TW482653B - New herbicidal method - Google Patents

Abstract

The invention relates to a method of reducing phytotoxicity to crop plants caused by a herbicidal cyclic amide derivative; which comprises applying to the locus of the crop plant an antidotally effective amount of an antidote; wherein said antidote is antidotally effective to said cyclic amide derivative.

Description

482653 V. Description of the invention (1) Field of invention The present invention relates to the safety of herbicidal compounds, especially the safety of herbicidal cyclic amidine derivatives which can be used for the growth of agricultural crops (especially rice and cereal crops, such as wheat and barley). And compositions useful in this treatment. Technical note-Many herbicides are known to damage crop plants at the rate of herbicide application required to control weed growth. It makes many herbicides unsuitable for weed control in the presence of certain crops. However, if weeds growing in crops are not controlled, weeds will compete with crops for nutrients, light and water, which will result in lower crop yields and lower crop quality. Herbicides reduce damage to crops and have herbicidal effects. Acceptable reductions can be achieved by using crop protection agents, called "antidote", sometimes called "safeners" or "antagonists". The safety of a compound is generally specific to crops to which the herbicide congeners and active ingredients are applied. Certain kinds of herbicidal cyclic amidine derivatives are disclosed, for example, in International Patent Publication I Tiger Stone Horse WO 9 3/1 5 0 6 4, WO 9 5/18113, WO 9 7/0 0 8 6 5, WO 9 5 / 2 2 5 2 3, and WO 9 6/3 8 4 1 3; European Patent Publication No. EP 5 5 7 6 9 1; German Patent Publication No. DE 1 9 5 3 5 8 4 2; and Japanese Patent Publication Case number J 8-3 1 1 0 2 6. Surprisingly, the applicant has discovered the presence of certain antidote (known to other herbicides and / or other crops) and certain cyclic amidine derivatives (optionally mixed with a homogeneous herbicide), Under certain conditions, phytotoxicity can be reduced for any crops of rice or indica crops such as wheat or barley, while still maintaining a good degree of weed control.

Page 4 482653 V. Description of the invention (2) Description of the invention The present invention provides a method for reducing the effects of the herbicidal cyclic amidine derivative of the following formula (I) on crops (especially rice or cereal crops such as wheat and barley). Phytotoxic methods;

Wherein: R4 and R5 are independent epialkyl groups; and i) -X-Y- table-C (Rla) = C (R2) -0-; w table NHR3 or R3a;

Rla epiphenyl or thienyl is optionally substituted with one to five groups, which may be the same or different, and are selected from the group consisting of II, hydroxy, alkyl, haloalkyl, alkoxy, haloalkoxy, -S (0 ) nR6, -C02R6, -COR6, cyano, nitro, -〇 (CH2) q-C02R6, and aryloxy; or Table RlbS (0) x; rule 11 " surface alkyl, halogenated, dilute , Dihalo, halo, haloalkynyl, or cycloalkyl; R2 epihydrogen, alkyl, haloalkyl, halooxyalkyl, haloalkoxyalkyl, dilute 'halo dialkyl' 'Halloyl' alkoxydiluted, -CΗ0, -COR6, -C02R6, -〇Η2NO2, or alkyl, via one selected from -S (0) nR6, OH, -0C0R6 and- NR7R8 is substituted by a group; or a group is selected from the group consisting of a gas group, a CH0, a COR6, a CO2H, a CO2R6,

482653

-COSR6, -C0NR7R8 '--CH = NOOH, --CH = NOR6, -CH = NOCOR6, -CH4NR7R8, -CH2CN, ... CH2N02, and ethylene oxide; R3 epiphenyl group selectivity ranges from one to five This group may be the same or different. It is selected from the group consisting of halogen, mesityl, alkyl, haloalkyl, halooxy, halooxy, -S (0) nR6, -C02R6, -COR6, cyano Group, nitro group, —NR7R8, benzyloxy group, carbamoyloxy group, and —M;

… &Quot; Table- (CH2) r- (benzyl or naphthyl), optionally substituted by one to five groups, which may be the same or different, selected from halogen, hydroxy, alkyl, haloalkyl, alkoxy , Alkoxy, -S (0) nR6, -C02R6, -C0R6, cyano, nitro, -0 (CH2) qC02R6, benzooxy, and -SF5; or substituted with a group selected from : -0C0R6, NR9R1Q, NHR6a, -CH2NR9R10, -CONR9Ri〇, -C0NHR6a, -0S02R6 ·, -〇S02R6a, -〇COR6a, -OCH2COR6a, -〇CH2R6a, -S (0) mR6a, R6a, -6 〇) (〇R6) (〇R6b), -P (= 0) (0R6) R6b, -CH2P (二 0) (0R6) (0R6b), -CH2P (= 〇) (〇R6) R6b, -C〇 2R6a, -CH2S (0) nW, -CH2S (0) mR6a, -CH2OR6, -CH20R6a, -Cii20C0R6a, -CH20S02R6a and alkenyl (phenyl and naphthyl rings may be substituted by one or more halogen or R6 groups) ; Or Table 1 benzene ring, optionally substituted by one to five groups, the group may be the same or different, and is selected from halogen, alkyl, haloalkyl, alkoxy, halooxy, -S (〇) nRs, CN, and N02, fused to a second five- or six-membered cyclohexyl or cycloalkenyl ring, or fused to a saturated five- or six-membered heterocyclic ring ( The obtained 1,3-metallocene or stupid Shu and two fathoms, 4-benzo-dioxane), containing one to three heteroatoms, the same or different, selected from nitrogen, oxygen and sulfur, which ring via selective

482653 V. Description of the invention (4) One or more R12 group substitutions, or cycloalkyl, cycloalkenyl, or saturated five- or six-membered heterocyclic ring can optionally form a carbonyl group (it should be clear that for fused Ring system, the benzene ring is connected to the carbonyl group, which forms a part of -C (= 0) W, where W is R3a); or a phenanthrene or anthracene ring, optionally substituted by one or more groups, the group is Selected from halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, -S (0) nR6, CN, and N02; or Table- (CH2) s- (five to seven-membered heteroaromatic ring) , Wherein the heteroaromatic ring has one to four ring heteroatoms, which may be the same or different, and is selected from nitrogen, oxygen, and sulfur, and the ring is selectively fused to a benzene ring or a second five to seven-membered heteroaromatic ring, It has one to four heteroatoms, which may be the same or different, and is selected from the group consisting of gas, oxygen, and sulfur to form a bicyclic system. In a monocyclic or bicyclic system, one ring is optionally substituted with one to four groups. The groups may be the same or different. Is selected from the group consisting of functional elements, hydroxy, alkyl, cyano, haloalkyl, alkoxy, haloalkyl, -S (0) nR6, -C02R6, -COR6, nitro, -〇 (CH2) q- C02R6, and benzene Or a selectively halogenated alkyl, alkenyl, or alkynyl group, containing up to ten carbon atoms; or a selectively halogenated alkyl, alkenyl, or alkynyl group, containing up to ten Carbon atom substituted with a cycloalkyl group containing three to six carbon atoms (the cycloalkyl ring may optionally be substituted with one or more halogen or alkyl groups); or ® a cycloalkane containing three to six carbon atoms Or a cycloalkenyl group containing five or six carbon atoms, the ring system is optionally substituted with an R6 group or one or more halogen atoms that are the same or different; or a cycloalkyl group containing three to eight carbon atoms or Contains four to eight carbon atoms

Page 7 482653 V. Description of the invention (5) The cycloalkenyl group, in which the ring system is substituted by an E group, the group is selected from the group consisting of C02H, C02R6, alkenyl, haloalkenyl, R6a, NR9R1G, alkoxy , Haloalkoxy, S (0) nR6, COR6, COR6a'CH2COR6a, C0CH2R6a, C02CH2R6a, S (0) mR6a, CN, S (〇) tCH2R6a, SCO) '14, CH2OR6, CHO, COR11, N02 , CONHR6a, CONR6R6a, CH20H and-(: [1 (01? 13) (01 ^ 1; ^) (-(:) 1 (01? 13) (01? 13 &) Cyclic acetals, optionally substituted with one or more R6 groups), or one of the cycloalkyl carbon · atoms to form part of a carbonyl group (a cycloalkyl or cycloalkenyl ring as defined above may be optionally contained, except E, one or more halogen or R6 group), the substituent E is preferably connected to the carbon atom of the cycloalkyl or cycloalkenyl group, and the carbonyl group forms a part of the -C (= 0) W group Part, where .W is R3a; or a cycloalkyl group containing five to seven carbon atoms or a dilute ring group containing five or six carbon atoms, the ring is optionally substituted by one or more R12 groups, where the ring system is thick Bound to a benzene ring (such as dihydro Group) optionally substituted with one to four groups, which may be the same or different, and are selected from halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, S (0) nR6, cyano, and nitro (It should be clear that, for fused ring systems, a cycloalkyl or cycloalkenyl ring is attached to the carbonyl group, which forms part of _C (= 0) W, where W is 1 ^); or epialkyl or halogen Alkyl, one of which is substituted with one or two R15 groups, optionally with one R16 group; or epienyl or ialkenyl, one of which is optionally with one or two R15 groups, and one selected from _R6a , The groups of R17 and R18 are substituted together; or the epialkynyl group is substituted by an R15 group (in the above definition, the R15 group is preferably located on the carbon atom of R3ai, which is at the α or / 5 position of the carbonyl group, the carbonyl group forms -C (= 0) One of W

Page 8 482653 V. Part (6) of the description of the invention, where W is R: 3a); R6 and R6b are epialkyl or haloalkyl; R6a is optionally substituted by one or more groups, and the group may be The same or different, is selected from the group consisting of halogen, alkynyl, haloalkyl, alkoxy, halooxy, -S (0) nR6, cyano, and nitro; R7, R8, R9, and R1Q are independently hydrogen, Alkyl, or haloalkyl; R11 represents a cycloalkyl containing three to seven carbon atoms or a cycloalkenyl containing five or six carbon atoms, wherein the ring system is optionally substituted with one or more R12 groups; R12 represents Halogen, alkyl, or haloalkyl; R13 and R13a epialkyl, or-(:( 01? 13) (01? 13〇-) means a five- or six-membered cyclic ketal, which is the formula -C ( OR13b) (OR13c)-1,3-dioxolane or 1,3-dioxolane, wherein R13b & R13c-starting from the C2 or C3 alkyl chain of Table 1, optionally substituted by alkyl; R14 table Cycloalkyl groups containing three to seven carbon atoms are optionally substituted with one or more R12 groups; R15 represents 10H, -OR6 > -S (0) nR6, -S (0) mR6a, -C02R6 , -C02CH2R6a, CN, N02, CHO, COR6, C0R6a, C0CH2R6a, -C02H, -C0NRiJR1Q, -S (0) tCH2R6a, -S (0) pR18 or a five- or six-membered cyclic acetal group is optionally substituted with one or more R6 groups; R16 represents Rk, alkynyl, or a three- to six-membered cycloalkane The base ring is optionally substituted with one or more R6 or halogen; R17 is optionally substituted with one or more R12 groups; R18 is a cycloalkyl containing three to seven carbon atoms. One or more R12 group substitutions:

482653 V. Description of the invention (7) 111, 11, port, 1 ;, 11 and table 0, 1 or 2; q table 1 or 2; and r and s table 0 or 1; or ii) -XY- table; R1 is optionally substituted with halogen, alkyl, haloalkyl, alkoxy, or haloalkoxy; 1 ^ epialkyl; and • W-NHR3c, where R3e is phenyl, naphthyl, or A five- or six-membered heterocyclic ring containing one to three heteroatoms selected from the group consisting of oxygen, nitrogen, and sulfur. The ring system is optionally halogenated, halogenated, halogenated, halogenated, halogenated, and -S (0) nR6, I-C02R6, nitro, cyano, or _C02H substitution; or W R3b, where R3b represents alkyl, haloalkyl; phenyl, optionally via halogen, alkyl, haloalkyl, or alkoxy Substituents; benzyl, alkenyl, haloalkenyl, alkynyl; C 3-7 cycloalkyl, optionally substituted with halogen or alkyl; or alkyl substituted with C 3-7 cycloalkyl; or R2a Hydroxy, alkoxy, halooxy, -S (0) nR6, amine, carbamoyl, or dialkylamino; and R3d, wherein R3d represents alkyl, alkenyl, alkynyl, Or stupid methyl, or phenyl, optionally via halogen, alkyl, haloalkyl, or -S (0) nR6 ; Or iii) -XY-Table-NUD-CHU23)-or -NUO-CHUN-CHr; wherein R2a is an alkyl group; and W-NHR3c4 R3b; or, iv) -XY-Table- NCR1)-N (Me) -CH ·] -or-N (.)-0-; and W-NHR3e4 R3b; and

Page 10 482653 V. Description of the invention (8) R3e epiphenyl, optionally substituted with halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, or -S (0) nR6; or v)- XY-table, -CHUD-lUR22)-or -cmRD-scoh-; and table NHR3c; and vtable 0, 1 or 2; or an agriculturally acceptable salt thereof; this method comprises applying a detoxifying effective amount to a crop site An antidote compound that is selective to a companion herbicide, wherein the antidote is effective in detoxifying the cyclic amidine derivative. φ The present invention also provides a composition comprising: (a) a herbicidally effective amount of a cyclic amidine compound of formula (Ί) or an agriculturally acceptable salt thereof, optionally in combination with a companion herbicide; and (b) A detoxifying effective amount of a detoxifying compound; and a herbicide-acceptable diluent or carrier and / or surfactant. It should be understood that the antidote used in the method of the present invention may form, for example, a salt, and the use of the salt is also included in the present invention. It should be understood that certain substituents in the compounds of formula (I) may form optical and / or stereoisomers. All such forms and mixtures are included in the invention. In this patent specification and the scope of the patent application, it should be clear that the term "agriculturally acceptable salt" means a cation or anion salt known in the art and accepted to form an agricultural or horticultural salt. The salt is preferably water-soluble. Suitable salts for testing include metal testing (such as Na and Shu), metal testing (such as calcium and magnesium), ammonium and amines (such as diethanolamine, triethanolamine, octylamine,

Page 11 482653 V. Description of the invention (9) Morpholine and dioctylmethylamine) salt. Suitable for acid addition salts, such as those formed from compounds of formula (I) containing monoamine groups, including salts of inorganic acids, such as hydrochloride, sulfate, phosphate, and nitrate, and salts of organic acids, such as Acetate. In the scope of this specification and the patent application, unless otherwise stated, the alkyl and alkyl portions contain one to six carbon atoms and are straight or branched; the alkenyl and alkenyl portions contain two to six carbon atoms, as Straight or branched chain; alkynyl and alkynyl portions contain two to six carbon atoms and are straight or branched. Compounds of-乂 -γ-(-:-( 1 ^) = (:( 1? 2) -0- in the above formula (1) are preferred. Rla in the formula (I) represents phenyl or thienyl selectivity After one to three radicals are selected, the radicals may be the same or different, and are preferably selected from the group consisting of halogen, alkyl, haloalkyl, and alkoxy; or compounds that are epialkylthio (Rla epibenzyl is optionally Compounds selected from halogen, fluorenyl, and methoxy are particularly preferred. Particularly preferred are the compounds of formula (I) above wherein R1 represents a phenyl group optionally substituted with fluorine, gas, or methyl. Table R2 in formula (ii) above. Alkyl, alkyl, or hydrogen compounds are preferred. R2 is most preferably methyl, ethyl, trifluoromethyl or hydrogen. Compounds of the formula W in the formula (I) W3 are also preferred (R3a optimally contains A cycloalkyl group of three to six carbon atoms or a cycloalkenyl group containing five or six carbon atoms, the ring system is optionally substituted with one R6 group or one or more halogen atoms (which may be the same or different); or R3a table selection Alkyl alkyl, containing up to four carbon atoms, is replaced by a cycloalkyl containing three and six carbon atoms (rings are burned, and the base ring can optionally be taken from one or more products or alkyl groups )) In the formula (I), W represents NHR3 and R3 table phenyl group substituted by one to three, the

Page 12 482653 V. Description of the invention (ίο) The groups may be the same or different, and compounds selected from halogen, alkyl, haloalkyl, and haloalkoxy are also preferred (R3 Table 3-Halophenyl, 2, 5 -Dihalophenyl, 3,5-dihalobenzyl, 2-halo-5 -haloalkoxyphenyl, 3-haloalkylphenyl, or 3-halo-5 -alkylbenzyl compounds good). Particularly preferred are compounds in which R4 and R5 are epimethyl groups in the above formula (I). The preferred compounds of the above formula (I) are: -X-Y- Table-C (Rla) = C (R2) +;

1 ^ 1 & epiphenyl or thienyl, each optionally substituted with one to three groups, the groups may be the same or different and are selected from halogen, alkyl, haloalkyl, and alkoxy; or epialkylthio; I R2 represents an alkyl group, a halogenated group, or hydrogen; W represents an NHR3 or R3a; · R3 represents a phenyl group optionally substituted by one to three groups, which may be the same or different and are selected from the group consisting of ifidin, alkyl, and halogen R3a represents a cycloalkyl group containing three to six carbon atoms or a dilute ring group containing five or six carbon atoms, and the ring system is optionally passed through an RG group or one or more of the same or different Ii element atom substitution; or R3a represents a selectively halogenated alkyl group containing up to four carbon atoms, substituted with a cycloalkyl group containing three to six carbon atoms (the cycloalkyl ring can be optionally substituted by one or more Halogen or alkyl)); and R4 and R5 are fluorenyl. A more preferred compound of the above formula (I) is a compound having one or more of the following characteristics: ^. -XY-epi-C (Rla) = C (R2) -0-; 1 ^ epiphenyl, 2-aerobenzene , 2-fluorobenzyl, 2-fluorenylbenzyl, or alkylthio

Page 13 482653 V. Description of the invention (11) Group; R2 represents methyl, ethyl, or fluoromethyl; W represents NHR3 or NHR3a; {^ 3 Table 3-_benzyl, 2,5-dihalophenyl , 3,5-di [| 1phenyl, 2-halo-5-haloalkoxybenzyl, 3-haloalkylbenzyl, or 3-halo-5-alkylbenzyl; R3a epicyclopentyl Or cyclopentenyl, optionally substituted with one R6 group or one or more halogen atoms that are the same or different; or R3a epimethyl, substituted with cyclopentyl or cyclopentenyl, optionally substituted with one or more halogens Or alkyl substituted; or 1 ^ 3 represents an alkyl group containing up to four carbon atoms, substituted with cyclopropyl, which is unsubstituted or substituted with alkyl; and R4 and R5 represent methyl. A particularly preferred compound of formula (I) is: 1-cyclopentyl-2- (2,3-dihydro-6-fluorenyl_4-oxy-5-phenyl-4H-1,3 -fluorene -3 -yl) -2-methylpropan-1-one; Bucyclobutyl-3- (2, 3-dihydro-6-methyl-4-oxy-5-phenyl-βΗ-ΐ, 3-shukoujing-3-yl) -4 -fluorenylbutan-2 -S is the same; 1 -cyclopentyl-2- (2,3 -dihydro-6 -ethyl-4-oxy-5- Phenyl-M-fluorenyl, 3-sulfonyl-3-yl)-2-fluorenylpropan-1-yl is self-identifying; Ν-(2,5-diphenylphenyl) -2-methyl-2-[6- Methyl-5-(2-fluorophenyl) -2,3-dihydro-4 -oxy-4'-1,3 -succinyl-3-yl] propionamine; ) -2-methyl-2- [6-fluorenyl-5- (2-fluorophenyl) -2,3-dihydro-4-oxy- 4fluorene-1,3-—oxo-3-yl] Promethazine; 2- (2,3-dihydro-6-methyl-4-oxy-5-phenyl-4} 1-1,3-pyrene-3-yl) -2 -fluorenyl -4-(1-methylcyclopropyl) butan-3-one;

Page 14 482653 V. Description of the invention (12) 4-Cyclopropyl-2-(2,3-dihydro-6-methyl-4-oxy-5 -phenyl-4H-1,3 -fluorene) -3-yl) -2-methylpentan-3-one; N- (2-fluoro-5-trifluorofluorenoxyphenyl) -2-methyl-2- (6-methyl-5-benzyl -2,3-dihydro-4-oxy-4H-1,3-fluoren-3-yl) propanamine; N- (3-fluoromethylbenzyl) -2-methyl-2- (6-methyl-5-benzyl-2,3-dihydro-4-oxy-4H-1,3-fluoren-3-yl) propanamide; N- (3-tri-I-fluorenyl) )-2 -methyl-2-[5- (2- -Alkyl) -2,3-dihydro-4-oxy-4H-1,3-fluoren-3-yl] propanilamide; N-(3-fluoro-5 -fluorenylphenyl) -2 -methyl-2-[5-(2-fluorobenzyl6-methyl-2,3-dihydro-4-oxy_4H- 1,3-pyrene-3-yl] propanamide; and N- (3,5-difluorophenyl) -2-methyl-2- (5-isopropylthio-6-fluorenyl- 2, 3 -dihydro-4-oxy-4H-1,3-P-co--3-yl) propanamine. The most preferred compound of formula (I) is: ^ (2,5-difluorobenzene ) -2-methyl-2- [6-methyl-5- (2-fluorophenyl) -2,3-dihydro-4-oxy-4H-1,3-fluoren-3-yl ] Propanamide; and N- (3-iodophenyl) -2-methyl-2- [6-methyl-5 (2-fluorophenyl) -2,3-dihydro-4-oxo -4H-1,3-Hydroxy-3-yl] propanamide. Certain compounds of formula (I) were not previously described and can be prepared as shown in the following examples. Example 1 Grass gas (0.2 ml ) Add 2-methyl-2-(6 -fluorenyl-5 -benzyl-2, 3 -dihydro-4-oxy-4H-1,3 -benzidine, -3- A) propionic acid (0.55 g) in a solution of dioxane containing 1 drop of N, N-dimethylamidamine, the mixture was stirred at 20 t for 10 minutes, and cooled to 15 ° C. 2- Fluoro-5 -trifluorophosphonium

Page 15 482653 V. Description of the invention (13) A solution of aniline (0.41 g) in methane gas was added during 1 minute, and then triethylamine (0.63 ml) was added in dichloromethane. . After 2.5 hours, the mixture was washed with hydrochloric acid (2 M), sodium carbonate solution, and water, dried (magnesium sulfate), and evaporated. After purification by chromatography on silica gel with ethyl acetate / isohexane, 1 ^ ((2-fluoro_5-trifluoromethoxybenzyl) -2-methyl-2- (6-methyl-5) was obtained. -Benzyl-2, 3 -dihydro-4-oxy- 4Η-1,3- 噚 co-3-yl) propanamide (0.1 g), melting point 1 0 1: 5-1 0 2 · 5 ° C. Following a similar 5 ^ formula, the following compounds were obtained: N-(3-trifluoromethylphenyl)-2-methyl-2-(6-methyl-5 -benzyl-2,3-dihydro-4 -Oxy- 4H-1,3-pyrene-3-yl) propanilamine, NMR 1.62 (s, Lu 6H), 1.88 (s, 3H), 5.23 (s, 2H), 5.2 and 5.35 (d, 2H), 7.0 (d, 1H), 7.25 (m; 7H), 7.5 (s, 1H), 8.4 (brs, 1H); 1 ^-(3-trifluoromethylphenyl) -2 -Methyl-2- [5- (2- | 1phenyl) -2,3-dihydro-4 -oxy-4H-1,3-fluoren-3-yl] propanamine, NMR 1 · 7 (s, 6H), 5.4 (s, 2H), 7.0-7.4 (m, 7Η), 7.65 (d, 1Η), 7. 8 (s, 1H), 8.43 (brs, 1H); N- (2 , 5-difluorophenyl) 2-methyl-2-[6-methyl-5- (2-fluorophenyl) -2, 3-dihydro-4-oxy-4H-1,3- Arsen-3-yl] propanamide, melting point N-(3-Ephenyl) -2-methyl-2- [6 -fluorenyl-5- (2-fluorobenzyl) -2,3-di Hydrogen-4-oxy- 4H-1,3 -naphthin-3-yl] propanamine, melting point 153-154 ° C; N- (3-fluoro-5 -fluorenylphenyl) -2- Fluorenyl- 2- [5- (2-IIbenzyl) -6- 曱

Page 16 482653 V. Description of the invention (14) Amino-2,3-dihydro-4-oxy-4 [1-1,3-amorphin-3-yl] propanilamide, title 1? 1.7 (s , 6H), 1.9 (s, 3H), 2.3 (s, 3H), 5.35 (s, 2H), 6.6 (d, 1H), 7.0-7.3 (m, 6H), 8.5 (brs, 1H); and N -(3,5-difluorophenyl) -2-methyl-2-(5-isopropylthio-6-methyl-2,3-dihydro-4-oxy-4H-1,3_ Fluoro-3-yl) propanamine, NMR 1.1 (d, 6H), 1.6 (s, 6H), 2.3 (s, 3H), 3.2 (m, 1H), 5.1 (s, 2H), 6.4 (t , 1H), 7.0 (d, 2H), 8.6 (s, 1H). The antidote compound has been found to be selected from a wide range of chemicals. Preferred compositions of the present invention may include one or more of the antidote and herbicide. Some of the more important types of antidote are halogenated sulfamic acid, ammonium amine, aromatic pollutants, tiwaconic acid and derivatives, and 1,8-naphthalenedicarboxylic acid needles. Examples of suitable antidotes are: (i) compounds of formula (II): R70-C0-NR72R71 wherein R7G is selected from ii alkyl; ii alkenyl; alkyl; alkenyl; cycloalkyl; cyclic Alkylalkyl; halogen; hydrogen; alkoxycarbonyl; N, N-alkynylaminofluorenyl; N-dilutedaminoaminomethylalkynyl; alkyl-N-quickylamine Methylformylalkoxyalkyl; alkynyloxy; haloalkoxy; thiocyanatoalkyl; alkenylaminoalkyl; alkylcarbonylalkyl; cyanoalkyl; cyanoalkyl

Page 17 482653 V. Description of the invention (15) base, fine base amine base, continuous base base, base base sulfur base, base base alkoxy base base; base base alkoxy base base; Alkynyl; alkynyl; alkynyl; alkynyl; alkynyl; alkynyl; benzyl; alkyl; thiophene; alkyldithiacenene Di thioleny 1; thienyl alkyl; benzyl; substituted benzyl, wherein the substituent may be selected from halogen, alkyl, haloalkyl, alkoxy, aminoformyl, nitro, carboxyl and Its salts, and i-alkylaminomethylmethyl; benzyl alkyl; benzyl i-alkyl; phenyl alkenyl; substituted phenyl alkenyl, wherein the substituent may be selected from the group consisting of halide, alkyl, and alkane Oxy, and halobenzyloxy, benzylalkoxy; phenylalkylcarboxyalkyl; phenylcycloalkyl; halobentenyloxy; halothiobenzylalkyl; iiphenoxyalkyl ; Bicycloalkyl; alkenylaminomethylamidinopyridyl; alkynylaminomethylamidinopyridyl; dienylaminomethylamidinobicycloalkenyl, and alkynylaminomethylamidinobicycloalkenyl; R71 And R72 can be the same or different Is selected from alkenyl; haloalkenyl; hydrogen; alkyl, alkynyl, fastyl; alkynyl; alkynyl; alkynyl; alkynyl; alkynyl; Alkenyl; alkoxyalkyl; thioalkyl; carboxyalkyl; alkoxyalkylcarbonyl; alkylaminomethylmethyloxyalkyl; amino; fluorenyl; haloalkyl-N-alkane Haloalkylamido; haloalkylamido; haloalkyl; alkyl; haloalkyl-N-alkyl; haloalkyl; alkyl halide; Cycloalkyl; alkylcycloalkyl; alkoxy_alkyl; alkylsulfonyloxyalkyl; mercaptoalkyl; alkylaminoalkyl; alkoxyguienyl; haloalkylcarbonyl; Alkylcarbonyl; Alkenylaminomethylamidooxyalkyl; Cycloalkylaminomethylamidooxyalkyl; Alkoxycarbonyl; Haloalkoxycarbonyl; Halomethylaminomethylamidooxy Alkyl; cycloalkenyl; benzene

Page 18 482653 V. Description of the invention (16) group; substituted phenyl group, wherein the substituent group may be selected from alkyl, halogen, halo group, alkoxy group, haloalkylamino group, phthalimino group Benzylamino, methylamino, methylamino, methylamine, amino, methyl, amino, alkyl, alkyl, and alkylcarbonyl alkenyl; benzylsulfonyl A substituted phenylalkyl group, wherein the substituent may be selected from a halogen or an alkyl group; a dioxyalkylene group; a phenoxyalkynylamino-alkynyl group, a thienylthiodiσ group, Hexazine ratio. Hexyl group; hexahydropyridylalkyl; dioxolylalkyl; thiazolyl; alkylthiazolyl; benzothiazolyl; halobenzothiazolyl; furanyl; alkyl-substituted furanyl; furanylalkyl ; Pyridyl; alkylpyridyl; alkoxyazolyl; tetrahydrofurylalkyl; 3-cyanothienyl; alkyl-substituted thienyl; 4,5-polyalkylenethienyl; α-halane Ethyl acetoaminophenyl phenyl alkyl, haloalkyl ethyl with amido sulfophenyl phenyl; halo acetyl ethyl amine alkyl phenyl phenyl; fluorenyl dialkyl; and table base (such as Natten (naptalan), or R71 and R72 together can form a structure including hexahydropyridyl; alkylhexahydropyridyl; pyridyl; di- or tetrahydropyridine. Benzyl; Alkyltetrahydropyridyl; Morpholinyl; 2, 3 -dihydro-1,4-benzopyridyl, azabicyclononyl; diazacycloalkyl; benzoalkylpyrrolidinyl Oxazolyl; perhydrooxazolyl; alkyloxazolyl; furyloxazolyl: fluorenyloxazolyl; _pyridyloxazolyl; pyrimidyloxazolyl; Benzoxazolidinyl group; C3.7 _ spirocycloalkyl-oxazolidinyl group; alkylamino alkenyl group; alkylene imino group; sulrolidyl group; hexaaziridinyl group; perhydroazaza Caps: perhydroacinyl. (A ζ occiny 1); pyrazolyl; tetrahydro- or perhydroquinolinyl or isoquinolinyl; fluorindolyl, or di- or perhydroindole Base; merged R71 and RT2 can be separated by the above

Page 19, 482653 V. Description of the invention (17) Substitutions shown by the R71 and R72 groups; or (ii) one of the following compounds: o: [(cyanomethoxy) imino] benzonitrile; a- [(1,3-dioxolane-2-ylmethoxy) imino] phenylacetonitrile; 0-[3-dioxolane-2-ylfluorenyl] -2, 2,2-trifluoro Fluorenyl-4'-air acetophenone contamination; benzylamine, N- [4- (digasmethylene) -1,3-dithiopentane ((111: 1! 1〇, 1 & 11 ) -2-yl] _ «-methyl, hydrochloride;. Dibenzylmethyloxyacetate; 1,8-naphthalenedicarboxylic anhydride; cloquintocet (5-Gaquinoline- 8-yloxy acid) or a salt or ester thereof, such as cloquintocet-mexyl ((5-methylquinolin-8-yloxy) acetic acid 1-methylhexyl); 4,6-difluoro-2-phenyl. Dense. Ding; 2-gas-N- [l- (2, 4, 6-trimethylphenyl) vinyl] acetamidine; 1,1-bis Ethylene glycol acetal of air acetone; fenchlorazole ((l- (2,4-difluorobenzyl) -5 -trichloromethyl) -1Η-1,2,4-triazole -3-carboxylic acid), or a salt or ester thereof, fenpropazole (especially 6.1101111 ^ 2〇16) -ethyl ((1- (2,4-difluorobenzene) ) -5-trifluoromethyl) -1 Η-1,2,4-triazole-3 -carboxylic acid ethyl ester); bannosac (be η ο X ac〇r); dichlormid Fenclorim; Fuli sit (Shi 11) ^ 13 2〇16) or Mifenpyr ([11 to 6111 ^ 1 >)-diethyl (([^)-1- (2,4 -Digas phenyl) -5-amidino-2-pyrazolin-3,5-dicarboxylic acid diethyl); flurazole; 5,5-diphenylisoxazolinone -3-carboxylic acid, and 5,5-

Page 20 482653 V. Description of the invention (18) Dibenzyl iso pf azolinone-3-carboxylic acid ethyl ester (AEF-129431) CMPI (N-4 -chlorophenyl) maleimide); 4 -Ethyl-1-fluorenyl-3-(1-Η-tetra-sigma-5-ylpyridine) -1H- 嗤 林 -2 -㈣: or 3-(5 of the following formula (II I) -Tetrazole carbonyl) -2 -quinolinone:

Where ArA3 shows a direct bond, -C (two Q)-, -C (two Q) -T-, -SO-,-SO factory or -S02NR86-; Q table 0 or S; T = 0; S; or NR86; R83-R86 independent table Η, selective substituted phenyl, selective substituted phenyl-C 6 alkyl, selective substituted C 2-6 alkenyl, selective substituted C 2 -6 alkynyl, optionally substituted C 3-9 cycloalkyl; or alkyl optionally via one or more functions 'Ν〇2' C Ν 'SC Ν' C 1-4 -4-sulfanyl, C1-4-sulfanylsulfenyl, C1-4 alkylsulfonyl, C2-4 alkenyl, and C2-4 alkynyl, or optionally substituted C 3-9 cycloalkyl, optionally substituted stupid, and / or optionally substituted 3-6 membered heterocyclyl, containing 1-3 N, 0 and / or S atoms; Tables R79-R82 Η, NH2, COOH, CH0, Η, halogen,

邶 Page 21 邶 2653 V. Description of the invention (19) t 'eN' SCN 'Bu R87, J-R88; or R79-R82 on the adjacent c atoms together with these C atoms to form a 5 or 6 member Unsaturated or partially saturated ring 1 optionally contains 1 to 3 O, S and / or N atoms and is optionally substituted with one or more: 'C1-4 alkyl groups, and / or oxy groups; or -heart- … And R82 together with the linked $ atom form a 5- to 7-membered unsaturated or partially saturated ring optionally containing 3 0 ′ S and / or N atoms and optionally via one or more halogen, cl-4 alkanes Group, and / or oxo substitution; J = a direct bond, s (= 〇), 0, s (= 〇) w-〇, C (= Q), C (= Q) -Q, 0-C02, NR89, NR89-〇, NR89- (C = 0), NR89C02, NR89-C0-NR9Q or 0; R87 represents optionally substituted n-6 alkyl, C2-6 alkenyl, or C2-6 alkynyl; R88 means optionally substituted unsaturated or partially saturated carbocyclic, C3_8 cycloalkyl, benzyl, or heterocyclyl; r89 and R90 represent Η, C1-6 alkyl, C3-6 cycloalkyl , C1-5 alkylcarbonyl, benzyl, or benzyl; w Table 0, 1 or 2; or iii) N-benzyl-N-carbylurea 'as daimuron [l- (1 -曱 基- 1-phenylethyl) -3-p-fluorenylphenyl dolphin] or (w-Uq; monofluorenylphenylfluorenyl) -3-p-fluorenylphenyl urea [(S) -MBU]; or Thiamine Esters such as dimepiperate (S-1-fluorenyl-1-benzylethylhexahydropyridine-1 -carboxythiothioate), and (i), (ii ) And agriculturally acceptable salts of the compounds described in (iii).

Mi detoxamine of haloalkanoic acids of formula (II), including those in which nitrogen forms part of a heterocyclic ring having substituents, is described in many publications, such as U.S. Patent Nos. 4,021,224, 4,256,481 4,294,764, and 5,201,933 and British patent 1,5 2 1,5 4 0. U.S. Patent No. 4,002,224 discloses this type of compound widely and shows many possibilities for one or two substitutions on the nitrogen atom.

Page 22 482653 V. Description of the invention (20) A group of preferred detoxifying compounds includes R7G in the formula (II_3_alkyl, R71 and R72 are independently C2_4 alkenyl, or haloalkenyl, or 2, 3- Dioxolane-2-yl-methyl, R71 and R72 combine to form a C4_1 () saturated or unsaturated heterocyclic ring containing 0, S and / or N atoms, which can be passed through alkyl, ii alkyl, alkoxy, Alkoxyalkyl or i-fluorenyl substituted compounds. The preferred iialkyl R7G member in formula (II) is dichloromethane. The preferred species in this class of detoxification compounds is N, N-dienepropylene- Dichloroacetamide, and N- (2-propenyl) -N- (1,3-dioxolane-2-yl-methyl) dichloroacetamide. Better detoxifying compounds of formula (II) Is a group of substituted 1,3-oxazolidinyl or thiazolidinyl diaziridine having the formula (IV): R > a CHC12 R75—IU-R78 R76 R77 (IV) where: Z is oxygen or Sulfur; R73, R74, R75, R76, {^ and R78 are independent epihydrogens; Ch alkyl, hydroxyalkyl, alkynyl or alkynyl; C 2-6 alkynyl; C! _ 4 Sulfanyl (Ch) alkyl; Chalkylsulfonylfluorenyl; groups having up to 10 carbon atoms A bicyclic hydrocarbon group; a benzyl group; or a saturated or unsaturated heterocyclic group having a C4_u ring atom and containing 0, S, and / or N atoms; wherein the phenyl group and the heterocyclic group are optionally passed through one or more Ch alkyl groups, haloalkanes , Ch alkoxy, c2_6alkoxyalkane

Page 23 482653 V. Description of the invention (21) Group, halogen, or nitro substitution; or R7: 3 and R74 together with adjacent carbon atoms to form a C3_7 spirocycloalkyl group optionally substituted with one or two methyl groups . Preferred members of formula (IV) are those in which R76, R "and R78 are hydrogen; RT5 is hydrogen, fluorenyl, benzyl, or heterocyclyl; R7 · 3 and R74 are independently epimethyl or trifluoromethyl, or A compound that forms a C 5 or C 6 ring with a carbon atom attached to it. An important example is 1 ^ 29148, which is 2,2-dichloro-1- (2,2,5-trifluorenyl)嗤 ° -3--3-))-B. The oxime derivatives suitable for use as antidote and herbicide are disclosed in, for example, U.S. Patent Nos. 4,0 7 0,3 8 9 and 4,2 6 9,7 7 5, Has the following formula:

Ar (NC) C-NOCH2R91 where Ar is phenyl or substituted benzyl, wherein the substituents are optionally fluorenyl, fluorenyloxy, gas, cyano, or trifluoromethyl, or Ar is naphthyl; R91 Is cyano, -C (NH2) (ORe) (ORf), -C (= 0) NHNH2,-(: (two 0) 1 ^ (1〇 (1 ^), or -〇 ^ (1 ^) ( [^), Wherein 1 ^ and 1 ^ are independent epialkyl groups, or together with carbon to form a 5- or 6-membered heterocyclic ring containing oxygen or sulfur, which is unsubstituted or low alkyl, halogen, and / or nitrate (R.) and (Rd) are independently hydrogen 'alkyl' cycloalkyl, which is unsubstituted, or substituted with one or more halogen 'alkyloxy' and / or cyano; (Rg) and (Rh) forms a 5- or 6-membered ring with nitrogen, which is unsubstituted or substituted with one or more halogen, cyano, and / or alkyl groups and may be interrupted by a nitrogen, oxygen or sulfur atom. Such representatives The compounds are 1T ", 1 is cyano, and R91 is 1,3-dioxolane-2-yl, such as oxabeticrin (〇X abetrini 1) (0-[2-(1, 3 -Dioxolane

Page 24 482653 V. Description of the invention (22) Group) fluorenyl] -α-cyanobenzoaldoxime). Thia saccharic acids and derivatives suitable for use as antidote are generally disclosed in U.S. Patent No. 4,199,506. Such a representative is the compound 2-gas-4-trifluoromethyl-5-thiazolecarboxylic acid phenylhydrazone. Another useful herbicide detoxification compound is disclosed in European Patent No. 0 1 044 9 5 and has the formula R96 _ γ ^ (CH2) zC02R97 〇 入 r98 where the haloalkyl group contains 1 to 3 halo atoms, or phenyl selection R96 represents a hydrogen atom, fluorenyl, or benzyl; R97 represents a hydrogen atom, fluorenyl, or phenyl; 1 ^ represents Crq alkyl, C5-C6 cycloalkyl, cyclohexylfluorenyl, benzene Group selectivity is substituted, benzyl group is optionally substituted, allyl, or propargyl; z is 0 or 1. The representative antidote of this class is: rj / CH3, N ^ X: H2C〇2CH3

0 Recognized " CH2CI A particularly good antidote for use in the present invention includes: 2,2,5-trisino-N-digas

Page 25 482653 V. Description of the invention (23) Ethylpyridinium; 2,2-dimethyl-5-benzyl-N-dichloroethyloxazodine; 2,2-difluorenyl-5 -(2-furanyl) -N-dichloroethenyloxazosin; 2,2-difluorenyl-5- (2-hexylyl) -N-dichloroacetoxysulfanil. N, N-di-di-propyldiazine; 2,2-spirocyclohexane-N-diazine oxazolidinium; 2,2-diazino-N-diazide Oxazosin; 4- (dichloroethylfluorenyl) -3,4-dihydro-3 -methyl-2H-1,4-benzopyrene; 3- [3- (difluoroethynyl) ) -2,2-Difluorenyl-5 -oxazolidinyl] pyridine; 4- (difluoroethenyl) -1 -fluorene-4 -azacyclo- (4,5) -decane; 2, 2-digas-1-(1,2,3,4-tetrahydro-1-methyl-2-isoquinolinyl) ethanone; cis / trans-1,4-bis (digasacetamidine) ) -2,5-Dimethylhexahydropyridine; N- (dichloroethenyl) -1,2,3,4-tetrahydro-2-methylquinoline; -1,5-bis (di Gas ethylfluorenyl) -1,5 -diazacyclononane; 1-(dichloroethylfluorenyl) -diazaspiro [4,4] nonane; α _- [(cyanomethoxy) Imino] benzonitrile; α-[(1,3-dioxolane-2-ylmethoxy) imino] benzonitrile; o- [1,3-dioxolane-2-ylmethyl Methylene] -2,2,2-tri | ^ methyl-4'-acetophenone oxime; benzamidine; N-[4-(digasmidinyl) -1,3-dithiopentane -2 -yl] -α-fluorenyl hydrochloride; diphenylmethoxyfluorenyl acetate; 1,8 -Naphthalenedicarboxylic anhydride; 4,6-digas-2-phenylpyrimidine; 2-gas-N- [l- (2,4,6-trimethylphenyl) ethenyl] -acetamidine; Cloquintocet-mex y 1; and 1,1-dichloroacetone glycol glycolic acid. The best antidote for rice in the present invention is da i muron, dimepiperate, fenc 1 orim, fenclazole 0611 仏 1. ]: 37〇16) ethyl, gas quinacetide ((: 1 is called 11; 1111: 0061:)-mexyl, 1,8-naphthalenedicarboxylic acid anhydride, mefenpyr diethyl Base, bannosac (6110 乂 3 (: 〇) :), and (8) -1- (0: -fluorenylbenzene)

Page 26 482653 V. Description of the invention (24) yl) -3-p-tolyl urea [(S) -MBU]. The best antidote for cereal crops (such as wheat and barley) in the present invention is mefenpyr diethyl, fenchlórazole 6-based, cloquintocet-a Hexyl, mexyl, oxabetrinil, flurazole, fenclorim, and naptalam. The herbicidal composition according to the present invention may also contain one or more other Harmful active ingredients, such as herbicides. Preferred crops that can be protected by the method of the present invention are rice, wheat, and barley. The mixture of the present invention can be used to obtain selective weed control and low crop damage, for a variety of crop plants, such as rice, corn, sorghum, soybeans, cotton, or cereals, such as wheat, barley, oats, and rye. Effective weed control and low crop damage are the result of a plant site treated with a combination of a herbicidal cyclic amidine compound and a detoxifying compound according to the present invention. By "plant area" is meant, for example, application to plant growth media such as soil, as well as seeds, germinating seedlings, roots, stems, leaves, or other plant parts. The term "combination of a herbicidal cyclic amidine compound and a detoxifying compound" includes various methods of treatment. For example, the soil of a plant site can be treated with a "tank-mix" composition containing a "combination" of herbicides and antidotes, or the soil can be treated separately with herbicides and antidotes compounds, so the "combination" is on the soil or the soil in. Treat the soil with a mixture of herbicides and antidotes, or apply the herbicides and antidotes to the soil separately or sequentially

Page 27 482653 V. Description of the invention (25) After the herbicide and antidote can be mixed into the soil, the soil can be mixed by tools and machinery, or by rain or irrigation> "both washed in". The soil of plant sites can also be treated with an antidote by applying an antidote in the form of a dispersible concentrate, such as granules. The granules can be applied to loquats, which are used to receive crop seeds, and herbicides can be applied to plant sites before or after the antidote-containing granules are placed in the loquats, so the herbicides and antidotes form a "composition" . Crop seeds may be treated or coated with antidote compounds after being planted in the mash, or, more commonly, crop seeds may be treated or coated with antidote before being planted in the mash. Herbicides can be applied to plant soil sites before or after sowing. When the herbicide and antidote coated seeds are in the soil, a "composition" is formed. In a specific embodiment, the method of the present invention is preferably performed by directly applying an antidote to the seeds before planting the seeds. Normally, a certain amount of crop seeds are coated with an antidote and then the coated seeds are planted. Among the various ways of applying herbicide-antidote compositions described above, the various forms of application inherently require the herbicide and antidote to be physically combined in some manner to form a "composition" of these agents. The amount of a specific cyclic amidine herbicide applied to a plant site or crop growing area depends on the nature of the weed, the specific herbicide used, the time of application, the climate, and the nature of the crop. A herbicide application rate of about 1 g / ha to 1000 g / ha is generally suitable, and a rate of about 25 g / ha to 250 g / ha is preferred. The amount of the antidote used in the method of the present invention varies depending on many parameters, including the specific antidote used, the crops to be protected, the amount and ratio of the herbicide used, and the soil and climatic conditions. Specific antidote used in the method of the present invention

Page 28 482653 V. Description of the invention (26). The choice, application method, and non-phytotoxicity-effective detoxification activity can also be easily determined according to the general practice in the art. The antidote is applied in combination with a herbicide in a non-phytotoxic effective amount. "Non-phytotoxic" means the amount of antidote that causes the least or no harm to the desired crop species. "Detoxifying effectively" means that the amount of antidote to the herbicide can effectively reduce the degree of damage caused by the herbicide to the desired crop species. The ratio of herbicide to antidote can depend on the crops to be protected, the weeds to be inhibited, the herbicide used, etc., but generally the ratio of herbicide to antidote can range from 1: 2 5 to 6 0 1 parts by weight Although a higher proportion of antidote can be used, such as 1: 1 to 1: 300 parts by weight of herbicide to antidote. A preferred weight ratio of herbicide to antidote is from about 1:20 to about 3 (h 1 (e.g., about 1.2 to about 1:20). In field applications, the herbicide, antidote, or The mixture can be applied to plant sites without any adjuvants except for solvents. Herbicides, antidote, or mixtures thereof are generally combined with one or more adjuvants. Applied in liquid or solid form. Contains suitable herbicides and antidote mixtures The composition or formulation is generally a mixture of herbicides and antidotes with one or more adjuvants, such as diluents, solvents, admixtures, carriers, conditioners, water, wetting agents, dispersants, or emulsifiers, Or any suitable combination of these adjuvants. These mixtures can be in the form of granular solids, granules, pellets, wettable powders, dusts, solutions, aqueous dispersions, or emulsions. Application of herbicides, antidotes, or mixtures thereof This can be done using conventional techniques using, for example, hand-held or tractor-mounted spreaders, dusters, booms (b 0 m) and hand sprayers, dusters, and particle applicators. If needed,

Page 29 482653 V. Description of the invention (27) The application of the composition of the present invention to plants can be achieved by incorporating the composition into soil or other media. A selective allogeneic herbicide that can be combined with a compound of formula (I) and an antidote for rice culture, preferably selected from pyrazosaflon (pyra ζ 〇su 1 fur ο η) ethyl, Bensaf Bensulfuron methyl, ethoxysulfuron, benzofenap, oxadiargyl, cinosulfuron, azimsulfuron , Ring> 'less; cyclosulfamuron, metsu 1 fur ο η), imazasulfuron (its 1- (2- -imidazole [1, 2_a ] Pyridin-3-ylsulfonyl) -3- (4, 6-dioxopyrimidin-2-yl) urea), clomeprop, pyrazolynate, mouth Pyrazoxyfen, cumyluron (which is 1- (2-airbenzyl) -3- (1-fluorenyl-1-phenylethyl) -urea), Dai Daimuron, dimepiperate, oxadiazon, 2,4-D, MCPA, simetry η, bromobutide, napu Aniline (naproanilide) Benfuresate, bentazone, asifolfen (ac 1 f 1 u 〇rfe η) 'and bifenox (X), fenfenacet (Kafens) Cafenstrole, pret 1 lachlor, thiobencarb, MY-100 (which is 6-fluorenyl-3- [l-fluorenyl-5-difluorophenyl) ethyl Phenyl]-5-phenyl-2,3-dihydro-4H-1,3 -shu coax-4-S iso) 'pentoxazone, anilofos' Sennik Luo (thenylchlor)

页 Page 30, 482653 V. Description of the invention (28) (pyributlcarb) 'esprocarb, fmccrolac' cinmethylin, cyhalof op Butyl, Pyramin (pyr imin〇bac), Etobenzanid, rice (moiinate), propanil 'Fenoxapr_p-B And a selective companion herbicide that can be combined with a compound of formula (I) and an antidote for use in cultures of the type 'preferably selected from quiza 丨 f f 〇 p); crodinafo (c 1 odinaf ο p); cyha 丨 〇f 〇p; diclofop (diclofop), Serving fenoxapr〇p; Fenxap ( fenthiaprop) ethyl; fluazifop; haloxyfop; propaquizafop-p-; trifluralin; pendimethalin; chlorsulfuron ); Tribenuron (tribenuron)-methyl; thifensulfuron (methyl); metsulfuron (metsulfuron); triasafron (tria sulfuron); prosulfuron; nicosulfuron l; primisu 1 fur ο η; rimsu 1 fur ο η; sulfosulfuron); flupyrsuifuron; (EPTC); butyl ate; verno late; triallate; simazine, cyanide ( cyanazine); atrazine; amtry η; metribuzin; imazapyr; {i mazaqu i η); imasha tb (i maze th apy r): Yimachamashaben in

country

Page 31 482653 V. Description of the invention (29) (imazamethabenz); imazamox;-(imazameth); isoxaf lutole; mesotrione; alloxydim Clethodim; cycloxydim; sethoxydim; tramoxydim; tepraloxydim; diflufenican; diflufenican flurtamone); isoproturon; alonifen; diuron; bromoxynil; ioxynil; isoxaben and mo Metosulam 〇 According to other features of the present invention, a product is provided comprising: (a) a herbicidally effective amount of a cyclamidine compound of formula (I) or an agriculturally acceptable salt thereof; and (b) a detoxifying effective amount of Antidote; wherein the antidote is effective for the cyclic amidine compound in detoxification; used in combination preparations separately, simultaneously, or sequentially for controlling weeds in a place. The following non-limiting examples serve to illustrate the invention. The antidote used is as follows: = Daimuron B2 = Dimepiperate B3 = fenclorim B4 = fenqi. Fenchlorazole ethyl group. B5 = cloquintocet-mexyl B 6 = naphthalenedihydroanhydride Sincerely _ 鲡! _ Mm

Page 32 482653 V. Description of the invention (30) B7 = Mefenpyr diethyl B8 = benoxacor B9 di (S) -bu (α-methylbenzylmethyl) -3 -P-methylbenzyl urea [(S) -MBU] Β10 fenchlorazole

Bll = oxabetrinil B12 = flurazole B13 = Naptalam The compounds of formula (I) used are as follows: A 1 = 1-cyclopentyl-2-(2, 3- Dihydro-6- • methyl-4-oxy-5-benzyl- 4H-1,3-hydrazine-3-yl) -2-methylpropanyl-1 monoketone 8 2 4- (2, 5-difluorophenyl) -2-fluorenyl-2- [6-methyl-5- (2-fluorophenyl) -2,3-dihydro-4 -oxy-4H-1,3-shu Coco-3-yl] propylamine amine 8.2! \ 1- (3-Ebenzyl) -2-fluorenyl-2- [6-methyl-5- (2-fluorobenzyl) -2, 3 -Dihydro-4-oxy-4H-1,3-fluoren-3-yl] propanamine A4 = 4-cyclopropyl-2- (2,3-dihydro-6-fluorenyl-4- Oxy-5-benzyl-4H-1,3-suzuki-3-yl) -3-methylpentan-3-one Example 1 A (transplanted rice) Sowing rice seeds (J a ρ ο nica) Supplement the lighting in the greenhouse (glass room) inside the compost (14 hours). Rice plants were transplanted into paddy pots containing narrow ridged clay loam (3 plants per pot) at the 2-3 leaf stage. After 2 days, the rice pot was applied with compound A 1 dissolved in 0.5 ml of acetone in a three-dose ratio, and an antidote (added in compound 0.5 before dissolved in 0.5 ml of acetone) to herbicide: Antidote ratios of 1: 1 and 1: 1 are applied for treatment. The pots were watered as needed to visually assess the decrease in rice growth 6 weeks after treatment

Page 33 482653 V. Description of the invention (31) Less than%. Table 1 shows the percentage of rice damage after treatment with compound A 1 alone or in combination with detoxifying compounds B 1, B2, B3, B4 or B5 (three sets of values are provided). Table 1 Compounds and ratio A1 ratio 125 (g / ha) 250 500 A1 50 70 70 70 95 70 90 90 95 A1 + B1 (1: 1) 10 10 30 70 80 7 0 85 80 60 A1 + B1 (1: 2) 0 10 0 70 7 0 80 80 95 95 A1 + B2 (1: 1) 40 20 40 80 75 70 85 90 90 A1 + B2 (1: 2) 40 50 50 75 85 60 90 90 95 A1 + B3 ( 1: 1) 40 50 0 one 60 70 90 95 95 A1 + B3 (1: 2) 40 50 10 65 80. 7 0 100 80 90 A1 + B4 (1: 1) 20 50 50 80 7 0 80 90 90 95 95 A1 + B4 (1: 2) 60 50 50 70 85 75 95 95 90 A1 + B5 (1: 1) 10 20 50 80 80 80 95 95 90 A1 + B5 (1: 2) 50 30 0 75 70 80 90 70 95 The results showed that the antidote B1 to B5 produced a significant detoxification effect. Similar experiments showed that when rice was replaced by weed species echinochloa crusga 1 1 i, there was no detoxification effect. Example 2 A (rice seed pretreated with antidote) This rice seed was shaken with antidote B 6 powder to obtain a seed with a coating of known weight. The seeds germinated in the dark for 5 days and were sown in pots containing a narrow ridge (pud d 1 e d) loam / sand mixture. Potted, held in a greenhouse (glass room) for supplemental lighting (14 hours). After 11 days, the soil surface was treated with an acetone solution of compound A 1 to obtain a dose ratio of 3-25 g / ha. Pot irrigation

Page 34 482653 V. Description of the invention (32) To overflow, the growth reduction in% is evaluated at 27 days. Table 2 shows the percentage of rice damage after treatment with compound A 1 alone or in combination with antidote B 6. Table 2 Compound A1 (g / ha)% B6 0 0.02 0.59 1.23 3.2 0 0 0 0 0 3 2.5 0 0 0 0 6 7.5 0 0 0 0 12 10 2.5 0 0 25 45 22 5 25 20 50 70 50 40 50 55 «The results show that when applied as a seed pretreatment, the antidote B 6 produces excellent detoxification.

Example 3 A rice (0 ryzasativavar Ariete) seeds were pre-germinated on filter paper soaked with water, and then sown on 20 ml of 1% agar supplement compound A2 or A3, with or without antidote, in dimethyl acer ( 0, 2%) inside the tube in solution. After growing at 26 ° C for 6 days in the dark, the percentage inhibition of root length (mm) of treated rice seedlings with A 2 or A3 with or without antidote is compared with the control value, as shown in Tables 3 and 4. Show.

Page 35 482653 V. Description of the invention (33) Table 3 A2 Amount Detoxifier Detoxification Amount 0πM 4nM 40nM 400nM 4τηΜ 4 0mM 8nM B1 72.6 66.9 60.4 49.5 31.4 27.5 8nM B7 72.6 71.3 68.7 60.1 37.9 4.3 8nM B8 72.6 59 72 68.7 59.9 32.6 8nM B9 72.6 69.4 52.7 26.2 5. 68.6 72.2 66.2 41.2 36.8 5nM B9 78.6 68 49.4 18.8 0 0 Antidote B 1, B 7, B 8 and B 9 produce excellent detoxification. Example 4 A (Rice test at room temperature) The pre-germinated seeds of rice (Oryza sativa var Ariete) have roots up to 5 millimeters long, and are sown in a paddy pot and watered to the surface of a saturated clay loam, The pots were kept in polyethylene awnings in a greenhouse (glass room). When the plants were growing at about half leaf stage, pots were sprayed with an acetone solution of compound A3 (30 g / ha) and antidote B1. After three days, the pot was irrigated with water to a depth of about 2 cm. One month after treatment, rice plants were evaluated, and shoot growth was reduced by% compared to untreated plants. Table 5 shows the detoxifying effects of B 1.

Page 36 482653 V. Description of the invention (34) Table 5 Gram / Male 0 _ ratio-are 62 125 250 500 8 5% 63% 63% 40% 40% Example 5 A (rice in the field) rice Field trials were carried out by spraying compound A 4 at 60 g / ha and antidote B 1 and B 3. Table 6 shows the percent reduction in rice growth compared to the untreated control at 35 days after treatment. The detoxifying effects of B 1 and B 3 were measured. Table 6 Dosage of antidote Antidote in g / ha of rice% Β1 〇73 60 35 Β3 0 73 60 23 Example 6 A (Aspiration method of wheat) A stack of microscope slides was placed on a filter paper and placed in a Petri dish base. A filter paper is placed on the stack of slides, so the two filter papers are combined to form a continuous absorption surface. Each wheat seed (variety R 1 a 1 to) was placed on a high bed of filter paper and microscope slide. A total of 6 ml of the antidote application solution was placed in a petri dish, and the seeds absorbed various proportions of the antidote. Cultivate m, replace the lid, seal, store in the dark at 24 t for 16 hours, and then plant the seeds in pots containing loam and applying compound A 2 in various proportions. Treated pots in a greenhouse

ＭιπύΙ Page 37 482653 V. Description of the invention (35) (Glass room) Under normal conditions, 21 days after treatment, the percentage of growth reduction of each plant was evaluated compared with the untreated control plants. Table 7 Application rate of antidote antidote concentration A2 g / ha μM 0 25 50 100 0 0 45 55 97.5 B7 0.1 0 20 60 60 1 15 30 60 70 10 10 60 60 80 B10 0.1 0 0 45 97.5 1 30 30 60 97.5 100 10 50 60 97.5 1000 0 30 65 100 B5 0.1 5 40 65 100 1 0 30 * 65 100 10 0 30 65 95 B11 0.1 0 • 40 97.5 100 1 0 35 75 95 100 0 90 100 100 B12 0.1 0 35 100 95 1 0 70 100 95 100 〇95 100 80 B3 0.1 0 35 15 100 1 0 30 20 95 100 0 15 50 65 Table

II Antidote Antidote concentration μΜ 0 Application of A2 g g / ha 16 32 * 0 0 50 50 Β13 0.1 100 0 0 30 00 35 45 30 40 page 38

482653 V. Description of the invention (36) Tables 7 and 8 show the detoxifying effects of B7, BIO, B5, B1, B12, B3 and B13. Example 7A (Wheat tank mix using A2 + antidote) Winter wheat seeds (variety R aa 110) were sown in loam pots, sprayed with various antidote in several application ratios, and then sprayed with compound A2. The pots were placed in a greenhouse (glass room) under normal conditions, and 21 days after treatment, the percentage of growth reduction of each plant was evaluated in comparison with untreated control plants. Table 9 Application rate of antidote A2 g / ha 25 50 0 RO 1 00 B7 32 60 100 63 50 100 125 60-80 B4 32 55 100 63 40 70 125 50 60 B5 32 7 0 100 63 67 100 125 50 85 Table 1 0 Antidote A2 application rate 25 50 0 GO B11 125 60 25 250 50 55 500 65 100 B12 125 35 82 250 25 97 500 20 100 B3 125 45 90 250 60 95 500 40 97 Table 9 and 10 shows the detoxifying effects of B7, B4, B5, Bll, B12 and B3.

Page 39 482653 Case number 88114632 Simple illustration

Fix »ίτ-!. Qianyue

Η1 O: \ 60 \ 60125.ptc Page 40

Claims (1)

482653 _Case No. 8 Sakaki] ^ 32 Quyu a month of February amendment: red ::: dagger :: 7 ^ 6. Patent application scope 1 ,: ______ ί '… | 1. A weeding ring that reduces the following formula (I) Method for phytotoxicity of crops caused by amidine derivatives or agriculturally acceptable salts thereof: Where: -X-Υ-epi-C (Rla) = C (R2) -0-; Rla epiphenyl, 2-chlorophenyl, 2-fluorophenyl, 2-fluorenylphenyl, or alkylthio ; R2 represents fluorenyl, ethyl, or fluorofluorenyl; W represents NHR3 or NHR3a; R3 represents 3-halophenyl, 2, 5-dihalophenyl, 3, 5-dihalophenyl, 2-halo- 5-haloalkoxyphenyl, 3-haloalkylphenyl, or 3-halo-5-alkylphenyl; R3a epicyclopentyl or cyclopentenyl, optionally via an R6 group or one or more Substituted with the same or different halogen atoms; or R3a epifluorenyl, substituted with cyclopentyl or cyclopentenyl, optionally substituted with one or more halogen or alkyl; or R3a contains up to four carbon atoms Alkyl, substituted with cyclopropyl, which is unsubstituted or substituted with alkyl; R4 and R5 are epimethyl; and R6 represents alkyl or haloalkyl; this method involves applying a detoxifying effective amount to a crop site Antidote compound, optionally with a companion herbicide, wherein the antidote is O: \ 60 \ 60125.ptc Page 41 482653 _Case No. 88114632_Amended on the last day of the year ___ 6. The scope of patent application for detoxification is effective for the cyclic amidine derivative and is selected from daimuron , Dimepiperate, dimepiperate, fenclorim, fenchlorazole ethyl, cloquintocet-methylhexyl (mexy!), 1,8-naphthalenedi Acetic anhydride, mefenpyr diethyl, benoxacor, (S) -1- (α-methylbenzyl) -3-p-phenylphenylurea [( S) —MBU], oxabetrinil, flurazole, and naptalam 0 2 · The method according to item 1 of the scope of patent application, wherein the crop is rice, wheat , Or barley. 3. The method according to item 1 of the scope of patent application, wherein the derivative of the formula (丨) is selected from the group consisting of N- (2, 5-difluorophenyl 2-fluorenyl-1 2- [6-fluorenyl-1 5-1 (2-monofluorophenyl) -2, 3 -dihydro-j-oxy ~ 4 H-1,3-pyrene-3 -yl] propanamide; and N-(3-carbonphenyl) -formyl Amidino-2a [6afluorenyl-5a (2-fluorophenyl) -2,3-dihydro-4-oxy-4H-1,3-fluoren-3-yl] propanamine. 4 · The method according to item 1, 2, or 3 of the scope of the patent application, wherein the weight ratio of the cyclic acid amine derivative of formula (1): the antidote is about 丨: 20 to about 30: 1.5. Herbicidal composition comprising: (a) a herbicidally effective amount of a cyclic amidine derivative of formula (I) or an agriculturally acceptable salt thereof according to item 1 of the scope of patent application, and selecting iron as a companion herbicide; and '(b) an effective amount of an antidote according to item 1 of the scope of the patent application; O: \ 60 \ 60125.ptc Page 42 482653 __ Case No. 88114632 6. Scope of patent application Last month last month Amendment and a diluent or carrier and / or surfactant acceptable in the industry. 6. The composition according to item 5 of the scope of patent application, wherein the cyclic amidine derivative is selected from the group consisting of: Ν-(2, 5 ~ monobasic radical) -2-amidino-2- 2- [6-amidino- 5- (2-Gasphenyl) -2, 3 -dihydro-4-oxy-4H-1,3-stilbene-3 -yl] propanamide; and N-(3 -iodophenyl 2- Fluorenyl-2- [6-fluorenyl-5-(2-fluorophenyl) -2,3-monogas-4-oxy-4H-1,3-codoxy-3-yl] propanamine. 7 The composition according to item 5 or 6 of the scope of the patent application, wherein the antidote is selected from daimuron, dimepiperate, fenclorim, fenchlorazole Ethyl, cloquintocet-cloquintocet, mexyl, 1,8-naphthalenedicarboxylic anhydride, mefenpyr diethyl, benoxacor, and (S) -1-(α-fluorenylbenzyl) -3 -p-fluorenylphenyl urea [(S) -MBU]. 8-The composition according to item 5 or 6 of the scope of patent application, wherein the antidote is selected from Mefenpyr diethyl, fenchlorazole ethyl, cloquintocet-mexyl, oxabetrinil ), Flurazole, fenclorim, and naptaian. 9-Composition according to item 5 or 6 of the scope of patent application, wherein the cyclic amidine of formula (I) is derived The composition is applied at a ratio of 1 g / ha to 1000 g / ha. 10 · The composition according to item 5 or 6 of the patent application scope, wherein the cyclic cyclic amidine derivative of formula (I) 5 g / ha to 250 g / ha. 1 1 · Composition according to item 5 or 6 of Shen Qing's patent scope, suitable for application O: \ 60 \ 60125.ptc Page 43 482653 Amendment _Case No. 88114632 Sixth, the scope of patent application is in rice. 1 2. A composition according to claim 5 or 6 which is suitable for application to wheat or barley. O: \ 60 \ 60125.ptc Page 44