CA2226165A1 - Benzylated cis-2,3-epoxycycloalkanol - Google Patents
Benzylated cis-2,3-epoxycycloalkanol Download PDFInfo
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- CA2226165A1 CA2226165A1 CA002226165A CA2226165A CA2226165A1 CA 2226165 A1 CA2226165 A1 CA 2226165A1 CA 002226165 A CA002226165 A CA 002226165A CA 2226165 A CA2226165 A CA 2226165A CA 2226165 A1 CA2226165 A1 CA 2226165A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
- C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
- C07D303/22—Ethers with hydroxy compounds containing no oxirane rings with monohydroxy compounds
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/20—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom three- or four-membered rings
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Abstract
Benzylated cis-2,3-epoxycycloalkanols of general formula (I), in which X, Y, R1, R2, R3 and n have the meanings given in the description, are useful as herbicides.
Description
-CA 0222616~ 1997-12-31 Benzylated cis-2,3-epoxycycloalkanols The invention relates to novel benzylated cis-2,3-epoxy-cycloalkanols, their production and intermediates ~or their production and their use as agents having a herbicidal and plant growth-regulating action.
It is already known that certain benzyl ethers have herbicidal properties (e.g. EP 081 893, EP 334 120 and EP 497 453). In J.
Org. Chem., vol. 45, no. 15, 1980, pages 3004-3009 (cited in Chemical Abstracts 93:94859g) is described an epoxycyclohexanol, namely 2-methyl-2,3-epoxycyclohexanol and Mol. Cryst. Liq. Sct.
Technol. Sect. A, pages 291-298 discloses 2,4,4-trimethyl-2,3-epoxy-cyclohexanol.
However, the herbicidal action o~ the known compounds is ~requently not adequate, or there are selectivity problems in agricultural main crops when the herbicidal action is suitable.
It was ~ound that benzylated cis-2,3-epoxycycloalkanols o~ the general ~ormula I
t-, R
X R1" ~ R3 ~o~~~(CH2) in which~ and Y can be the same or di~erent and stand ~or H, halogen, Cl_6-alkyl or Cl 6-halogen alkyl, R1 stands ~or Cl 6-alkyl, C2 6-alkenyl, C2 6-alkinyl, halogen-Cl_6-alkyl, halogen-C2 6-alkenyl or halogen-C2 6- alkinyl,~2, R3 can be the same or di~erent and stand ~or H, Cl 6-alkyl, C2 6-alkenyl, C2_6-alkinyl, halogen-Cl_6-alkyl, halogen-C2 6-alkenyl, halogen-C2 6-alkinyl, optionally phenyl substituted once or repeatedly, identically or di~erently with halogen, Cl 6-alkyl, halogen-Cl 6-alkyl, nitro or cyano, Cl 6-alkoxycarbonyl, Cl 6-alkoxy, halogen-Cl 6-alkoxy, -CH2-oR4 (R4 equals Cl 6-alkyl, allyl, benzyl or propargyl) ~~~
CA 0222616~ 1997-12-31 W O 97/02258 P~~ /02gl8 or R2 and R3 together stand for -~CH2)m- (m equals 2, 3, 4 or 5), and n stands for O or 1, have a superior effectiveness compared with the known compounds.
Halogen is taken to mean fluorine, chlorine, bromine and iodine.
The terms "alkyl", "alkenyl" and "alkinyl" are taken to mean both straight-ch~ine~ and branched hydrocarbon radicals.
The invention also relates to intermediates of the general ~ormula II
R "", ~ R
f (CH2)n HO (11~
for the production of compounds of the formula I, in which R1, R2, R3 and n have the me~n;ng given under the general formula I.
The compounds according to the invention of the general fo ~1 A
I can be produced by reacting a compound of the general formula II with a compound of the general formula III
~z ~ Y (111~.
in which X and Y have the me~n;ng given under the general formula I and Z stands for chlorine, bromine, iodine, an alkyl or arylsulphoxy group, by methods known per se in the presence of a base.
The reaction is carried out in a suitable solvent such as e.g.
benzene, toluene, xylene, diethyl ether, tetrahydrofuran, dimethylformamide or 1,4-dioxan in the presence of a base such SUBSTITUTE SHEET ~RULE 26~
CA 0222616~ 1997-12-31 W O 97/02258 PCT~EP96/02918 as sodium hydride or potassium-t-butylate at temperatures between 0 ~C and the boiling point of the solvent in question.
The compounds of the general formula II which are used as intermediate can be produced by reacting 2-cycloalkenols of the general formula IV
R' i R3 J~ ~CHz)n HO (IV).
in which R1, R2, R3 and n have the m~n ; ng given under the general formula I, analogously to methods described in the literature (see e.g. P. Kocovksy, Tetrahedron Lett. 29, 2475 (1988)).
The compounds of the general formula IV can be produced by reacting 2-cycloalkenones of the general formula V
R~
(C~2),.
O (V), in which R1, R2, R3 and n have the ~e~n;ng given under the general formula I, analogously to methods described in the literature (see e.g. M. Mousseron, R. Jarquier, M. Mousseron-Lauet, R. Zagdonn, Bull. Soc. Chim. Fr. 1042 (19~2)).
The compounds of the general ~ormula V are commercially available or can be produced by methods known from the literature or analogously to these (e.g.: N.W.A. Geraghty and N.M. Morris, Synthesis 1989, 603, Yanagita, Inayama, J. Org. Chem., 19, 1732 (1954)).
The compounds according to the invention produced according to the methods described above can be isolated from the reaction mixture by usual methods, for example by distilling off the solvent at normal or reduced pressure, by precipitation with SUBSTITVTE ~}~EE ~ (RULE 26~
CA 0222616~ 1997-12-31 W O 97/02258 PCT/~l_SI~518 water or by extraction An increased degree o~ purity can as a rule be obtained by column chromatographic cleaning and by fractional distillation or crystallization.
The cG...~unds according to the invention are as a rule almost colourless and odourless liquids or crystals which are limitedly soluble in water, aliphatic hydrocarbons, such as petroleum ether, hexane, pentane and cyclohexane, well soluble in halogenated hydrocarbons, such as chloroform, methylene chloride and carbon tetrachloride, aromatic hydrocarbons, such as benzene, toluene and xylene, ethers, such as diethyl ether, tetrahydrofuran and dioxan, carboxylic acia nitriles, such as acetonitrile, alcohols, such as ethanol and methanol, carboxylic acid amides, such as dimethylformamide, sulphoxides, such as dimethyl sulphoxide or organic bases, such as for example pyridine.
The compounds according to the invention have a good herbicidal action in the case of broad-leaved weeds and grasses. A selective use is possible in various crops, e.g. in rice, rape, beet, soybeans, cotton, maize, barley, wheat and other types of cereal.
Individual compounds are also particularly suitable as selective herbicides in rice, beet, cotton, soya, maize and cereals. The compounds can also be used to control weeds in perennial crops, such as e.g. in forest, ornamental woodland, fruit, wine, citrus, nut, banana, coffee, tea, rubber, oil palm, cocoa, berry fruit and hop plantations, and for selective weed control in annual crops.
The compounds according to the invention can be used e.g. with the following plant species:
Dicotyledonous weeds of the species such as Sinapis, Lepidium, Galium, Stellania, Matricaria, Anthemis, Galinsoga, Chenopodium, srassica~ Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Sonchus, Solanum, Lamium, Veronica, Abutilon, Datura, Vio~a, SUBSTITUTE SHEET (RULE 26~
CA 02226l6~ l997-l2-3l W O 97/02258 PCT~EP96/02918 Galeopsis, Papaver, Centaurea and Chrysanthemum;
Monocotyledonous weeds of the species such as Avena, Alopecurus, Echinochloa, Setaria, Panicum, Digitaria, Poa, Eleusine, Rrachiaria, Lolium, sromus~ Cyperus, Elymus, Sagittaria, Monochoria, Fimbristylis, Eleocharis, Ischaemum and Apera.
The quantities used vary according to the type of application, post-sowing and post-emergence, between 0.001 and 5 kg/ha.
The compounds according to the invention can be used either alone, mixed with one another or with other active ingredients.
The intensity of action and speed of ef~ect can be promoted for example by action-increasing additives such as organic solvents, wetting agents and oils. Such additives therefore optionally permit a reduction in the active ingredient dosage.
The active ingredients according to the invention or their mixtures are expediently applied in the form of preparations, such as powders, products for scattering, granules, solutions, emulsions or suspensions, with addition of liquid and/or solid carriers or diluents and optionally adhesion, wetting, emulsifying and/or dispersion auxiliaries.
Suitable liquid carriers are for example aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylene, cycloh~one, isophorone, dimethyl sulphoxide, dimethylformamide, also mineral oil fractions and vegetable oils.
Suitable as solid carriers are minerals, such as for example bentonite, silica gel, talc, kaolin, attapulgite, limestone and vegetable products, such as for example flours.
Surfactants to be named include for example calcium lignine sulphonate, polyethylene alkyl phenyl ether, naphthalene sulphonic acids and their salts, phenolsulphonic acids and their salts, formaldehyde condensates, fatty alcohol sulphates as well SUBSTITUTE SHEET ~RULE 26) CA 0222616~ 1997-12-31 WO 97/02258 PCT~EP96/02918 as substituted benzene-sulphonic acids and their salts.
The proportion of active ingredient(s) in the various preparations can vary within wide limits. For example, the products contain roughly 10 to 90 percent by weight active ingredient, roughly 90 to 10 percent by weight liquid or solid carriers as well as optionally up to 20 percent by weight surfactants.
The products can be applied in the usual way, ~or example with water as carrier in spray mixture quantities of roughly 100 to 1000 litres/ha. An application of the products in the so-called low-volume and ultra-low procedures is just as possible as their application in the form of so-called microgranules.
The production of these preparations can take place in a manner known per se, for example by grinding or mixing processes. If desired, p~eparations of the individual components can also be mixed only shortly before they are used, such as is carried out in practice for example in the so-called tank mix procedure.
The following examples explain the production of the compounds according to the invention.
ExamPle 1 (1RS, 2RS, 6SR)-2-(2-chloro-6-fluorobenzyloxy)-1,5,5-trimethyl-7-oxabicyclo[4.1.0] heptane 718 mg (6.40 mmol) potassium-tert.-butylate are dissolved in 50 ml tetrahydrofuran and then reacted with 1.15 g (6.40 mmol) 2-chloro-6-fluorobenzyl chloride and 1 g (6.40 mmol) ~1RS, 2RS, 6SR)-2-hydroxy-1,5,5-trimethyl-7-oxabicyclo[4.1.0] heptane. The mixture is stirred overnight, then compressed at the rotary evaporator and the residue is absorbed with 50 ml acetic ester.
The mixture is washed with saturated sodium chloride solution, SUBSTITUTE StlEET ~RULE 26) dried over magnesium sulphate and compressed anew at the rotary evaporator. The residue is purified by column chromatography using silica gel with hexane:acetic ester = 9:1.
Yield: 1.37 g (4.5g mmol A 72% of theory) colourless oil Rf (acetic ester) = 0.73 n20/D = 1.51232 SUBSTlllJTE S~EE~ (RULE 26) CA 02226l65 l997-l2-3l 2~8 PcT/h~55~ 518 The following compounds of ~ormula I are produced in an analogous manner:
No n X Y Rl R2 R3 Fp~toc] or n20/D
2 0 Cl F CH~ H H 1. 520S2 3 0 CH~ H CH~ H H 1~51312 4 1 CH~ H CH~ H H 1, 51590 1 Cl F CH~ H H 1. 52274 6 1 Cl H CH~ H H 1. 53744 7 1 F H CH~ H H 1. 50556 8 1 Cl Cl CH~ H H 145-146 9 1 F F CH~ H H 1. 49896 1 Cl F CH~ CH~ CH~ 1~51232 11 1 Cl H CH~ CH~ CH~ 1. 52242 12 1 CH~ H CH~ CH~ CH~ 1.51440 13 0 Cl F C~HC H H
14 0 CH~ H C~Hc H H R~(EE) =0.68 0 Cl H C~Hc H H Rr(EE)=0.68 16 0 F F C7Hc H H
17 0 Cl F CH? CH~ CH~ R~ ( EE ) =C 69 18 0 CH~ H CH, CH~ CH~ 1. S082 19 0 Cl F C~HC CH~ CH~
0 CH~ H C~Hc CH~ CH~
21 1 Cl F C~HC CH~ CH~ 1~50774 22 1 CH~ H C~HC CH~ CH~ 1. S0868 23 1 F H C~Hc CH~ CH~ 1. 49480 24 1 Cl H C~Hc CH~ CH~ 1.51692 2S ~ Cl F C~Hc C~Hc H 1.50910 26 0 CH~ H C~Hc C~Hc H 1. 50814 SUBSTITUTE SHEET (RULE 26) CA 02226l6~ l997-l2-3l W O 97/02258 PCT~EP96/02918 No n X Y Rl R2 R3 Fp.t~C] or n20/D
27 0 Cl H C~H~ C~H~ H
28 1 Cl F CH~ CH~ H 1.3928 29 1 H CH~ CH~ H 1,3990 30 1 Cl H CH~ CH1 H 1.3879 31 1 Cl F CH~ tR,,I H 1.4019 32 1 Cl H CH~ tq"~ H 1.387G
33 1 CH~ H CH~ tR,,I H 1.3954 34 1 Cl F CH3 CH3 Ph 1,3910 (Diastereomer B) 35 1 Cl F CH3 Ph CH3 . 1.3895 (Dlastereomer B) 36 1 Cl H CH3 CH3 Ph 37-39 (Diastereomer A) 37 1 Cl H CH3 Ph CH3 1.3887 (Diastereomer B) 38 1 CH3 H CH3 CH3 Ph 1.3880 (Diastereomer A) 39 1 CH3 H CH3 Ph CH3 (Diastereomer B) 40 1 Cl F CH~ C~H~ C~H~ 1.3898 41 1 CH~ H CH~ C~H~ C~H~ 1.3928 42 1 Cl H CH~ C~Hc C7H~ 1.3978 43 0 Cl H C~H~ CH~ H 1.51040 44 0 CH~ H C~H~ CH~ H 1.51336 45 0 Cl H C~H~ CH~ H 1.52210 46 0 Cl F C~H~ i-prop H 1.50210 47 0 CH~ H C7H~ i-prop H 1.49896 48 0 Cl H C~H~ i-prop H
49 0 Cl F C~H~ C~H~ H 1,50910 SUBSTITUTE SHEET (RULE 2~) CA 02226l6~ l997-l2-3l W O 97/02258 P~ /02gl8 No. n X Y Rl R2 R3 F2~0.[~C] or S0 0 CH~ H C?H~C?H~ H 1.50814 Sl 0 Cl H C~H~C~H~ H
52 0 Cl F Me Et Et 1 50922 53 0 F H Me Et Et 1.49622 54 0 Cl H Me Et Et 1.51740 0 CH~ H Me Et Et 1.50886 56 0 Cl F Et Et Et 1.50884 57 0 F F Et Et Et 1.48768 58 0 CH~ H Et Et Et 1.50742 S9 0 F H Et Et Et 1.49718 0 Cl F Et -(CH?)~- 1.51090 61 0 Cl H Et -(CH?)~- 1.51868 62 0 CH~ H Et -(CH?)~- 1.53270 63 0 F F Et -(CH~)A- 1.49754 64 0 Cl Cl Et -(CH?)A- 1.53396 0 F H Et - (CH~)A - 1.51000 66 0 Cl H Me -(CH~)~- 68-69 67 0 CH~ H Me -(CH~)~- 68-69 68 0 Cl F Me -(CH?)~- 1.52154 69 0 F H Me -(CH?)c- 58-S9 0 Cl Cl Me -(CH~ 1.53158 71 0 F F Me -(CH?)~- 1.50218 72 0 Cl F Et -(CH~)~- 1.51726 73 0 Me H Et -(CH?)~- 54-SS
74 0 Cl H Et -(CH?)~- 48-49 0 F H Et -(CH?)~- 1.51262 SUBSTITUTE SHEET (RULE 26~
CA 02226l6~ l997-l2-3l W O 97/02258 PCT~EP96/02918 No. n X Y Rl R2 ¦ R3 F~o[ C] or 76 0 Cl Cl Et -(CB~)~- 1.53850 77 0 F F Et -(CH~)C- 1.50444 78 0 Cl F Me -(CH~)~- 1.52178 79 0 Me H Me -(CH~)~- 1.52334 0 Cl H Me -(CH7)~- 1.53310 81 0 F H Me -(CH~)~- 1.51132 82 0 Cl Cl Me -(CH~
83 0 F F Me -(CY~)~- 1.50086 84 0 F H Me Me Me 1.49336 0 Cl H Me Me Me 1.51756 86 0 F H Et H H Rf = 0.66 87 0 Cl F Et Ph H 74-7S
88 1 H H Et Me Ph ?????
(Diastereomer A) 89 1 H H Et Ph Me 1.54074 (Diaste~. -r B ) 1 Cl F Et Me Ph 1.3985 (Diastereomer B ) 91 1 Cl H Et Me Ph 1.3892 (Diastereomer B) 92 1 Me H Et Me Ph 1.3918 (Diastereomer B) 93 1 H H Me Et Et 1.51402 94 1 H H Et Et Et 1.51242 1 Cl H Et Et Et 1.3805 96 1 Me H Et Et Et 1.3970 97 1 Cl F Et Et Et 1.3885 98 1 Cl F Me Me Et 1.3800 99 1 Cl H Me Me Et 1.3984 SUBSTITUTE SHEET (RULE 26) CA 02226l6~ l997-l2-3l W O 97/02258 ~ /02918 ~No. n X Y Rl R2 R3 F~0'~t C] or 100 1 CH~ H Me Me Et 1.3890 101 1 Cl F Me -(CH~)C- 59-61 102 1 Me H Me -(CH~)c- 1.3897 103 1 Cl H Me -(CH~)C- 1.3992 104 1 Cl F Et ?????-(Me~OH 1.50868 105 1 Cl F Me Ph Ph 65-67 106 1 Me H Me Ph Ph 1.3629 107 1 Cl H Me Ph Ph 1.3870 108 1 Cl F Et Ph Ph 1.3509 109 1 Me H Et Ph Ph 1.3705 110 1 Cl H Et Ph Ph 1.3662 111 1 Cl F Et ~ )4- 1 .4012 112 1 Cl F Me Me ~N((~)~ 1.5196 113 1 Me H Me Me CN 1.50240 (Diastel, - B) 114 1 Me H Me CN Me 1.51918 (Diastereomer D) 115 1 Cl F Me Me CN 1.52270 (Diaste ~ - A) 116 1 Cl F Me CN Me 1.51552 (Diaste~. - B) 117 1 Cl H Me Me c-hexyl 1.3870 (Diastereomer A) 118 1 Cl H Mec-hexyl Me 1.3910 (Diastereomer B) 119 1 Me H Me Me c-hexyl 43-44 (Diastereomer A) 120 1 Me H Mec-hexyl Me 58-61 (Diastereomer B) 121 1 Cl F Me Me c-hexyl 1.3775 (Diast~l. -r A) SU85TITUTE !jHEE~ tRULE 26~
CA 02226l65 l997-l2-3l WO g7102258P~ .S/02918 No n X Y Rl R2 R3 Ep.toc] or n20/n 122 1 Cl F Mec-hexyl Me1.3824 (Diastereomer B) 123 1 Cl F Et Me c-hexyl1.3870 (Diastereomer A) 124 1 Cl F Etc-hexyl Me1.3855 (Diaste~ - B) 125 1 Me H Etc-hexyl Me1.3668 (Diastereomer A) 126 1 Me ~ H Et c-hexyl Me 1.3714 (Diaste ~ ~ B) 127 1 Cl H Etc-hexyl Me1.3777 (Diaste~ - A) 128 1 Cl H Et Me c-hexyl1.3685 (Diastereomer B) 129 1 Cl F Me Me CH2CH3Rf=0.71 (Diastereomer A) 130 1 Cl F MeCH2CH3 MeR =0.84 (Diastereomer B) c-hexyl = cyclohexyl SUBSTITUTE SHEET ~RULE 26 CA 0222616~ 1997-12-31 W O 97/02258 P~~ -t02918 The following application examples explain the usability of the compounds according to the invention.
In the examples:
AS = active substance CYPDI Cyperus difformis 0 = no damage ECHCG ~h;nochloa crus-galli 1 = 1-24% damage GOSHI Gossypium hirsutum 2 = 25-74% damage MOOVA Monochoria vaginalis 3 = 75--89% damage ORYSA Oryza sativa,japonica Koc:h;h;kari 4 = 90--100% damage ORYSW Oryza sativa, indica IR&$
SAGPY Sagittaria pygmaea SCPJU Scirpus juncoides SETVI Setaria viridis Application examPle A
The plant species listed below were treated in the glass house post-sowing with the listed compounds in an application quantity of 1.0 kg active ingredient/ha. To this end, the active ingredients were sprayed uniformly over the plants as an emulsion with 500 litres of water/ha. Three weeks after the treatment, the compounds according to the invention displayed an e~c~llent action against the weed.
Compound G S
acc. to O E
example S T
no. H V
Untreated 0 0 SUBSTITUTE $HEET (RULE 26) CA 0222616~ 1997-12-31 W O 97/02258 PcT/~-~s~ 5l8 Application exam~le B
}n the glass house the compounds listed in the table were applied by pipetting onto a water surface of ca. 170cm2, the test plants being used both in the post-sowing phase and in the 1-2 leaf stage. After 2 weeks it was shown that the compounds according to the invention are very effective against important rice weeds and at the same time are selective as regards water rice.
Co~ d O E S S M C
acc. towater R C C A O Y
exampleapplication Y H P G O P
no. tkg AS/ha~ S C J P V D
A G U Y A
2 0.05 0 3 3 3 4 4 0.05 0 4 3 3 3 3 11 0.05 0 4 3 3 4 3 12 0.5 0 4 - - 4 Untreated O O O O O O
SUBSTITUTE SHEET (RULE 26) CA 02226l6~ l997-l2-3l W O 97/02258 ~ /02918 Application examPle C
(C~mrA~ative example) In the glass house, the compound listed in the table and the _~ison compound were applied by pipetting onto a water surface of ca. 170 cm2, the test plants being used both in the post-sowing stage and the 1-3 leaf stage. After 2 weeks it was shown that thq compound according to the invention is much more effective ;~g~inct ; ~ Lant rice weeds than is the ~5 ,~Tison product. Specially at higher doses, the compatibility of the compound zccording to the invention is better ,_ p-~ed with the known compound in the case of seed rice and plant rice.
Compound O O E S S M C
acc. to water R R C C A O Y
example application Y Y ~ P G O P
no. [kg AS/ha] S S C J P V D
A W G U Y A
89 0.006 0 - 4 3 2 2 3 0.025 0 2 - - - - -Cinmethylin0.006 0 - 3 3 1 0 2 0.025 1 4 Untreated 0 0 0 0 0 0 0 SUBSTITUTE SHEET (RULE 26)
It is already known that certain benzyl ethers have herbicidal properties (e.g. EP 081 893, EP 334 120 and EP 497 453). In J.
Org. Chem., vol. 45, no. 15, 1980, pages 3004-3009 (cited in Chemical Abstracts 93:94859g) is described an epoxycyclohexanol, namely 2-methyl-2,3-epoxycyclohexanol and Mol. Cryst. Liq. Sct.
Technol. Sect. A, pages 291-298 discloses 2,4,4-trimethyl-2,3-epoxy-cyclohexanol.
However, the herbicidal action o~ the known compounds is ~requently not adequate, or there are selectivity problems in agricultural main crops when the herbicidal action is suitable.
It was ~ound that benzylated cis-2,3-epoxycycloalkanols o~ the general ~ormula I
t-, R
X R1" ~ R3 ~o~~~(CH2) in which~ and Y can be the same or di~erent and stand ~or H, halogen, Cl_6-alkyl or Cl 6-halogen alkyl, R1 stands ~or Cl 6-alkyl, C2 6-alkenyl, C2 6-alkinyl, halogen-Cl_6-alkyl, halogen-C2 6-alkenyl or halogen-C2 6- alkinyl,~2, R3 can be the same or di~erent and stand ~or H, Cl 6-alkyl, C2 6-alkenyl, C2_6-alkinyl, halogen-Cl_6-alkyl, halogen-C2 6-alkenyl, halogen-C2 6-alkinyl, optionally phenyl substituted once or repeatedly, identically or di~erently with halogen, Cl 6-alkyl, halogen-Cl 6-alkyl, nitro or cyano, Cl 6-alkoxycarbonyl, Cl 6-alkoxy, halogen-Cl 6-alkoxy, -CH2-oR4 (R4 equals Cl 6-alkyl, allyl, benzyl or propargyl) ~~~
CA 0222616~ 1997-12-31 W O 97/02258 P~~ /02gl8 or R2 and R3 together stand for -~CH2)m- (m equals 2, 3, 4 or 5), and n stands for O or 1, have a superior effectiveness compared with the known compounds.
Halogen is taken to mean fluorine, chlorine, bromine and iodine.
The terms "alkyl", "alkenyl" and "alkinyl" are taken to mean both straight-ch~ine~ and branched hydrocarbon radicals.
The invention also relates to intermediates of the general ~ormula II
R "", ~ R
f (CH2)n HO (11~
for the production of compounds of the formula I, in which R1, R2, R3 and n have the me~n;ng given under the general formula I.
The compounds according to the invention of the general fo ~1 A
I can be produced by reacting a compound of the general formula II with a compound of the general formula III
~z ~ Y (111~.
in which X and Y have the me~n;ng given under the general formula I and Z stands for chlorine, bromine, iodine, an alkyl or arylsulphoxy group, by methods known per se in the presence of a base.
The reaction is carried out in a suitable solvent such as e.g.
benzene, toluene, xylene, diethyl ether, tetrahydrofuran, dimethylformamide or 1,4-dioxan in the presence of a base such SUBSTITUTE SHEET ~RULE 26~
CA 0222616~ 1997-12-31 W O 97/02258 PCT~EP96/02918 as sodium hydride or potassium-t-butylate at temperatures between 0 ~C and the boiling point of the solvent in question.
The compounds of the general formula II which are used as intermediate can be produced by reacting 2-cycloalkenols of the general formula IV
R' i R3 J~ ~CHz)n HO (IV).
in which R1, R2, R3 and n have the m~n ; ng given under the general formula I, analogously to methods described in the literature (see e.g. P. Kocovksy, Tetrahedron Lett. 29, 2475 (1988)).
The compounds of the general formula IV can be produced by reacting 2-cycloalkenones of the general formula V
R~
(C~2),.
O (V), in which R1, R2, R3 and n have the ~e~n;ng given under the general formula I, analogously to methods described in the literature (see e.g. M. Mousseron, R. Jarquier, M. Mousseron-Lauet, R. Zagdonn, Bull. Soc. Chim. Fr. 1042 (19~2)).
The compounds of the general ~ormula V are commercially available or can be produced by methods known from the literature or analogously to these (e.g.: N.W.A. Geraghty and N.M. Morris, Synthesis 1989, 603, Yanagita, Inayama, J. Org. Chem., 19, 1732 (1954)).
The compounds according to the invention produced according to the methods described above can be isolated from the reaction mixture by usual methods, for example by distilling off the solvent at normal or reduced pressure, by precipitation with SUBSTITVTE ~}~EE ~ (RULE 26~
CA 0222616~ 1997-12-31 W O 97/02258 PCT/~l_SI~518 water or by extraction An increased degree o~ purity can as a rule be obtained by column chromatographic cleaning and by fractional distillation or crystallization.
The cG...~unds according to the invention are as a rule almost colourless and odourless liquids or crystals which are limitedly soluble in water, aliphatic hydrocarbons, such as petroleum ether, hexane, pentane and cyclohexane, well soluble in halogenated hydrocarbons, such as chloroform, methylene chloride and carbon tetrachloride, aromatic hydrocarbons, such as benzene, toluene and xylene, ethers, such as diethyl ether, tetrahydrofuran and dioxan, carboxylic acia nitriles, such as acetonitrile, alcohols, such as ethanol and methanol, carboxylic acid amides, such as dimethylformamide, sulphoxides, such as dimethyl sulphoxide or organic bases, such as for example pyridine.
The compounds according to the invention have a good herbicidal action in the case of broad-leaved weeds and grasses. A selective use is possible in various crops, e.g. in rice, rape, beet, soybeans, cotton, maize, barley, wheat and other types of cereal.
Individual compounds are also particularly suitable as selective herbicides in rice, beet, cotton, soya, maize and cereals. The compounds can also be used to control weeds in perennial crops, such as e.g. in forest, ornamental woodland, fruit, wine, citrus, nut, banana, coffee, tea, rubber, oil palm, cocoa, berry fruit and hop plantations, and for selective weed control in annual crops.
The compounds according to the invention can be used e.g. with the following plant species:
Dicotyledonous weeds of the species such as Sinapis, Lepidium, Galium, Stellania, Matricaria, Anthemis, Galinsoga, Chenopodium, srassica~ Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Sonchus, Solanum, Lamium, Veronica, Abutilon, Datura, Vio~a, SUBSTITUTE SHEET (RULE 26~
CA 02226l6~ l997-l2-3l W O 97/02258 PCT~EP96/02918 Galeopsis, Papaver, Centaurea and Chrysanthemum;
Monocotyledonous weeds of the species such as Avena, Alopecurus, Echinochloa, Setaria, Panicum, Digitaria, Poa, Eleusine, Rrachiaria, Lolium, sromus~ Cyperus, Elymus, Sagittaria, Monochoria, Fimbristylis, Eleocharis, Ischaemum and Apera.
The quantities used vary according to the type of application, post-sowing and post-emergence, between 0.001 and 5 kg/ha.
The compounds according to the invention can be used either alone, mixed with one another or with other active ingredients.
The intensity of action and speed of ef~ect can be promoted for example by action-increasing additives such as organic solvents, wetting agents and oils. Such additives therefore optionally permit a reduction in the active ingredient dosage.
The active ingredients according to the invention or their mixtures are expediently applied in the form of preparations, such as powders, products for scattering, granules, solutions, emulsions or suspensions, with addition of liquid and/or solid carriers or diluents and optionally adhesion, wetting, emulsifying and/or dispersion auxiliaries.
Suitable liquid carriers are for example aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylene, cycloh~one, isophorone, dimethyl sulphoxide, dimethylformamide, also mineral oil fractions and vegetable oils.
Suitable as solid carriers are minerals, such as for example bentonite, silica gel, talc, kaolin, attapulgite, limestone and vegetable products, such as for example flours.
Surfactants to be named include for example calcium lignine sulphonate, polyethylene alkyl phenyl ether, naphthalene sulphonic acids and their salts, phenolsulphonic acids and their salts, formaldehyde condensates, fatty alcohol sulphates as well SUBSTITUTE SHEET ~RULE 26) CA 0222616~ 1997-12-31 WO 97/02258 PCT~EP96/02918 as substituted benzene-sulphonic acids and their salts.
The proportion of active ingredient(s) in the various preparations can vary within wide limits. For example, the products contain roughly 10 to 90 percent by weight active ingredient, roughly 90 to 10 percent by weight liquid or solid carriers as well as optionally up to 20 percent by weight surfactants.
The products can be applied in the usual way, ~or example with water as carrier in spray mixture quantities of roughly 100 to 1000 litres/ha. An application of the products in the so-called low-volume and ultra-low procedures is just as possible as their application in the form of so-called microgranules.
The production of these preparations can take place in a manner known per se, for example by grinding or mixing processes. If desired, p~eparations of the individual components can also be mixed only shortly before they are used, such as is carried out in practice for example in the so-called tank mix procedure.
The following examples explain the production of the compounds according to the invention.
ExamPle 1 (1RS, 2RS, 6SR)-2-(2-chloro-6-fluorobenzyloxy)-1,5,5-trimethyl-7-oxabicyclo[4.1.0] heptane 718 mg (6.40 mmol) potassium-tert.-butylate are dissolved in 50 ml tetrahydrofuran and then reacted with 1.15 g (6.40 mmol) 2-chloro-6-fluorobenzyl chloride and 1 g (6.40 mmol) ~1RS, 2RS, 6SR)-2-hydroxy-1,5,5-trimethyl-7-oxabicyclo[4.1.0] heptane. The mixture is stirred overnight, then compressed at the rotary evaporator and the residue is absorbed with 50 ml acetic ester.
The mixture is washed with saturated sodium chloride solution, SUBSTITUTE StlEET ~RULE 26) dried over magnesium sulphate and compressed anew at the rotary evaporator. The residue is purified by column chromatography using silica gel with hexane:acetic ester = 9:1.
Yield: 1.37 g (4.5g mmol A 72% of theory) colourless oil Rf (acetic ester) = 0.73 n20/D = 1.51232 SUBSTlllJTE S~EE~ (RULE 26) CA 02226l65 l997-l2-3l 2~8 PcT/h~55~ 518 The following compounds of ~ormula I are produced in an analogous manner:
No n X Y Rl R2 R3 Fp~toc] or n20/D
2 0 Cl F CH~ H H 1. 520S2 3 0 CH~ H CH~ H H 1~51312 4 1 CH~ H CH~ H H 1, 51590 1 Cl F CH~ H H 1. 52274 6 1 Cl H CH~ H H 1. 53744 7 1 F H CH~ H H 1. 50556 8 1 Cl Cl CH~ H H 145-146 9 1 F F CH~ H H 1. 49896 1 Cl F CH~ CH~ CH~ 1~51232 11 1 Cl H CH~ CH~ CH~ 1. 52242 12 1 CH~ H CH~ CH~ CH~ 1.51440 13 0 Cl F C~HC H H
14 0 CH~ H C~Hc H H R~(EE) =0.68 0 Cl H C~Hc H H Rr(EE)=0.68 16 0 F F C7Hc H H
17 0 Cl F CH? CH~ CH~ R~ ( EE ) =C 69 18 0 CH~ H CH, CH~ CH~ 1. S082 19 0 Cl F C~HC CH~ CH~
0 CH~ H C~Hc CH~ CH~
21 1 Cl F C~HC CH~ CH~ 1~50774 22 1 CH~ H C~HC CH~ CH~ 1. S0868 23 1 F H C~Hc CH~ CH~ 1. 49480 24 1 Cl H C~Hc CH~ CH~ 1.51692 2S ~ Cl F C~Hc C~Hc H 1.50910 26 0 CH~ H C~Hc C~Hc H 1. 50814 SUBSTITUTE SHEET (RULE 26) CA 02226l6~ l997-l2-3l W O 97/02258 PCT~EP96/02918 No n X Y Rl R2 R3 Fp.t~C] or n20/D
27 0 Cl H C~H~ C~H~ H
28 1 Cl F CH~ CH~ H 1.3928 29 1 H CH~ CH~ H 1,3990 30 1 Cl H CH~ CH1 H 1.3879 31 1 Cl F CH~ tR,,I H 1.4019 32 1 Cl H CH~ tq"~ H 1.387G
33 1 CH~ H CH~ tR,,I H 1.3954 34 1 Cl F CH3 CH3 Ph 1,3910 (Diastereomer B) 35 1 Cl F CH3 Ph CH3 . 1.3895 (Dlastereomer B) 36 1 Cl H CH3 CH3 Ph 37-39 (Diastereomer A) 37 1 Cl H CH3 Ph CH3 1.3887 (Diastereomer B) 38 1 CH3 H CH3 CH3 Ph 1.3880 (Diastereomer A) 39 1 CH3 H CH3 Ph CH3 (Diastereomer B) 40 1 Cl F CH~ C~H~ C~H~ 1.3898 41 1 CH~ H CH~ C~H~ C~H~ 1.3928 42 1 Cl H CH~ C~Hc C7H~ 1.3978 43 0 Cl H C~H~ CH~ H 1.51040 44 0 CH~ H C~H~ CH~ H 1.51336 45 0 Cl H C~H~ CH~ H 1.52210 46 0 Cl F C~H~ i-prop H 1.50210 47 0 CH~ H C7H~ i-prop H 1.49896 48 0 Cl H C~H~ i-prop H
49 0 Cl F C~H~ C~H~ H 1,50910 SUBSTITUTE SHEET (RULE 2~) CA 02226l6~ l997-l2-3l W O 97/02258 P~ /02gl8 No. n X Y Rl R2 R3 F2~0.[~C] or S0 0 CH~ H C?H~C?H~ H 1.50814 Sl 0 Cl H C~H~C~H~ H
52 0 Cl F Me Et Et 1 50922 53 0 F H Me Et Et 1.49622 54 0 Cl H Me Et Et 1.51740 0 CH~ H Me Et Et 1.50886 56 0 Cl F Et Et Et 1.50884 57 0 F F Et Et Et 1.48768 58 0 CH~ H Et Et Et 1.50742 S9 0 F H Et Et Et 1.49718 0 Cl F Et -(CH?)~- 1.51090 61 0 Cl H Et -(CH?)~- 1.51868 62 0 CH~ H Et -(CH?)~- 1.53270 63 0 F F Et -(CH~)A- 1.49754 64 0 Cl Cl Et -(CH?)A- 1.53396 0 F H Et - (CH~)A - 1.51000 66 0 Cl H Me -(CH~)~- 68-69 67 0 CH~ H Me -(CH~)~- 68-69 68 0 Cl F Me -(CH?)~- 1.52154 69 0 F H Me -(CH?)c- 58-S9 0 Cl Cl Me -(CH~ 1.53158 71 0 F F Me -(CH?)~- 1.50218 72 0 Cl F Et -(CH~)~- 1.51726 73 0 Me H Et -(CH?)~- 54-SS
74 0 Cl H Et -(CH?)~- 48-49 0 F H Et -(CH?)~- 1.51262 SUBSTITUTE SHEET (RULE 26~
CA 02226l6~ l997-l2-3l W O 97/02258 PCT~EP96/02918 No. n X Y Rl R2 ¦ R3 F~o[ C] or 76 0 Cl Cl Et -(CB~)~- 1.53850 77 0 F F Et -(CH~)C- 1.50444 78 0 Cl F Me -(CH~)~- 1.52178 79 0 Me H Me -(CH~)~- 1.52334 0 Cl H Me -(CH7)~- 1.53310 81 0 F H Me -(CH~)~- 1.51132 82 0 Cl Cl Me -(CH~
83 0 F F Me -(CY~)~- 1.50086 84 0 F H Me Me Me 1.49336 0 Cl H Me Me Me 1.51756 86 0 F H Et H H Rf = 0.66 87 0 Cl F Et Ph H 74-7S
88 1 H H Et Me Ph ?????
(Diastereomer A) 89 1 H H Et Ph Me 1.54074 (Diaste~. -r B ) 1 Cl F Et Me Ph 1.3985 (Diastereomer B ) 91 1 Cl H Et Me Ph 1.3892 (Diastereomer B) 92 1 Me H Et Me Ph 1.3918 (Diastereomer B) 93 1 H H Me Et Et 1.51402 94 1 H H Et Et Et 1.51242 1 Cl H Et Et Et 1.3805 96 1 Me H Et Et Et 1.3970 97 1 Cl F Et Et Et 1.3885 98 1 Cl F Me Me Et 1.3800 99 1 Cl H Me Me Et 1.3984 SUBSTITUTE SHEET (RULE 26) CA 02226l6~ l997-l2-3l W O 97/02258 ~ /02918 ~No. n X Y Rl R2 R3 F~0'~t C] or 100 1 CH~ H Me Me Et 1.3890 101 1 Cl F Me -(CH~)C- 59-61 102 1 Me H Me -(CH~)c- 1.3897 103 1 Cl H Me -(CH~)C- 1.3992 104 1 Cl F Et ?????-(Me~OH 1.50868 105 1 Cl F Me Ph Ph 65-67 106 1 Me H Me Ph Ph 1.3629 107 1 Cl H Me Ph Ph 1.3870 108 1 Cl F Et Ph Ph 1.3509 109 1 Me H Et Ph Ph 1.3705 110 1 Cl H Et Ph Ph 1.3662 111 1 Cl F Et ~ )4- 1 .4012 112 1 Cl F Me Me ~N((~)~ 1.5196 113 1 Me H Me Me CN 1.50240 (Diastel, - B) 114 1 Me H Me CN Me 1.51918 (Diastereomer D) 115 1 Cl F Me Me CN 1.52270 (Diaste ~ - A) 116 1 Cl F Me CN Me 1.51552 (Diaste~. - B) 117 1 Cl H Me Me c-hexyl 1.3870 (Diastereomer A) 118 1 Cl H Mec-hexyl Me 1.3910 (Diastereomer B) 119 1 Me H Me Me c-hexyl 43-44 (Diastereomer A) 120 1 Me H Mec-hexyl Me 58-61 (Diastereomer B) 121 1 Cl F Me Me c-hexyl 1.3775 (Diast~l. -r A) SU85TITUTE !jHEE~ tRULE 26~
CA 02226l65 l997-l2-3l WO g7102258P~ .S/02918 No n X Y Rl R2 R3 Ep.toc] or n20/n 122 1 Cl F Mec-hexyl Me1.3824 (Diastereomer B) 123 1 Cl F Et Me c-hexyl1.3870 (Diastereomer A) 124 1 Cl F Etc-hexyl Me1.3855 (Diaste~ - B) 125 1 Me H Etc-hexyl Me1.3668 (Diastereomer A) 126 1 Me ~ H Et c-hexyl Me 1.3714 (Diaste ~ ~ B) 127 1 Cl H Etc-hexyl Me1.3777 (Diaste~ - A) 128 1 Cl H Et Me c-hexyl1.3685 (Diastereomer B) 129 1 Cl F Me Me CH2CH3Rf=0.71 (Diastereomer A) 130 1 Cl F MeCH2CH3 MeR =0.84 (Diastereomer B) c-hexyl = cyclohexyl SUBSTITUTE SHEET ~RULE 26 CA 0222616~ 1997-12-31 W O 97/02258 P~~ -t02918 The following application examples explain the usability of the compounds according to the invention.
In the examples:
AS = active substance CYPDI Cyperus difformis 0 = no damage ECHCG ~h;nochloa crus-galli 1 = 1-24% damage GOSHI Gossypium hirsutum 2 = 25-74% damage MOOVA Monochoria vaginalis 3 = 75--89% damage ORYSA Oryza sativa,japonica Koc:h;h;kari 4 = 90--100% damage ORYSW Oryza sativa, indica IR&$
SAGPY Sagittaria pygmaea SCPJU Scirpus juncoides SETVI Setaria viridis Application examPle A
The plant species listed below were treated in the glass house post-sowing with the listed compounds in an application quantity of 1.0 kg active ingredient/ha. To this end, the active ingredients were sprayed uniformly over the plants as an emulsion with 500 litres of water/ha. Three weeks after the treatment, the compounds according to the invention displayed an e~c~llent action against the weed.
Compound G S
acc. to O E
example S T
no. H V
Untreated 0 0 SUBSTITUTE $HEET (RULE 26) CA 0222616~ 1997-12-31 W O 97/02258 PcT/~-~s~ 5l8 Application exam~le B
}n the glass house the compounds listed in the table were applied by pipetting onto a water surface of ca. 170cm2, the test plants being used both in the post-sowing phase and in the 1-2 leaf stage. After 2 weeks it was shown that the compounds according to the invention are very effective against important rice weeds and at the same time are selective as regards water rice.
Co~ d O E S S M C
acc. towater R C C A O Y
exampleapplication Y H P G O P
no. tkg AS/ha~ S C J P V D
A G U Y A
2 0.05 0 3 3 3 4 4 0.05 0 4 3 3 3 3 11 0.05 0 4 3 3 4 3 12 0.5 0 4 - - 4 Untreated O O O O O O
SUBSTITUTE SHEET (RULE 26) CA 02226l6~ l997-l2-3l W O 97/02258 ~ /02918 Application examPle C
(C~mrA~ative example) In the glass house, the compound listed in the table and the _~ison compound were applied by pipetting onto a water surface of ca. 170 cm2, the test plants being used both in the post-sowing stage and the 1-3 leaf stage. After 2 weeks it was shown that thq compound according to the invention is much more effective ;~g~inct ; ~ Lant rice weeds than is the ~5 ,~Tison product. Specially at higher doses, the compatibility of the compound zccording to the invention is better ,_ p-~ed with the known compound in the case of seed rice and plant rice.
Compound O O E S S M C
acc. to water R R C C A O Y
example application Y Y ~ P G O P
no. [kg AS/ha] S S C J P V D
A W G U Y A
89 0.006 0 - 4 3 2 2 3 0.025 0 2 - - - - -Cinmethylin0.006 0 - 3 3 1 0 2 0.025 1 4 Untreated 0 0 0 0 0 0 0 SUBSTITUTE SHEET (RULE 26)
Claims (5)
1. Benzylated cis-2,3-epoxycycloalkanols of the general formula I
in which X and Y can be the same or different and stand for H, halogen, C1-6-alkyl or C1-6-halogen alkyl, R1 stands for C1-6-alkyl, C2-6-alkenyl, C2-6-alkinyl, halogen-C1-6-alkyl, halogen-C2-6-alkenyl or halogen respect C2-6-alkinyl, R2,R3 can be the same or different and stand for H, C1-6-alkyl, C2-6-alkenyl, C2-6-alkinyl, halogen-C1-6 alkyl, halogen-C2-6-alkenyl, halogen C2-6-alkinyl, optionally phenyl substituted once or repeatedly, identically or differently with halogen, C1-6-alkyl, halogen-C1-6-alkyl, nitro or cyano, cyano, C1-6 alkoxycarbonyl, C1-6-alkoxy, halogen-C1-6-alkoxy, -CH2-OR4 (R4 equals C1-6-alkyl, halogen-C1-6-alkyl, allyl, benzyl or propargyl) or R2 and R3 together stand for -(CH2)m- (m equals 2, 3, 4 or 5), and n stands for 0 or 1.
in which X and Y can be the same or different and stand for H, halogen, C1-6-alkyl or C1-6-halogen alkyl, R1 stands for C1-6-alkyl, C2-6-alkenyl, C2-6-alkinyl, halogen-C1-6-alkyl, halogen-C2-6-alkenyl or halogen respect C2-6-alkinyl, R2,R3 can be the same or different and stand for H, C1-6-alkyl, C2-6-alkenyl, C2-6-alkinyl, halogen-C1-6 alkyl, halogen-C2-6-alkenyl, halogen C2-6-alkinyl, optionally phenyl substituted once or repeatedly, identically or differently with halogen, C1-6-alkyl, halogen-C1-6-alkyl, nitro or cyano, cyano, C1-6 alkoxycarbonyl, C1-6-alkoxy, halogen-C1-6-alkoxy, -CH2-OR4 (R4 equals C1-6-alkyl, halogen-C1-6-alkyl, allyl, benzyl or propargyl) or R2 and R3 together stand for -(CH2)m- (m equals 2, 3, 4 or 5), and n stands for 0 or 1.
2. Compounds of the general formula II
as intermediates for the production of compounds of the formula I, in which R1, R2, R3 and n have the meaning given under the general formula I, with the proviso that compounds of the formula II wherein n is 1, R1 is methyl, R2 is H and R3 is H, or n is 1, R1 is methyl, R2 is methyl and R3 is methyl are excluded.
as intermediates for the production of compounds of the formula I, in which R1, R2, R3 and n have the meaning given under the general formula I, with the proviso that compounds of the formula II wherein n is 1, R1 is methyl, R2 is H and R3 is H, or n is 1, R1 is methyl, R2 is methyl and R3 is methyl are excluded.
3. Products with herbicidal action characterized by a content of at least one compound according to claim 1.
4. Product with herbicidal action according to claim 3 mixed with carrier and/or auxiliary substances.
5. Use of compounds according to claim 1 for the control of monocotyledonous and dicotyledonous weeds.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19524143A DE19524143A1 (en) | 1995-07-03 | 1995-07-03 | Benzylated cis-2,3-epoxycycloalkanols |
| DE19524143.6 | 1995-07-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2226165A1 true CA2226165A1 (en) | 1997-01-23 |
Family
ID=7765849
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002226165A Abandoned CA2226165A1 (en) | 1995-07-03 | 1996-07-03 | Benzylated cis-2,3-epoxycycloalkanol |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP0842167A1 (en) |
| JP (1) | JPH11508245A (en) |
| KR (1) | KR19990028679A (en) |
| AU (1) | AU6518096A (en) |
| BR (1) | BR9609304A (en) |
| CA (1) | CA2226165A1 (en) |
| DE (1) | DE19524143A1 (en) |
| MX (1) | MX9800053A (en) |
| PL (1) | PL324381A1 (en) |
| TR (1) | TR199600557A2 (en) |
| WO (1) | WO1997002258A1 (en) |
| ZA (1) | ZA965652B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19640351A1 (en) * | 1996-09-23 | 1998-04-02 | Hoechst Schering Agrevo Gmbh | Herbicidal cis-1-heteroaryloxy-2,3-epoxycycloalkane derivatives |
| AU6522498A (en) * | 1997-04-07 | 1998-10-30 | Nissan Chemical Industries Ltd. | Cycloalkyl benzyl ether compounds |
| JP2003171211A (en) * | 1999-08-30 | 2003-06-17 | Kumiai Chem Ind Co Ltd | 2-benzyloxy-7-oxabicyclo[4.1.0]heptane derivative and agrochemical, especially herbicide comprising the same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4670041A (en) * | 1981-12-16 | 1987-06-02 | E. I. Du Pont De Nemours And Company | Oxabicycloalkane herbicides |
| DE3809765A1 (en) * | 1988-03-23 | 1989-10-05 | Basf Ag | ISOXAZOLINE, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS HERBICIDES |
| EP0497453A1 (en) * | 1991-01-30 | 1992-08-05 | E.I. Du Pont De Nemours And Company | Herbicidal bicyclic ethers |
-
1995
- 1995-07-03 DE DE19524143A patent/DE19524143A1/en not_active Withdrawn
-
1996
- 1996-07-03 AU AU65180/96A patent/AU6518096A/en not_active Abandoned
- 1996-07-03 ZA ZA965652A patent/ZA965652B/en unknown
- 1996-07-03 PL PL96324381A patent/PL324381A1/en unknown
- 1996-07-03 KR KR1019970710002A patent/KR19990028679A/en not_active Application Discontinuation
- 1996-07-03 MX MX9800053A patent/MX9800053A/en unknown
- 1996-07-03 EP EP96924867A patent/EP0842167A1/en not_active Withdrawn
- 1996-07-03 CA CA002226165A patent/CA2226165A1/en not_active Abandoned
- 1996-07-03 JP JP9503431A patent/JPH11508245A/en active Pending
- 1996-07-03 WO PCT/EP1996/002918 patent/WO1997002258A1/en not_active Application Discontinuation
- 1996-07-03 BR BR9609304A patent/BR9609304A/en not_active Application Discontinuation
- 1996-07-03 TR TR96/00557A patent/TR199600557A2/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| MX9800053A (en) | 1998-03-29 |
| DE19524143A1 (en) | 1997-01-09 |
| BR9609304A (en) | 1999-05-25 |
| ZA965652B (en) | 1997-01-27 |
| WO1997002258A1 (en) | 1997-01-23 |
| KR19990028679A (en) | 1999-04-15 |
| AU6518096A (en) | 1997-02-05 |
| TR199600557A2 (en) | 1997-01-21 |
| EP0842167A1 (en) | 1998-05-20 |
| PL324381A1 (en) | 1998-05-25 |
| JPH11508245A (en) | 1999-07-21 |
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