AU607993B2 – Glycol monoethers as intermediates in organic synthesis
– Google Patents
AU607993B2 – Glycol monoethers as intermediates in organic synthesis
– Google Patents
Glycol monoethers as intermediates in organic synthesis
Download PDF
Info
Publication number
AU607993B2
AU607993B2
AU15504/88A
AU1550488A
AU607993B2
AU 607993 B2
AU607993 B2
AU 607993B2
AU 15504/88 A
AU15504/88 A
AU 15504/88A
AU 1550488 A
AU1550488 A
AU 1550488A
AU 607993 B2
AU607993 B2
AU 607993B2
Authority
AU
Australia
Prior art keywords
formula
alkyl
dichlorophenyl
acid
phenyl
Prior art date
1983-05-19
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
AU15504/88A
Other versions
AU1550488A
(en
Inventor
Robert Nyfeler
Elmar Sturm
Helmut Zondler
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Novartis AG
Original Assignee
Ciba Geigy AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
1983-05-19
Filing date
1988-05-02
Publication date
1991-03-21
1988-05-02
Application filed by Ciba Geigy AG
filed
Critical
Ciba Geigy AG
1988-07-21
Publication of AU1550488A
publication
Critical
patent/AU1550488A/en
1991-03-21
Application granted
granted
Critical
1991-03-21
Publication of AU607993B2
publication
Critical
patent/AU607993B2/en
2004-05-18
Anticipated expiration
legal-status
Critical
Status
Ceased
legal-status
Critical
Current
Links
Espacenet
Global Dossier
Discuss
Classifications
C—CHEMISTRY; METALLURGY
C07—ORGANIC CHEMISTRY
C07D—HETEROCYCLIC COMPOUNDS
C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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
A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
A01N43/647—Triazoles; Hydrogenated triazoles
A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
C—CHEMISTRY; METALLURGY
C07—ORGANIC CHEMISTRY
C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
C—CHEMISTRY; METALLURGY
C07—ORGANIC CHEMISTRY
C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
C07C43/00—Ethers; Compounds having groups, groups or groups
C07C43/02—Ethers
C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
C07C43/14—Unsaturated ethers
C07C43/178—Unsaturated ethers containing hydroxy or O-metal groups
C07C43/1782—Unsaturated ethers containing hydroxy or O-metal groups containing six-membered aromatic rings
C—CHEMISTRY; METALLURGY
C07—ORGANIC CHEMISTRY
C07D—HETEROCYCLIC COMPOUNDS
C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
C—CHEMISTRY; METALLURGY
C07—ORGANIC CHEMISTRY
C07D—HETEROCYCLIC COMPOUNDS
C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
Abstract
Essentially, a process is described for the preparation of the 1-triazolylethyl ether derivatives, defined in claim 1, of the general formula I
Description
i. I- i- ii- i m ll- Iliii–iiY C I i i 607993 S F Ref: 52268 FORM COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952 COMPLETE SPECIFICATION
(ORIGINAL)
FOR OFFICE USE: Class Int Class Complete Specification Lodged: Accepted: Published: i I 4 rt~ Priority: Related Art: Name and Address of Applicant: Address for Service: Address for Service: 4 4 Ciba-Geigy AG Patent Department 4002 Basle
SWITZERLAND
Spruson Ferguson, Patent Attorneys Level 33 St Martins Tower, 31 Market Street Sydney, New South Nal°s, 2000, Australia Complete Specification for the invention entitled: Glycol Monoethers as Intermediates in Organic Synthesis The following statement is a full description of this invention, including the best method of performing it known to me/us 5845/3 .1 nl 11 GLYCOL MONOETHERS AND A PROCESS FOR THEIR PREPARATION The present invention relates to novel glycol monoethers valuable as intermediates in the synthesis of the microbicidal 1-triazolylethyl ether derivatives of Australian patent 572 145 and to a process for the preparation of said intermediates. The glycol monoethers of the present invention also possess biocidal properties, in particular insecticidal properties. The invention thus further relates to biocidal compositions and their use to control insects and to the use of the compounds of the invention as emulsifying agents.
In Australian patent 572 145 the present applicants disclose a process for the preparation of microbicidal 1-triazolylethyl ether derivatives of the formula A
OR
3 S0o° R1 C CH2 N (A’
R
2 in which
R
1 is C -C 12 -alkyl, C -C 6 -alkyl which is substituted by
C
1
-C
6 -alkoxy or C 3
-C
8 -cycloalkyl; C 3
-C
8 -cycloalkyl; phenyl which is unsubstituted or monosubstituted to trisubstituted by halogen,
C
1
-C
6 -halogenoalkyl, C 1 -C6-halogenoalkoxy, C -C6-alkoxy,
C
1
-C
6 -alkyl, phenoxy, halogenophenoxy, phenyl, benzyl, halogenobenzyl, nitro and/or cyano; or benzyl which is unsubstituted or monosubstituted to trisubstituted by halogen, C 1
-C
6 -halogenoalkyl, C 1 -C6-alkoxy,
C
1
-C
6 -alkyl, nitro and/or cyano;
R
2 is C 1
-C
12 -alkyl, C 1
-C
6 -alkyl which is substituted by
C
1
-C
6 -alkoxy or C 3
-C
8 -cycloalkyl; C 3
-C
8 -cycloalkyl; phenyl which is unsubstituted or monosubstituted to trisubstituted by halogen,
C
1 -C6-halogenoalkyl, C 1 -C6-halogenoalkoxy, C 1
-C
6 -alkoxy,
C
1
-C
6 alkyl, phenoxy, halogenophenoxy, phenyl, benzyl, halogenobenzyl, nitro and/or cyano; or benzyl which is unsubstituted or monosubstituted to trisubstituted by halogen, C 1
-C
6 -halogenoalkyl, Cl-C6-alkoxy,
C
1
-C
6 -alkyl, nitro and/or cyano; and
R
3 is C 1
-C
6 -alkyl which is unsubstituted or substituted by CI-C 3 alkoxy, or is C 3
-C
4 -alkenyl, benzyl or halogenobenzyl.
The term alkyl itself or as a constituent of another substituent, such as alkoxy, halogenoalkyl, halogenoalkoxy etc, is to be understood, depending on the number of carbon atoms indicated, as meaning, for example, the following linear or branched groups: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and the like, SD/606m 2 and isomers thereof, for example isopropyl, isobutyl, tert.-butyl, isopentyl and the like. Here and in the text which follows, the prefix halogeno in the designation of a substituent means that this substituent can be monohalogenated to perhalogenated. Halogen and halogeno represent fluorine, chlorine, bromine or iodine. Halogenoalkyl is therefore a monohalogenated to perhalogenated alkyl radical, for example CHC1 2
CH
2 F, CC1 3
CH
2 C1, CHF 2
CH
2
CH
2 Br, C 2 C1 5 CHBr 2 CHBrC1 and the like, or preferably CF 3 Examples of alkenyl are 1-propenyl, allyl, 1-butenyl, 2-butenyl and 3-butenyl. Examples of cycloalkyl, depending on the number of carbon atoms mentioned, are cyclopropyl.
cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like.
In accordance with a first aspect of the present invention there is .00 provided a compound of the formula I: o -o
OR
3 2 a R 1
-C-CH
2 0H (I o0 R2 S in which R1 is C 1
-C
6 -alkyl which is substituted by C 1 -C6-alkoxy or C 3
-C
6 -cycloalkyl; C 3
-C
8 -cycloalkyl; phenyl; 00 o phenyl which is mono-, di- or tri-substituted by halogen, C 1
-C
6 o0 halogeno-alkyl, C 1 -C -halogenoalkoxy, C 1 -C -alkoxy, C 1 -C -alkyl, 0 r, 11 6 1 6 1 6 Sn0 nitro and/or cyano; 0 2q(. phenyl which is substituted by phenoxy, halogenophenoxy, phenyl, oo halogenophenyl, benzyl or halogenobenzyl; benzyl; or o 0 benzyl which is mono-, di- or tri-substituted by halogen, C 1
-C
6 halogenoalkyl, C 1
-C
6 -halogenoalkoxy, C 1
-C
6 -alkoxy, C 1
-C
6 -alkyl, nitro and/or cyano; R2 is C 1
-C
12 -alkyl or a radical indicated under R 1 and R3 is Cl -C 6 -alkyl, C 1
-C
6 -alkyl which is substituted by Ci-C 3 -alkoxy, or is C 3
-C
4 -alkenyl, benzyl or halogenobenzyl.
Preferred compounds of formula I are those in which R 1 is phenyl which is rmonosubstituted to trisubstituted by halogen or phenyl which is monosubstituted by phenoxy or halogenophenoxy; R1 is C 1
-C
6 -alkyl or C 3
-C
7 -cycloalkyl; and
R
3 is C 1
-C
6 -alkyl, C 1
-C
g -alkyl which is substituted by C1-C 3 -alkoxy, C 3
-C
4 -alkenyl, benzyl or halogenobenzyl.
In accordance with a further aspect of the present invention there is provided a process for the production of a compound of the formula I SD/606m 3 comprising reacting an oxirane of formula II
R
1 -C
(II)
R2 at temperatures of -20° to +100C, in the presence of an acid catalyst or an acid condensation agent, with an alcohol of formula III:
R
3 -OH (III) in which R 1
R
2 and R 3 have their previous significance.
The following are examples of suitable acid catalysts or acid condensation agents: a) Proton acids, such as HC10 4
H
2
SO
4 HC1, HF, HBr, Si) H 3 P0 4 alkylsulfonic acids (CH 3
SO
3 H, C2H 5 SO3H, CF3SO3H etc), arylsulfonic acids (benzenesulfonic acid, p-bromobenzenesulfonic acid, p-toluenesulfonic acid and the like) or ion exchangers in the H form; HC1O 4
H
2
S
4 and ion exchangers are preferred; and r 04) 2 4 b) Lewis acids, such as BF BF 3 -etherate S [BF 3
-(C
2
H
5 2 0, BC1 3 AlCl 3 AlBr 3 SnCl 4 TiCl 4 Znl 2 ZnC12 etc; BF 3 and BF 3 -etherate are preferred.
-3 In general, 10 3 to 1 equivalent of catalyst or condensation agent is employed per equivalent of oxirane of formula II, preferably 0.1 to 1 o’ equivalent of catalyst or condensation agent.
The reaction of the oxirane of formula II with the alcohol of formula o^ o° III, can be carried out in the presence or absence of a customary organic solvent or solvent mixture which is inert towards the reaction. Examples of possible solvents are aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylenes or petroleum ether; halogenated hydrocarbons, such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride or tetrachloroethylene; ethers and ether-like compounds, such as dialkyl ethers (diethyl ether, diisopropyl ether, tert.-butyl. methyl ether and the like), anisole, dioxane or tetrahydrofuran; nitriles, such as acetonitrile, propionitrile and the like; N,N-dimethylformamide or N,N-dimethylacetamide; dialkyl sulfoxides, such as dimethvl sulfoxide; ketones, such as acetone, diethyl ketcne, methyl ethyl ketone and the like, and mixtures of such solvents with one another. Excess alcohol of the formula III is, however, particularly suitable as a solvent. The reaction temperatures are preferably between 0° and 40 0 C. The duration of the reaction is approx. 0.5 to 72 hours, mainly to 16 hours.
SD/606m 4 -L The reaction can, in principle, also be carried out without a catalyst or condensation agent, but it is then necessary to select drastic reaction conditions, in particular high temperatures, which results in numerous by-products and long reaction times and thus does not constitute an economically practicable method of preparation.
The ring-opening of an oxirane with an alkanol in accordance with the above reaction is known in principle from the literature. Thus, for example, the preparation of 2-phenyl-2-methoxyethan-l-ol in accordance with the following equation: 0 OCH3 2S04 I
CH-CH
2 CH30H H 4 CH-CH2OH is described in: W. Reeve and I. Christoffel, J. Amer. Chem. Soc. 72, 1480 (1950). The preparation of further glycol monoethers of the formula I in S which R 1 H, CH 3
CF
3
CH
3 CHBr or (CH 3 3
CCH
2
R
2 H or
CH
3 and R 3
CH
3 or C 2
H
5 from corresponding oxiranes is reported in: Epoxy Resins, Chemistry and Technology’, C.A. May, Y. Tanaka, Marcel Dekker (1973).
The glycol monoethers of the formula I are novel and constitute S intermediate products which have been specially developed for the preparation of the valuable agrochemically active compounds which are the o0° o subject of Australian Patent 572 145. By virtue of their structural nature, they can be converted easily into the compounds of AU-572 145. In addition, compounds of the formula I possess biocidal properties, in «3 particular insecticidal properties. They also possess emulsifying properties.
In accordance with another aspect of the present invention there are provided insecticidal compositions which comprise as an active ingredient at least one compound of formula I combined with carriers diluents and/or adjuvants customarily used in the art of formulation.
In accordance with a further aspect 6f the present invention there is provided a method of producing an emulsion which comprises adding at least one compound of the formula I to an emulsifiable mixture followed by subjecting said mixture to dispersion, agitation, or other operations customary in the art of emulsification.
The following are examples of typical representatives of the formula I: SD/606m 5 2-(2,4-dichlorophenyi )-2-methoxypentan-i -ci 2-(2,4-dichlorophenyi)-2-ethoxypentan-I-cl 2-(2,4-dichiorophenyl)-2-isopropcxypentan-i-oI 2-(2 ,4-di chlcrophenyl )-2-(2-methoxyethoxy)-pentan-i -ci 2-(2,4-dichlorophenyD)-2-(2-fiuorobenzyloxy)-pentan-1-oI 2-(4-fluorophenyl )-2-butoxyprcpan-l-oI 2-(4-fi uorophenyl )-2-butoxybutan-i -oI 2-(4-fiuorophenyl )-2-(buten-2-yloxy)-butan-i -cI 2-(4-chlorophenyi )-2-benzyloxypentan-l-ol 2-(2,4-dichlorophenyl)-2-methoxypropan-1-ol 2-(2,4-dichlorcphenyl)–2-propoxypropan-i-ol 2-(2,4–dichlorophenyl )-2-butoxyprcpan-i-ol 2-(2,4-dichloroph~enyl)-2-allylxyprpan–cl 2-(2,4-dichlorophenyl)-2-methallyloxypropan-i-oI 2-(2,4-dichlorophenyl)-2-(4-chlorobenzyloxy)-propan–ol 2-(2,4-dichlorophenyl)-2-methoxybutan-1-oI 2-(2,4-dichlorophenyl)-2-prcpoxybutan-i-ol 2-(2,4-dichlorophenyl)-2-aiiyloxybutan-i-cI 2-(2,4-dichlorophenyi)-2-propoxypentan-i-ol 2-(2,4-dichlorophenyl)-2-butoxypentan-i-ol 2-(2,4-dichicrophenyl)-2-allyloxypentan-1-oI 2-(2,4-dichlorophenyl)-2-(2-buten-2-yloxy)-pentan-1-oI 2-(2,4-dichlcrophenyi )-2-benzyicxypentan-1-ol J 2-(2,4-dichlorophenyl)-2-methoxy-3-methylbutan-i-ol 2-(2,4-.dichicrophenyl )-2-methoxyheptan-1-oI 2-(2,4-dichlorophenyl)-2-cyclohexyl-2-methoxyethan-i-cl 2-(4–bromc-2-chicrophenyl)–2-methoxypropan-i-oI 2-(4-bromo-2-chicrophenyi )-2-niethoxybutan-1-oI 2-(2-chloro-4-fluorcphenyl )-2-methoxypropan-i-ol 2-(2-chicro-4-fiucrophenyl )-2-methoxybutan-1 -ci 2-(4-(4–chlorophenoxy)-phenyi )-2-methcxybutan-1-cl 2-(4-(4-chicrcphencxy)-phenyl )-2-methcxyprcpan-i-cI 2-(2-ch icrc-4-fi ucrophenyl )-2-ai iyicxypentan-1 -ci 2-(4-brcmc-2-chicrcphenyi )-2-butcxypentan-i-cI 2-(4-(4-flucrcphencxy)-phenyi )-2-methcxybutan-1-cl 2-(4-(2,4-dichicrcphencxy)-phenyi )-2-methcxybutan-i-ci Fcr insecticidal purpcses active ingredients cf the formula I are customarily used in the form cf compositions and can be applied tcgether with further active ingredients, simultaneously cr successively, to the SD! 606m- 6 area or plant to be treated. These further active ingredients can be either fertilisers and trace element donors or other preparations which affect plant growth. They can, however, also be selective herbicides, insecticides, fungicides, bactericides, nematocides, molluscicides or mixtures of several of these preparations, together, if appropriate, with further carriers, surfactants or other application-promoting additives which are customary in the technology of formulation.
Suitable carriers and additives can be solid or liquid and correspond to the substances which are useful in the technology of formulation, for example natural or regenerated mineral substances, solvents, dispersing agents, wetting agents, tackifiers, thickeners, binders or fertilisers.
The compounds of the formula I are used either in an unmodified form or preferably together with the auxiliaries customarily employed in formulation practice, and are therefore processed, in a known manner, to give, for example, emulsion concentrates, brushable pastes, directly I o o» sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts or granules, and also encapsulations in, for example, polymeric substances. The applications processes, such as spraying, atomising, dusting, scattering, brushing or pouring, and likewise the type of composition, are selected to suit the object to be achieved and S the given conditions.
The formulations, i.e. the compositions, preparations or combinations 0. 0 containing the active ingredient of the formula I and optionally a solid or liquid additive, are produced in a known manner, for example by intimately mixing and/or grinding the active ingredients with extenders, for example S’ solvents, solid carriers and optionally surface-active compounds (surfactants). Those skilled in the art are familiar with these measures.
The following are suitable solvents: aromatic hydrocarbons, preferably the fractions from C 8 to C 12 for example mixed xylenes or substituted naphthalenes, phthalic acid esters, such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons, such as cyclohexane or paraffins, alcohols and glycols and also ethers and esters thereof, such as ethanol, ethylene glycol and ethylene glycol monomethyl or monoethyl ether, ketones, such as cyclohexanone, strongly polar solvents, such as N-methyl-2pyrrolidone, dimethyl sulfoxide or dimethyl formamide, and also optionally epoxidised vegetable oils, such as epoxidised coconut oil or soybean oil; or water.
The solid carriers used, for example for dusts and dispersible powders, are as a rule natural mineral fillers, such as calcite, talc, SD/606m -7- L -I I LI li If 1 I kaolin, montmorillonite or attapulgite. In order to improve the physical properties, it is also possible to add highly disperse silica or highly disperse absorbent polymers. Suitable granulated adsorptive carriers are porous types, for example pumice, ground brick, sepiolite or bentonite; and suitable non-sorptive carriers are materials such as calcite or sand. It is also possible to use a large number of pre-granulated materials of an inorganic or organic nature, such as, in particular, dolomite or comminuted plant residues.
Depending on the nature of the active ingredient of the formula I to be formulated, suitable surface-active compounds are nonionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties. Surfactants are also to be rnderstood as meaning mixtures of surfactants.
The surfactants customarily used in formulation practice are described, inter alia, in the following publications: «McCutcheon’s Detergents and Emulsifiers Annual», BC Publishing Corp., Ridgewood, New Jersey, 1981.
Helmuth Stache «Tensid-Taschenbuch» («Surfactants Handbook»), Carl Hanser-Verlag, Munich/Vienna 1981.
The agrochemical preparations contain, as a rule, 0.1 to 99%, in particular 0.1 to 95%, of an active ingredient of the formula I, 99.9 to in particular 99.8 to of solid or liquid additives and 0 to 25%, in on o» particular 0.1 to 25% of a surfactant.
Whereas commercial products are preferably in the form of concentrated compositions, the compositions employed by the end user are 0 o0 usually diluted.
The Examples which follow illustrate the invention in greater detail, without limiting it.
Example 1 Preparation of 2 -(2,4-dichlorophenyl)-2-methoxypentan-1-ol Cl Cl OCH3 Cl Cl C-CH 2
-OH
C
3
H
7 -n
C
3
H
7 -n a) 12.5mL of boron trifluoride ethyl etherate are added dropwise slowly to a solution of 20.7g (90mmoles) of 2 -(2,4-dichlorophenyl)-l,2epoxypentane in 100mL of absolute methanol. The temperature is kept at SD/606m 8-
I
.i S18-20°C by occasional cooling. The temperature is then kept at 18-20°C for a further 6 hours, and the mixture is then stirred for a further hour at 0 C. The solution is poured into ice-cold, dilute sodium bicarbonate solution, and the resulting mixture is extracted twice with diethyl ether.
The combined ether extracts are washed twice with half-saturated sodium bicarbonate and then twice with sodium chloride solution and are dried over sodium sulfate, filtered and concentrated. This gives 26.2g of a yellowish, slightly viscous liquid, which is distilled in a high vacuum using a Vigreux column. The 2-(2,4-dichlorophenyl)-2-methoxypentan-l-ol thus obtained is a colourless, viscous oil of boiling point 88-90 0
C/
10.7 x l- 3 mbar and n 50 D 1.5322. Yield 12.1g 51% of theory), lOOmHz H-NMR (CDC13): 6 7.15-7.6ppm 3H, aromatic); 4.1ppm (dd, 2H,-CH 2 0H); 3.25ppm bH, -OCH 3 1.7-2.3ppm 3H, -0-C-CH 2
-CH
2
CH
3 1H disappears on adding D 2 0.7-1.25ppm 5H, -CH CH 2
CH
3 o Calculated Found o 0 analysis C 54.8 55.0 H 6.1 6.2 C1 26.9 26.9 ~0 o b) A solution of 3.1g (13.5mmoles) of 2-(2,4-jichlorophenyl)- 1,2-epoxypentane in 15mL of absolute methanol is added dropwise at 22-25°C o. to a solution of 0.3mL of concentrated (95-97%) sulfuric acid in 15mL of absolute methanol, and the mixture is stirred at 22-25″C. After 5.5 hours epoxide can no longer be detected by gas chromatography, but the desired o. product is detected in a yield of approx. 75%. The solution is poured into ice-cold dilute sodium bicarbonate solution, and the mixture is extracted twice with diethyl ether. The combined extracts are washed three times with half-saturated sodium chloride solution, dried over sodium sulfate, filtered and concentrated. The yield of crude product is 3.8g of a yellowish, slightly viscous liquid. After purification by column chromatography (silica gel; 1:4 ethyl acetate/petroleum ether), 2.3g 65.9% of theory) of pure 2-(2,4-dichlorophenyl)-2-methoxypentan-l-ol is obtained, the data of which agree with those indicated under a).
SD/606m 9 -i c) Varying the parameters of the reaction leads to the following result: Starting Reaction material Reaction time Yield Catalyst [equivalents] temp [hours] [%1 i) perchloric acid 70% 0.5 00 86 75 perchloric acid 70% 0.5 20° 22 2) perchloric acid 70% 0.5 200 22 70 1) perchloric acid 70% 0.5 650 0.25 64 Dowex 50W(H+)* 0.5 200 18 62 (Registered Trade Mark) 1) determined by gas chromatography, using calibration curves and an internal standard, 2) yield of product isolated.
o, a very strongly acid ion exchanger having SO 3 H groups in the H+ ,I form.
Example II Preparation of 2-(2,4-dichlorophenyl)-2-ethoxy-pentan-l-ol Cl C1 j C) C1 -C-CH2-OH o« ,C3H7-n C3H7-n 27.6g (120mmoles) of 2-(2,4-dichlorophenyl)-1,2-epoxypentane are dissolved in 60mL of ethanol. A solution of 17.4g (120mmoles) of boron trifluoride-etherate in 60mL of ethanol is added dropwise at 0°C, the internal temperature being kept at 0°-5°C by cooling with ice water. The mixture is then left at +7°C to react further slowly. As soon as epoxide can no longer be detected by gas chromatography, the reaction mixture is exctracted with methylene chloride. The combined extracts are washed with 4 water, dried .ver sodium sulfate, filtered and concentrated in vacuo. The yield of crude product is 32.3g. Purification by column chromatography (silica gel; 4:1 petroleum ether/ethyl acetate) gives 15.96g (53% of theory, taking into account that the epoxide employed is 90% pure).
Boiling point 90°C/0.07 mbar. 1OOMHz-H-NMR (CDC13): 6 7.0-7.6ppm aromatic 3.7-4.4ppm -CH2OH.); 3.2-3.6ppm -OCH 2
CH
3 1.6-2.2ppm -CH OH); 0.7-1.4ppm -OCH2CH3 and m, -C-CH2CH3)
-C-CH
2
CH
3
I
SD/606m 10 «4F i i ;g :i i i-I analysis C
H
C1 calculated 56.3 6.5 25.6 found 56.3 6.8 25.6 Example III Preparation of 2-(2,4-dichlorophenyl)-2-isopropoxypentan-l-ol Cl OCH (CH 3 )2 Cl C-CH2-OH
C
3
H
7 -n 9.3mL (75mmoles) of boron trifluoride-etherate are added dropwise at S 20-24 0 C to a solution of 17.3g (75mmoles) of 2-(2,4-dichlorophenyl)i0C 1,2-epoxypentane in 90mL of 2-propanol. The clear solution is allowed to S stand at room temperature for 24 hours and is then poured into dilute, icecold sodium bicarbonate solution, and the mixture is extracted twice with diethyl ether. The combined ether extracts are washed again with halfsaturated sodium chloride solution, dried over sodium sulfate and filtered, o’ and the filtrate is concentrated and purified by column chromatography o o. (silica gel; 1:7 ethyl acetate/petroleum ether). The product is obtained in the form of a colourless oil. n 50 D 1.5168. 1OOMHz-H-NMR So (CDC1 6 7.1-7.8ppm 3H aromatic); 3.7-4.4ppm 3H, -CH OH, -OCH(CH 3 1.5-2.3ppm 3H, -CH 2 -CH CH 3 -OH, the signal of 1H disappears on adding 020); 1.25ppm (dd, 6H, -OH(CH 3 2 0 .2 3 2 C C i 0.8-1.4ppm (m, 5H, -C-CH 2
CH
2
CH
3 SD/606m 11 Example IV L Preparation of 2-(2,4-dichlorophenyl)-2-(2-methoxyethoxy)-peltan-l-oI C1 C1
OCH
2
CH
2
OCHI
3 -0 1 C1 C1C-CH 2
-OH
Cl- n
C
3 H-nC 3
H
7 2.OmL (16.5mmoles) of boron trifluoride ethyl etherate are added dropwise at 24-28 0 C to a solution of 3.45g (l5mmoles) of 2-(2,4dichlorophenyl)-l ,2-epoxypentane in 6OmL of 2-methoxy-ethanol The reaction solution is allowed to stand at room temperature for a further 1 .75 hours and is then poured into ice-cold, dilute sodium bicarbonate solution. The mixture is extracted twice with diethyl ether. The combined 2ether extracts are washed twice with water and once with half-saturated L> sodium chloride solution, dried over sodium sulfate, filtered and Sconcentrated. Purification by column chromatography (silica gel; 1:8 ethyl acetate/petroleum ether, then 1:4) gives 2.Og 43.3% of theory) of the pure product in the form of a colourless, viscous oil. n 50 D 1.5161.
10MHz_ H-NMR (ml 6 7.l-7.6ppm (in, 31′ aromatic); 4.Osppm (dd, i~o 2H, -CH 3.2-3.7ppm (in, 8H, -0CH CH 0-CH, -OH, lH disappears after adding 020); l.7-2.4ppm ZH -C-CH- 2
-CH
2
-CH
3 O.75-l.4ppm H, -C-CH 2
CH
2
CH
3 calculated found analysis [i]C 54.7 55.1 H 6.6 6.7 Cl 23.1 22.
Example V Preparation of 2-(2,4-dichlorophenyl)-2-(2–fluorobenz/1oxy)-pentn–01O
F,
0i ci C 2
C:
3
H
7 -n A mixture of 11.6g (92mmoles) of 2-fluorobenzyl alcohol and 21.9g SD/606m 12- (92mmoles) of 2-(2,4-dichlorophenyl)-1,2-epoxypentane is added dropwise at 0I 0 -2 0 C to a solution of 2.0mL (16.5mmoles) of boron trifluoride ethyl etherate in 10mL of diethyl ether. The solution is allowed to react further overnight at +7 0 C and is worked up as in Example I by extraction i and column chromatography. 2.95g of the pure product are obtained in the form of a colourless oi.. 100MHz-H-NMR (CDCI3): 6 6.8-7.7ppm (m, 7H aromatic); 4.5ppm 2H, -C-OCH 2 3.9-4.4ppm 2H, 1.7-2.3ppm 3H, -CH 2
CH
2
CH
3 and OH); 0.7-1.4ppm -CH CH 3 calculated found analysis C 60.5 60.4 H 5.4 F 5.3 5.3 Cl 19.9 19.6 Example VI o Preparation of 2-(4-fluorophenyl)-2-(n-butoxy)-propan-l-ol
OC
4 H9-n F-
C-CH
2
-OH
CH
3
CH
3 A solution of 4.56g (30mmoles) of 2-(4-fluorophenyl)-1,2-epoxypropane in 5.55g (75mmoles) of n-butanol is added dropwise slowly at an internal temperature of 5-7 0 C, with cooling, to a solution of 2.13g (0.O16mole) of boron trifluoride ethyl etherate in 5.55g (75mmoles) of n-butanol, and the temperature is kept at +7°C for a further 4 hours. The reaction mixture is then worked up by extraction (methylene chloride) and washing with water. The organic phase is dried over sodium sulfate, filtered and concentrated in vacuo. Distillation of the crude product gives 4.48g 66% of theory) of the pure end product in the form of a -l colourless oil. Boiling point 120-125°C/20 mbar. 100MHz H-NMR (CDC1 3 6 6.8-7.5ppm 4H aromatic); 3.5ppm 2H, -CH 2
OH);
3.2ppm 2H, -OCH 2 2.3ppm (broad, 1H, 1.6ppm 3H, -CH 1.4ppm 4H, -CH2CH2-); 0.9ppm 3H, -CH -2-2 -3 calculated found analysis C 69.0 69.2 H 8.5 8.3 F 8.4 SD/606m 13
Y-
I Example VII Preparation of 2-(2,4-dichloropheny1)-2-methoxvbutan-l-ol Cl C1
O-CH
3 Cl C CH2+ CH30H—– C C-CH 2
-OH
C2H 5
C
2
H
10.64g of boron trifluoride-etherate, dissolved in 30m1 of methanol, are added dropwise at 4-60C to a solution of 16.25g (75mmoles) of 2-(2,4dichlorophenyl)-1,2-epoxybutane of purity 95%, in 30m1 of methanol. The clear solution is then allowed to reach room temperature (20 0 C) in a water bath and, after 16 hours, is worked up by extraction with water and chloroform. The chloroform solution is washed with NaHCO 3 and dried with Na 2
SO
4 and the solvent is removed on a rotary evaporator. This gives 19g of crude product, which is purified by chromatography, using silica gel and a mixture of 4 parts of petroleum ether and one part of ethyl acetate.
Removing the solvent at 60 0 C in vacuo (20mbar) gives 13.35g of pure product in the form of a colourless oil. 60MHz-1H-NMR (DCC13): 6o 7.1-7.6pp 3H, aromatic); 3.7-4.6ppm -CH2OH); 3.28ppm (s, o OCH3); 1.6-2.3ppm CH2CH OH); 0.67ppm CHCH 3 2 3′ 3J Ji.
Example
VIII
Preparation of 2-(2,4-dichlorophenyl)-2-allyloxybutan-l-ol Cl Cl
O-CH
2
CH=CH
2 S° CH 2
HOCH
2
CH=CH
2 C C-CH2-OH I C 2
H
5 C2H 8.68g (38mmoles) of 2-(2,4-dichlorophenyl)-1,2-epoxybutane of purity are added dropwise at 7-80C to a solution of 5.67g (40mmoles) of boron trifluoride-etherate in 23.2g (400mmoles) of allyl alcohol. The mixture is kept at 200C overnight in a water bath, and the solution is extracted with chloroform and water. Drying the organic phase with Na2SO 4 and removing the solvent on a rotary evaporator gives 11.3g of crude product, which is purified by column chromatography (silica gel; mobile phase: 4 parts of petroleum ether/l part of ethyl acetate). The yield of pure product is 5.28g (50.5% of theory) of a colourless oil.
Refractive index n50D 1.5291. 60MHz-H-NMR (DCC 3 SD/606m 14 8 7.l-7.Gppm (m 3H, aromatic); 5.O.-6.5ppm (in, 3H; olefinic): 3,.8-4.4ppm (in, 4H; 2 x O21 .5-2.5ppn (in; 3H, CH2CH3 OH); 0 .G7ppm 3H, CHH 2
CH
2
H
Example IX Preparation of 2-(2,4–dichlorophenyl.)-2-propoxybutan-l-oI 7 C1 C1
O-CH
2
CH
2
CH
3 C/ H CH 3
CH
2
CH
2 Cl-
CCH
2
C-CH
2
OH
C2H 5 C Hq, 8.68g (O.O4mole) of 2-(2,4–dichlorophenyl)-1l,2-epoxybutane of purity are dissolved in 12g (O.2inole) of n-propanol and a solution of 5.68g (0.O4inole) of boron trifluoride-etherate in 12g (O.2inole) of 140 n-propanol is added dropwise at 20’C. After 24 hours, the mixture is extracted with chloroform, the solvent is removed on a rotary evaporator and the residue is purified by column chromatography using silica gel. The yield is 5.41g of a colourless oil. 60 MHz H-NMR (DCCl 6 -7.O-7.6ppm (mn, 3H, aromatic); 3.7-4.4ppm (in, 2H, CH OH); 3 .3ppm 2H, flCH CH-) l.4-2.6ppm (mn, 5H, 2 x CH, OH); O.5-3.lppm (mn, 6H, 2 xH9.calculated found o analysis EM] C 56.33 56.69 H 6.55 6.62 Cl 25.58 25.18 Example X Preparation of 2-E2-chloro-4-(4-chloroplenoxy)-plenylj-2-methoxypropa–l-oI C1 C1
OCH
3 C -C 2
CH
3 0H->Cl H 2 0H 3
CH
3 10.0g (0.034mole) of 2-[2-chloro-4-(4-chlorophenoxy)-phienyll-l,2epoxypropare are dissolved in 3OmL of methanol at room temperature and are reacted by ddding 10 drops of a solution of 4.8g of boron trifluorideetherate in l~mL of methanol. The temperature is kept below 25*C by cooling in ice; epoxide can no longer be detected in a thin layer chromatogram after only 10 minutes. Working up the crude product by SD! 606mn-1 15 extraction with water and chloroform, followed by column chromatography (silica gel; 4 parts of petroleum ether/l part of ethyl acetate) gives 9.37g of pure product in the form of a colourless oil. MHz-1H-NMR (DCC1 6 6.7-7.6ppm 7H, aromatic); 3.7-4.2ppm (m, 2H, OCH 2 3.2ppm 3H, OCH 2.1-2.4ppm 1H, OH); 1.7ppm 3H, CH calculated found analysis C 58.73 59.36 H 4.93 5.18 C1 21.67 21.04 Examples of formulations of active ingredients of the formula I percent by weight) o F1 Emulsion concentrates/wettable powders a) b) c) o 0 Active ingredient of Formula I 25% 40% Ca dodecylbenzenesulfonate 5% 8% 6% S Caster oil polyethylene glycol ether S (36 moles of ethylene oxide) 5% Tributylphenyl polyethylene glycol ether moles of ethylene oxide) 12% 4% Cyclohexanone 15% Mixed xylenes 65% 25% Emulsions of any desired concentration can be prepared from such S concentrates by dilution with water. Wettable powders are obtained if the xylene component is replaced by silica and/or kaolin.
S F2 Solutions a) b) c) (d) I 00 Active ingredient of Formula I 80% 10% 5% Ethylene glycol monomethyl ether 20% Polyethylene glycol MW 400 N-methyl-2-pyrrolidone 20% Epoxidised coconut oil 1% Petroleum ether (boiling range 160-190 0 C) 94% (MN molecular weight) The solutions are suitable for application in the form of very fine drops.
F3 Granules a) b) Active ingredient of Formula I 5% Kaolin 94% Highly disperse silica 1% Attapulgite SD/606m 16 The active ingredient is dissolved in methylene chloride, the solution is sprayed onto the carrier, and the solvent is then removed by evaporation in vacuo.
F4 Dusts a) b) Active ingredient of Formula I 2% Highly disperse silica 1% Talc 97% Kaolin Dusts ready for use are obtained by mixing the active ingredient intimately with the carriers.
0 Ca S 0g I0 SD/606m 17
Claims (7)
2. A compound having the formula I according to claim 1 wherein S, RI is phenyl which is monosubstituted to trisubstituted by halogen or phenyl which is monosubstituted by phenoxy or halogenophenoxy; R2 is C 1 -C 6 -alkyl or C 3 -C 7 -cycloalkyl; and R 3 is C 1 -C 6 -alkyl, C 1 -C 6 -alkyl which is substituted by C 1 -C 3 -alkoxy, C 3 -C 4 -alkenyl, benzyl or halogenobenzyl.
3. A glycol monoether substantially as hereinbefore described with reference to any one of the Examples.
4. A process for the production of a compound of formula I as defined in claim 1, comprising reacting an oxirane of formula II: 0\ RI-C II R2 wherein R 1 and R 2 are as defined in claim 1, at temperatures of -200 to +100 0 C, in the presence of an acid catalyst or an acid condensation agent, with an alcohol of formula III: R 3 -OH III in which R 3 is as defined in claim 1. SD/606m 18 L A process for the preparation of a glycol monoether which process is substantially as hereinbefore described with reference to any one of the Examples.
6. The product of a process according to claim 4 or claim
7. An insecticidal composition which comprises at least one compound according to any one of claims 1 to 3 or 6 combined with a carrier diluent and/or adjuvant therefor.
8. An insecticidal composition substantially as hereinbefore described with reference to any one of the formulation examples FI to F4.
9. A method of combating insects which method comprises applying to the insects or to the locus thereof an effective amount of at least one compound according to any one of claims 1 to 3 or 6 or of a composition according to claim 7 or claim 8. hydrophilic phase and a hydrophobic ‘prp esence of at least onc 0 0 DATED this TNENTY-FIRST day of APRIL 1988 Ciba-Geigy AG 0 O Patent Attorneys for the Applicant SSPRUSON FERGUSON 19
AU15504/88A
1983-05-19
1988-05-02
Glycol monoethers as intermediates in organic synthesis
Ceased
AU607993B2
(en)
Applications Claiming Priority (2)
Application Number
Priority Date
Filing Date
Title
CH273083
1983-05-19
CH2730/83
1983-05-19
Related Parent Applications (1)
Application Number
Title
Priority Date
Filing Date
AU28358/84A
Division
AU572145B2
(en)
1983-05-19
1984-05-18
1-triazolylethyl ether derivatives
Publications (2)
Publication Number
Publication Date
AU1550488A
AU1550488A
(en)
1988-07-21
AU607993B2
true
AU607993B2
(en)
1991-03-21
Family
ID=4240315
Family Applications (2)
Application Number
Title
Priority Date
Filing Date
AU28358/84A
Ceased
AU572145B2
(en)
1983-05-19
1984-05-18
1-triazolylethyl ether derivatives
AU15504/88A
Ceased
AU607993B2
(en)
1983-05-19
1988-05-02
Glycol monoethers as intermediates in organic synthesis
Family Applications Before (1)
Application Number
Title
Priority Date
Filing Date
AU28358/84A
Ceased
AU572145B2
(en)
1983-05-19
1984-05-18
1-triazolylethyl ether derivatives
Country Status (25)
Country
Link
US
(1)
US4945100A
(en)
EP
(1)
EP0126430B1
(en)
JP
(3)
JPS59222434A
(en)
KR
(2)
KR890000533B1
(en)
AT
(1)
ATE66676T1
(en)
AU
(2)
AU572145B2
(en)
BR
(1)
BR8402388A
(en)
CA
(1)
CA1223264A
(en)
CS
(2)
CS247179B2
(en)
DD
(2)
DD248274A5
(en)
DE
(1)
DE3484968D1
(en)
DK
(1)
DK248184A
(en)
ES
(1)
ES8600635A1
(en)
GB
(2)
GB2143815B
(en)
GR
(1)
GR79954B
(en)
HU
(1)
HU196693B
(en)
IE
(2)
IE57489B1
(en)
IL
(3)
IL71862A
(en)
MX
(1)
MX5769A
(en)
MY
(1)
MY102774A
(en)
NZ
(2)
NZ208209A
(en)
PH
(3)
PH20959A
(en)
PT
(1)
PT78602A
(en)
TR
(1)
TR22379A
(en)
ZA
(1)
ZA843774B
(en)
Families Citing this family (74)
* Cited by examiner, † Cited by third party
Publication number
Priority date
Publication date
Assignee
Title
DE3484968D1
(en)
*
1983-05-19
1991-10-02
Ciba Geigy Ag
METHOD FOR PRODUCING 1-TRIAZOLYL ETHYL ETHER DERIVATIVES, AND NEW 1-TRIAZOLYL PHENOXYPHENYL ETHYL ETHER DERIVATIVES CONTAINING MICROBICIDAL AGENTS AS ACTIVE SUBSTANCES AND THE USE THEREOF.
DE3579347D1
(en)
*
1984-04-05
1990-10-04
Ici Plc
AZOLYL PROPANOLE.
DE3682023D1
(en)
*
1985-08-07
1991-11-21
Ici Plc
TRIAZOLYLMETHYL-TERT.-BUTYL-CARBINOL DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS PLANT GROWTH REGULATORS.
GB8603951D0
(en)
*
1986-02-18
1986-03-26
Ici Plc
Heterocyclic compounds
EP0275955B1
(en)
*
1987-01-21
1990-07-04
Ciba-Geigy Ag
Microbicidal composition
DE3732387A1
(en)
*
1987-09-25
1989-04-06
Bayer Ag
AZOLYLMETHYLCYCLOPROPYL DERIVATIVES CONTAINING ANTIMYCOTIC AGENTS
EP0354183B1
(en)
*
1988-08-04
1993-01-20
Ciba-Geigy Ag
Microbicidal agents
US4940720A
(en)
*
1989-08-02
1990-07-10
Ciba-Geigy Corporation
Microbicidal compositions
US5358939A
(en)
*
1992-06-25
1994-10-25
Rohm And Haas Company
Fungicidal 2-aryl-2,2-disubstituted ethyl-1,2,4-triazoles
NZ270418A
(en)
1994-02-07
1997-09-22
Eisai Co Ltd
Polycyclic triazole & imidazole derivatives, antifungal compositions
KR20020037652A
(en)
*
2000-11-15
2002-05-22
김응필
A separation of specific gravity ore separator
PH12009500961A1
(en)
2006-11-22
2008-05-29
Basf Se
Liquid water based agrochemical formulations
CA2694778A1
(en)
2007-08-08
2009-02-12
Basf Se
Aqueous microemulsions containing organic insecticide compounds
CA2730743A1
(en)
*
2008-07-24
2010-01-28
Basf Se
Oil-in-water emulsion comprising solvent, water, surfactant and pesticide
TW201018400A
(en)
2008-10-10
2010-05-16
Basf Se
Liquid aqueous plant protection formulations
UA106213C2
(en)
2008-10-10
2014-08-11
Басф Се
Liquid preparations for protecting plants comprising pyraclostrobin
MX356322B
(en)
2011-07-13
2018-05-23
Basf Se
Fungicidal substituted 2-[2-halogenalkyl-4-(phenoxy)-phenyl]-1-[1 ,2,4]triazol-1-yl-ethanol compounds.
WO2013010862A1
(en)
*
2011-07-15
2013-01-24
Basf Se
Fungicidal alkyl-substituted 2-[2-chloro-4-(4-chloro-phenoxy)-phenyl]-1-[1,2,4]triazol-1-yl-ethanol compounds
JP2014520833A
(en)
2011-07-15
2014-08-25
ビーエーエスエフ ソシエタス・ヨーロピア
Bactericidal phenylalkyl-substituted 2- [2-chloro-4- (4-chloro-phenoxy) -phenyl] -1- [1,2,4] triazol-1-yl-ethanol compounds
JP2014520831A
(en)
2011-07-15
2014-08-25
ビーエーエスエフ ソシエタス・ヨーロピア
Bactericidal alkyl- and aryl-substituted 2- [2-chloro-4- (dihalo-phenoxy) -phenyl] -1- [1,2,4] triazol-1-yl-ethanol compounds
WO2013024077A1
(en)
2011-08-15
2013-02-21
Basf Se
Fungicidal substituted 1-{2-[2-halo-4-(4-halogen-phenoxy)-phenyl]-2-alkoxy-3-methyl-butyl}-1h-[1,2,4]triazole compounds
BR112014003216A2
(en)
2011-08-15
2017-04-25
Basf Se
compounds, processes for preparing compounds of formula i, agrochemical compositions, use of compounds of formula i or viii and use of at least one compound of formula i or viii
EP2744789A1
(en)
2011-08-15
2014-06-25
Basf Se
Fungicidal substituted 1-{2-[2-halo-4-(4-halogen-phenoxy)-phenyl]-2-alkoxy-hexyl}-1h [1,2,4]triazole compounds
EP2559688A1
(en)
2011-08-15
2013-02-20
Basf Se
Fungicidal substituted 1-{2-[2-halo-4-(4-halogen-phenoxy)-phenyl]-2-butoxy-ethyl}-1h [1,2,4]triazole compounds
PE20141393A1
(en)
2011-08-15
2014-10-22
Basf Se
SUBSTITUTE 1- {2- [2-HALO-4- (4-HALOGEN-PHENOXY) -PHENYL] -2-ALUINYLOXY-ETHYL} -1H- [1,2,4] TRIAZOLE FUNGICIDE COMPOUNDS
MX2013014348A
(en)
2011-08-15
2014-04-30
Basf Se
Fungicidal substituted 1-{2-[2-halo-4-(4-halogen-phenoxy)-phenyl ]-2-alkoxy-2-cyclyl-ethyl}-1h [1,2,4]triazole compounds.
BR112014003412A2
(en)
2011-08-15
2017-03-14
Basf Se
compounds of formula i, process, compounds of formula xii, viii and xi, agrochemical compositions, use and coated seed
KR20140054236A
(en)
*
2011-08-15
2014-05-08
바스프 에스이
Fungicidal substituted 1-{2-[2-halo-4-(4-halogen-phenoxy)-phenyl]-2-ethoxy-ethyl}-1h-[1,2,4]triazole compounds
US9752105B2
(en)
2012-09-13
2017-09-05
Ecolab Usa Inc.
Two step method of cleaning, sanitizing, and rinsing a surface
EP2735563A1
(en)
*
2012-11-27
2014-05-28
Basf Se
Meta substituted 2-[phenoxy-phenyl]-1-[1,2,4]triazol-1-yl-ethanol compounds and their use as fungicides
WO2014082871A1
(en)
2012-11-27
2014-06-05
Basf Se
Substituted 2-[phenoxy-phenyl]-1-[1,2,4]triazol-1-yl-ethanol compounds and their use as fungicides
WO2014082879A1
(en)
2012-11-27
2014-06-05
Basf Se
Substituted [1,2,4]triazole compounds
EP2928873A1
(en)
2012-11-27
2015-10-14
Basf Se
Substituted 2-[phenoxy-phenyl]-1-[1,2,4]triazol-1-yl-ethanol compounds and their use as fungicides
US20150313229A1
(en)
2012-11-27
2015-11-05
Basf Se
Substituted [1,2,4] Triazole Compounds
BR112015012003A2
(en)
*
2012-11-27
2018-05-15
Basf Se
compounds of formula I, composition, use of a compound, method for combating harmful fungi, seed, process for preparing the compounds and intermediate compounds
CN106632107A
(en)
*
2012-12-19
2017-05-10
巴斯夫欧洲公司
Substituted [1,2,4]triazole and their use as fungicides
CA2894264C
(en)
*
2012-12-20
2023-03-07
BASF Agro B.V.
Compositions comprising a triazole compound
CN104936450A
(en)
*
2012-12-20
2015-09-23
巴斯夫欧洲公司
Compositions comprising triazole compound
CN104903315A
(en)
*
2013-01-09
2015-09-09
巴斯夫欧洲公司
Substituted [1,2,4]triazole and imidazole compounds
MX2015008927A
(en)
2013-01-09
2016-04-04
Basf Agro Bv
Process for the preparation of substituted oxiranes and triazoles.
WO2014124850A1
(en)
2013-02-14
2014-08-21
Basf Se
Substituted [1,2,4]triazole and imidazole compounds
WO2014198557A1
(en)
*
2013-06-12
2014-12-18
Basf Se
Substituted [1,2,4]triazole and imidazole compounds
WO2014198553A1
(en)
*
2013-06-12
2014-12-18
Basf Se
Substituted [1,2,4]triazole and imidazole compounds
EP2813499A1
(en)
2013-06-12
2014-12-17
Basf Se
Substituted [1,2,4]triazole and imidazole compounds
PL3019013T3
(en)
2013-07-08
2021-10-25
BASF Agro B.V.
Compositions comprising a triazole compound and a biopesticide
EP2839745A1
(en)
2013-08-21
2015-02-25
Basf Se
Agrochemical formulations comprising a 2-ethyl-hexanol alkoxylate
WO2015059791A1
(en)
2013-10-24
2015-04-30
三菱電機株式会社
Information processing device, information processing method, and program
UA118214C2
(en)
2014-02-14
2018-12-10
Басф Агро Б.В.
Emulsifiable concentrate comprising pesticide, fatty amide and lactamide
EA201892682A1
(en)
*
2014-06-25
2019-04-30
Басф Агро Б.В.
PESTICIDAL COMPOSITIONS
EP3166932B1
(en)
2014-07-08
2018-06-20
BASF Agro B.V.
Process for the preparation of substituted oxiranes and triazoles
UA120058C2
(en)
2014-07-14
2019-09-25
Басф Се
Pesticidal compositions
UA120628C2
(en)
2014-11-07
2020-01-10
Басф Се
Pesticidal mixtures
EP3028573A1
(en)
2014-12-05
2016-06-08
Basf Se
Use of a triazole fungicide on transgenic plants
WO2016174042A1
(en)
2015-04-27
2016-11-03
BASF Agro B.V.
Pesticidal compositions
EP3294700B1
(en)
2015-05-08
2020-01-29
BASF Agro B.V.
A process for the preparation of limonene-4-ol
US10344008B2
(en)
2015-05-08
2019-07-09
BASF Agro B.V.
Process for the preparation of terpinolene epoxide
BR112017028388B1
(en)
2015-07-02
2022-02-22
Basf Agro B.V
COMPOSITION, USE OF A COMPOSITION, METHODS TO COMBAT PHYTOPATOGENIC FUNGI, DEPROTECTION OF SEEDS, ROOTS AND SPROUTS OF RESULTING PLANTS, CONTROL OF INSECTS, ACARIDES OR NEMATOIDS FOR PLANT PROTECTION AND IMPROVEMENT OF PLANT HEALTH AND USE OF A COMPOSITION
EP3111763A1
(en)
2015-07-02
2017-01-04
BASF Agro B.V.
Pesticidal compositions comprising a triazole compound
CA3015744A1
(en)
2016-03-16
2017-09-21
Basf Se
Use of 1-[2-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol-5-one for combating resistant phytopathogenic fungi on cereals
BR112018068695B1
(en)
2016-03-16
2022-12-27
Basf Se
USE OF A COMPOUND AND METHOD TO CONTROL PHYTOPATHOGENIC FUNGI
US11241012B2
(en)
2016-03-16
2022-02-08
Basf Se
Use of tetrazolinones for combating resistant phytopathogenic fungi on soybean
AU2017286055B2
(en)
2016-06-15
2021-07-01
BASF Agro B.V.
Process for the epoxidation of a tetrasubstituted alkene
EP3472139B1
(en)
2016-06-15
2021-04-07
BASF Agro B.V.
Process for the epoxidation of a tetrasubstituted alkene
US20190211002A1
(en)
2016-09-22
2019-07-11
Bayer Cropscience Aktiengesellschaft
Novel triazole derivatives
WO2018054829A1
(en)
2016-09-22
2018-03-29
Bayer Cropscience Aktiengesellschaft
Novel triazole derivatives and their use as fungicides
WO2018145933A1
(en)
2017-02-08
2018-08-16
Bayer Aktiengesellschaft
Triazolethione derivatives
EP3580218A1
(en)
2017-02-08
2019-12-18
Bayer CropScience Aktiengesellschaft
Novel triazole derivatives
EP3580210A1
(en)
2017-02-08
2019-12-18
Bayer CropScience Aktiengesellschaft
Triazole derivatives and their use as fungicides
EP3579695A1
(en)
2017-02-10
2019-12-18
Bayer Aktiengesellschaft
Composition for controlling harmful microorganisms comprising 1 -(phenoxy-pyridinyl)-2-(1,2,4-triazol-1 -yl)-ethanol derivatives
EP3421460A1
(en)
2018-03-15
2019-01-02
Bayer Aktiengesellschaft
2-[(4-alkylphenoxy)-pyridinyl]-1-(1,2,4-triazol-1-yl)alkan-2-ol fungicides
WO2020020813A1
(en)
2018-07-25
2020-01-30
Bayer Aktiengesellschaft
Fungicidal active compound combinations
WO2020020816A1
(en)
2018-07-26
2020-01-30
Bayer Aktiengesellschaft
Novel triazole derivatives
WO2020070050A1
(en)
2018-10-01
2020-04-09
Bayer Aktiengesellschaft
Fungicidal 5-substituted imidazol-1-yl carbinol derivatives
EP3620053A1
(en)
2018-12-14
2020-03-11
Bayer Aktiengesellschaft
Fungicidal active compound combinations
Citations (1)
* Cited by examiner, † Cited by third party
Publication number
Priority date
Publication date
Assignee
Title
AU2835884A
(en)
*
1983-05-19
1984-11-22
Ciba-Geigy Ag
1-triazolylethyl ether derivatives
Family Cites Families (14)
* Cited by examiner, † Cited by third party
Publication number
Priority date
Publication date
Assignee
Title
DE2547953A1
(en)
*
1975-10-27
1977-04-28
Bayer Ag
(1-PHENYL-2-TRIAZOLYL-AETHYL) -AETHER- DERIVATIVES, PROCESS FOR THEIR MANUFACTURING AND THEIR USE AS FUNGICIDES
AU515134B2
(en)
*
1976-08-10
1981-03-19
Janssen Pharmaceutica N.V.
1-(2-aryl-2-r-ethyl)-1h-1,2,4-triazoles
DE2650831A1
(en)
*
1976-11-06
1978-05-11
Basf Ag
MEANS OF INFLUENCING PLANT GROWTH
DE2725214A1
(en)
*
1977-06-03
1978-12-14
Bayer Ag
METAL SALT COMPLEXES OF 1-PHENYL-2-TRIAZOLYL-AETHYL DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS FUNGICIDES
DE2725314A1
(en)
*
1977-06-04
1978-12-14
Bayer Ag
1- (2-PHENYLAETHYL) TRIAZOLIUM SALTS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS FUNGICIDES
US4654332A
(en)
*
1979-03-07
1987-03-31
Imperial Chemical Industries Plc
Heterocyclic compounds
CH647513A5
(en)
*
1979-11-13
1985-01-31
Sandoz Ag
TRIAZOLE DERIVATIVES, THEIR PRODUCTION AND USE.
AU542623B2
(en)
*
1980-05-16
1985-02-28
Bayer Aktiengesellschaft
1-hydroxyethyl-azole derivatives
EP0047594A3
(en)
*
1980-08-18
1982-06-09
Imperial Chemical Industries Plc
Triazole compounds, a process for preparing them, their use as plant fungicides and plant growth regulators and compositions containing them
DE3175673D1
(en)
*
1980-11-19
1987-01-15
Ici Plc
Triazole compounds, a process for preparing them, their use as plant fungicides and fungicidal compositions containing them
DE3140276A1
(en)
*
1981-10-10
1983-04-28
Bayer Ag, 5090 Leverkusen
PHENOXYPHENYL-AZOLYLMETHYL-KETONE AND CARBINOLS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS FUNGICIDES AND AS INTERMEDIATE PRODUCTS
ATE49200T1
(en)
*
1981-11-27
1990-01-15
Ciba Geigy Ag
MICROBICIDES TRIAZOLYL ETHYL AETHER.
DE3202604A1
(en)
*
1982-01-27
1983-08-04
Bayer Ag, 5090 Leverkusen
ETHER DERIVATIVES OF SUBSTITUTED 1-HYDROXYALKYL-AZOLES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS FUNGICIDES AND PLANT GROWTH REGULATORS
US4610716A
(en)
*
1982-12-14
1986-09-09
Ciba-Geigy Corporation
Fluorinated azolyl ethanol growth regulators and microbicides
1984
1984-05-16
DE
DE8484105582T
patent/DE3484968D1/en
not_active
Expired – Lifetime
1984-05-16
AT
AT84105582T
patent/ATE66676T1/en
active
1984-05-16
EP
EP84105582A
patent/EP0126430B1/en
not_active
Expired – Lifetime
1984-05-16
GB
GB08412506A
patent/GB2143815B/en
not_active
Expired
1984-05-17
DD
DD84281418A
patent/DD248274A5/en
not_active
IP Right Cessation
1984-05-17
IL
IL71862A
patent/IL71862A/en
unknown
1984-05-17
IL
IL8483707A
patent/IL83707A/en
unknown
1984-05-17
GR
GR74745A
patent/GR79954B/el
unknown
1984-05-17
DK
DK248184A
patent/DK248184A/en
not_active
Application Discontinuation
1984-05-17
CA
CA000454548A
patent/CA1223264A/en
not_active
Expired
1984-05-17
PT
PT78602A
patent/PT78602A/en
not_active
IP Right Cessation
1984-05-17
DD
DD84263132A
patent/DD226882A5/en
not_active
IP Right Cessation
1984-05-18
HU
HU841926A
patent/HU196693B/en
not_active
IP Right Cessation
1984-05-18
NZ
NZ208209A
patent/NZ208209A/en
unknown
1984-05-18
PH
PH30696A
patent/PH20959A/en
unknown
1984-05-18
TR
TR3611/84A
patent/TR22379A/en
unknown
1984-05-18
IE
IE2779/88A
patent/IE57489B1/en
not_active
IP Right Cessation
1984-05-18
AU
AU28358/84A
patent/AU572145B2/en
not_active
Ceased
1984-05-18
CS
CS843769A
patent/CS247179B2/en
unknown
1984-05-18
ZA
ZA843774A
patent/ZA843774B/en
unknown
1984-05-18
BR
BR8402388A
patent/BR8402388A/en
not_active
IP Right Cessation
1984-05-18
ES
ES532604A
patent/ES8600635A1/en
not_active
Expired
1984-05-18
MX
MX576984A
patent/MX5769A/en
unknown
1984-05-18
NZ
NZ219282A
patent/NZ219282A/en
unknown
1984-05-18
IE
IE1247/84A
patent/IE57488B1/en
not_active
IP Right Cessation
1984-05-19
KR
KR1019840002741A
patent/KR890000533B1/en
not_active
IP Right Cessation
1984-05-19
JP
JP59101625A
patent/JPS59222434A/en
active
Granted
1985
1985-08-08
CS
CS855782A
patent/CS247200B2/en
unknown
1985-10-25
PH
PH32974A
patent/PH22876A/en
unknown
1985-10-25
PH
PH32973A
patent/PH21667A/en
unknown
1986
1986-09-22
GB
GB08622763A
patent/GB2179659B/en
not_active
Expired
1987
1987-08-31
IL
IL83707A
patent/IL83707A0/en
unknown
1987-09-30
MY
MYPI87002496A
patent/MY102774A/en
unknown
1988
1988-05-02
AU
AU15504/88A
patent/AU607993B2/en
not_active
Ceased
1988-09-02
US
US07/240,441
patent/US4945100A/en
not_active
Expired – Fee Related
1988-11-10
KR
KR1019880014855A
patent/KR900003367B1/en
not_active
IP Right Cessation
1989
1989-05-01
JP
JP1112794A
patent/JPH0285265A/en
active
Granted
1989-05-01
JP
JP1112793A
patent/JPH0296544A/en
active
Granted
Patent Citations (1)
* Cited by examiner, † Cited by third party
Publication number
Priority date
Publication date
Assignee
Title
AU2835884A
(en)
*
1983-05-19
1984-11-22
Ciba-Geigy Ag
1-triazolylethyl ether derivatives
Also Published As
Publication number
Publication date
JPH0285265A
(en)
1990-03-26
GB2179659B
(en)
1988-01-27
MY102774A
(en)
1992-10-31
PH20959A
(en)
1987-06-10
IE841247L
(en)
1984-11-19
GB2179659A
(en)
1987-03-11
US4945100A
(en)
1990-07-31
KR900003367B1
(en)
1990-05-16
DD226882A5
(en)
1985-09-04
ZA843774B
(en)
1985-01-30
JPH0552819B2
(en)
1993-08-06
MX5769A
(en)
1993-10-01
AU1550488A
(en)
1988-07-21
EP0126430A2
(en)
1984-11-28
GR79954B
(en)
1984-10-31
AU2835884A
(en)
1984-11-22
IE57488B1
(en)
1992-10-07
IL71862A0
(en)
1984-09-30
NZ219282A
(en)
1988-02-12
BR8402388A
(en)
1985-04-02
CS247200B2
(en)
1986-12-18
IL71862A
(en)
1988-08-31
ES532604A0
(en)
1985-10-16
PH22876A
(en)
1989-01-19
NZ208209A
(en)
1988-01-08
DK248184A
(en)
1984-11-20
IL83707A
(en)
1988-08-31
DK248184D0
(en)
1984-05-17
GB2143815A
(en)
1985-02-20
IL83707A0
(en)
1988-01-31
HU196693B
(en)
1989-01-30
DD248274A5
(en)
1987-08-05
GB8412506D0
(en)
1984-06-20
GB2143815B
(en)
1988-01-20
IE57489B1
(en)
1992-10-07
PH21667A
(en)
1988-01-13
JPH0296544A
(en)
1990-04-09
PT78602A
(en)
1984-06-01
AU572145B2
(en)
1988-05-05
EP0126430A3
(en)
1986-05-14
TR22379A
(en)
1987-03-11
GB8622763D0
(en)
1986-10-29
HUT34011A
(en)
1985-01-28
KR900008926A
(en)
1990-06-03
CS247179B2
(en)
1986-12-18
DE3484968D1
(en)
1991-10-02
EP0126430B1
(en)
1991-08-28
ES8600635A1
(en)
1985-10-16
CA1223264A
(en)
1987-06-23
IE882779L
(en)
1984-11-19
KR890000533B1
(en)
1989-03-20
JPH0361666B2
(en)
1991-09-20
JPS59222434A
(en)
1984-12-14
ATE66676T1
(en)
1991-09-15
KR850000417A
(en)
1985-02-27
JPH0420912B2
(en)
1992-04-07
Similar Documents
Publication
Publication Date
Title
AU607993B2
(en)
1991-03-21
Glycol monoethers as intermediates in organic synthesis
KR950003999B1
(en)
1995-04-22
Alpha-aryl-alpha-phenylethyl-1h-1,2,4-triazole-1-propanenitriles
IE832933L
(en)
1984-06-14
1-azolyl-2-aryl-3-fluoroalkan-2-ols.
AU593337B2
(en)
1990-02-08
New hydroxyalkylazolyl derivatives
HU189293B
(en)
1986-06-30
Fungicide compositions containing hydroxy-alkinyl-azolyl derivatives as active agents and process for producing the active agents
IE48600B1
(en)
1985-03-20
Novel 1-(2-aryl-1,3-dioxan-2-ylmethyl)-1h-imidazoles and 1h-1,2,4-triazoles
JP2921862B2
(en)
1999-07-19
2,2-difluorocyclopropyl derivative
EP0625139B1
(en)
1997-04-16
Substituted benzyl carbamates with herbicidal properties
IE45522B1
(en)
1982-09-22
Novel herbicidally active phenoxy-alkanecarboxylic-acid derivatives and use thereof for controlling grass-like weeds
AU597146B2
(en)
1990-05-24
Novel compound, process for its preparation and use thereof
CA1195334A
(en)
1985-10-15
Dihydropyrones, processes for producing them, novel starting products used therein, compositions containing the novel dihydropyrones as active ingredients, and the use thereof for combating weeds
US4343742A
(en)
1982-08-10
Process for the manufacture of 2,3-perfluoro-1,4-dioxanes as well as some special representatives of compounds of this class
HUT51240A
(en)
1990-04-28
Fungicide compositions containing acrylic acid derivatives as active components and process for producing the acrylic acid derivatives
US4429154A
(en)
1984-01-31
Fluorinated azomethine compounds
US3213127A
(en)
1965-10-19
Cyclooctyl trichloroacetate
WO1998022417A1
(en)
1998-05-28
Process for the preparation of benzyl-ethers by use of phase transfer
EP0186989B1
(en)
1990-09-26
5-(2-chloro-4-trifluoromethylphenoxy)-2-nitro-alpha-substituted-acetophenone, oxime derivative thereof, process for preparing thereof, herbicidal composition, and method for the destruction of undesirable weeds
CS214846B2
(en)
1982-06-25
Method of making the new substitute of the trisubs. benzyl-oximethers
IE45464B1
(en)
1982-08-25
Herbicidal 1,3-dioxanes
DE2358690B2
(en)
1980-09-18
Substituted succindialdehyde monoacetals and a process for their preparation
US2794054A
(en)
1957-05-28
Alpha-chloromethylbenzhydryl ethers
HU185887B
(en)
1985-04-28
Compositions containing 1-imidazolyl-bethan derivatives as active agents, and process for producing the active agents
HU192157B
(en)
1987-05-28
Fungicides comprising substituted azolyl ether ketones and carbinols as active substance and process for preparing substituted azolyl ether ketones and carbinols
EP0056933A1
(en)
1982-08-04
Process for the preparation of 1-aryloxy-methylketones
None