Phenylforamidines and pesticidal methods using same

The present invention relates to phenylformamidines, to processes for 
producing them, and to their use for combating pests. The 
phenylformamidines have the formula 
##STR2## 
wherein R.sub.1, R.sub.2 and R.sub.3 each represent hydrogen, C.sub.1 
-C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy or halogen; R.sub.4 represents 
methyl or ethyl; and R.sub.5 represents C.sub.1 -C.sub.8 -alkyl or C.sub.3 
-C.sub.6 -cycloalkyl. Halogen denotes herein fluorine, chlorine, bromine 
and/or iodine, especially chlorine and/or bromine. The alkyl and alkoxy 
groups denoted by R.sub.1, R.sub.2, R.sub.3 and R.sub.5 can be 
straight-chain or branched-chain. Examples of such groups are: methyl, 
methoxy, ethyl, ethoxy, propyl, isopropyl and n-, i-, sec.- or 
tert.-butyl. As cycloalkyl, R.sub.5 is in particular cyclopropyl or 
cyclohexyl. 
Phenylformamidines preferred by virtue of their effectiveness are those of 
the formula I wherein R.sub.1, R.sub.2 and R.sub.3 each represent 
hydrogen, methyl, chlorine or bromine; R.sub.4 represents methyl or ethyl; 
and R.sub.5 represents methyl or cyclopropyl. 
The phenylformamidines of the formula I can be produced by processes known 
per se, for example by reacting a compound of the formula 
##STR3## 
in the presence of an acid-binding agent, with a compound of the formula 
##STR4## 
In the formulae II and III, R.sub.1 to R.sub.5 have the meanings given for 
the formula I, and "Hal" denotes a halogen atom, particularly chlorine or 
bromine. Suitable acid-binding agents are, in particular, tertiary amines 
such as trialkylamines and pyridine, also hydroxides, oxides, carbonates 
and bicarbonates of alkali metals and alkaline-earth metals, and also 
alkali metal alcoholates such as potassium-t.-butylate and sodium 
methylate. The process is performed at a reaction temperature of between 
-20.degree. and +30.degree. C., under normal or elevated pressure, and 
optionally in an inert solvent or diluent, or in an excess of the 
acid-binding agent used. Suitable solvents or diluents are, for example, 
ethers and ethereal compounds, such as diethyl ether ether, dipropyl 
ether, dioxane, dimethoxyethane and tetrahydrofuran; amides such as 
N,N-dialkylated carboxylic acid amides; aliphatic, aromatic as well as 
halogenated hydrocarbons, particularly benzene, toluene, xylenes, 
chloroform and chlorobenzene; nitriles such as acetonitrile; 
dimethylsulphoxide and ketones such as acetone and methyl ethyl ketone. 
The starting materials of the formulae II and III are known or can be 
produced by methods analogous to known methods. The compounds of the 
formula I are suitable for combating various animal and plant pests. The 
compounds thus have nematocidal properties, and can be used for example 
for combating phytopathogenic nematodes. They are also suitable for 
combating viruses, bacteria and phytopathogenic fungi. 
The compounds of the formula I are especially suitable for combating 
insects, and phytopathogenic mites and ticks, for example of the orders: 
Lepidoptera, Coleoptera, Homoptera, Heteroptera, Diptera, Acarina, 
Thysanoptera, Orthoptera, Anoplura, Siphonaptera, Mallophaga, Thysanura, 
Isoptera, Psocoptera and Hymenoptera. 
The compounds of the formula I are suitable in particular for combating 
insects that damage plants, especially insects that damage plants by 
eating, in crops of ornamental plants and useful plants, particularly in 
cotton crops (e.g. against Spodoptera littoralis and Heliothis virescens) 
and in crops of vegetables (e.g. against Leptinotarsa decemineata and 
Myzus persicae). The active substances of the formula I also have a very 
favourable action against flies, such as Musca domestica, and against 
mosquito larvae. 
The acaricidal and insecticidal action can be substantially broadened and 
adapted to suit given circumstances by the addition of other insecticides 
and/or acaricides. Suitable additives are, for example, organic phosphorus 
compounds; nitrophenols and derivatives thereof; formamidines; ureas; 
other pyrethrin-like compounds; as well as carbamates and chlorinated 
hydrocarbons. Compounds of the formula I are combined particularly 
advantageously with substances having an intensifying effect. Examples of 
such compounds are, inter alia: piperonyl butoxide, propynyl ethers, 
propynyl oximes, propynyl carbamates and propynyl phosphonates, 
2-(3,4-methylenedioxyphenoxy)-3,6,9-trioxaundecane and 
S,S,S-tributylphosphorotrithioates. 
The compounds of the formula I can be used on their own or together with 
suitable carriers and/or additives. Suitable carriers and additives may be 
solid or liquid, and they correspond to the substances common in 
formulation practice, such as natural or regenerated substances, solvents, 
dispersing agents, wetting agents, adhesives, thickeners, binders and/or 
fertilisers. For application, the compounds of the formula I can be 
processed into the form of dusts, emulsion concentrates, granulates, 
dispersions, sprays or solutions, the formulation of these being effected 
in a manner commonly known in the art. Also to be mentioned are cattle 
dips and spray races, in which aqueous preparations are used. 
The compositions according to the invention are produced in a manner known 
per se by the intimate mixing and/or grinding of active substances of the 
formula I with suitable carriers, optionally with the addition of 
dispersing agents and solvents which are inert to the active substances. 
The active substances can be obtained and used in the following forms: 
Solid Preparations: dusts, scattering agents or granules (coated, 
impregnated or homogeneous granules); 
Liquid Preparations: 
(a) water-dispersible concentrates of active substance: wettable powders, 
pastes or emulsions; 
(b) solutions. 
The content of active substance in the compositions described is between 
0.1 and 95%. The active substances of the formula I can be formulated for 
example as follows: 
Dusts 
The following substances are used to produce (a) a 5% dust 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 dispersed silicic acid, 
97 parts of talcum. 
The active substances are mixed and ground with the carriers. 
Granulate 
The following substances are used to produce a 5% granulate: 
5 parts of active substance, 
0.25 part of epichlorohydrin, 
0.25 part of cetyl polyglycol ether, 
3.50 parts of polyethylene glycol, 
91 parts of kaolin (particle size 0.3-0.8 mm). 
The active substance is mixed with the epichlorohydrin and dissolved with 6 
parts of acetone; the polyethylene glycol and cetyl polyglycol ether are 
then added. The solution obtained is sprayed onto kaolin, and the acetone 
is evaporated off in vacuo. 
Wettable powders 
The following constituents are used to produce (a) a 40%, (b) and (c) a 
25%, and (d) a 10% wettable powder: 
(a) 
40 parts of active substance, 
5 parts of sodium lignin sulphonate, 
1 part of sodium dibutyl-naphthalene sulphonate, 
54 parts of silicic acid; 
(b) 
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 of Champagne chalk, 
28.1 parts of kaolin; 
(c) 
25 parts of active substance, 
2.5 parts of isooctylphenoxy-polyoxyethylene-ethanol, 
1.7 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1), 
8.3 parts of sodium aluminum silicate, 
16.5 parts of kieselguhr, 
46 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 condensate, 
82 parts of kaolin. 
The active substances are intimately mixed in suitable mixers with the 
additives, and the mixture is then ground in the appropriate mills and 
rollers. There are obtained wettable powders which can be diluted with 
water to give suspensions of the desired concentration. 
Emulsifiable concentrate 
The following substances are used to produce (a) a 10%, (b) a 25%, and (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 consisting of fatty alcohol 
polyglycol ether and alkylarylsulphonate calcium salt, 
40 parts of dimethylformamide, 
43.2 parts of xylene; 
(b) 
25 parts of active substance, 
2.5 parts of epoxidised vegetable oil, 
10 parts of alkylarylsulphonate/fatty alcohol polyglycol ether mixture, 
5 parts of dimethylformamide, 
57.5 parts of xylene; 
(c) 
50 parts of active substance, 
4.2 parts of tributylphenol-polyglycol ether, 
5.8 parts of calcium-dodecylbenzenesulphonate, 
20 parts of cyclohexanone, 
20 parts of xylene. 
Emulsions of the desired concentration can be prepared from these 
concentrates by dilution with water. 
Spray 
The following constituents are used to produce (a) a 5% spray and (b) a 95% 
spray: 
(a) 
5 parts of active substance, 
1 part of epichlorohydrin, 
94 parts of ligroin (boiling limits 160.degree.-190.degree. C.), 
(b) 
95 parts of active substance, 
5 parts of epichlorohydrin.

The invention is further illustrated by the following Examples. 
EXAMPLE 1 
Production of 
1-(2-methyl-4-chlorophenyl)-3,5-dimethyl-1,3,5-triaza-4-sulpha-5-0,0-dimet 
hyl-phosphonyl-hex-1-ene 
9.5 g of triethylamine is added to a solution of 16.6 g of 
N-methyl-N'-(4-chloro-2-methylphenyl)-formamidine in 100 ml of methylene 
chloride. There is then slowly added dropwise at 0.degree. C. with 
continuous stirring 18.5 g of the compound of the formula 
##STR5## 
The mixture is stirred for a further half hour without cooling, and 100 ml 
of water is thereupon added. The methylene chloride solution is dried and 
then evaporated off under high vacuum to yield the compound of the formula 
##STR6## 
as yellow oil having a refractive index of n.sub.D.sup.20.degree. =1.5624. 
The following compounds are produced in an analogous manner: 
______________________________________ 
##STR7## n.sub.D.sup.20.degree. = 1,5512 
##STR8## n.sub.D.sup.20.degree. = 1,5563 
##STR9## n.sub.D.sup.20.degree. = 1,5661 
##STR10## n.sub.D.sup.20.degree. = 1,5434 
##STR11## n.sub.D.sup.20.degree. = 1,5592 
##STR12## n.sub.D.sup.20.degree. = 1,5401 
##STR13## n.sub.D.sup.20.degree. = 1,5488 
##STR14## n.sub.D.sup.20.degree. = 1,5439 
##STR15## n.sub.D.sup.20.degree. = 1,5266 
##STR16## n.sub.D.sup.20.degree. = 1,5215 
##STR17## n.sub.D.sup.20.degree. = 1,5266 
##STR18## n.sub.D.sup.20.degree. = 1,5306 
##STR19## n.sub.D.sup.20.degree. = 1,5091 
##STR20## n.sub.D.sup. 20.degree. = 1,5435 
##STR21## n.sub. D.sup.20.degree. = 1,5516 
##STR22## n.sub.D.sup.20.degree. = 1,5390 
##STR23## n.sub. D.sup.20.degree. = 1,5387 
______________________________________ 
EXAMPLE 2 
(A) Insecticidal stomach-poison action 
Cotton plants were sprayed with a 0.05% aqueous emulsion of the active 
substance (obtained from a 10% emulsifiable concentrate). 
After drying of the coating, larvae of Spodoptera littoralis in the L.sub.3 
-stage and of Heliothis virescens in the L.sub.3 -stage were placed onto 
the cotton plants. The test was carried out at 24.degree. C. with 60% 
relative humidity. 
Compounds according to Example 1 exhibited in the above test a good 
insecticidal stomach-poison action against larvae of Spodoptera littoralis 
and Heliothis virescens. 
(B) Systemic insecticidal action 
In order to determine the systemic action, rooted bean plants (Vicia faba) 
were placed into a 0.01% aqueous solution of the active substance 
(obtained from a 10% emulsifiable concentrate). After 24 hours, bean 
aphids (Aphis fabae) were placed onto the parts of the plants that had 
been above the soil. By means of a special device, the bean aphids were 
protected from the effects of contact and of gas. The test was carried out 
at 24.degree. C. with 70% relative humidity. 
Compounds according to Example 1 exhibited in the above test a systemic 
insecticidal action against Aphis fabae. 
EXAMPLE 3 
Action against Chilo suppressalis 
Rice plants of the variety Caloro were planted six plants per pot in 
plastic pots having an upper diameter of 17 cm, and grown to a height of 
about 60 cm. Infestation with Chilo suppressalis larvae (L.sub.1 ; 3-4 mm 
long) was carried out 2 days after application of the active substance in 
granular form (amount applied=8 kg of active substance per hectare) to the 
paddy water. An evaluation of the insecticidal action was made 10 days 
after application of the granules. 
Compounds according to Example 1 exhibited in the above test a good action 
against Chilo suppressalis. 
EXAMPLE 4 
Acaricidal action 
Phaseolus vulgaris plants were infected, 12 hours before the test for 
acaricidal action, with an infested piece of leaf from a mass culture of 
Tetranychus urticae. The transferred mobile stages were sprayed with the 
emulsified test preparations from a chromatography-sprayer in a manner 
ensuring no overflow of the spray liquor. An assessment was made after 2 
and 7 days, by examination under a binocular microscope, of the living and 
of the dead larvae, adults and eggs, and the results were expressed as 
percentages. The treated plants were kept during the "holding time" in 
greenhouse compartments at 25.degree. C. 
Compounds according to Example 1 exhibited in the above test a good action 
against adults, larvae and eggs of Tetranychus urticae. 
EXAMPLE 5 
Action against soil nematodes 
In order to test their action against soil nematodes, the active substances 
were added to soil infested with root-gall nematodes (Meloidogyne 
arenaria), and intimately mixed with the soil. In one test series, tomato 
seedlings were planted immediately after preparation of the soil in this 
manner, and in the other test series tomatoes were sown after a waiting 
time of 8 days. An assessment of the nematocidal action was made by 
counting the galls present on the roots 28 days after planting and sowing, 
respectively. 
Active substances according to Example 1 exhibited in this test a good 
action against Meloidogyne arenaria. 
EXAMPLE 6 
Action against ticks 
(A) Rhipicephalus bursa 
For each concentration, 5 adult ticks and 50 tick larvae, respectively, 
were counted into a small glass test tube, and immersed for 1 to 2 minutes 
in 2 ml of an aqueous emulsion from a dilution series of 100, 10, 1 and 
0.1 ppm of test substance. The tubes were then sealed with a standardised 
cotton plug, and inverted so that the active-substance emulsion could be 
absorbed by the cotton wool. 
The evaluation in the case of the adults was made after 2 weeks and in the 
case of the larvae after 2 days. There were two repeats for each test. 
(B) Boophilus microplus (larvae) 
With a dilution series analogous to that of Test A, tests were carried out 
with 20 sensitive larvae and OP-resistant larvae, respectively (resistance 
is with respect to diazinon compatibility). 
Compounds according to Example 1 were effective in these tests against 
adults and larvae of Rhipicephalus bursa and against sensitive and 
OP-resistant larvae, respectively, of Boophilus microplus. 
EXAMPLE 7 
Action against Erysiphe graminis on Hordeum vulgare 
Barley plants about 8 cm in height were sprayed with a spray liquor 
prepared from wettable powder of the active substance (0.05% of active 
substance). After 48 hours, the treated plants were dusted with conidia of 
the fungus. The infested barley plants were placed in a greenhouse at 
about 22.degree. C. and the fungus infestation was assessed after 10 days. 
Compound according to Example 1 were effective in this test against 
Erysiphe graminis.