CA1048049A

CA1048049A - Esters

Info

Publication number: CA1048049A
Application number: CA180,394A
Authority: CA
Inventors: Alexis A. Oswald; George N. Schmit; Paul L. Valint
Original assignee: Ciba Geigy AG
Current assignee: Novartis AG
Priority date: 1972-09-08
Filing date: 1973-09-06
Publication date: 1979-02-06
Also published as: ZA737167B; BE804567A; SU724075A3; CH569417A5

Abstract

Abstract of the Disclosure New thiophosphoric and dithiophosphoric acid esters of the formula

Description

The present invention relates to thiophosphoric and dithiophosphoric acid esters, process for their manufac-ture, and to their use in pest control. The compounds have the formula P-O-C=CH-COOR3 (I) wherein Rl represents methyl or ethyl, R2 represénts alkyl with 3 to 5 carbon atoms, R3 represents alkyl with 1 to 3 carbon atoms, allyl,alkinyl with 3 to 6 carbon atoms, benzyl, ~-methyl-benzyl, methoxyethyl, methoxy-ethoxyethyl or 1-methyl-2-methoxy-ethyl, and X represents oxygen or sulphur.
The alkyl and alkinyl groups represented by R2 and R3 can be straîght-chain or branched. Examples of such groups include: methyl, ethyl3 n-propyl, isopropyl, n-, i-, sec. and tert. butyl, n-pen~yl, propargyl, l-methyl-

2-propinyl, 1,1-dimethyl-2-propinyl, l-methyl-l-ethyl-2-propinyl.
Preferred compounds on account of their acti~ity are those of the formula I, wherein Rl represents ethyl, R2 represents n-propyl, isobutyl or sec. butyl, R3 represents methyl, isopropyl, benzyl~ ~-methylbenzyl, l-methyl-2-metho~yethyl or l-methyl-l-ethyl-propinyl, and X repre-sents oxygen or sulphur.
The compounds are manufactured by the following methods which are known per se:

1) R10 ~ 11 / P-Cl + CH3COCH2COR3 acid acceptor~ I

~II) (III) 2) PXC13 + CH3COCH2COR3 acid acceptor ~IV) ~III) tl I
(Cl)2p-o-c=cH-coR3 + 1 ~VI) acid accepto_~ I
(V) 2. R2SH ~VII) or 1. R2SH (VII) 2- RlH (VI) Suitable acid acceptors are: tertiary amines, e.g. trialkylamines, pyridine, dialkyl anilines; inorganic bases, e.g. hydroxides; carbonates and bicarbonates of alkali metals and alkaline earth metals.
Processes 1 and 2 are carried out at a reaction temperature between -10C and +100C, in particular between 20 and 80C, at normal pressure and in solvents or diluents.

Suitable solvents or diluents are, for example, ethers and ethereal compounds, e.g. diethyl ether, dipropyl ether, dioxan, dimethoxyethane, tetra-hydrofuran; amides, e.g. N,N-dialkylated carboxylic amides; aliphatic, aromatic, and halogenated hydrocarbons in particular benzene, toluene, xylene, chloroform, chlorobenzene; nitriles, e.g. acetonitrile; dimethyl sulphoxide;
ketones, e.g. acetone, methyl ethyl ketone.

-3--48~49 Some of the starting materials of the formulae II, III, and IV are known and can be manufactured by methods analogous to known ones.
The compounds of the formula I have a broad biocidal activity and are therefore suitable for combating a variety of plant and animal pests.
In particular, the compounds of the formula I
possess insecticidal and acaricidal properties and can be used against all development stages, for example, eg~s, larvae, pupae, nymphs, and adults of insects of the families:
Delphacidae, Blattidae, Gryllidae, Gryllotalpidae, Tettigoniidae, Cimicidae, Phyrrhocoridae, Reduviidae, Aphididae, Diaspididae, Pseudococcidae, Chrysomelidae, Coccinellidae, Bruchidae, Scarabae;dae, DermQstidae, Tenebrionidae, Tineidae, Noctuidae, Lymantriidae, Pyralidae, Culicidae, Tipulidae, Stomoxydae, Muscidae, Calliphoridae~ Trypetidae, Pulicidae, as well as Acaridae of the families Tetranychidae and Dermanyssidae.
The insecticidal or acaricidal action can be sub-stantially broadened and adapted to given circumstances by the addition of other insec~icides and/or acaricides.
Examples of suitable additives are: organic phosphorus compounds, derivatives of nitrophenols, formamidines, ureas, carbamates, and chlorinated hydrocarbons.
The compounds o~ the formula I may be used as pure active substance or together with suitable carriers and/
or additives. Suitable carriers and additives can be solid or liquid and correspond to the substances conven-~L~48~1~9 tionally used in formulation technology, for example natural or regenerated substances, solvents, dispersants, wetting agents, adhesives, thickeners, binders and/or fertilisers.
For application, the compounds of the formulae I and Ia may be processed to dusts, emulsion concentrated, gra-nules, dispersions, sprays, to solutions or suspensions, in the conventional formulation which is commonly employed in application technology.
The agents according to the invention are manufactured in known manner by intimately mixing and/or grinding ac-tive substances of the formuIae I with the suitable carriers, optionally with the addition of dispersants or solvents which are inert towards the active substances~
The active substances may take, and be used in, the following forms:
Solid forms:
Dus~s, tracking agents, granules, coated granules, impregnated granules and homogeneous granules.
Liquid forms:
: a) active substances which are dispersible in water:
wettable powders, pasts~ emulsions;
b) sol.utions.
The con~ent of active substance in the above des-cribed agents is between 0.1% to 95%, in which connection it should be mentioned that, in the case of application from aircraft or some other suitable means of application, it is possible to use concentrations of up to 99.5% or even pure active substance.

~ 9 The active substances of the formula I can, for example, be formula~ed as follows:
Dusts The following substances are used to manufacture a) a 5% and b) a 2% dust:
a) 5 parts of active substance 95 parts of talcum b) 2 parts of active substance 1 part of highly disperse silicic acid 97 parts of talcum.
The acti~e substances are mixed with the carriers and ground Granules The following substances are used to produce 5%
granules:
5 parts of active substance, 0.25 parts of epichlorohydrin, 0.25 parts of cetyl polyglycol ether, 3.50 parts of polyethylene glycol, 91 parts of kaolin ~particle si~e 0.3-0.8 mm).
The active substance is mixed with epichlorohydrin and dissolved with 6 par,s of acetone; the polyethylene glycoland cetyl polyglycol ether are then added. The thus obtained solu-tion is sprayed`on kaolin, and the aceton~
subsequently evaporated in vacuo.
Wettable powder:
The following constituents are used for the prepara-tion of a) a 40%, b) and c) a 25%land d) a 10% wettable powder:

û49 a) 40 parts of active substance, 5 parts of sodium lignin sulphonate, 1 part of sodium dibutyl-naphthalene sulphonate, 54 parts o silicic acid.
5b) 25 parts of active substance,

4.5 parts of calcium lignin sulphonate, 1.9 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1), 1.5 parts of sodium dibutyl naphthalene sulphonate, 19.5 parts of silicic acid, 19.5 parts o Champagne chalk, 28.1 parts of kaolin.
c) 25 parts of active substance, 2.5 parts of isooctylphenoxy-polyoxyethylene-15ethanol, , 1 7 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1), 8.3 parts of sodium aluminium silicate, 16 5 parts of kieselguhr, 2046 parts of kaolin d) 10 parts of active substance, 3 parts of a mixture of the sodium salts of saturated fatty alcohol sulphates,

5 parts of naphthalenesulphonic acid/formaldehyde 25condensate, 82 parts of kaolin.
The active substances are int~nate3y mixed, in suitable mixers, with the additives~ the mixture being then ground in the appropriate mills and rollers~ Wettable .

~ ~ 8~ ~9 powders are obtained which can be diluted with water to give suspensions of any desired concentration En~llsifiable concentrates The following substances are used to produce a) a S 10% and b) a 25% emulsifiable concentrate:
a) 10 parts of active substance, 3.4 parts of epoxidised vegetable oil, ; 13.4 parts of a combination emulsifier cons;.sting of fatty alcohol polyglycol ether and alkyl-arylsulphonate calcium salt, parts of dimethylformamide, ~ 3.2 parts of xylene.
b) 25 parts of active substance, 2.5 parts of epoxidised vegetable oil, 10 parts of an alkylarylsulphonate/fatty alcohol-polyglycol ether mixture, S parts of dimethylformam:ide, 57.5 par~s of xylene.
From these concentra~es it is possible to produce, by dilution with water, emulsions of any desired concen-tration.
Spray:
The ollowing constituents are used to prepare a 5% spray:
5 parts of active substance, 1 part of epichlorohydrin, 94 parts of benzine (boiling limits 160~190C).

8~
Example 1 O-eth~l S~ y~-O~ carbomethoxy~
thiolphosphate .
22 . 4 g of po-tassium-t-butylate and 23.2 g of methyl acetate are added to 100 ml of dimethyl formamide. 40 g of O-ethyl-S-(Il)propyl-thiochlorophosphate are added dropwise at 20 to 30C and the reaction mixture is stirred for 16 hours at room temperature. The solvent is subsequently re.moved in vacuo at 60C bath temperature, the residue is taken up in 100 ml of methylene chloride and washed twice with 30 ml of normal sodium hydroxide solution each time. The solvent is evaporated in vacuo to yield the compound of the formula C2H50 ll I 3 P-O-C=CH-COOCH3 (n ) C3HjS
.
with a boiling poînt pf 90C/O.OOl Torr and a refractive index of nD25 = 1. 4818.
The following compounds are also manu~ac~ured in analogous manner:

~8~

C2~5 1i 1 3 (n)C3H7S> ~I COOCX2C~I=CH2 n25 = 1,4815 0 H o CHS ~ = 1,5198 C2H50 ll 1 3 IH3 25 >~0--C=cH-~oocH~3 nD =1, 5140 C2~-I50 ll 1 3 (n~C3H~7s> ~I COOC2H40C2H40CH~S n~ a 1~4795 .
C H 0 C~I3 ~n)c3Hr7s> CX {~OCCH2C-CH n25 = 1,504 C H o S C11~3 >~0--C=CH~COCCH3 n25 =1,5180 - 10 - ' ' C H o S CIH ~;
(n)C3H7s> OH CoocH2-~H=cH2 nD5 = 1, 5051 C 2H5 o ISl I 3 >P-C~C=CH~OOCH2~_CH n25 = 1, 504 C2H50 ISl I 3 1 3 25 >~O~=C~I--COOC~ nD = L, 5223 ~' C2H50 ll 1 3 >~O~-~C~I--COOCH2-~ n25 = 1, 5276 .

C2E5 o S I 3 n ) C3H7S> ~ C OOC2H~1 OC 2H~ 0CH3 n~ 5 = 1, 4 93 9 ~L~48V~

.

- ' C2H 0\ 11 1 3 5 ~ P-0-C-CH-COOC H (i) nD3 = 1,4833 ,.
C2H 0 11 1 3 CIH~ -5 > P-0-C-CH-cOOcH-cH2ocH3 nD4 - 1~5085 .
.
S CH CH
- C2H5\ ll 1 3 1 3 23 P-0-C=CH-C00-CH-C-CH ~D= 1~5179 - .
0 CH~ CH

(n)CSH7S~ C CH COOCH-C-CH nD3 = 1,4938 " , ' ' 2 5 > P-0-C-CE~-COOC H (i) n23 ~ 1,5093 2 5 >p-0-C=CH COOCH-CE20CH3 nD3 = 1,4865 C2H50\ ll ¦ 1 3 (n)C3H7S ~ C_CH COOCI-C-CH n~3 =.1,4935 C2H5 . .
~....

C2H50 !sl ICH3 ClH3 > P-O-C=CH-COOC~C-CH nD3 = 1,5382 (n)C3H7S C2H5 > P-O-C-CH-COOCH ~ ~ nD = 1~5248 C2H50 11 IH3 nD = 1~5222 (sek,)C4HgS

> P-O-C=CH COOCH2 ~ n = 1,52B7 5 > 1l 1 3 / ~ nD = 1,5152 ( ) C5HllS

Example 2 A) Insecticidal ingest poison action Tobacco plants were sprayed with a 0.05% aqueous emulsion (obtained from a 10% emulsifiable concentrate).
After the coating had dried, the tobacco plants were populated with Spodoptera littoralis larvae L3 and Heliothis virescens larvae L3. The test was carried out at 24C and 60% relative humidity. In the above test, the compounds according to Example 1 exhibited good ingest poison action against Spodoptera littoralis and ~eliothis virescens.

B) Insecti.cidal cbntact action , Broad beans (Vicia faba) reared in pots were infec-ted with about 200 lea1ice ~Aphis fabae) per plant one day before the application. A spray broth in a concentra-tion of 1000 ppm (prepared from a 25% wettable powder) was applied with a compressed air spray to the leaves populated with lice. ~valuation took place 24 hours after the application. In the above test, the compounds accor-ding to Example 1 exhibited good contact action againstAphis fabae.

-- 1~ --Exam~le 3 Action a~ainst Chilo suppressalis Six rice plants at a time of the variety Caloro were transplanted into plastic pots (diameter at the top = 17 cm) and reared to a height of about 60 cm.
Infestation with Chilo suppressa~lis larvae (Ll: 3-4 mm long) took place 2 days after the active substance had been applied in granule form to the paddy water (rate of application: 8 kg of active substance per hectare). Eva-luation of the insecticidal action took place 10 daysafter application of the granules.
The compounds according to Example 1 exhibited good activity in the above test against Chilo suppressalis.

Example 4 Action agai st spider mites Phaseolus vulgaris (dwarf beans) had an infested piece of leaf from a mass culture o~ Tetranychus urticae placed on them 12 hours before the test for the acaricidal action. The mobile stages which have migrated were sprayed with the emulsified test preparations from a chromatogra-phy atomiser so that the` spray broth did not run off~ The number of living and dead larvae, adults and eggs were evaluated after 2 to 7 days under a stereoscopic micros-cope and the result expressed in percentages. During the "interiml'9 the treated plants were kept in greenhouse compartments at 25C.

The compo~mds according to Exarnple 1 exhibited good activity in the above test against eggs, larvae and adults of Tetranychus urticae.

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. Compounds of the formula wherein R1 represents methyl or ethyl, R2 represents alkyl with 3 to 5 carbon atoms, R3 represents alkyl with 1 to 3 carbon atoms, allyl, alkinyl with 3 to 6 carbon atoms, benzyl, .alpha.-methylbenzyl, methoxyethyl, methoxyethoxyethyl or 1-methyl-2-methoxyethyl, and X represents oxygen or sulphur.

2. Compounds according to claim 1, wherein R1 represents ethyl, R2 represents n-propyl, isobutyl or sec. butyl, R3 represents methyl, ethyl, isopropyl, benzyl, .alpha.-methylbenzyl, 1-methyl-2-methoxyethyl or 1-methyl-1-ethyl-2-propinyl, and X represents oxygen or sulphur.

3. O-ethyl-S-(n)-propyl-O-(1-carbomethoxy-1-propen-2-yl)-thiolphosphate, according to claim 2.

4. O-ethyl-S-(n)-propyl-O-(1-benzyloxycarbonyl-1-propen-2-yl)-thiol-phosphate, according to claim 2.

5. O-ethyl-S-(n)-propyl-O-[1-(.alpha.-methylbenzyloxycarbonyl)-1-propen-2-yl]-thiolphosphate, according to claim 2.

6. O-ethyl-S-(n)-propyl-O-(1-carbomethoxy-1-propen-2-yl)-dithiophos-phate, according to claim 2.

7. O-ethyl-S-(n)-propyl-O-(1-benzyloxycarbonyl-1-propen-2-yl)-dithio-phosphate, according to claim 2.

8. O-ethyl-S-(n)-propyl-O-(1-isopropoxycarbonyl-1-propen-2-yl)-thiol-phosphate, according to claim 2.

9. O-ethyl-S-(n)-propyl-O-(1-isopropoxycarbonyl-1-propen-2-yl)-dithiophosphate, according to claim 2.

10. O-ethyl-S-(n)-propyl-O- {1-[1-methyl-1-ethyl-2-propinyloxy)-carbonyl]-1-propen-2-yl} -thiolphosphate, according to claim 2.

11. O-ethyl-S-isobutyl-O-(1-benzyloxycarbonyl-1-propen-2-yl)thiolphos-phate, according to claim 2.

12. O-ethyl-S-sec.butyl-O-(1-benzyloxycarbonyl-1-propen-2-yl)-thiol-phosphate, according to claim 2.

13. A method of combatting pests of the class Insecta or of the order Acarina at a locus, which method comprises applying to the locus a compound as claimed in claim 1.

14. A method according to claim 13 wherein the locus comprises growing agricultural or horticultural crops or plants.