above can be carried out under conditions similar to those of the process reaction (b). In the process (c), examples of compounds of formula (VI) used as starting materials are as follows: l-formylmethyl-5 (4H) -tetrazolinone, l-acetonyl-5 (4H) -tetrazolinone, 1- (2-oxobutyl) -5 (4H) -tetrazolinone, 1- (1-methyl-2-oxopropyl) -5 (4H) -tetrazolinone, 1- (1-ethyl-2-oxopropyl) -5 (4H) -tetrazolinone , l- (1-methyl-2-oxobutyl) -5 (4H) -tetrazolinone, 1- (1-ethyl-2-oxobutyl) -5 (4H) -tetrazolinone, 1- (2-oxo-cyclopentyl) -5 (4H) -tetrazolinone, l- (2-oxo-cyclohexyl) -5 (4H) -tetrazolinone, etc. In process (c), the compounds of formula (VI) used as starting materials are new and such compounds can be obtained by the following processes: (d) compounds of formula (VII) are reacted
wherein R 3 and R 4 are defined as above and X 1 and X 2 independently represent hydrogen or C 1 -C 4 alkyl with trimethylsilylazide, if appropriate in the presence of catalysts, and then reacted with protic solvents or (e) in the case wherein R3 and R4 represent hydrogen, compounds of formula (VIII) are hydrolyzed:
X-O N H (VIII) X-0 N = N
wherein X1 and X2 are defined as above. Process (d) above can be carried out by a procedure similar to those described in the Journal of the Chemical Society, Perkin Transactions 1, 1995, 1101-1104 and using the compounds of the formula (VII) above instead of the chlorides described in said publication. The compounds of formula (VII) are well known in the field of organic chemistry and the example thereof includes 2,2,6-trimethyl-4H-l, 3-dioxin-4-one. In process (e) above, the reaction is well known per se in the field of organic chemistry. The compounds of formula (VIII) used as starting materials are new and such compounds can be produced by a process similar to that described in Japanese Patent Publication Hei 8-82258. That is, 2,2-dialcoxyethylamine is reacted with carbon disulfide and the reaction product is reacted with dimethyl sulfate to obtain N- (2,2-dialkoxyethyl) -dithiocarbamate. The compounds are then reacted with sodium azide to obtain l- (2,2-dialkoxyethyl) - (4H) -tetrazoline-5-thiones. These compounds are further reacted with propylene oxide to obtain the desired compounds of formula (VIII). An example of the compounds of formula (VIII) includes l- (2,2-dimethoxyethyl) -5 (4H) -tetrazolinone. In process (c) above, the compounds of formula (V) used as starting materials are the same as the starting materials used in process (b). In the process (a) according to the invention, the compounds of formula (III) represent those based on the above definitions of R1, R2 and hal, and preferably those based on the above preferred definitions of R1 and R2, and preferably Hal is chlorine or bromine. The compounds of formula (III) used as a starting material in process (a) above are well known in the field of organic chemistry and examples thereof include the following compounds: diisopropylcarbamoyl chloride and bromide, chloride and bromide. diethylcarbamoyl, dimethylcarbamoyl chloride and bromide, N-methyl-N-ethylcarbamoyl chloride and bromide, N-methyl-Nn-propylcarbamoyl sluride and bromide, N-methyl-N-isopropylcarbamoyl bromide, chloride and N-bromide Methyl-N-cyclopropylcarbamoyl, N-methyl-Ns-butylcarbamoyl chloride and bromide, N-methyl-N-cyclopentylcarbamoyl chloride and bromide, N-methyl-N-cyclohexylcarbamoyl chloride and bromide, N-methyl-N-methyl bromide and bromide N-Phenylcarbamoyl, N-methyl-N-methyl-2-propenylcarbamoyl chloride and bromide, N-ethyl-Nn-propylcarbamoyl chloride and bromide, N-ethyl-N-isopropylcarbamoyl chloride and bromide, N-bromide and bromide ethyl-N-cyclopropylcarbamoyl, chloride and bromide of N-ethyl-Ns-butylcarba N-ethyl-N-cyclopentylcarbamoyl molar, chloride and bromide, N-ethyl-N-cyclohexylcarbamoyl chloride and bromide, N-ethyl-N-phenylcarbamoyl chloride and bromide, Nn-propyl-N-isopropylcarbamoyl chloride and bromide, Nn-propyl-N-cyclopropylcarbamoyl chloride and bromide, Nn-propyl-Ns-butylcarbamoyl chloride and bromide, Nn-propyl-N-cyclopentylcarbamoyl bromide, Nn-propyl-N-cyclohexylcarbamoyl chloride and bromide, and N-isopropyl-N-cyclohexylcarbamoyl bromide, N-isopropyl-N-phenylcarbamoyl chloride and bromide, N-isopropyl-N-allylcarbamoyl bromide, chloride and N-isopropyl-N-propargylcarbamoyl bromide, chloride and bromide N-isopropyl-N- (2-chloro-2-propenyl) -carbamoyl, N-isopropyl-N- (2-methyl-2-propenyl) -carbamoyl bromide, chloride and bromide of N, N- N, N-di-ropargylcarbamoyl diallylcarbamoyl, chloride and bromide of N, N-di (2-chloroethyl) carbamoyl, chloride and morpholino carbonyl bromide, chloride and bromide of 2-methylpiperidino carbonyl, chloride and 2,5-dimethylpyrrolidin-1-ylcarbonyl bromide, chloride and 2,6-dimethylpiperidino carbonyl bromide, chloride and 2-methyl-l, 2,3,4-tetrahydroquinoline-1-bromide Ilcarbonyl, 2,2-dimethyl-1,2-dihydroquinolin-1-yl-carbonyl chloride and bromide, pyrrolidin-1-ylcarbonyl chloride and bromide, piperidinocarbonyl bromide, chloride and bromide 2, 5-dimethyl-3-pyrrolin-1-ylcarbonyl, and others. In process (b) above, examples of compounds of formula (IV) used as starting materials, include the following compounds: 1- (formylmethyl) -4- (N-isopropyl-N-phenylcarbamoyl) -5 (4H) - tetrazolinone, 1- (formylmethyl) -4- [N-isopropyl-N- (4-fluorophenyl) carbamoyl] -5 (4H) -tetrazolinone, l-formylmethyl) -4- [N-isopropyl-N- (4-chlorophenyl) ) carbamoyl] - 5 (4H) -tetrazolinone, 1- (formylmethyl) -4- [N-isopropyl-N- (4-methylphenyl) carbamoyl] -5 (4H) -tetrazolinone, 1- (formylmethyl) -4- ( N-ethyl-N-phenylcarbamoyl) -5 (4H) -tetrazolinone, 1- (formylmethyl) -4- (2-methyl-1, 2,3,4-tetrahydroquinolin-1-ylcarbonyl) -5 (4H) -tetrazolinone , l- (formylmethyl) -4- (2,2-dimethyl-1,2-dihydroquinolin-l-ylcarbo-nyl) -5 (4H) -tetrazolinone, 1- (formylmethyl) -4- (2,2-dimethyl) 6-fluor-l, 2-dihydroquinolin-1-ylcarbonyl) -5 (4H) -tetrazolinone, 1- (acetonyl) -4- (N-isopropyl-N-phenylcarbamoyl) -5 (4H) -tetrazo-linone, l- (acetonyl) -4- [N-isopropyl-N- (4-fluorophenyl) carbamoyl] -5 (4H) -tetrazolinone, 1- (acetonyl) -4- [ N-isopropyl-N- (4-chlorophenyl) carbamoyl] -5 (4H) -tetrazolinone, 1- (acetonyl) -4- [N-isopropyl-N- (4-methylphenyl) carbamoyl] -5 (4H) -tetrazolinone , 1- (acetonyl) -4- (N-ethyl-N-phenylcarbamoyl) -5 (4H) -tetrazolinone, 1- (acetonyl) -4- [N-ethyl-N- (4-fluorophenyl) carbamoyl] -5 (4H) -tetrazolinone, 1- (acetonyl) -4- (N-sec-butyl-N-phenylcarbamoyl) -5 (4H) -tetrazolinone, 1- (acetonyl) -4- [N-sec-butyl-N- (4-fluorophenyl) carbamoyl] -5 (4H) -tetrazolinone, 1- (acetonyl) -4- (2-methyl-1, 2,3,4-tetrahydroquinoline-1-carbo-nyl) -5 (4H) - tetrazolinone, l- (acetonyl) -4- (2,2-dimethyl-1,2-dihydroquinolin-l-ylcarbo-nyl) -5 (4H) -tetrazolinone, 1- (acetonyl) -4- (2, 2- dimethyl-6-fluoro-1,2-dihydroquinolin-1-ylcarbonyl) -5 (4H) -tetrazolinone, 1- (acetonyl) -4- (N-isopropyl-N-methylcarbamoyl) -5 (4H) -tetrazolinone, - (2-oxobutyl) -4- (-isopropyl-N-phenylcarbamoyl) -5 (4H) -tetrazolinone, 1- (2-oxobutyl) -4- [N-isopropyl-N- (4-fluorophenyl) carbamoyl] - 5 (4H) -tetrazolinone, 1- (2-oxobutyl) -4- [N-isopropyl-N- (4-cl orophenyl) carbamoyl] - 5 (4H) -tetrazolinone, 1- (2-oxobutyl) -4- [N-isopropyl-N- (4-methylphenyl) carbamoyl] -5 (4H) -tetrazolinone, 1- (2-oxobutyl) ) -4- (N-ethyl-N-phenylcarbamoyl) -5 (4H) -tetrazolinone, 1- (2-oxobutyl) -4- (2-methyl-1,2,4,4-tetrahydroquinolin-1-ylcarbonyl) -5 (4H) -tetrazolinone, 1- (2-oxobutyl) -4- (2,2, -dimethyl-1,2-dihydroquinolin-l-ylcarbo-nyl) -5 (4H) -tetrazolinone, 1- (2 -oxobutyl) -4- (2,2-dimethyl-6-fluoro-l, 2-dihydroquinolin-1-ylcarbonyl) -5 (4H) -tetrazolinone, 1- (1-methyl-2-oxopropyl) -4- ( N-isopropyl-Nf-enylcarbamoyl) -5 (4H) -tetrazolinone, 1- (1-methyl-2-oxopropyl) -4- [N-isopropyl-N- (4-f-lurthyl) carba -moyl] -5 ( 4H) -tetrazolinone, 1- (1-methyl-2-oxopropyl) -4- (2-methyl-1, 2, 3, 4-tetrahydroquin-lin-1-ylcarbonyl) -5 (4H) -tetrazolinone, 1- (l-methyl-2-oxopropyl) -4- (2,2-dimethyl-1,2-dihydroquinolin-1-ylcarbonyl) -5 (4H) -tetrazolinone, 1- (1-ethyl-2-oxopropyl) -4 - (N-isopropyl-Nf-enylcarbamoyl) -5 (4H) -tetrazolinone, l- ( l-ethyl-2-oxopropyl) -4- [N-isopropyl-N- (4-f luorfyl) carbamoyl] -5 (4H) -tetrazolinone, 1- (1-methyl-2-oxobutyl) -4 - (N-isopropyl-N-phenylcarbamoyl) -5 (4H) -tetrazolinone, 1- (1-methyl-2-oxobutyl) -4- [N-isopropyl-N- (4-fluorophenyl) carbamoyl] -5 (4H) -tetrazolinone, 1- (1-ethyl-2-oxobutyl) -4- (N-isopropyl-N-phenylcarbamoyl) -5 (4H) -tetrazolinone, 1- (1-ethyl-2-oxobutyl) -4 - [N-isopropyl-N- (4-fluorophenyl) carbamoyl] -5 (4H) -tetrazolinone, 1- (2-oxo-cyclopentyl) -4- (N-isopropyl-N-phenylcarbamoyl) -5 (4H ) -tetrazolinone, 1- (2-oxo-scylpentyl) -4- [N-isopropyl-N- (4-fluorophenyl) carbamoyl] -5 (4H) -tetrazolinone, 1- (2-oxo-cyclohexyl) - 4- (N-isopropyl-N-phenylcarbamoyl) -5 (4H) -tetrazolinone, 1- (2-oxo-cyclohexyl) -4- [N-isopropyl-N- (4-fluorophenyl) carbamoyl] -5 ( 4H) -tetrazolinone, and the like. The compounds of formula (IV) are new and such compounds can be obtained, for example, by the following processes: (f) the compounds of formula (VI) above are reacted with compounds of formula (III) above under similar to the process (a); or (g) in the case where R3 and R4 represent hydrogen, compounds of formula (IX) are hydrolyzed:
wherein R1, R2, X1 and X2 are defined as above. The compounds of formula (IX) are new and include, for example, the following compounds: 1- (2,2-dimethoxyethyl) -4- (N-isopropyl-N-phenylcarbamoyl) -5 (4H) -tetrazolinone, l- (2,2-dimethoxyethyl) -4- (N-isopropyl-N- (4-fluorophenyl) carbamoyl) -5 (4H) -tetrazolinone, 1- (2,2-dimethoxyethyl) -4- (N-isopropyl-N) - (4-chlorophenyl) carbamino) -5 (4H) -tetrazolinone, 1- (2, 2-dimethoxyethyl) -4- (N-isopropyl-N- (4-methylphenyl) carbamoyl) -5 (4H ) -tetrazolinone, 1- (2, 2-dimethoxyethyl) -4- (N-ethyl-N-phenylcarbamoyl) -5 (4H) -tetrazolinone, 1- (2,2-dimethoxyethyl) -4- (2-methyl- 1, 2, 3, 4-tetrahydroquinolin-1-ylcarbonyl) -5 (4H) -tetrazolinone, 1- (2,2-dimethoxyethyl) -4- (2,2-methyl-1,2-dihydroquinolin-1-ylcarbonyl) ) -5 (4H) -tetrazolinone, l- (2, 2-dimethoxyethyl) -4- (2, 2-methyl-6-fluoro-l, 2-dihydroquin-lin-l-ylcarbonyl) -5 (4H) - tetrazolinone, etc. The compounds of formula (IX) can be obtained, for example, by the following process: (h) the compounds of formula (VIII) above are reacted with the compounds of formula (III) above under conditions similar to those of process (a). In process (b), the compounds of formula (V) are already well known in the field of organic chemistry and examples thereof include the following compounds: O-methylhydroxylamine and its hydrochloride salt, O-ethylhydroxylamine and its hydrochloride salt , O-allylhydroxylamine and its hydrochloride salt, O-benzylhydroxylamine and its hydrochloride salt, etc. The compounds of formulas (II), (IV), (VI), (VII) and (IX) which are starting materials for the production of the compounds of formula (I) according to the invention are novel and such compounds are generally represented by the following formula (X):
where: T1 is hydrogen,
T2 is hydrogen or with the condition that when
3 R T1 is F * 1, einnttoonnces T2 is hydrogen, \ > R-0
R1 and R2 are independently C ^ alkyl, C1.6 haloalkyl, C3.8 cycloalkyl, C2.6 alkenyl, C2.6 haloalkenyl, C3.6 alkynyl or optionally substituted phenyl; or R1 and R2 together with the nitrogen atom to which they are linked, can form a 5- or 6-membered heterocyclic ring which can be benzo-fused or can be substituted by halogen or Cx.4 alkyl; R3 is hydrogen or C ^ alkyl; R4 is hydrogen or C ^ alkyl; or R3 and R4, together with the carbon atoms to which they are attached, form cyclopentylidene or cyclohexylidene; R5 is C2_6alkyl, C3.6alkenyl or benzyl; and ^ is a simple link of the Anti form or the Sin form; and X1 and X2 independently are hydrogen or C1-alkyl. Preferred compounds of formula (X) are compounds and mixtures of geometric isomers, wherein:
T2 is hydrogen or < rp - Rr, with the proviso that when < 2 R
T1 is then T2 is hydrogen,
R1 and R2 independently are C3-4 alkyl, C2.4 haloalkyl, cyclopropyl, cyclopentyl, cyclohexyl, C2.4 alkenyl, C2.4 haloalkenyl or C3.4 alkynyl or represent phenyl which may be substituted by halogen or Cx_4alkyl; or Rx and R2 together with the nitrogen atom to which they are bound, form pyrrolidin-1-yl, 2,5-dimethylpyrrolidin-1-yl, 3-pyrrolin-1-yl, 2, 5-dimethyl-3- pyrrolin-1-yl, piperidino, 2-methylpiperidino, 2,6-dimethylpididino, piperazin-1-yl, morpholino, 1,2,3,4-tetrahydroquinolin-1-yl, 2-methyl- 1, 2,3,4-tetrahydroquinolin-1-yl, 2, 2-dimethyl-1, 2, 3, 4-tetrahydroquinolyl, 2,2-dimethyl-1,2-dihydroquinolyl or 6-fluoro-2, 2- dimethyl-l, 2- dihydroquinolyl; R3 is hydrogen or Cj_4 alkyl; R 4 is hydrogen or Ca 4 alkyl; or R3 and R4, together with the carbon atoms to which they are attached, form cyclopentylidene or cyclohexylidene;
R5 is Cj.4 alkyl, C2.4 alkenyl or benzyl; and it is a simple link of the Anti form or the Sin form; and X1 and X2 independently are hydrogen or C ^ alkyl. More preferred compounds of formula (X) are compounds and mixtures of geometric isomers, wherein:
T1 is hydrogen,
T2 is hydrogen or Ais with the proviso that when 12 R
T1 is then T2 is hydrogen,
R1 and R2 independently are C1.4 alkyl, C haloalkyl, cyclopropyl, cyclopentyl, cyclohexyl, C2.4 alkenyl, C2.4 haloalkenyl or C3 alkynyl. or represent phenyl which may be substituted by methyl, fluorine, chlorine or bromine; or R1 and R2 together with the nitrogen atom to which they are bound, form pyrrolidin-1-yl, 2,5-dimethylpyrrolidin-1-yl, 3-pyrrolin-1-yl, 2, 5-dimethyl-3- pyrrolin-1-yl, piperidino, 2-methylpiperidino, 2,6-dimethylpididino, piperazin-1-yl, morpholino, 1,2,3,4-tetrahydroquinolin-1-yl, 2-methyl- 1, 2, 3, 4-tetrahydroquinolin-1-yl, 2,2-dimethyl-1,2,3,4-tetrahydroquinolyl, 2,2-dimethyl-1,2-dihydroquinolyl or 6-fluoro-2, 2- dimethyl-l, 2- dihydroquinolyl; R3 represents hydrogen or methyl; R 4 represents hydrogen, methyl or ethyl; or R3 and R4, together with the carbon atoms to which they are attached form cyclopentylidene or cyclohexylidene; R 5 represents methyl, ethyl, allyl or benzyl; and t ^ represents a single bond of the Anti form or the Sin form; and X1 and X2 independently are hydrogen or methyl. The reaction of process (a) above can be carried out, for example, according to the process for obtaining tetrazolinones described in Japanese Patent Publication Kokai Hei 7-118 246. The reaction of process (a) above can be carried out in a diluent appropriate. Examples of useful diluents include aliphatic, alicyclic and aromatic hydrocarbons (which may be optionally chlorinated) such as pentane, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetraeloride, and the like. , 2-dichloroethane, chlorobenzene and dichlorobenzene; ethers such as diethyl ether, methyl t-butyl ether, diisopropyl ether, dibutyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF) and diethylene glycol dimethyl ether (DGM); nitriles such as acetonitrile and propionitrile; acid amides such as dimethylformamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone, 1,3-dimethyl-2-imidazolium-dinone and hexamethylphosphatriamide (HMPA); sulfones and sulfoxides such as dimethylsulfoxide (DMSO) and sulfolane; bases such as pyridine. Process (a) can be carried out in the presence of an acid-accepting agent and useful acid-binding agents are, for example, inorganic bases such as alkali metal or alkaline earth metal hydroxides, carbonates, bicarbonates and alcoholates, including sodium bicarbonate, potassium bicarbonate , sodium carbonate, potassium carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium methoxide, potassium methoxide, potassium tert-butoxide and the like; inorganic alkali metal amides, including lithium amides, sodium amide, potassium amide and the like; and organic bases such as tertiary amines, dialkylaminoanilines and pyridines, including triethylamine, 1, 1,4,4-tetramethylethylenediamine (TMEDA), N, N-di-ethylaniline, N, N-diethylaniline, pyridine, 4-dimethylaminopyridine (DMAP) ), 1,4-diazabicyclo [2, 2, 2] octane (DABCO), 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) and the like; including organic lithium compounds such as methyl lithium, n-butyllithium, sec-butyllithium, tert-butyllithium, phenyllithium, dimethyl-copper-lithium, lithium diisopropylamide, lithium cyclohexyl-sopropylamide, dicyclohexylamide of lithium, n-butyl-lithium. DABCO, n-butyl-lithium.DBU and n-butyl-lithium. TMEDA. The reaction of process (a) can be carried out substantially at temperatures within a wide range, but it is preferable to carry it out generally in a temperature range between -30 and 200 ° C, preferably between -20 and 130 ° C approximately. Likewise, the reaction can be carried out under atmospheric pressure, but it can also be carried out optionally under a higher pressure or under a reduced pressure. The process (a) can be carried out by reacting, for example, from 1 to 1, 5 moles of the compound of formula (III) with 1 mole of the compound of formula (II), in a diluent (such as toluene), in the presence of 1 to 1.5 moles of an acid-binding agent, to thereby obtain the desired compound of formula (I). In addition, the reaction of process (b) above can be carried out in a suitable diluent. Examples of useful diluents include aliphatic, alicyclic and aromatic hydrocarbons (which may be optionally chlorinated) such as pentane, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetraeloride. , 1,2-dichloroethane, chlorobenzene and dichlorobenzene; ethers such as diethyl ether, methyl t-butyl ether, diisopropyl ether, dibutyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF) and diethylene glycol dimethyl ether (DGM); nitriles such as acetonitrile, propionitrile and acrylonitrile; alcohols such as methanol, ethanol, isopropanol, butanol and ethylene glycol; esters such as ethyl acetate and amyl acetate; acid amides such as dimethylformamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone, 1, 3-dimethyl-2-imidazolidinone and hexamethylphosphatriamide (HMPA); sulfones and sulfoxides such as dimethyl sulfoxide (DMSO) and sulfolane. The reaction of process (b) can be carried out in the presence of an acidic material as a catalyst. Examples of useful acidic materials are: mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, hydrobromic acid, sodium bisulfite; organic acids such as formic acid, acetic acid, trifluoroacetic acid, propionic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid; hydrochloric acid salts of organic amines such as a pyridine hydrochloric acid salt, triethylamine hydrochloric acid salt; etc. The reaction of process (b) can be carried out at a temperature within a substantially broad range, but in general it is possible to employ a reaction temperature of from -10 to 200 ° C approximately, preferably from
In addition, the reaction will preferably be carried out under normal pressure, but can optionally be carried out under elevated or reduced pressure In order to carry out process (b), for example, one mole of the compound of formula can be reacted (IV) with 1 to 2 moles of the compound of the formula (V) in a diluent such as tetrahydrofuran and in the presence of sodium acetate, to thereby obtain the desired compound of the formula (I) The active compounds of the formula (I) according to invention can be used as herbicides By the term "weeds" in its broadest sense, it is meant all those plants that grow at points where they are undesirable The fact that the substance according to the invention act as total herbicides or selective agents will essentially depend on the amount used The active compounds according to the invention can be used, for example, in relation to the following plants: Dichotil weeds edóneas of the genres; synapse, Lepi-dium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthi- um. Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Conchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver and Centaurea. Cultures of dicotyledonous genera; Gossypium,
Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucu is and Cucurbita. Monocotyledonous weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Oats, Cyperus, Sorghum, Agropyr-on, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocha-ris , Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactylocte-nium, Agrostis, Alopecurus and Apera. Cultures of monocotyledons of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Sécale, Sorghum, Panicum, Saccha-rum. Ananas, Asparagus and Allium. However, the use of the active compounds according to the invention is in no way limited to said genera, but also extends in the same way to other plants. The compounds are suitable, depending on the concentration, to combat all weeds, for example on industrial land and on railroad tracks and also on trails and squares with or without tree planting. Likewise, the compounds can be used to control weeds in perennial crops, for example forests, decorative tree plantations, orchards, vineyards, citrus plantations, walnut plantations, plantations of bananas, coffee plantations, tea plantations, rubber plantations. , palm plantations, cocoa plantations, fruit tree plantations and hop fields, as well as to selectively combat weeds in annual crops. The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, foams, pastes, granules, aerosols, natural and synthetic materials impregnated with the active compound, very thin capsules in polymeric substances, compositions of coating for use in seeds and formulations used with scouring devices, such as fumigation cartridges, cans and streamers, as well as ULV cold and hot spray formulations. These formulations can be obtained in known manner, for example, by mixing the active compounds with extenders, i.e. diluents or liquid, gaseous liquefied or solid vehicles, optionally with the use of surface active agents, i.e., emulsifying and / or dispersing agents and / or foam formers. When using water as extender, auxiliary solvents can also be used, for example, organic solvents. As diluents or liquid solvent vehicles, aromatic hydrocarbons are particularly suitable, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatic or aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, such as butanol or glycol, as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexane-na, or strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, as well as water. By the expression "liquefied gaseous diluents or vehicles" is meant liquids which would be gaseous at normal temperature and pressure, for example aerosol propellants, such as halogenated hydrocarbons, as well as butane, propane, nitrogen and carbon dioxide. As solid carriers, ground natural minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, ontmorillenite or diatomaceous earth can be used, as well as ground synthetic minerals, such as highly dispersed silicic acid, alumina and silicates. As solid carriers for the granules, crushed and fractionated natural stones such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic flours, and granules of organic material such as sawdust powder, peel can be used. of coconut, corn cobs and tobacco stems. Emulsifying and / or foaming agents which may be used are nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates, arylsulfone-coughs and also albumin and hydrolysis products. Dispersing agents include, for example, residual ligninsulfite liquors and methylcellulose. Adhesives such as carboxymethyl cellulose and natural and synthetic polymers in the form of powders, granules or latexes, such as gum arabic, polyvinyl alcohol and polyvinyl acetate can be used in the formulation. It is possible to use dyes such as inorganic pigments, for example iron oxide, titanium oxide and Prussian blue, and organic dyes, such as alizarin dyes, azo dyes or metal phthalocyanine dyes, as well as traces of nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc. The active compounds according to the invention, either as such or in the form of their formulations, can also be used to control weeds, in the form of mixtures with known herbicides, the use of finished formulations or mixtures in tanks being possible. Mixtures with other known active compounds are also possible, such as herbicides, fungicides, insecticides, acaricides, nematicides, bird repellers, plant nutrients and agents that improve the structure of the earth. The active compounds can be used as such, in the form of their formulations or in the forms of use prepared therefrom by further dilution, such as solutions, suspensions, emulsions, powders, pastes and granules ready for use. They are used in the usual way, for example by means of irrigation, spraying, atomization or dispersion. The active compounds according to the invention can be applied either before or after the outbreak of the plants. They can also be incorporated into the soil before planting. In particular, they are used after the bud of the plants. The amount of active compound used can vary within a substantial range. Essentially, it will depend on the nature of the desired effect. In general, the amounts used are from 0.001 to 10 kg of active compound per hectare of land surface, preferably from 0.01 to 5 kg per hectare. The preparation and use of the active compounds according to the invention can be seen from the following examples, which should not be considered as limiting the scope of the invention. Examples of Synthesis Example of Synthesis 1
OCH.CHCHCH- Concentrated hydrochloric acid (20 ml) was added to a solution in tetrahydrofuran (30 ml) of l- (2-dimethoxyethyl) -4- (N-isopropyl-N-phenylcarbamoyl) -5 (4H) -tetrazolinone ( 5.8 g) and the mixture was allowed to stand for 1 day. to the oily product (5.1 g) obtained by separation of the solvent by distillation, O-allylhydro-xylamine hydrochloride (2.4 g), sodium acetate (2 g) and ethanol (70 ml) were added and the mixture was added. it was heated under reflux for 6 hours. The ethanol was distilled off under reduced pressure. Then, the resulting residue was extracted with ethyl acetate and the ethyl acetate solution was washed with water and then dried. The ethyl acetate was distilled off under reduced pressure and the resulting oily product was subjected to column chromatography on silica gel (n-hexane: ethyl acetate * 2: 1) to obtain an isomer mixture of 1- (2- allyloxyiminoethyl) -4- (N-isopropyl-N-phenylcarbamoyl) -5 (4H) -tetrazollnone (3.1 g) as an oily product; refractive index (nD20) = 1.5305 Example of Synthesis 2
They were dissolved in ethanol (50 ml) 1- (acetonyl) -4- (N-isopropyl-N-phenylcarbamoyl) -5 (4H) -tetrazolinone (0.8 g), O-methylhydroxylamine hydrochloride (0.4 g) and sodium acetate (0.4 g) and the mixture was heated under reflux for 4 hours. The reaction solution was filtered under suction and the crystals were separated by filtration. The filtrate was distilled under reduced pressure and the resulting crude product was extracted with dichloromethane. The product was washed with water and dried over anhydrous magnesium sulfate. The solvent was then removed by distillation under reduced pressure and the residue purified by column chromatography on silica gel (ethyl acetate: chloroform-1: 100) to obtain firstly Sin-l- (2-methoxyiminopropyl) - 4- (N-isopropyl-N-phenylcarbamoyl) -5 (4H) -tetrazolinone (0.4 g, mp 82-84 ° C) and then Anti-l- (2-methoxyiminopropyl) -4- (-isopropyl-N-phenylcarbamoyl) -5 (4H) -tetrazolinone (0.3 g, mp 84.5-92 ° C). The Rf value of the Sin form was 0.3 and the Rf value of the Anti form was 0.2. Synthesis Example 3
4-Dimethylaminopyridine (0.7 g) was added to a toluene solution of the Anti form of 1- (2-methoxyiminopro-pyl) - 5 (4H) -tetrazolinone (0.7 g) and N- ( 4-fluorfe-nyl) -N-isopropylcarbamoyl (0.9 g) at room temperature and then the mixture was reacted at about 60 ° C for 8 hours. The reaction solution was washed successively with water, dilute hydrochloric acid and water and then dried over anhydrous magnesium sulfate. The solvent was distilled off and the resulting residue was purified by column chromatography on silica gel (ethyl acetate: chloroform »1: 100) to obtain the Anti form of 1- (2-methoxyiminopropyl) -4-N- ( 4-fluorophenyl) -N-isopropylcarba-moyl-5 (4H) -tetrazolinone (1.2 g) as crystals; p.f .: 82.5-83.5ßC. Tables 4 and 5 show the compounds obtained in the same manner as those of the above Synthesis Examples 1 to 3. Table 4 also shows the compounds of the above Synthesis Examples 1 to 3.
Table 4 Table 4 rContinuacirtr
Tgbl 5
Synthesis of intermediate compounds: Synthesis Example 4 (Synthesis of the starting material for the production of the compound of Synthesis Example 1)
To an aqueous solution (5 ml) of sodium hydroxide (2.2 g), a solution in methanol (50 ml) of l- (2,2-dimethoxyethyl) - (4H) -tetrazoline-5-thione (8 ml) was added. , 4 g) and then propylene oxide (3.4 g) was added while stirring and cooling with ice, and the mixture was allowed to stand at room temperature overnight. The aqueous solution obtained by separation of the methanol by distillation was washed with ethyl acetate and then the water was distilled off under reduced pressure. To the residue anhydrous methanol was added and the solution was acidified by introducing gaseous hydrochloric acid at room temperature. The methanol was then distilled off under reduced pressure and the resulting residue was extracted with ethyl acetate. Then, to a toluene solution of the residue (6.3 g) obtained by distillative separation of ethyl acetate and N-isopropyl-N-phenylcarbamoyl chloride (7.2 g), 4-dimethylamino-pyridine and the mixture was reacted at approximately 50 [deg.] C. for 6 hours. The reaction solution was washed with water, with dilute hydrochloric acid and with water, after which it was dried over magnesium sulfate and the toluene was distilled off. Then, the resulting residue was purified by column chromatography on silica gel (ethyl acetate: hexane = 1: 3) to obtain l- (2,2-dimethoxyethyl) -4- (N-isopropyl-N-phenyl- carbamoyl) -5 (4H) -tetrazolinone (7.1 g) as an oily product; refractive index (nD20) = 1.5160 Synthesis Example 5 (Synthesis of the starting material for the production of the compound of Synthesis Example 2)
4-Dimethylaminopyridine (6.8 g) was added to a toluene solution of l-acetonyl-5 (4H) -tetrazolinone (5 g) and N-isopropyl-N-phenylcarbamoyl chloride (7.3 g) and the mixture was reacted at 65 ßC for 10 hours. The reaction solution was filtered under suction, the filtrate was washed with water, dilute hydrochloric acid and water and then dried over anhydrous magnesium sulfate. Then, the solvent was distilled off under reduced pressure and the resulting residue was purified by column chromatography on silica gel (ethyl acetate: chloroform = 1: 25) to obtain l- (acetonyl) -4- (N- isopropyl-N-phenylcarbamoyl) -5 (4H) -tetrazolinone (9.1 g); refractive index (nD20) - 1.5228 On the other hand, l- (2-oxopropyl) -4- (2-methyl-1, 2,3,4-tetrahydroquinolin-1-ylcarbonyl) -5 (4H) was obtained. -tetrazolinone in a manner similar to that indicated in Synthesis Example 5; p.f. 103-105 ° C. Example of Synthesis 6
An ethanol solution of l-acetonyl-5 (4H) -tetrazolinone (1.4 g), O-allylhydroxylamine hydrochloride (2.4 g) and sodium acetate (1.8 g) was heated under reflux for 4 hours. ). The ethanol was removed by distillation under reduced pressure and the residue was extracted with ethyl acetate. The product of the extraction with ethyl acetate was subjected to column chromatography on silica gel (ethyl acetate: hexane = 1: 1) to obtain l- (2-allyloxyiminopropyl) -tetrazolin-5 (4H) -one (Anti : Sin = 5: 1) (1.8 g); p.f. 57-60.5 ° C. On the other hand, l- (2-methoxyiminopropyl) -tetrazolin-5 (4H) -one (Anti form) (mp 99.5-101ßC) was obtained as the main product in a manner similar to that described in Synthesis Example 6. Synthesis Example 7 (Synthesis of the starting material for the production of the compound of Synthesis Example 6)
A catalytic amount of boron trifluoride ether complex was added to a mixed solution of 2,2,6-trimethyl-4H-1,3-dioxin-4-one (14.2 g) and trimethylsilylazide (25 g) at room temperature and the mixture was reacted at 100-110 ° C. for 6 hours.The unreacted trimethylsilylazide was distilled off under reduced pressure, the resulting residue was dissolved in methanol by the addition of methanol and then the methanol was removed by low distillation. reduced pressure The residue was subjected to column chromatography on silica gel (ethyl acetate) to obtain 1-acetonyl-5 (4H) -tetrazolinone (10.6 g) as colorless crystals, mp 120-122 ° C. On the other hand, l- (2-oxobutyl) -5 (4H) -tetrazolinone (mp 99-111, 5 ° C) was obtained as colorless crystals in a manner similar to that described in Synthesis Example 7. Synthesis Example 8
To an aqueous solution (water: 5 ml) of sodium hydroxide (2.3 g), a methanol solution of l- (2,2-dimethoxyethyl) -4H-tetrazolin-5-thione (8.7 g) was added. and then propylene oxide (3.5 g) was added while stirring and cooling with ice. Then, the mixture was allowed to stand at room temperature overnight. After the methanol was distilled off under reduced pressure, it was acidified with concentrated hydrochloric acid, after which an extraction was carried out with a methanol: chloroform solution (1:10). To the residue (6.1 g) obtained by solvent removal by distillation, O-methylhydroxylamine hydrochloride (8.6 g), sodium acetate (8.6 g) and ethanol were added and the mixture was heated under reflux for 4 hours. The ethanol was distilled off under reduced pressure and the resulting oily product was subjected to column chromatography on silica gel (ethyl acetate: hexane = 1: 1) to obtain the Anti form of 1- (2-methoxyiminoethyl) -5. (4H) -tetrazolinone (3.3 g) as the main product; p.f. 115-116, 5ßC. Synthesis Example 9 (Synthesis of the starting material for the production of the compound of Synthesis Example 8)
An aqueous solution of methyl N- (2, 2-dimethoxyethyl) dithiocarbamate (9.8 g) and sodium azide (3.7 g) was heated to 100 ° C. After the methyl mercaptan release, the reaction solution was cooled to room temperature and washed with ethyl acetate. Ethyl acetate was poured into the aqueous solution. Then, the acid material obtained by acidification with dilute hydrochloric acid was extracted with ethyl acetate. The ethyl acetate solution was washed with saturated saline, dried over magnesium sulfate and then the ethyl acetate was distilled off to obtain l- (2,2-dimethoxyethyl) - (4H) -tetrazolin-5-thione ( 8.4 g); refractive index (nD20) = 1.5264 Synthesis Example 10 (Synthesis of the starting material for the production of the compound of Synthesis Example 9)
Sodium tert-butoxide (17.1 g) was added to a methanol solution of 2,2-dimethoxyethylamine (14.5 g) and carbon disulfide (15 g) while stirring and cooling with ice and the mixture was reacted for 30 minutes. Then dimethyl sulfate (17.5 g) was added and the mixture was reacted for 1 hour under cooling with ice. After the reaction was complete, water was added to the reaction solution and then the toluene was distilled off under reduced pressure to obtain methyl N- (2,2-dimethoxyethyl) dithiocarbamate (22.5 g) as a yellow oily product. This was used for the reaction of Synthesis Example 9 without purification. Test Examples Test example 1 (Pre-flare soil treatment test against weeds in plowed land). Preparation of the vehicle test solutions: acetone, 5 parts by weight emulsifier: benzyloxy polyglycol ether, 1 part by weight A part of an active compound and the above amounts of vehicle and emulsifier were mixed to obtain a formulation of the active substance as an emulsion . A prescribed amount of this formulation is diluted with water to prepare test solutions. Test procedure In the greenhouse, seeds of each of the species Echinochloa crusgalli and Amaranthus lividus were seeded in the layer of plowed earth surface deposited in a pot of 120 cm2 with earth covering and on the earth surface layer of each One of the test sherds was uniformly sprayed a prescribed amount of the test solution prepared by the above process. The herbicidal effect was evaluated 4 weeks after sowing. In this test, for example, the active compounds Nos. 1, 2, 14, 21, 23 and 25 of the invention (see Table 4 above) in a proportion of 1.0 kg / ha exhibited a 100% herbicidal activity against Echinochloa crusgalli and Amaranthus lividus. Test Example 2 (Post-emergence soil treatment trial against weeds in plowed land). Test procedure In the greenhouse, seeds of each of the species Echinochloa crusgalli and Amaranthus lividus were sown in a pot of 120 cm2 filled with plowed earth and covered with soil. At 10 days after sowing and soil cover (when the weeds were in the second middle phase of foliage), it was sprayed uniformly on the foliage part of the test plant of each of the sherds, a prescribed amount of the test solution prepared in a manner similar to that described in Test Example 1 above. At 3 weeks after application, the herbicidal effect was evaluated. In this test, active compounds Nos. 1, 10, 13, 21 and 25 of the invention (see Table 4 above) at an application rate of 2 kg / ha exhibited a herbicidal activity of 90% or higher against Echinochloa crusgalli and Amaranthus lividus. Test Example 3 (Test of the herbicidal effect against weeds in rice fields) Preparation of formulations of active ingredients vehicle: acetone, 5 parts by weight emulsifier: benzyloxy polyollether, 1 part by weight. The formulations of the active ingredients are obtained by mixing 1 part by weight of the active compounds and the above amounts of vehicle and emulsifier. The prescribed amount of the formulation is diluted with water to prepare a test formulation. Test procedure In the greenhouse, 3 rice seedlings (variety: Nipponbare) are transplanted in the 2.5-leaf stage (15 cm high) at two points of a large pot (25 x 25 x 9 cm) filled with soil of paddy and saturated with water. Then seeds of cerreig, small flower, monocoria, broadleaf weeds (Lindernia pyxidaria, Rotala indica, Elatine triandra, ammannia muí iflora Roxb, Dopatrium junceura Hamilt) and common mace and a tuber of Japanese ribbon apato are poured and water is poured on the ground to a depth of 2-3 cm approximately. Each of the prescribed amounts of the active compound formulation, prepared in a manner similar to that indicated in the previous preparation method, was applied to the surface of the water 7 days after transplanting the paddy. The herbicidal activity and the degree of phytotoxicity against the plants of the harvest were examined on the day after 3 weeks after the treatment, during which period the water depth was maintained at 3 cm. The herbicidal activity was classified as 100% in the case of complete destruction and as 0% in the case where no herbicidal effect was observed or in the case where no phytotoxicity was observed.
In this test, for example, the active compounds
Nos. 1, 2, 6, 9, 13, 14, 22, 23 and 24 of the invention (see
Table 4 above) exhibited a herbicidal activity of 90% or greater against cerreig, small flower, monochoria, broadleaf weeds, medium cmun and Japanese ribbon wapato per application of 0.5 kg / hectare of each active compound. FORMULATION EXAMPLES Formulation Example 1 (granules) Water (25 parts) is added to a mixture of compound No. 3 (10 parts) of the invention (for "compound No." see Table 4 above), bentonite ( ontmorillonite) (30 parts), talc (58 parts) and lignin sulphonate salt (2 parts) with good kneading and the resulting mixture is formed into 10-40 mesh granules using an extrusion type granulator, followed by 40-50 drying °, to obtain granules. Formulation Example 2 (granules) Clay mineral (95 parts) having a particle size distribution of 0.2-2 mm is introduced in a rotary mixer and compound No. 1 (5 parts) of the mixture is then sprayed. invention (for "Compound No." see Table 4 above) together with a liquid diluent under rotation, to achieve uniform wetting, followed by drying at 40-50 ° C to obtain granules. Formulation Example 3 (emulsion) An emulsion is obtained by mixing the compound No.
3 (30 parts) of the invention (for "Compound No." see Table 4 above), xylene (5 parts), polyoxyethylenealkylphenethylether (8 parts) and calcium alkylbenzene sulfonate (7 parts) with stirring. Formulation Example 4 (Wettable Powder) A wettable powder is prepared by mixing compound No. 5 (15 parts) of the invention (for "Compound No." see Table 4 above), a mixture (1: 5) of White Carbon (fine powder of non-crystalline hydrated silicon oxide) (80 parts) and powdered clay, sodium alkylbenzenesulphonate (2 parts) and a condensate of sodium alkylnaphthalenesulphonate and formaldehyde (3 parts) in pulverulent state. Formulation Example 5 (wettable granules) Wettable granules are prepared by thoroughly mixing compound No. 2 (20 parts) of the invention (for "Compound No." see Table 4 above), sodium ligninsulfonate (30 parts), bentonite ( 15 parts) and calcined diatomaceous earth powder (35 parts), followed by addition of water and extrusion through a 0.3 mm screen and subsequent drying. A person skilled in the art, after reading this specification, can now design variations and other modalities using the principles described herein. All of these considered to be within the scope of this invention are defined in the appended claims. Having described the invention as above, property is claimed as contained in the following: