GB1577181A - Substituted alkyl ethers of phenoxyphenols their preparation and herbicidal compositions containing them - Google Patents
Substituted alkyl ethers of phenoxyphenols their preparation and herbicidal compositions containing them Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/49—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups
- C07C205/57—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups having nitro groups and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C305/00—Esters of sulfuric acids
- C07C305/02—Esters of sulfuric acids having oxygen atoms of sulfate groups bound to acyclic carbon atoms of a carbon skeleton
- C07C305/04—Esters of sulfuric acids having oxygen atoms of sulfate groups bound to acyclic carbon atoms of a carbon skeleton being acyclic and saturated
- C07C305/10—Esters of sulfuric acids having oxygen atoms of sulfate groups bound to acyclic carbon atoms of a carbon skeleton being acyclic and saturated being further substituted by singly-bound oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/63—Esters of sulfonic acids
- C07C309/64—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms
- C07C309/65—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms of a saturated carbon skeleton
- C07C309/66—Methanesulfonates
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/08—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
- C07D295/084—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
- C07D295/088—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
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Abstract
The herbicide contains a compound of the formula I in which the individual substituents have the meaning given in Patent Claim 1. It has a broad spectrum of action against grass weeds and is tolerated by dicotyledon crop plants and various cereal species. <IMAGE>
Description
(54) SUBSTITUTED ALKYL ETHERS OF PHENOXYPHENOLS,
THEIR PREPARATION AND HERBICIDAL
COMPOSITIONS CONTAINING THEM (71) We, HOECHST AKTIENGESELLSCHAFT, a body corporate organised according to the laws of the Federal Republic of Germany, of 6230 Frankfurt/Main 80, Postfach 80 03 20, Federal Republic of Germany, do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:
This invention relates to herbicidally active compounds and to herbicidal compositions containing them.
The present invention provides herbicidal compositions comprising a carrier and, as active substance, a compound of the general formula
in which each R is a halogen atom or a CF3, CH3 or C2H5 group; each R1 is a halogen atom or a CF3 group; R2 is a hydrogen atom or a (Cl-C4)-alkyl group; n is 1 or 2; nl is 0, 1 or 2; each of X and Y is O or S; and
Z is -OH, -SH. -F, -Cl -Br. -I or a group of the formula
in which R3 is a (C1-C12)alkyl, (C3-C8)cycloalkyl, (C2-C10) alkenyl, (C5-C6)cycloalkenyl, (C3-C8)alkynyl, phenyl or benzyl group which may carry one or more substituents selected from halogen atoms and CF3, NO2, CN, (C1-C4) alkyl, (C1-C4)alkylthio, (C1-C4)alkoxy, -OH, -NH2, (C1-C6)alkylamino, di-(C1-C6)alkylamino and (C1-C6)alkoxycarbonyl groups;
R4 is a hydrogen atom or a (C1-C4)alkyl, (C2-C4)alkenyl, cyclopentyl, cyclohexyl, (C1-C4)alkoxy or phenyl group which may carry one or more substituents selected from halogen atoms and CF3, NO2, CN, (C1-C4)alkyl, (C1-C4)alkylthio, (C1-C4)alkoxy, OH,
NH2, (C1-C6)alkylamino, di-(C1-C6)alkylamino and (C1-C6)alkoxycarbonyl groups;
R5 is a hydrogen atom or a (C1-C4)alkyl group, or
R4 and R5 together with the nitrogen atom to which they are attached form a saturated heterocycle having from 2 to 5 carbon atoms and which may contain an oxygen or sulphur atom or a group of the formula NR5;
R6 has the meanings given for R3 or is a phenoxy-(C1-C4)-alkyl group the phenyl group of which may carry from 1 to 3 substituents selected from F, Cl and Br atoms and methyl groups;
R7 is a hydrogen atom or a (C1-C4)alkyl group or cat#; and cat# is the cation of an inorganic or organic base, or Z is a group of the formula
The present invention also provides the compounds of the general formula I with the proviso that, when Z is OH or -OCOR6 in which R6 is a (Cl-C3)alkyl group and X and Y are both oxygen, then (R)n cannot be a halogen atom in the 4-position.
The alkyl, alkenyl and alkynyl groups represented by R3 to R7 may be straight-chained or branched.
Preferred compounds of the general formula I are those in which (R)n is one to two -Cl and/or -Br atoms and/or -CF3 groups, especially 4-Cl, 2,4-Cl, 2-Cl-4-Br, 4-CF3 and 2-Cl-4-CF3; n1 is O or (R1)n, is Cl or Br in the 2-position to Y;
R2 is CH3,
X, Y are both O,
Z is -OH, -Cl, -Br; the group of the formula II; in which (R)n and n, have the preferred meanings given above; and the groups
in which R4 is a hydrogen atom or a (C1-C4)alkyl, phenyl, halophenyl, methylphenyl or trifluoromethylphenyl group, and R5 has the meaning given above; -O-SO2-R3, in which R3 is a CH3, phenyl, methylphenyl or chlorophenyl group; -O-SO3-R7, in which R7 is a (C1-C4)alkyl group or cat#;
in which R6 is a (C-C9)alkyl or (C1-C4)chloroalkyl group, a phenoxy-(C1-C3)alkyl group the phenyl group of which may carry one or two substituents selected from halogen atoms and methyl groups, a (C2-C5)alkenyl group or a phenyl group which may carry one or two substituents selected from -Cl, -Br, -NO2, -CH3, -CF3 and - OCH3; and cat # is Na+, K+, NH4+, 1/2 Ca++, H3N+C2H5, H3N+CH2CH2OH, H2N+(C2H5)2,
H2N+(CH3)2, H3N+CH3, HN+(C2H5)3. NH2# o or NH+ (CH2CH2OH)3.
Especially preferred, owing to their biological properties, are those compounds in which
Z is -OH, -O-CO-NH2 or -O-CO-R6.
The compounds of the general formula I can be prepared from phenoxyphenols of the formula
or the corresponding phenolates, by many methods generally known in the art. Thus, compounds of the formula III can be reacted in a known manner with compounds of the formula
in which B is a halogen atom or a sulpho-ester group, for example 2-bromopropane, 2-bromo-1-chloropropane or 2-bromopropanol, optionally in the presence of an acidbinding agent, and then converted into further compounds of the formula I by conventional reactions, especially by esterification of the resulting propanols.
The following are preferred methods for preparing the compounds of the general formula
I.
1. Alcohols of the formula I (Z = OH) can be obtained, as described above, by the reaction of compounds of the formula III with haloalcohols of the formula IV, by hydrolysis of the corresponding haloalkyl compounds (Z = halogen) or by reduction of the corresponding carboxylic acid esters of the formula II preferably with metal hydrides, for example lithium aluminium hydride. When K2 iS a hydrogen atom, alcohols of the formula 1 can also be obtained by reacting a compound of the formula III or, preferably, an alkali metal salt thereof, with ethylene oxide.
2. Halocompounds of the formula I (Z = halogen) can be prepared by reacting the corresponding alcohols with halogenating agents, for example thionyl chloride.
3. Mercaptans of the formula I (Z = SH) are obtained, for example, from the corresponding halocompounds of the formula I (Z = halogen) by reaction with metal hydrogen sulphides, preferably alkali metal hydrogen sulphides or xanthates or by reaction with thiourea and subsequent alkaline cleavage of the resulting isothiouronium salts.
4. Esters are prepared, for example, by the reaction of alcohols of the formula I (Z =
OH) in the presence of acid-binding agents (bases), with the appropriate acid halides, preferably acid chlorides, or acid anhydrides, preferably in inert organic solvents, or by direct esterification in the presence of acid catalysts and solvents which form azeotropes with water or in the presence of water-binding agents. As acid halides, preferably chlorides, there may be used those of monobasic acids, for example alkane carboxylic acids, benzoic acids, and benzenesulphonic acids, or those of polybasic acids such as carbonic acid, sulphuric acid, dicarboxylic acids, in which then the other acid group or groups are, for example, esterified or amidated, for example, by ester groups OR6 or amide groups
(Carbonate esters can be obtained by reacting compounds of the formula I (E = ( OH) with appropriate carbamic acid halides in the presence of acid-binding agents or by reaction with isocyanates of the formula R4NCO.
5. Amines of the formula I (Z = NR4Rs) are obtained by reaction of the corresponding halides, preferably chlorides, of the formula I (Z = halogen, preferably chlorine) with amines HNR4Rn in known manner.
The starting compounds of the formula III can be prepared by methods in themselves known, for example, in a manner analogous to the processes described in German
Offenlegungsschriften 1,668.896 and 2,433.067.
The compounds of the formula I have a wide spectrum of action against weed grasses, but are well tolerated by dicotyledonous crop plants and by various types of cereals, and can therefore be used for selectively combating weed grasses in crop plants.
The present invention therefore also provides a method for selectively combating weed grasses in an area of crop plants, which comprises applying to said area a herbicidal composition as described above.
The compositions of the present invention generally contain from 2 to 95% by weight of the active substance of the formula 1. They may be used in the form of wettable powders, emulsifiable concentrates, sprayable solutions, dusting preparations or granulates.
Wettable powders are preparations capable of being dispersed uniformly in water, which contain, in addition to the active substance and a diluent or inert substance, wetting agents, for example, polyoxethylated alkyl-phenols, polyoxethylated oleyl- or stearyl-amines, alkylsulphonates or alkylphenylsulphonates and dispersing agents, for example, sodium lignum sulphonate, sodium 2,2'-dinaphthylmethane-6,6'- disulphonate, sodium dinaphthylmethane disulphonate or sodium oleylmethyl-taurinate.
Emulsifiable concentrates are obtained by dissolving the active substance in an organic solvent, for example, butanol, cyclohexanone, dimethylformamide, xylene or a high boiling aromatic compound and adding of a non-ionic wetting agent, for example, a polyoxethylated alkylphenol or a polyoxethylated oleyl- or stearyl-amine.
Dusting preparations are obtained by grinding the active substance with finely divided solid substances, for example, talcum, natural clays, such as kaolin, bentonite, pyrophyllite or diatomaceous earths.
Sprayable solutions, which are often marketed in spraying cans, contain the active substance dissolved in an organic solvent, as well as, for example, a mixture of fluorochlorohydrocarbons as a propellant.
Granulates can be prepared either by spraying the active substance onto an absorptive granulated inert material or by applying concentrates of the active substance by means of adhesives, for example, polyvinyl alcohol, sodium polyacrylate or mineral oils, onto the surface of carrier substances, such as sand, kaolinites, or of granulated inert material. Also, suitable active substances may be formulated in the manner usual for producing fertiliser granules, if desired in admixture with fertilisers.
In the herbicidal compositions, the concentrations of the active substances in the ordinary commercial formulations may vary. In wettable powders the concentration of active substance varies, for example, between about 10% and 95%, the remainder consisting of the formulation additives mentioned above. In the case of emulsifiable concentrates the concentration of active substance is about 10% to 80%. Dusting formulations contain generally from 5 to 20% of active substance, and sprayable solutions contain about 2 to 20%. In the case of granulates, the content of active substance depends in part on whether the active compound is present in liquid or solid form and on what granulating auxiliaries, fillers, etc. are used.
For use, the ordinary commercial concentrates may be diluted in the usual manner, for example, with water in the case of wettable powders and emulsifiable concentrates. Dusting and granulated preparations and sprayable solutions are not diluted with further inert substances before use. The quantities required for use vary with the external conditions such as temperature and humidity. They may vary within wide limits, for example, between 0.1 and ]0.0 kg of an active substance per hectare, but preferably between 0.5 and 5 kg per hectare.
The active substances of the invention may be combined with other herbicides and soil insecticides.
The following Examples illustrate the invention.
FORMULATING EXAMPLES
Example A
An emulsifiable concentrate is obtained from
15 parts by weight of active substance
75 parts by weight of cyclohexanone as solvent and 10 parts by weight of oxethylated nonyl-phenyl (10 EO) as emulsifier.
Example B
A wettable powder easily dispersible in water is obtained by mixing together
25 parts by weight of active substance
64 parts by weight of kaolin-containing quartz as
inert substance
10 parts by weight of potassium lignin sulphonate and 1 part by weight of sodium oleylmethyl-taurinate as
wetting and dispersing agent
and ground in a rod mill.
Example C
A dusting preparation is obtained by mixing together
10 parts by weight of active substance and 90 parts by weight of talcum as inert substance and pulverised in a hammer mill
Example D
A granulate consists, for example, of about
2-15 parts by weight of active substance
98-85 parts by weight of inert granulate materials
such, for example, as atapul
gite, pumice, and quartz sand.
PROCEDURAL EXAMPLES
Example 1 2-[4'-(2",4"-Dichlorophenoxy)phenoxy]-propanol
28.6 grams (0.75 mol) of lithium aluminium hydride are introduced into 2 litres of absolute ether. 354.3 grams (1 mol) of 2-[4'-(2",4"-dichlorophenoxy)-phenoxy]-propionic acid ethyl ester dissolved in 500 ml of absolute ether are added dropwise while stirring, in a manner such that the reaction mixture is maintained at the boil. After the addition, the mixture is further stirred for 1 hour at the boiling temperature. After the addition of one litre of water and one litre of sulphuric acid of 10% strength, the ether phase is separated and the aqueous phase is extracted by agitation twice with 300 ml of ether each time. The combined ether phases are washed neutral with water and dried. After removing the ether, the residue that remains behind is distilled in vacuo. By distillation there are obtained 303 grams (96.7% of theory) of 2-[4'-(2",4"-dichlorophenoxy)-phenoxy]-propanol of Bp.0.1: 181 C.
In an analogous manner there were prepared:
Example Compound of the formula I Bp ("C)
Example 8 2-[4'-(4"-Trifluoromethylphenoxy)-phenoxy]-1-chloro-propane
31.2 grams (0.1 mol) of the alcohol obtained in Example (4) are introduced into 150 ml of toluene together with 7.9 grams (0.1 mol) of pyridine, and the mixture is cooled to -50C.
To the mixture are added dropwise 13.1 grams (0.11 mol) of thionyl chloride in a manner such that the temperature does not exceed 10 C. After the addition, the mixture is further stirred for V2 an hour, and the temperature is slowly raised to 110 C, and maintained at that temperature for 2 hours. The mixture is cooled, about 150 ml of hydrochloric acid of 20% strength are added and the mixture is stirred for 1/2 an hour. The toluene phase is separated off and the aqueous phase is extracted by agitation twice with 100 ml of toluene each time.
The combined toluene extracts are washed neutral with water and dried. The toluene is distilled off and the residue that remains is distilled. By the distillation there are obtained 31.3 grams (94.6% of theory) of 2-[4'-(4"-trifluoromethylphenoxy)-phenoxy]-1-chloro- propane Bp1.2: 182 C., which solidifies after 4 days and has an Mp. of 38"-39"C.
In an analagous manner there were prepared:
Example No. Compound of the formula I Bp.("C)
Example 12
Benzoic acid 2-[4'-(4"-chlorophenoxy)-phenoxy]-prop-1-yl) ester
23 grams (0.083 mol) of the alcohol obtained in Example (2) are dissolved together with 9.3 grams (().()92 mol) of triethylamine in 50 ml of toluene, and is added dropwise in the course of 15 minutes to a prepared solution at room temperature of 11.7 grams (0.083 mol) of benzoyl chloride in 150 ml of toluene. After the addition, during which the solution heats up to about 4()"C, it is stirred for 2 hours. and washed twice with 200 ml of water each time to remove the triethylamine hydrochloride. The toluene phase is dried. and the toluene is distilled off. Drying the residue yields 31.4 grams (99% of theory) of benzoic acid- < 2-[4'-(4"-chlorophenoxy)-phenoxy]-prop-1-yl > ester, which becomes solid after 3 days and has a Bp. of 68.5 C.
With the use of the appropriate acid components there were prepared in an analogous manner:
Example Compound of the formula I nD/Mp. ( C)
No.
Example Compound of the formula I nD/Mp. ( C)
No.
Example Compound of the formula I nD/Mp. ( C)
No.
Example Compound of the formula I
No. nD/Mp. ( C)
Example 50 2,2-Dichloropropionic acid < 2-[4'-(2", 4"-dichlorophenoxy) -phenoxy-prop-1 -yl > ester
31.3 grams (0.1 mol) of the alcohol obtained in Example (1) are boiled under reflux for 6 hours with 21.5 grams (0.15 mol) of dichloropropionic acid, 50 ml of chloroform and 1 ml of concentrated sulphuric acid. The water of reaction formed is distilled off azeotropically.
The mixture is cooled and washed three times with 60 ml of water each time, neutralised with bicarbonate solution, washed with 100 ml of water, dried and distilled to dryness. The oily residue that remains behind is distilled in vacuo. By the distillation there are obtained 39.1 grams (91% of theory) of 2,2-diebloropropionic acid < 2-[4'-(2",4"-dichlorophenoxy) phenoxy]-prop-1-yl > ester Bp.oos: 204 to 206"C.; nD23: 1.5602.
In an analogous manner there were obtained
Example Compound of the formula I nD/Bp ("C)
Example 55 1 -Methylamznocarbonyloxy-2-[4' -(2"-chloro-4"-trifluoromethylphenoxy) -phenoxy]propane
15 grams (0.043 mol) of the alcohol obtained in Example (7) are maintained for 7 hours at 100"C. with 6.3 grams (0.11 mol) of methyl isocyanate and 1 ml of triethylamine in 150 ml of toluene. The mixture is cooled, washed with 100 ml of water, dried and the toluene is distilled off in vacuo. The residue that remains behind is dried at 100"C. in vacuo. By drying there are obtained 17.1 grams (98.5% of theory) of 1-methylaminocarbonyloxy-2-[4'-(2"chloro-4"-trifluoromethylphenoxy)-phenoxy]-propane Mp. 64 -65 C.
In an analogous manner there were obtained (see the Table):
Example Compound of the formula I nD/Mp. ( C)
No.
Example Compound of the formula I nD/Mp. ( C)
No.
Example Compound of the formula I
No. nD/Mp. ( C)
Example 74 1-Dimethylaminocarbonyloxy-2-[4'-(2",4"-dichlorophenoxy)-phenoxy]-propane
25 grams (0.08 mol) of the alcohol obtained in Example (1) are heated under reflux with 21.5 grams (0.2 mol) of dimethylcarbamic acid chloride and 20 grams (0.198 mol) of triethylamine in 150 ml of toluene, until no starting material can be detected in the thin layer chromatogram. The mixture is filtered off while hot, and after cooling washes with 150 ml of water and dried. The toluene is distilled off in vacuo. The residue remaining behind is purified by column chromatography over aluminium oxide neutral with ethyl acetate as eluting agent. By distilling off the ethyl acetate there are obtained 26.6 grams (86.4% of theory) of 1-dimethylaminocarbonyloxy-2-[4'-(2",4"-dichlorophenoxy)-phenoxy]-propane having an nD24; 1.5609
In an analogous manner were prepared:
Example No. Compound of the formula I
C H N
Calc. 59.5 5.3 3.7
Fnd. 59.4 5.2 3,4
Example 78 1-Ethoxycarbonyloxy-2-[4'-(2",4"-dichlorophenoxy)-phenoxy)-propane
31.3 grams (0.1 mol) of the alcohol obtained in Example (1) are heated at the boil with 15.9 gratis (0.105 mol) of ce-chlorocarbonic acid ethyl ester and 16.6 grams (0.12 mol) of potassium carbonate in 100 ml of acetone. A slight splitting off of carbon dioxide takes place. After 18 hours the salt constituent is filtered off and the acetone is distilled off. The residue is purified by column chromatography with aluminium oxide and ethyl acetate as eluting agent. The eluting agent is split off and the residue is dried in vacuo. After drying, 18.5 grams (48% of theory) of 1-ethoxycarbonyloxy-2-[4'-(2",4"-dichlorophenoxy)phenoxy]-propane having an nD24; 1.5516 is obtained.
Example 79.
Methanesulphonic acid < 2-[4' - (4"-trifluoromethylphenoxy) -phenoxy]-prop-1 -yl > ester.
25 grams (0.08 mol) of the alcohol obtained in Example (4) are dissolved with 10.1 grams (0.1 mol) of triethylamine in 50 ml of toluene, and the solution is introduced dropwise in the course of 10 minutes into a solution of 9.2 grams (0.08) of methane sulphonyl chloride in 140 ml of toluene. After the addition, the mixture is further stirred for 2 hours and washed three times with 150 ml of water each time. Drying is carried out, and the toluene is distilled off in vacuo. Drying in vacuo of the residue remaining behind yields 29 grams (92.7% of theory) of methane sulphonic acid < 2-[4'-(4"trifluoromethylphenoxy)-phenoxy]-prop-1- yl > ester.
Analysis:
Calculated. C 52.3%. H 4.4%; S 8.2%
Found: C52.0%; H 4.3%; S 8.0%
In an analogous manner were prepared:
Example Compound of the formula I nD/Mp. ( C)
No.
Example 84.
1-N-Piperidino-2-[4'-(2",4"-dichlorophenoxy)-phenoxy]-propane.
27.5 grams (0.083 mol) of the chloride obtained in Example (10) are maintained at 140 C. in an autoclave with 150 ml of piperidine for 10 hours. After cooling, the product is taken up in 400 ml of methylene chloride and washed neutral with water. Methylene chloride is distilled off and the residue remaining behind is dried in vacuo. After the drying, 28.5 grams (90.4% of theory) of 1-N-piperidono-2-[4'-(2"-4"-dichlorophenoxy)-phenoxy]-propane, are obtained: nD22: 1.5688.
In an analogous manner were prepared.
Example Compound of the formula I nD
No.
Example 90: 1-Aminocarbonyloxy-2-[4'-(4"-trifluoromethylphenoxy)-phenoxy]-propane.
31.2 grams (0.1 mol) of the alcohol obtained in Example (4) were introduced with 13 grams (0.2 mol) of sodium cyanate into 200 ml of methylene chloride, and 24 grams of trifluoroacetic acid were added dropwise, while stirring, in the course of one hour. After the addition the mixture is heated at the boil (about 2 days) until no starting material is detected by thin layer chromatography. The mixture is cooled and stirred into 400 ml of water, the organic phase is separated and washed neutral with water. The methylene chloride is distilled off, and the residue remaining behind is recrystallised from ethanol/water. After recrystallisation there are obtained 27.2 grams (80.4% of theory) of 1-aminocarbonyloxy-2-[4'-(4"-trifluoromethylphenoxy)-phenoxy]-propane melting at 80 82 C.
In an analogous manner are prepared:
Example
Example 95:
Sodium 2-[4' - (4"-trifluoromethylphenoxy) -phenoxy]-propyl sulphate.
13.4 grams (0.115 mol) of chlorosulphonic acid are cautiously mixed with about 15 ml of diethyl ether, the mixture is cooled to -10 C. and 31.2 grams (0 1 mol) of 2-[4'-(4" trifluoromethyl-phenoxy)-phenoxy]-propanol-(1) are added dropwise. After the addition, the temperature is maintained for 2 hours and then the mixture is warmed up to room temperature. The ether is removed in vacuo, and to the free acid so obtained is added dropwise a solution of 9 grams (0.225 mol) of sodium hydroxide in 50 ml of water.
Immediately on the addition the salt precipitates out, it is filtered off with suction, washed well with water and then dried. 36.6 grams (95.7% of theory) of sodium 2-[4'-(4"trifluoromethylphenoxy)-phenoxy]-propyl sulphate melting at 235.50"C (with decomposition), are obtained.
In an analogous manner the following compounds can be prepared: Example
Mp ( C) 226-7 (decomp.) 206-209(decomp)
136-137 (d)
127-128 (d)
215 (d.)
In a manner analogous to that in Example 12 the following further compounds were prepared;
Example nD or Bp ( C)
The following further compounds can be prepared by the process described as under
Example
as under
Example
as under
Example
as under
Example
as under
Example
as under
Example
as under
Example
as under
Example
as under
Example
as under
Example
as under
Example
as under
Example
as under
Example
as under
Example
BIOLOGICAL EXAMPLES
Example I:
The seeds of grasses were sown in pots and the preparations of the invention formulated as scatterable powders were sprinkled at various dosages onto the surface pf the soil. The pots were then placed in a greenhouse for 4 weeks. The result of the treatment (as also in the case of the following Examples) was assessed by the method of evaluation according to tbe system of Bolle (Nachrichtenblatt des Deutschen Pflanzenschutzdienstes 16, 1964, 92 - 94):
Value Percentage degree of damage number Weeds Crop plants
1 100 0
2 97.5 to < 100 > 0 to 2.5
3 95 to < 97.5 > 2.5 to 5
4 90 to < 95 > 5 to 10
5 85 to < 90 > 10 to 15
6 75 to < 85 > 15 to 25
7 65 to < 75 > 25 to 35
8 32.5 to < 65 > 35 to 37.5
9 0 to < 32.5 > 67.5 60 100
The procedure was the same with the herbicidal agents used for comparison, fluorodifen (4-nitrophenyl-(2'nitro-4'-trifluoromethylphenyl) ether) and mecoprop (2-(4'-chloro-2'methylphenoxy)-propionic acid). The results collated in Table I show that the claimed compounds are on the average more active against grasses than the two herbicides for comparison. A similar action against grasses is shown also by the claimed compounds according to Examples 2, 9, 10, 12, 13, 14, 15, 21, 26, 27, 28, 36, 37, 38, 39, 40, 41, 57, 59, 60, 61, 63, 68, 69, 71, 74 and 80.
TABLE I
Example Dosage Type of plants
No. (kg/ha A.S.) AL SA LO EC
1 2.5 2 1 1 2
0.6 3 2 1 2
4 2.5 1 1 1 1
0.6 1 1 1 1
8 2.5 1 1 2 1
0.6 2 2 2 2 22 2.5 3 1 1 1
0.6 4 2 2 2 30 2.5 1 1 1 1
0.6 3 2 1 1 29 2.5 2 1 1 1
0.6 3 1 1 1 24 2.5 4 2 2 2
0.6 5 4 3 2 62 2.5 4 3 1 3
0.6 4 5 4 5 70 2.5 1 1 1 1
0.6 2 1 1 1 79 2.5 2 2 1 1
0.6 5 3 3 3
Fluoro- 2.5 7 1 1 4 difen 0.6 8 5 8 8
Mecoprop 2.5 4 3 5 3
0.6 7 6 8 7
AL = Alopecurus myosuroides,
SA = Setaria lutescens,
LO = Lolium multiflorum,
EC = Echinochloa crus-galli.
Example ll: The seeds of grasses were sown in pots and grown in a greenhouse. 3 weeks after sowing the preparations of the invention formulated as scatterable powders were sprinkled at different dosages on the plants and the effect of the preparations were evaluated after a period of 4 weeks in the greenhouse. Also in this case fluorodifen and mecoprop served as herbicidal agents for comparison. The claimed compounds in this method of application did indeed have a somewhat weaker action than in the pre-emergence method described in
Example I, but had a better action against grasses than the two agents for comparison (Table II). A similar action against grasses was exhibited by the claimed compounds according to Examples 2, 10, 24, 36, 37, 39 and 41.
TABLE II Evaluation numbers against weeds in post-emergence.
Example Dosage Type of plants
No. (kg/ha A.S.) AL SA LO EC
1 2.5 5 1 1 1 0.6 8 2 1 1
4 2.5 1 1 1 1
0.6 2 1 2 1
8 2.5 1 1 2 1
0.6 2 2 2 2 22 2.5 8 3 2 1
0.6 9 3 5 1 30 2.5 3 2 2 1
0.6 9 4 3 1 29 2.5 2 1 1 1
0.6 7 2 2 2 70 2.5 4 1 1 1
0.6 6 2 6 1
Fluoro- 2.5 8 2 6 4 difen 0.6 8 3 8 6
Mecoprop 2.5 8 7 8 8
0.6 9 8 9 9
Example lll: The seeds for a large number of crop plants were inserted in pots. Some of the pots were placed in a greenhouse for 2 to 3 weeks for germination and sprouting, and treated with the substances of the invention after the plants had developed 2 to 3 true leaves. The other pots were sprinkled immediately after being sown in the same manner as is given in Example II.
The result was ascertained 4 to 41/2 weeks after the treatment, and is given in Table III. In particular, the results show that almost all dicotyledonous crop plants at the highest dosage (2.5 kg per hectare) tolerate very well the preparations of the invention both in pre-emergence and post-emergence. As the effective dosage is about 0.6 kg per hectare, the active substances of the invention have a good selectivity in these crops.
TABLE III
The effect in pre- and post-emergence on crop plants, dosages 2.5 and 0.6 kg/ha A.S.
Example 1 2 2 4 4 preem. preem. postem. preem. postem.
2.5 0.6 2.5 0.6 2.5 0.6 2.5 0.6 2.5 0.6
Barley 2 1 - - 1 1 - - 1 1
Wheat 2 1 - - 3 1 - - 4 1
Beetroot 1 1 3 2 2 1 3 1 2 1
Spinach 1 1 3 1 1 1 2 1 1 1
Sunflower 1 1 1 1 1 1 1 1 1 1
Lettuce 3 1 1 1 1 1 3 1 2 1
Rape 1 1 2 1 1 1 2 1 2 1
White cabbage 1 1 3 1 2 1 2 1 3 1
Cauliflower 1 1 2 1 1 1 2 1 1 1
Cucumber 1 1 1 1 5 1 3 1 5 1
Soya 1 1 1 1 1 1 3 1 2 1
Lucerne 1 1 2 1 3 1 1 1 2 1
Bush bean 1 1 3 1 3 1 3 1 1 1
Pea 1 1 2 1 1 1 2 1 1 1
Example IV
Seeds of maize and rice and of a few weed grasses that occur in these crops were sown in pots and allowed to germinate in a greenhouse for 3 weeks. The preparations formulated in accordance with the invention as scattering powders and the agents for comparison were then sprinkled on the plants in various dosages, and after 4 weeks the effect of the preparations was ascertained.
As agents for comparison the following compounds were used:
A = 2- 4'-(2",4"-dichlorophenoxy)-phenoxy-propionic acid methyl ester (DT-OS 2223 894)
B = 2-4'-(4"-chlorophenoxy)-phenoxy-propionic acid isobutyl ester (DT-OS 22 23 894)
C = 2-[4'-(4"-trifluoromethylphenoxy)-phenoxy]-propionic acid methyl ester (DT-OS 24 33 067)
The claimed compounds showed, as compared with the herbicides used for comparison, a distinctly better tolerability by maize and/or rice. At the dosages which did not, or only very slightly, damage the crop plants, they were outstandingly effective against the weed grasses tested. On the other hand, the compounds for comparison were not selective in maize and rice.
TABLE IV
Evaluation numbers in post-emergence treatment.
Dose Crop plants Weed grases
Compound (kg/ha) Maize Rice EV SA
1 2.5 6 3 1 1
0.6 3 3 1 2
0.15 1 1 5 3
2 2.5 6 7 1 1
0.6 2 3 2 1
0.15 1 2 6 2
4 2.5 8 - 1 1
0.6 3 - 1 1
0.15 1 - 6 8 22 2.5 - 3 1
0.6 - 1 1
0.15 - 1 6
A 2.5 8 8 1 1
0.6 7 7 1 1
0.15 6 6 3 1
B 2.5 9 8 1 1
0.6 9 7 1 1
0.15 8 4 2 7
C 2.5 9 - 1 1
0.6 9 - 1 1
0.15 9 - 3 1
Example V
In a further test the compounds 8, 45, 90 and 111 were used together with the comparison compound C at post-emergence in a manner corresponding to that in Example I.
The results given in Table V show that the claimed compounds are superior to the agents for comparison with regard to tolerability by crop plants compound 8), and, coupled with the same good tolerability by the soya bean, they exhibit advantageous actions against the weed grasses tested.
TABLE V
Evaluation numbers in pre-emergence treatment.
Dose Crop plants Weed grasses
Compound (kg/ha) Barley Wheat Soya bean AL DI SA EC
8 2.5 1 1 1 2 - 1 1
0.6 1 1 1 4 - 2 4
0.15 1 1 1 7 - 5 5 45 2.5 - - 1 1 1 1 1
0.6 - - 1 2 1 1 2
0.15 - - 1 3 1 2 2 90 2.5 - - 1 1 1 1 1
0.6 - - 1 1 1 1 1
0.15 - - 1 3 1 1 2 111 2.5 - - 1 1 14 1 1
0.6 - - 1 1 1 1 1
0.15 - - 1 3 1 2 3
C 2.5 9 9 1 1 1 1 1 0.6 9 9 1 1 2 1 2
0.15 8 5 1 5 6 4 4
DI = Digitaria sanguinalis
Example VI
The efficiency of further compounds of the invention in pre-emergence is shown in the following Table.
TABLE VI
Evaluation results in pre-emergence treatment against important weed grasses.
Dose Dose Action against weed grasses
Compound (kg/ha) AL EC SA DI 2 2.5 1 1 1
0.6 2 1 3
3 2.5 2 1 1
0.6 3 1 3
7 2.5 1 1 1 1
0.6 3 1 2 1 13 2.5 2 1 1
0.6 3 1 3 14 2.5 2 1 1
0.6 4 2 3 15 2.5 2 1 2
0.6 3 3 3 12 2.5 1 1 -
0.6 3 3 16 2.5 - 1 1
0.6 - 1 3 17 2.5 - 1 1
0.6 - 4 4 20 2.5 - 1 1
0.6 - 3 3 21 2.5 3 2 3
0.6 3 3 4 24 2.5 - 2 2
0.6 - 3 4 26 2.5 - 2 3
0.6 - 3 4 27 2.5 - 3 -
0.6 - 4 - 28 2.5 - 2 3
0.6 - 3 3 - 31 2.5 3 3 2 -
0.6 4 3 3 - 32 2.5 2 1 1
0.6 4 4 4 33 2.5 1 1 1 1
0.6 4 1 2 1 34 2.5 - 1 -
0.6 - 3 - 35 2.5 - 3 -
0.6 - 4 - 36 2.5 1 1 1 1
0.6 3 1 1 1 37 2.5 - 1 1 1
0.6 - 1 1 2 38 2.5 - 1 1 1
0.6 - 2 1 1 39 2.5 1 1 1 1
0.6 2 2 2 1 41 2.5 2 1 1 -
0.6 3 1 1 42 2.5 1 1 1
0.6 2 2 1
TABLE VI cont'd
Compound Dose Action against weed grasses
(kg/ha) AL EC SA DI 44 2.5 2 1 11 @ 0.6 3 4 3 47 2.5 2 2 2
0.6 4 6 4 46 2.5 1 1 1
0.6 3 2 - - 45 2.5 1 1 1 1
0.6 2 2 1 1 51 2.5 3 3 2
0.6 4 4 4 53 2.5 1 1 1
0.6 1 2 1 55 2.5 - 3 -
0.6 - 5 - 57 2.5 - 1 3
0.6 - 2 4 60 2.5 - 2 2
0.6 - 3 4 61 2.5 - 4 1
0.6 - 5 2 62 2.5 4 3 3
0.6 4 5 5 63 2.5 - 2 2
0.6 - 3 4 68 2.5 - 3 2
0.6 - 4 3 69 2.5 - 1 1 -
0.6 - 2 2 - 71 2.5 1 1 1 -
0.6 4 1 2 74 2.5 - 2 2
0.6 - 3 3 - 77 2.5 - 2 1 -
0.6 - 3 3 @ 78 2.5 2 2 2 -
0.6 4 4 4 - 79 2.5 - 1 2 -
0.6 - 3 3 @ 80 2.5 - 2 1 -
0.6 - 2 4 - 81 2.5 - 1 1 @
0.6 - 2 6 90 2.5 1 1 1 1
0.6 1 1 1 1 111 2.5 1 1 1 1
0.6 1 1 1 1 112 2.5 1 1 1
0.6 2 1 2 - 115 2.5 1 1 1 -
0.6 2 2 1 - 113 2.5 1 1 1
0.6 3 2 1 110 2.5 3 3 1
0.6 4 4 3 109 2.5 3 1 1
0.6 4 2 1 -
95 2.5 2 2 1 1
0.6 3 4 2 1
Claims (11)
- TABLE VI (cont...) Compound Dose Action against weed grasses (kg/ha) AL EC SA DI 100 2.5 1 1 4 0.6 3 2 5 107 2.5 2 1 1 0.6 3 2 2 108 2.5 1 1 1 0.6 3 2 2 103 2.5 2 1 1 0.6 3 2 2 104 2.5 1 2 2 0.6 3 2 3 105 2.5 3 3 2 0.6 4 4 3 106 2.5 4 3 2 0.6 4 4 3 - WHAT WE CLAIM IS 1. A herbicidal composition comprising a carrier and, as active substance, a compound of the general formulain which each R is a halogen atom or a CF3, CH3 or C2H5 group; each R1 is a halogen atom or a CF3 group; R2 is a hydrogen atom or a (C1-C4)-alkyl group; n is 1 or 2; n1 is 0, 1 or 2; each of X and Y is O or S; and Z is -OH, -SH, -F, -Cl, -Br, -I or a group of the formula-O-CO-R6, -O-SO2-R6 or -O-SO3-R7 in which R3 is a (C1-C12)alkyl, (C3-C8)cycloalkyl, (C2-C10) alkenyl, (C5-C6) cycloalkenyl, (C3-C8)alkynyl, phenyl or benzyl group which may carry one or more substituents selected from halogen atoms and CF3, NO2, CN, (C,-C4)alkyl, (Cl-C4) alkylthio, (C,-C4)alkoxy, -OH, -NH2, (C1 -C6)alkylamino, di-(C1 -C6)alkylamino and C 1-C6)alkoxycarbonyl groups; R4 is a hydrogen atom or a (C1-C4)alkyl, (C2-C4)alkenyl, cyclopentyl, cyclohexyl, (C1-C4)alkoxy or phenyl group which may carry one or more substituents selected from halogen atoms and CF3, NO2, CN, (C,-C4)alkyl, (C-C4)alkylthio, (Cl-C4)alkoxy, OH, NH2, (C1-C6)alkylamino, di-(C1-C6)alkylamino and (C1-C6)alkoxycarbonyl groups; R5 is a hydrogen atom or a (C1-C4)alkyl group, or R4 and R5 together with the nitrogen atom to which they are attached form a saturated heterocycle having from 2 to 5 carbon atoms and which may contain an oxygen or sulphur atom or a group of the formula NR5; R6 has the meanings given for R3 or is a phenoxy- (C1-C4)-alkyl group the phenyl group of which may carry from 1 to 3 substituents selected from F, Cl and Br atoms and methyl groups; R7 is a hydrogen atom or a (C1-C4)alkyl group or cat and cat is the cation of an inorganic or organic base, or Z is a group of the formula
- 2. A herbicidal composition according to claim 1 in which (R)n is one to two chlorine and/or bromine atoms and/or CF3 groups, n1 is O; R2 is CH3; X, Y are both oxygen, Z is -OH, -Cl, -Br; the group of the formula II, in which (R)n and nl have the meanings specified above; or a group of the formulain which R4 is a hydrogen atom or a (C1-C4)alkyl, phenyl, halophenyl, methylphenyl or trifluoromethylphenyl group and R5 has the meaning specified in claim 1; -O-SO2-R3, in which R3 is a CH3, phenyl, methylphenyl or chlorophenyl group; -O-SO3-R7, in which R7 is a (C1-C4)alkyl group or cat;in which R6 is a (C1-C9)alkyl or (C1-C4)chloroalkyl group, a phenoxy-(C1-C3)alkyl group the phenyl group of which may carry one or two substituents selected from F,Cl and Br atoms and methyl groups, a (C2-C5) alkenyl group or a phenyl group which may carry one or two substituents selected from -Cl, -Br, -NO2, -CR3, -CF3 and -OCH3; and cat03 is Na+, K+, NH4+, 1/2 Ca++, H2N+ (C2H5)2, H3N CH2CH20H, R3N+CH3 or H3N+C2H5,
- 3. A herbicidal composition according to claim 2, in which (R)n is 4-chloro, 2,4-dichloro, 2-chloro-4-bromo, 4-trifluoromethyl or 2-chloro-4-trifluoromethyl, n is zero, R2 is CH3, X and Y are both oxygen, and Z has the meanings specified in claim 2.
- 4. A herbicidal composition according to claim 1, in which each of QR)n, n1, R2, X, Y, Z, R4, R5, R6 and R7 has the meaning specified in claim 2 and cat 3 is H2N+(CH3)2, HN+(C2H5)3, HN+(CH2CH2OH)3 or
- 5. A herbicidal composition according to claim 1, in which (R)n has the meaning specified in claim 3, each of nl, R2, X, Y, Z, R4, R5, R6 and R7 has the meaning specified in claim 2 and cat has the meaning specified in claim 4.
- 6. A herbicidal composition according to claim 2, in which Z is -OH, -Cl, -Br; the group of the formula II in which (R)n and n1 have the meanings specified in claim 3; or a group of the formula(R)n, n1, R2, X, Y, R4, R5 and R6 have the meanings specified in claimed 3, and cat# is Na+, K+ or NH4+.
- 7. A herbicidal composition according to claim 1, in which each of Z, (R)n n1, R2, X, Y, R4, R5 and R6 has the meaning specified in claim 4 and cat+ is
- 8. A herbicidal composition according to claim 1, in which each of (R)n, R2, X, Y, Z, R4, R5, R6, and catO has the meaning specified in any one of claims 2 to 7 and (R,)n, is a chlorine or bromine atom in the 2-position to Y.
- 9. A herbicidal composition according to claim 1 substantially as hereinbefore described.
- 10. A method for selectively combating weed grasses in an area of crop plants, which comprises applying to said area a herbicidal composition according to any one of claims 1 to 5.
- 11. A compound as specified in claim 1 with the proviso that, when Z is OH or -OCOR6 in which R6 is a (C,-C3)alkyl group and X and Y are both oxygen, then (R)n cannot be a halogen atom in the 4-position.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19762611695 DE2611695A1 (en) | 1976-03-19 | 1976-03-19 | HERBICIDAL AGENTS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1577181A true GB1577181A (en) | 1980-10-22 |
Family
ID=5972943
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB11375/77A Expired GB1577181A (en) | 1976-03-19 | 1977-03-17 | Substituted alkyl ethers of phenoxyphenols their preparation and herbicidal compositions containing them |
Country Status (25)
| Country | Link |
|---|---|
| JP (1) | JPS52114020A (en) |
| AR (1) | AR224331A1 (en) |
| AT (1) | AT354800B (en) |
| AU (1) | AU509124B2 (en) |
| BE (1) | BE852701A (en) |
| BG (1) | BG27714A3 (en) |
| BR (1) | BR7701656A (en) |
| CA (1) | CA1117122A (en) |
| CH (1) | CH627916A5 (en) |
| DD (1) | DD128799A5 (en) |
| DE (1) | DE2611695A1 (en) |
| EG (1) | EG12622A (en) |
| FR (1) | FR2360253A1 (en) |
| GB (1) | GB1577181A (en) |
| GR (1) | GR71448B (en) |
| HU (1) | HU178576B (en) |
| IE (1) | IE44653B1 (en) |
| IL (1) | IL51685A (en) |
| IT (1) | IT1125764B (en) |
| NL (1) | NL7702985A (en) |
| OA (1) | OA05607A (en) |
| PL (1) | PL104153B1 (en) |
| PT (1) | PT66324B (en) |
| SU (1) | SU882403A3 (en) |
| ZA (1) | ZA771606B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0128648A1 (en) * | 1983-04-25 | 1984-12-19 | Sumitomo Chemical Company, Limited | Nitrogen-containing heterocyclic compounds, and their production and use |
| US4625048A (en) * | 1982-08-13 | 1986-11-25 | Hoffmann-La Roche Inc. | Carbamic acid esters |
| US5012017A (en) * | 1988-08-18 | 1991-04-30 | Dowelanco | Phenoxyphenoxypropionates, intermediates thereof and methods of preparation |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1512189A (en) * | 1975-10-29 | 1978-05-24 | Ishihara Mining & Chemical Co | Herbicidal composition and method of use thereof |
| DE2748658A1 (en) * | 1977-10-29 | 1979-05-10 | Hoechst Ag | HERBICIDES BETA-NAPHTHYL-PHENYL ETHER |
| DE2961917D1 (en) | 1978-01-18 | 1982-03-11 | Ciba Geigy Ag | Herbicidal active unsaturated esters of 4- (3',5'-dihalogenpyridyl-(2')-oxy)-alpha-phenoxy propionic acids, process for their preparation, herbicidal compositions containing them and their use |
| EP0003877B1 (en) * | 1978-02-15 | 1988-02-03 | Imperial Chemical Industries Plc | Herbicidal derivatives of 2-(4(2-pyridyloxy)phenoxy)propane, processes for preparing them, and herbicidal compositions containing them |
| PH18417A (en) * | 1981-06-25 | 1985-06-24 | Nihon Tokushu Noyaku Seizo Kk | Substituted phenoxypropionates and herbicidal compositions |
| EP0072475B1 (en) * | 1981-08-17 | 1986-08-20 | F. HOFFMANN-LA ROCHE & CO. Aktiengesellschaft | Carbamic esters, preparation thereof, pesticidal compositions on the basis of these compounds and their use in combating pests |
| US4550192A (en) * | 1983-09-01 | 1985-10-29 | The Dow Chemical Company | Fluorophenoxyphenoxypropionates and derivatives thereof |
| DE3823521A1 (en) * | 1988-07-12 | 1990-02-15 | Basf Ag | CYCLOPROPANCARBOXAMIDES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE FOR CONTROLLING Pests |
| YU52303A (en) * | 2001-01-31 | 2006-05-25 | Warner-Lambert Company | Method for carbamoylating alcohols |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2415867A1 (en) * | 1974-04-02 | 1975-10-09 | Merck Patent Gmbh | PHENOXY ALCANOL DERIVATIVES AND THE PROCESS FOR THEIR PRODUCTION |
| FR2285859A1 (en) * | 1974-09-30 | 1976-04-23 | Lafon Labor | PHENYLSULFINYL-AMIDINES AND DERIVATIVES |
-
1976
- 1976-03-19 DE DE19762611695 patent/DE2611695A1/en not_active Withdrawn
-
1977
- 1977-03-15 BG BG7735671A patent/BG27714A3/en unknown
- 1977-03-16 EG EG161/77A patent/EG12622A/en active
- 1977-03-16 CH CH328077A patent/CH627916A5/en not_active IP Right Cessation
- 1977-03-17 IL IL51685A patent/IL51685A/en unknown
- 1977-03-17 BR BR7701656A patent/BR7701656A/en unknown
- 1977-03-17 GR GR53011A patent/GR71448B/el unknown
- 1977-03-17 GB GB11375/77A patent/GB1577181A/en not_active Expired
- 1977-03-17 IT IT7721376A patent/IT1125764B/en active
- 1977-03-17 DD DD7700197912A patent/DD128799A5/en unknown
- 1977-03-17 ZA ZA00771606A patent/ZA771606B/en unknown
- 1977-03-17 AT AT181677A patent/AT354800B/en not_active IP Right Cessation
- 1977-03-17 AR AR266886A patent/AR224331A1/en active
- 1977-03-18 NL NL7702985A patent/NL7702985A/en not_active Application Discontinuation
- 1977-03-18 PL PL1977196753A patent/PL104153B1/en not_active IP Right Cessation
- 1977-03-18 HU HU77HO1969A patent/HU178576B/en unknown
- 1977-03-18 AU AU23417/77A patent/AU509124B2/en not_active Expired
- 1977-03-18 IE IE583/77A patent/IE44653B1/en unknown
- 1977-03-18 JP JP2939477A patent/JPS52114020A/en active Pending
- 1977-03-18 SU SU772462914A patent/SU882403A3/en active
- 1977-03-18 CA CA000274314A patent/CA1117122A/en not_active Expired
- 1977-03-18 PT PT66324A patent/PT66324B/en unknown
- 1977-03-19 OA OA56109A patent/OA05607A/en unknown
- 1977-03-21 BE BE175972A patent/BE852701A/en not_active IP Right Cessation
- 1977-03-21 FR FR7708352A patent/FR2360253A1/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4625048A (en) * | 1982-08-13 | 1986-11-25 | Hoffmann-La Roche Inc. | Carbamic acid esters |
| EP0128648A1 (en) * | 1983-04-25 | 1984-12-19 | Sumitomo Chemical Company, Limited | Nitrogen-containing heterocyclic compounds, and their production and use |
| US5012017A (en) * | 1988-08-18 | 1991-04-30 | Dowelanco | Phenoxyphenoxypropionates, intermediates thereof and methods of preparation |
Also Published As
| Publication number | Publication date |
|---|---|
| OA05607A (en) | 1981-04-30 |
| HU178576B (en) | 1982-05-28 |
| EG12622A (en) | 1981-12-31 |
| IE44653L (en) | 1977-09-19 |
| AR224331A1 (en) | 1981-11-30 |
| ZA771606B (en) | 1978-01-25 |
| AU509124B2 (en) | 1980-04-24 |
| CA1117122A (en) | 1982-01-26 |
| AT354800B (en) | 1979-01-25 |
| IL51685A (en) | 1981-11-30 |
| IT1125764B (en) | 1986-05-14 |
| FR2360253A1 (en) | 1978-03-03 |
| BG27714A3 (en) | 1979-12-12 |
| CH627916A5 (en) | 1982-02-15 |
| NL7702985A (en) | 1977-09-21 |
| FR2360253B1 (en) | 1983-10-07 |
| PL104153B1 (en) | 1979-08-31 |
| BR7701656A (en) | 1978-01-03 |
| IL51685A0 (en) | 1977-05-31 |
| BE852701A (en) | 1977-09-21 |
| ATA181677A (en) | 1979-06-15 |
| SU882403A3 (en) | 1981-11-15 |
| PL196753A1 (en) | 1978-01-16 |
| PT66324A (en) | 1977-04-01 |
| IE44653B1 (en) | 1982-02-10 |
| GR71448B (en) | 1983-05-18 |
| PT66324B (en) | 1978-11-07 |
| DD128799A5 (en) | 1977-12-14 |
| AU2341777A (en) | 1978-09-21 |
| JPS52114020A (en) | 1977-09-24 |
| DE2611695A1 (en) | 1977-09-29 |
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| Date | Code | Title | Description |
|---|---|---|---|
| PS | Patent sealed [section 19, patents act 1949] | ||
| PCNP | Patent ceased through non-payment of renewal fee |