CA1074326A - Esters - Google Patents

Esters

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Publication number
CA1074326A
CA1074326A CA265,476A CA265476A CA1074326A CA 1074326 A CA1074326 A CA 1074326A CA 265476 A CA265476 A CA 265476A CA 1074326 A CA1074326 A CA 1074326A
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CA
Canada
Prior art keywords
formula
parts
triazole
pests
active substance
Prior art date
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.)
Expired
Application number
CA265,476A
Other languages
French (fr)
Inventor
Laurenz Gsell
Willy Meyer
Dag Dawes
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.)
Filing date
Publication date
Priority claimed from CH1479675A external-priority patent/CH602012A5/en
Application filed by Ciba Geigy AG filed Critical Ciba Geigy AG
Application granted granted Critical
Publication of CA1074326A publication Critical patent/CA1074326A/en
Expired legal-status Critical Current

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Classifications

    • 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
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D249/12—Oxygen or sulfur 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
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
    • A01N57/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing heterocyclic radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having three nitrogen atoms as the only ring hetero atoms
    • C07F9/6518—Five-membered rings

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Biochemistry (AREA)
  • Molecular Biology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

Abstract of the Disclosure 1,2,4-Triazole derivatives of the formula

Description

10743;~
The present invention provides derivatives of 1,2,4-triazole, a process for the manufacture thereof, and a method of controlling pests which comprises the use of these derivatives.
` S The 1,2,4-triazole derivatives have the formula :~ CH30C~I2 ~CH3 H
~ o-i~

wherein each of Rl, R2 and R3 represents a Cl-C6-alkyl group and X represents an oxygen or sulphur atom.
The alkyl groups represented by Rl to R3 can be straight-chain or branched. Examples of such groups include:
methyl, ethyl. propyl, iso-propyl, n-butyl, iso-butyl, sec.
butyl, tert. butyl, n-pentyl, n-hexyl and isomers thereof.
Preferred compounds on account of their action are those of the formula I, wherein each of Rl, R2 and R3 represents a methyl or ethyl group and X represents a sulphur atom.
The compounds of the formula I can be obtained by methods which are known per se, for example as follows:

. ~

.

., . ~, , ~ . -.
.. . - . -., ~ ~ ~ , . .. .

1(~7432~ .

~ 3 X
A) IN N + Hal-P ' 1 acid acceptor ~ I

(III) (II) 30CH~ / CH3 X
,CH " / OR
B) N N ~ Hal-P
R 3S ~ N OMe ~ -(IV) ~III) In the formulae II, III and IV, the symbols Rl to R3 ; and X are as defined for formula I and Hal represents a halogen atomJ preferably a chlorine or bromine atom, and Me represents an alkali metal, ammonium or trialkylammoniu~.
Suitable acid acceptors are for example the following bases: tertiary amines, such as triethylamine, dimethyl aniline, pyridine; inorganic bases, such as hydroxides and carbonates of alkali metals and alkaline earth metals, preferably sodium and potassium carbonate.
Processes A and B are carried out at a reaction temperature of 0 to 120C, preferably at 20 to 80C, at normal pressure and in solvents or diluents. Suitable solvents 10743Z~i or diluents are for example: ethers and ethereal compounds, such as diethyl ether, dipropyl ether, dioxan, dimethoxy-ethane, tetrahydrofuranei amides, such as N,N-dialkylated carboxamides; aliphatic, aromatic and halogenated hydrocarbons, in particular benzene, toluene, xylenes, chloroform, chloro-benzenei nitriles, such as acetonitrile; dimethyl sulphoxide;
ketones, such as acetone, methyl ethyl ketone,and water.
The starting materials of the formula III are known.
They can be prepared in analogy to known processes.
The starting materials of the formula II and IV are new and can be prepared according to the following known reaction scheme:

3 \C/ 3 hydrogen + 3 ~CH 3 " catalyst NH
N ~ ^ b H~O ~ e.g. palladium-calcium NHCOOC2u5 N C OC2 5 carbonate or platinum~carbon ~V) (VI) ¦ ClCN
l NaHC03 3 ~2~ 3 NC-N

(Vll) . ~

7~3;~

NaSR3 3 2 ~CH CH30CH2 ~ 3 Vll (VIII) ~35 N QH ~35 OMe CII) ~IV) In the formulae II, IV to VIII, R3 is as defined in formula I and Me represents an alkali metal. The reaction of the compound VII with the compound VIII is carried out in a solvent at 10 to 120C, preferably at 20 to 90C, and lasts a few minutes to several hours, depending on the sub-stituents and reaction conditions. Suitable solvents are for example ketones, such as acetone or methyl ethyl ketone;
tetrahydrofurane, and water.

The active substances of the formula I are suitable for controlling a variety of animal and plant pests. Thus they possess nematocidal properties and can be used for example, for controlling phytopathogenic nematodes. The active sub-stances of the formula I are also partly suitable for use as herbi-cides and plant regulators and for controlling viruses, bacteria, and phytopathogenic fungi. Above all, however, they act on all development stages, such as eggs, larvae, nymphs pupae and adults, of insects and representatives of the order Acarina, such as mites and ticks.

.

10743'~i The compounds of the formula I have, for example, a lethal or repellant action on the following insects or representatives of the order Acarina:
Blattidae, Gryllidae, ~ryllotalpidae, Tettigoniidae, Cimicidae, Pyrrhocoridae, Reduviidae, Aphididae, Delphacidae, Diaspididae, Pseudococcidae, Chrysomilidae, Coccinellidae, Bruchidae, Scarabaeidae, Dermestidae, Tenebrionidae, Tineidae, Noctuidae, Lymantriidae, Pyralidae, Culicidae, Tipulidae, Stomoxydae, Muscidae, Calliphoridae, Trypetidae, and Pulicidae, and of the families: Txodidae, Argasidae, Tetranychidae and Dermanyssidae .
The acaricidal and/or insecticidal action can be sub-stantially broadened and adjusted to prevailing conditions by adding other insecticides and/or acaricides.
Examples of suitable additives include: nitrophenols and derivatives thereof; formamidinesi ureasi pyrethroids;
carbamates and chlorinated hydrocarbons.
The compounds of formula I can be used as pur~ active substance or together with suitable carriers and/or additives.
Suitable additives can be solid or liquid and correspond to the substances conventionally used in the art of formulation, such as natural or regenerated substances, solvents, disper-sants, wetting agents, tackifiers, thickeners, binding agents and/or fertilizers. For application, the compounds of the ~0~7~3Z6 formula I can be processed to dusts, emulsion concentrates, granulates, dispersions, sprays, to solutions and suspensions in the conventional formulations, which are co~monly employed in application technology. Mention is also to be made of cattle dips and spray races, in which aqueous preparations are used.
The compositions of the present invention are ob-tained in known manner by intimately mixing and/or grinding active substances of formula I with the suitable carriers, with or without the addition of dispersants or so~vents which are inert to the active substances.
The active substances can be in the form of and used in the following application forms:
Solids: dusts, tracking agents, granulates (coated granulates, impregnated granulates and homogeneous granulates) Liquids:
a) active substance concentrates which are dispersible in water: wettable powders, pastes, emulsionsi b) solutions:
The content of active substances in the compositions describ-ed above is between 0.1 and 95%.
The active substances of formula I can for example be formulated as follows:

107432~i Dust:
The following substances are used to prepare (a~ a 5% and (b) a 25% dust:
a)5 parts of active substance, 95 parts of talcum.
b)2 parts of active substance, 1 part of highly dispersed silicic acid, 97 parts of talcum.
The active substance are mixed with the carriers and ground.
Granulate:
The following ingredients are used to prepare a 5% granulate:
5 parts of active substance, 0.25 part of epichlorohydrine, 0.25 part of cetyl polyglycol ether, 3.50 parts of polyethylene glycol, 91 parts of kaolin (particle size 0.3 to 0.8 mm).
The active substance is mixed with epichlorohydrin and dissolved in 6 parts of acetone, then polyethylene glycol and cetyl polyglycol ether are added. The resultant solution is sprayed onto kaolin and the acetone is subsequently evaporated in vacuo.
Wettable Powder:
The following ingredients are used to prepare a) a 40%, b) and c) a 25% and d) a 10% ~ettable powder:

.

107432~i a) 40 parts of active substance, 5 parts of sodium lignin sulphona~e, 1 part of sodium dibu~yl-naphthalene sulphonate, 54 parts of silicic acid;
5 b) 25 parts of active substance~
4.5 parts of calcium lignin sulphonate, 1.9 parts of Champagne-chalk/hydroxyethylcellulose mixture (1:1), 1.5 parts of sodium dibutyl-naphthalenesulphonate, 19.5 parts of silicic acid, 19.5 parts of Champagne-chalk, 28.1 parts of kaolini c) 25 parts of active substance,
2.5 parts of isooctylphenoxy-polyethylene-ethanol, 1.7 parts of Champagne-chalk/hydroxyethylcellulose mixture (1:1), 8.3 parts of sodium aluminium silicate, 16.5 parts of kieselguhr, 46 parts of kaolin;
20 d) 10 parts of active substance,
3 parts of a mixture of sodium salts of saturated fatty alcohol sulphonates, 5 parts of naphthalenesulphonic acid/formaldehyde condensate, 82 parts of kaolin.

- _ g _ ,:, 1~)7432~

The active substances are intimately mixed with the additives in suitable mixers and ground in appropriate mills and rollers to yield wettable powders, which can be diluted with water to give suspensions of the required concentration.
Emulsifiable concentrates -The following substances are used to prepare a) a 10%, b) a 25%, c) a 50% emulsifiable concentrate:
a) 10 parts of active substance, 3.4 parts of epoxidised vegetable oil, 3.4 parts of a combination emulsifier, composed of fatty alcohol polyglycol ether and calcium alkylarylsulphona~e, 40 parts of dimethyl formamide, 43.2 parts of xylene;
15 b) 25 parts of active substance, 2.5 parts of epoxidised vegetable oil, 10 parts of an alkylarylsulphonate/fatty alcohol polyglycol ether mixture, 5 parts of dimethyl formamide 57.5 parts of xylenei c) 50 parts of active substance,
4.2 parts of tributylphenol polyglycol ether, ~.5 parts of calcium dodecylbenzenesulfonate, 20 parts of cyclohexanone, 20 parts of xylene.

- ~O -107432~ `

Emulsions of any required concentration can be prepared by diluting the above described concentrates with water.
Spray The following ingredients are used to prepare a) a 5% and b) a 95% spray a) 5 parts of active substance, 1 part of epichlorohydrin, 94 parts of ligroin (boiling range 160-190C);
b) 95 parts of active substance,
5 parts of epichlorohydrin.
The following Examples will serve to illustrate the invention in more detail.

1~7432f~i Example 1 a) Preparation of l-(l'-methyl-2'-methoxy-ethyl)-3-hydroxy-5-methylthio-1,2,4-triazole 0.5 Mole of the compound of the formula C~30C~l2~c~ C~13 N ~ ooC2~T5 CN
(n20 = l.47~.2) is added dropwise at room temperature to a solution consisting of 0.5 mole of sodium hydroxide in 100 ml of water and into which 0.5 mole of CH3SH has been introduced. The reaction proceeds exothermically (70C). The reaction mixture is keptforl hour at 80C. After cooling, the product which crystallises out is collected by filtration and recrystallised from ether/
hexane to yield the compound of the formula 3 `2CH C~13 N - N
CH3S ~N ~ 0ll with a melting point of 102-104C. The compound of the formula C~330C~2 ~ CH3 N-- N

2 5 ~N~ 011 10743Zf~
(m.p. 94-96C) is obtained in analogous manner.
b) Preparation of 0,0-diethyl-0-~1-(1'-methyl-2'-methoxy-ethyl)-5-methylthio-1,2,4-triazolyl-(3)-thiophosphoric acid ester _ .
0.1 mole of 1-(1'-methyl-2'-methoxy-ethyl)-3-hydroxy-5-methylthio-1,2,4-triazole and 0.1 mole of potassium carbonate in 200 ml of methyl ethyl ketone are refluxed for 2 hours.
After the dropwise addition of 0.1 mole of diethylthiophos-phoric chloride at 40C, the mixture is refluxed once more for 2 hours, then left to stand for 15 hours at 20C. The salts are filtered off and the filtrate is concentrated in vacuo. The oiiy residue is purified through a column of silica gel with chloroform as eluant to yield the compound of the formula Cll30C~l2 / CH3 N - N

CH3S~ P(C2~l5)2 in the form of an oil with a refractive index of n20= 1.5033.
The following compounds are obtained in analogous manner:

10-~3Z6i CH30CH2~CH~ CH3 C2H5S~N ~P COC2H5) 2 n D = 1.5072 CH30CH2~CH~CH3 N--N S
(oc2H5)2 nD20 = 1.4970 3 2 \ ~CH3 --N
3 2 J~ ~L ,S, nD20 = 1.4935 3 2 \ / CH3 CH
~_ N S
2 5 J~NJI O-P(OC4Hg(n))2 nD20 = 1.4960 ,CH nD20 = 1.4770 C2H5S ~N/J O-P (C2H5) 2 CH

C2H5S~ N~LO-P(OCH3)2 nD - 1.5025 1074~

Example 2 A) Insec~icidal stomach poison action Cotton plants were sprayed with a 0.05% aqueous emulsion of active substance (obtained from a 10% emulsifiable concentrace).
After the spray coating had dried, the cotton plants were populated respectively with Spodoptera littoralis and Heliothis virescens larvae in the L3 stage.
In this test, the compounds of Example lb exhibited a good insecticidal stomach poison action on Spodoptera and Heliothis larvae.
B) System insecticidal action The systemic action was determined by immersing rooted bean plants (Vicia faba) in a 0.01% aqueous solution of active substance (obtained from a 10% emulsifiable concentrate).
After 24 hours the parts of the plants above the soil were populated with aphids (Aphis fabae). The aphids were protected from the contact and gas action by a special dev;ce. The test was carried out at 24C and 70% relative humidity.
In this test, the compounds of Example lb exhibited systemic insecticidal action on Aphis fabae.

Example 3 Action on Chilo suppressalis Six rice plants of the variety Caloro were transplanted into 10~3'~

each of a number of plastic pots having a diameter of 17 cm at the top, and reared to a height of approx. 60 cm. Infestation with larvae of Chilo suppressalis (Ll stage; 3 to 4 ~ in length) took place 2 days after the active substance had been added to the paddy water in granulate form (rate of application 8 kg of active substance/hectare). Evaluation of the insect-icidal action took place 10 days after addition of the granulate. The compounds of formula Ib acted in this test on Chilo suppressalis.

Example 4 Acaricidal action Phaseolus vulgaris (dwarf beans) had an infested piece of leaf from a mass culture of tetranychus urticae placed on them 12 hours before the test for the acaricidal action.
The mobile stages which had migrated to the plants were sprayed with the emulsified test preparations from a chroma-tography atomiser so that the sprayed preparation did not run off. The number of living and dead larvae, adults and eggs were evaluated after 2 to 7 days under a stereoscopic micro-scope and the result expressed in percentages. During thecourse of the test, the treated plants were kept in green-house compartments at 25C. The compounds of Example lb acted in the above test on eggs, larvae and adults of Tetranychus urticae.

107432~i Example 5 Action on soil nematodes The action on soil nematodes was tested by applying the active substances in the respe~tive concentration indicated to and intimately mixing them with soil infected with root gall nematodes (Meloidgyne arenaria). Im~ediately afterwards, tomato cuttings were planted in the thus prepared soil in a test run and after 8 days tomato seeds were sown in another test run.
In order to assess the nematocidal action, the galls present on the roots were counted 28 days after planting and sowing respectively. In this test the compounds according to Example lb exhibited good action on Meloidgyne arenaria.

EY.ample 6 Action on ticks A) Rhipicephalus bursa Five adult ticks and 50 tick larvae were counted into each of a number of test tubes and imersed for l to 2 minutes in 2 ml of an aqueous emulsion containing a concentration of lO0, lO, l or O.l ppm of test substance. Each test tube was then sealed with a cotton-wool plug and placed on its head to enable the cotton wool to absorb the acti~e substance emulsion.
The adults were evaluated after 2 wee'~s and the larvae after 2 days. Each ~est was repeated twice.

lOt7~3~

B) Boophilus_~icroDI~s (larvae) Tests were carried out on 20 OP- sensitive and 20 OP-resistant larvae with aqueous emulsions similar to those used in test A.
(The resistance refers to the tolerance towards diazinone).
The compounds of Example lb acted in these tests on adults and larvae of Rhipicephalus bursa and OP-sensitive and of resistant larvae of Boophilus microplus.

Example 7 Action of Erysiphe ~raminis on Hordeum vulgare Barley plants (approx. 8 cm in height) were sprayed with a spray broth (active subs~ance content: 0.05%) prepared from a wettable powder of the active substance.
After 48 hours the trea~ed plants were dusted with conidia of the fungus. The infec~ed barley plants were stood in a green-house at approx. 22C and the fungus attack was evaluatedafter 10 days.
The compounds of Example lb acted in this test on Erysiphe graminis.

Claims (14)

Claims:
1. A 1,2,4-triazole of the formula wherein each of R1, R2 and R3 represents a C1-C6-alkyl group and X represents an oxygen or sulphur atom.
2. A 1,2,4-triazole according to claim 1, wherein each of R1, R2 and R3 represents a methyl or ethyl group and X
represents a sulphur atom.
3. A 1,2,4-triazole according to claim 2 of the formula
4. A 1,2,4-triazole according to claim 2 of the formula
5. A 1,2,4-triazo1e according to claim 1 of the formula
6. A 1,2,4-triazole according to claim 1 of the formula
7. A 1,2,4-triazole according to claim 1 of the formula
8. A 1,2,4-triazole according to claim 1 of the formula
9. A 1,2,4-triazole according to claim 1 of the formula
10. A process for the manufacture of compounds according to claim 1, wherein a compound of the formula wherein R1, R2 and X are as defined in claim 1 and Hal represents a halogen atom, is reacted with a compound of the formula wherein R3 is as defined in claim 1 and Me represents a hydrogen atom or alkali metal, ammonium or trialkylammonium, optionally in the presence of an acid acceptor.
11. A method of controlling animal and plant pests, which comprises contacting the pests with a compound as claimed in claim 1.
12. A method according to claim 11, wherein the pests to be control-led are insects and representatives of the order Acarina.
13. A method according to claim 11, wherein the pests to be control-led are phytopathogenic nematodes.
14. A method according to claim 11, wherein the pests to be control-led are phytopathogenic fungi.
CA265,476A 1975-11-14 1976-11-12 Esters Expired CA1074326A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH1479675A CH602012A5 (en) 1975-11-14 1975-11-14 (5)-Alkylthio-(1,2,4)-triazolyl-(3)-(thio)phosphates
CH1200276 1976-09-22

Publications (1)

Publication Number Publication Date
CA1074326A true CA1074326A (en) 1980-03-25

Family

ID=25709393

Family Applications (1)

Application Number Title Priority Date Filing Date
CA265,476A Expired CA1074326A (en) 1975-11-14 1976-11-12 Esters

Country Status (8)

Country Link
JP (1) JPS5262277A (en)
AT (1) AT341830B (en)
CA (1) CA1074326A (en)
DE (1) DE2651556A1 (en)
FR (1) FR2331566A1 (en)
GB (1) GB1563733A (en)
NL (1) NL7612543A (en)
PH (1) PH12226A (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4265897A (en) * 1978-11-14 1981-05-05 Ciba-Geigy Corporation N-N-Dimethyl-1-(1'-methyl-2'-methoxyethyl)-1,2,4-triazolylcarbamates

Also Published As

Publication number Publication date
NL7612543A (en) 1977-05-17
PH12226A (en) 1978-11-29
ATA844776A (en) 1977-06-15
GB1563733A (en) 1980-03-26
FR2331566A1 (en) 1977-06-10
FR2331566B1 (en) 1978-04-14
AT341830B (en) 1978-02-27
DE2651556A1 (en) 1977-05-26
JPS5262277A (en) 1977-05-23

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