Combating arthropods with O-methyl-O-n-propyl-O-(2-carbalkoxy-2-alkoxy-vinyl)-thionophosphoric acid esters

Novel O-methyl-O-n-propyl-O-(2-carbalkoxy-2-alkoxy-vinyl)-thionophosphoric acid esters of the formula ##STR1## in which R and R.sup.1, which may be identical or different, each represent alkyl, Which possess arthropodicidal properties.

The present invention relates to and has for its objects the provision of 
particular new 
O-methyl-O-n-propyl-O-(2-carbalkoxy-2-alkoxy-vinyl)-thionophosphoric acid 
esters which possess arthropodicidal properties, active compositions in 
the form of mixtures of such compounds with solid and liquid dispersible 
carrier vehicles, and methods for producing such compounds and for using 
such compounds in a new way especially for combating pests, e.g. insects 
and acarids, with other and further objects becoming apparent from a study 
of the within specification and accompanying examples. 
It has been disclosed in Belgian Patent Specification No. 755,934 and 
German Published Specification DOS No. 1,199,251 that certain symmetrical 
O,O-dialkyl-O-vinyl-(thiono)-phosphoric acid esters, for example 
O,O-diethyl-O-(2-ethoxy-2-carbethoxy-vinyl)-thiono-(Compound A) and 
O,O-diethyl-O-(1-ethoxy-2-carbethoxy-vinyl)-phosphoric acid esters 
(Compound B), and in Belgian Patent Specification No. 654,748 that 
O-ethyl-O-(2-carbethoxy-2-cyano-1-methyl-vinyl)-ethanephosphonic acid 
ester (Compound C) possess insecticidal and acaricidal properties. 
The present invention provides as new compounds, the asymmetrical 
O,O-dialkyl-O-vinylthionophosphoric acid esters of the general formula 
##STR2## 
in which R and R.sup.1 each independently is alkyl. 
Preferably, R and R.sup.1 are alkyl with 1 to 6, especially 1 to 4, carbon 
atoms. 
The general formula (I) includes the corresponding cis- and trans-isomers 
of the structures (II) and (III) and the mixtures of these isomers: 
##STR3## 
Surprisingly, the asymmetrical O,O-dialkyl-O-vinyl-thionophosphoric acid 
esters according to the invention exhibit a better insecticidal and 
acaricidal action than the known symmetrical 
O,O-dialkyl-O-vinyl(thiono)phosphoric acid esters and the 
O-alkyl-O-vinylphosphonic acid esters of analogous structure and of the 
same type of action. The compounds according to the present invention thus 
represent a genuine enrichment of the art. 
The invention also provides a process for the preparation of an 
asymmetrical O,O-dialkyl-O-vinylthionophosphoric acid ester of the formula 
(I), in which an O-methyl-O-n-propylthionophosphoric acid diester halide 
of the general formula 
##STR4## 
in which Hal denotes halogen, preferably chlorine, is reacted with a 
1-alkoxy-1-formyl-acetic acid ester derivative of the general formula 
##STR5## 
and/or its enol form of the formula 
##STR6## 
in which R and R.sup.1 have the above-mentioned meanings, 
if appropriate in the presence of an acid acceptor and, if appropriate, in 
the presence of a solvent or diluent. 
If, for example, O-methyl-O-n-propyl-thionophosphoric acid diester chloride 
and 1-ethoxy-1-formyl-acetic acid isopropyl ester are used as starting 
materials, the course of the reaction can be represented by the following 
equation: 
##STR7## 
The O-methyl-O-n-propyl-thionophosphoric acid diester halides (IV) required 
as starting materials are known and can be prepared in accordance with 
processes known from the literature, as can the 1-alkoxy-1-formylacetic 
acid ester derivatives (V) and (Va), which are prepared by condensing 
1-alkoxyacetic acid alkyl esters with formic acid alkyl esters, if 
appropriate in the presence of an alcoholate. 
The following may be mentioned as individual examples of the 
1-alkoxy-1-formyl-acetic acid ester derivatives (V): 1-methoxy-, 
1-ethoxy-, 1-n-propoxy-, 1-isopropoxy-, 1-n-butoxy-, 1-sec.-butoxy- and 
1-isobutoxy-1-formylacetic acid methyl ester, ethyl ester, n-propyl ester, 
isopropyl ester, n-butyl ester, isobutyl ester and sec.-butyl ester. 
The process for the preparation of the compounds according to the invention 
is preferably carried out in the presence of a suitable solvent or 
diluent. Virtually all inert organic solvents can be used for this 
purpose, especially aliphatic and aromatic, optionally chlorinated, 
hydrocarbons, such as benzene, toluene, xylene, benzine, methylene 
chloride, chloroform, carbon tetrachloride and chlorobenzene; ethers, for 
example diethyl ether, dibutyl ether and dioxane; ketones, for example 
acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl 
ketone; and nitriles, such as acetonitrile and propionitrile. 
All customary acid-binding agents can be used as acid acceptors. Alkali 
metal carbonates and alkali metal alcoholates, such as sodium carbonate 
and potassium carbonate, sodium methylate and ethylate and potassium 
methylate, ethylate or tert.-butylate, have proved particularly suitable, 
as have aliphatic, aromatic or heterocyclic amines, for example 
triethylamine, trimethylamine, dimethylaniline, dimethylbenzylamine or 
pyridine. 
The reaction temperature can be varied within a substantial range. In 
general, the reaction is carried out at from 0.degree. to 100.degree. C., 
preferably at from 10.degree. to 60.degree. C. 
In general, the reaction is allowed to take place under normal pressure. 
In a preferred embodiment of the process, the 1-alkoxy-1-formylacetic acid 
ester derivative, preferably in 6 to 20% excess, is initially introduced, 
together with the acid acceptor, into one of the above-mentioned solvents, 
and the O-methyl-O-n-propylthionophosphoric acid diester halide is added 
dropwise to the mixture. After completion of the reaction an organic 
solvent, for example toluene, is added, and the organic phase is worked up 
in the usual manner by washing and drying it, and distilling off the 
solvent. 
The new compounds are obtained in the form of oils which in most cases 
cannot be distilled without decomposition but are freed from the last 
volatile constituents by so-called "slight distillation", that is to say 
by prolonged heating under reduced pressure to moderately elevated 
temperatures, and are purified in this manner. They are characterized by 
the refractive index. 
As already mentioned, the asymmetrical O,O-dialkyl-O-vinylthionophosphoric 
acid esters according to the invention are distinguished by an excellent 
insecticidal and acaricidal activity. They are active against plant pests, 
pests harmful to health and pests of stored products. They combine a low 
phytotoxicity with a good action against both sucking and biting insects 
and mites. 
For this reason, the compounds according to the invention can be employed 
successfully as pesticides in plant protection as well as in the hygiene 
field and the field of protection of stored products. 
The active compounds are well tolerated by plants, have a favorable level 
of toxicity to warm-blooded animals, and can be used for combating 
arthropod pests, especially insects and arachnids, which are encountered 
in agriculture, in forestry, in the protection of stored products and of 
materials, and in the hygiene field. They are active against normally 
sensitive and resistant species and against all or some stages of 
development. The above-mentioned pests include: 
from the class of the Isopoda, for example Oniscus asellus, Armadillidium 
vulgare and Porcellio scaber; from the class of the Diplopoda, for example 
Blaniulus guttulatus; from the class of the Chilopoda, for example 
Geophilus carpophagus and Scutigera spec.; from the class of the 
Symphyla, for example Scutigerella immaculata; from the order of the 
Thysanura, for example Lepisma saccharina; from the order of the 
Collembola, for example Onychiurus armatus; from the order of the 
Orthoptera, for example Blatta orientalis, Periplaneta americana, 
Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa 
spp., Locusta migratoria migratorioides, Melanoplus differentialis and 
Schistocerca gregaria; from the order of the Dermaptera, for example 
Forficula auricularia; from the order of the Isoptera, for example 
Reticulitermes spp.; from the order of the Anoplura, for example 
Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, 
Haematopinus spp. and Linognathus spp.; from the order of the Mallophaga, 
for example Trichodectes spp. and Damalinea spp.; from the order of the 
Thysanoptera, for example Hercinothrips femoralis and Thrips tabaci; from 
the order of the Heteroptera, for example Eurygaster spp.; Dysdercus 
intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus and 
Triatoma spp.; from the order of the Homoptera, for example Aleurodes 
brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, 
Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, 
Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., 
Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, 
Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax 
striatellus, Nilaparvata lugens, Aonidiella auranti, Aspidiotus hederae, 
Pseudococcus spp. and Psylla spp.; from the order of the Lepidoptera, for 
example Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, 
Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, 
Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix 
thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia 
spp., Earias insulana, Heliothis spp., Laphygma exigua, Mamestra 
brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia 
ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, 
Ephestia kuehniella, Galleria mellonella, Cacoecia podana, Capua 
reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima 
and Tortrix viridana; from the order of the Coleoptera, for example 
Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, 
Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, 
Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., 
Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., 
Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus 
sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera 
postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., 
Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium 
psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus 
spp., Melolontha melolontha, Amphimallon solstitialis and Costelytra 
zealandica; from the order of the Hymenoptera, for example Diprion spp., 
Hoplocampa spp., Lasius spp., Monomorium pharaonis and Vespa spp.; from 
the order of the Diptera, for example Aedes spp., Anopheles spp., Culex 
spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora 
erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., 
Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma 
spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia 
spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae and Tipula 
paludosa; from the order of the Siphonaptera, for example Xenopsylla 
cheopis and Ceratophyllus spp.; from the class of the Arachnida, for 
example Scorpio maurus and Latrodectus mactans; from the order of the 
Acarina, for example Acarus siro, Argas spp., Ornithodoros spp., 
Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus 
spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., 
Psoroptes spp., Chorioptes spp, Sarcoptes spp., Tarsonemus spp., Bryobia 
praetiosa, Panonychus spp. and Tetranychus spp.. 
The plant-parasitic nematodes include Pratylenchus spp., Radopholus 
similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., 
Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp. and 
Trichodorus spp.. 
The active compounds can be converted to the customary formulations, such 
as solutions, emulsions, wettable powders, suspensions, powders, dusting 
agents, foams, pastes, soluble powders, granules, aerosols, 
suspension-emulsion concentrates, seed-treatment powders, natural and 
synthetic materials impregnated with active compound, very fine capsules 
in polymeric substances and in coating compositions, for use on seed, and 
formulations used with burning equipment, such as fumigating cartridges, 
fumigating cans and fumigating coils, as well as ULV cold mist and warm 
mist formulations. 
These formulations are produced in known manner, for example by mixing the 
active compounds with extenders, that is to say, liquid or solid or 
liquefied gaseous diluents or carriers, optionally with the use of 
surface-active agents, that is to say, emulsifying agents and/or 
dispersing agents and/or foaming agents. In the case of the use of water 
as an extender, organic solvents can, for example, also be used as 
auxiliary solvents. 
As liquid diluents or carriers, especially solvents, there are suitable in 
the main, aromatic hydrocarbons, such as xylene, toluene, benzene or 
alkyl-naphthalenes, chlorinated aromatic or chlorinated aliphatic 
hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene 
chloride, aliphatic or alicyclic hydrocarbons, such as cyclohexane or 
paraffins, for example mineral oil fractions, alcohols, such as butanol or 
glycol as well as their ethers and esters, ketones, such as acetone, 
methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, or strongly 
polar solvents, such as dimethylformamide and dimethylsulphoxide, as well 
as water. 
By liquefied gaseous diluents or carriers are meant liquids which would be 
gaseous at normal temperature and under normal pressure, for example 
aerosol propellants, such as dichlorodifluoromethane or 
trichlorofluoromethane. 
As solid carriers there are preferably used ground natural minerals, such 
as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or 
diatomaceous earth, and ground synthetic minerals, such as highly 
dispersed silicic acid, alumina and silicates. 
Preferred examples of emulsifying and foam-forming agents include nonionic 
and anionic emulsifiers, such as polyoxyethylene-fatty acid esters, 
polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycol 
ethers, alkyl sulphonates, alkyl sulphates and aryl sulphonates as well as 
albumin hydrolysis products; and preferred examples of dispersing agents 
include lignin sulphite waste liquors and methylcellulose. 
Adhesives such as carboxymethylcellulose and natural and synthetic polymers 
in the form of powders, granules or latices, such as gum arabic, polyvinyl 
alcohol and polyvinyl acetate, can be used in the formulations. 
It is possible to use colorants such as inorganic pigments, for example 
iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such 
as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, 
and trace nutrients such as salts of iron, manganese, boron, copper, 
cobalt, molybdenum and zinc. 
The formulations in general contain from 0.1 to 95 percent by weight of 
active compound, preferably between 0.5 and 90 percent. 
The active compounds according to the invention may be used in the form of 
their formulations of the types that are commercially available 
formulations or in the use forms prepared from these formulations. 
The active compound content of the use forms prepared from the formulations 
of the types that are commercially available can vary within wide ranges. 
The active compound concentration of the use forms can be from 0.0000001 
to 100% by weight of active compound, preferably from 0.01 to 10% by 
weight. 
The compounds are employed in a customary manner appropriate for the use 
forms. 
When used against pests harmful to health and pests of stored products, the 
active compounds are distinguished by an excellent residual activity on 
wood and clay as well as a good stability to alkali on limed substrates. 
The active compounds according to the instant invention can be utilized, if 
desired, in the form of the usual formulations or compositions with 
conventional inert (i.e. plant compatible or herbicidally inert) pesticide 
diluents or extenders, i.e. diluents, carriers or extenders of the type 
usable in conventional pesticide formulations or compositions, e.g. 
conventional pesticide dispersible carrier vehicles such as gases, 
solutions, emulsions, suspensions, emulsifiable concentrates, spray 
powders, pastes, soluble powders, dusting agents, granules, etc. These are 
prepared in known manner, for instance by extending the active compounds 
with conventional pesticide dispersible liquid diluent carriers and/or 
dispersible solid carriers optionally with the use of carrier vehicle 
assistants, e.g. conventional pesticide surface-active agents, including 
emulsifying agents and/or dispersing agents, whereby, for example, in the 
case where water is used as diluent, organic solvents may be added as 
auxiliary solvents. The following may be chiefly considered for use as 
conventional carrier vehicles for this purpose: aerosol propellants which 
are gaseous at normal temperature and pressures, such as halogenated 
hydrocarbons, e.g. dichlorodifluoromethane and trichlorofluoromethane, as 
well as butane, propane, nitrogen and carbon dioxide; inert dispersible 
liquid diluent carriers, including inert organic solvents, such as 
aromatic hydrocarbons (e.g. benzene, toluene, xylene, alkyl naphthalenes, 
etc.), halogenated, especially chlorinated, aromatic hydrocarbons (e.g. 
chlorobenzenes, etc.), cycloalkanes, (e.g. cyclohexane, etc.), paraffins 
(e.g. petroleum or mineral oil fractions), chlorinated aliphatic 
hydrocarbons (e.g. methylene chloride, chloroethylene, etc.), alcohols 
(e.g. methanol, ethanol, propanol, butanol, glycol, etc.) as well as 
ethers and esters thereof (e.g. glycol monomethyl ether, etc.), amines 
(e.g. ethanolamine, etc.), amides (e.g. dimethyl formamide, etc.), 
sulfoxides (e.g. dimethylsulfoxide, etc.), acetonitrile, ketones (e.g. 
acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 
etc.), and/or water; as well as inert dispersible finely divided solid 
carriers, such as ground natural minerals (e.g. kaolins, clays, alumina, 
silica, chalk, i.e. calcium carbonate, talc, attapulgite, montmorillonite, 
kieselguhr, etc.) and ground synthetic minerals (e.g. highly dispersed 
silicic acid, silicates, e.g. alkali silicates, etc.); whereas the 
following may be chiefly considered for use as conventional carrier 
vehicle assistants, e.g. surface-active agents, for this purpose: 
emulsifying agents, such as non-ionic and/or anionic emulsifying agents 
(e.g. polyethylene oxide esters of fatty acids, polyethylene oxide ethers 
of fatty alcohols, alkyl sulfates, alkyl sulfonates, aryl sulfonates, 
albumin hydrolyzates, etc., and especially alkyl or polyglycol ethers, 
magnesium stearate, sodium oleate, etc.); and/or dispersing agents, such 
as lignin, sulfite waste liquors, methyl cellulose, etc. 
Such active compounds may be employed alone or in the form of mixtures with 
one another and/or with such solid and/or liquid dispersible carrier 
vehicles and/or with other known compatible active agents, especially 
plant protection agents, such as other insecticides and acaricides, or 
nematocides, bactericides, fungicides, rodenticides, herbicides, 
fertilizers, growth-regulating agents, bird repellents, plant nutrients, 
agents for improving soil structure, etc., if desired, or in the form of 
particular dosage preparations for specific application made therefrom, 
such as solutions, emulsions, suspensions, powders, pastes, and granules 
which are thus ready for use. 
As concerns commercially marketed preparations, these generally contemplate 
carrier composition mixtures in which the active compound is present in an 
amount substantially between about 0.1-95% by weight, and preferably 
0.5-90% by weight, of the mixture, whereas carrier composition mixtures 
suitable for direct application or field application generally contemplate 
those in which the active compound is present in an amount substantially 
between about 0.0001-10%, preferably 0.01-1%, by weight of the mixture. 
Thus, the present invention contemplates overall compositions which 
comprise mixtures of a conventional dispersible carrier vehicle such as 
(1) a dispersible inert finely divided carrier solid, and/or (2) a 
dispersible carrier liquid such as an inert organic solvent and/or water, 
preferably including a surface-active effective amount of a carrier 
vehicle assistant, e.g. a surface-active agent, such as an emulsifying 
agent and/or a dispersing agent, and an amount of the active compound 
which is effective for the purpose in question and which is generally 
between about 0.0001-95%, and preferably 0.01-95%, by weight of the 
mixture. 
The active compounds can also be used in accordance with the well known 
ultra-low-volume process with good success, i.e. by applying such compound 
if normally a liquid, or by applying a liquid composition containing the 
same, via very effective atomizing equipment, in finely divided form, e.g. 
average particle diameter of from 50-100 microns, or even less, i.e. mist 
form, for example by airplane crop spraying techniques. Only up to at most 
about a few liters/hectare are needed, and often amounts only up to about 
15 to 1000 g/hectare, preferably 40 to 600 g/hectare, are sufficient. In 
this process it is possible to use highly concentrated liquid compositions 
with said liquid carrier vehicles containing from about 20 to about 95% by 
weight of the active compound or even the 100% active substance alone, 
e.g. about 20-100% by weight of the active compound. 
Furthermore, the present invention contemplates methods of selectively 
killing, combating or controlling pests, e.g. insects and acarids, which 
comprises applying to at least one of correspondingly (a) such insects, 
(b) such acarids, and (c) the corresponding habitat thereof, i.e. the 
locus to be protected, e.g. to a growing crop, to an area where a crop is 
to be grown or to a domestic animal, a correspondingly combative or toxic 
amount, i.e. an insecticidally or acaridically effective amount, of the 
particular active compound of the invention alone or together with a 
carrier vehicle as noted above. The instant formulations or compositions 
are applied in the usual manner, for instance by spraying, atomizing, 
vaporizing, scattering, dusting, watering, squirting, sprinkling, pouring, 
fumigating, dry dressing, moist dressing, wet dressing, slurry dressing, 
encrusting, and the like. 
It will be realized, of course, that the concentration of the particular 
active compound utilized in admixture with the carrier vehicle will depend 
upon the intended application. Therefore, in special cases it is possible 
to go above or below the aforementioned concentration ranges.

The unexpected superiority and outstanding activity of the particular new 
compounds of the present invention are illustrated, without limitation, by 
the following examples: 
EXAMPLE 1 
a. The 1-alkoxy-1-formyl-acetic acid alkyl esters required as starting 
compounds were prepared, for example, as follows: 
EQU OCH--CH(OC.sub.2 H.sub.5)CO--OC.sub.2 H.sub.5 
112 g (1 mol) of potassium tert.-butylate were added incrementally to a 
mixture of 132 g (1 mol) of ethoxyacetic acid ethyl ester and 81.5 g (1.1 
mol) of formic acid ethyl ester, in such a way that the reaction 
temperature did not exceed 40.degree. C. The reaction mixture was then 
stirred further for 4 hours at 20.degree. C., after which it was poured 
into 1 liter of water and extracted once with 200 ml of methylene 
chloride. The methylene chloride extract was discarded and the aqueous 
phase was acidified with hydrochloric acid while cooling with ice, and was 
extracted with methylene chloride. After drying the extract over sodium 
sulphate, the methylene chloride was stripped off. 103 g (64% of theory) 
of 1-ethoxy-1-formyl-acetic acid ethyl ester having a refractive index 
n.sub.D.sup.24 of 1.4452 were obtained. 
The following compounds could be synthesized analogously: 
______________________________________ 
OCH--CH(OC.sub.2 H.sub.5)CO--OCH.sub.3 
in 51% yield with a 
refractive index of 
n.sub.D.sup.21 : 1.4398 
OCH--CH(OC.sub.3 H.sub.7 -iso)CO--OC.sub.2 H.sub.5 
in 65% yield with a 
refractive index of 
n.sub.D.sup.21 : 1.4484 
OCH--CH(OC.sub.3 H.sub.7 -iso)CO--OC.sub.3 H.sub.7 -iso 
in 67% yield with a 
refractive index of 
n.sub.D.sup.20 : 1.4400 
OCH--CH(OC.sub.3 H.sub.7 -iso)CO--OCH.sub.3 
in 35% yield with a 
refractive index of 
n.sub.D.sup.20 : 1.4470 
OCH--CH(OCH.sub.3)CO--OC.sub.2 H.sub.5 
in 51% yield with a 
refractive index of 
n.sub.D.sup.19 : 1.4370 
OCH--CH(OCH.sub.3)CO--OCH.sub.3 
in 39% yield with a 
refractive index of 
n.sub.D.sup.24 : 1.4422 
______________________________________ 
##STR8## 
18.8 g (0.1 mol) of O-methyl-O-n-propylthionophosphoric acid ester chloride 
were added dropwise to a mixture of 17.6 g (0.11 mol) of 
1-ethoxy-1-formyl-acetic acid ethyl ester and 16 g (0.115 mol) of 
potassium carbonate in 200 ml of acetonitrile. The mixture was allowed to 
continue to react for 3 hours at 40.degree. C., after which the reaction 
mixture was poured into 300 ml of toluene. The toluene solution was washed 
with saturated sodium bicarbonate solution and with water and was dried 
over sodium sulphate. The solvent was then stripped off and the residue 
was subjected to slight distillation. 23 g (74% of theory) of 
O-methyl-O-n-propyl-O-(2-carbethoxy-2-ethoxy-vinyl)-thionophosphoric acid 
ester were obtained in the form of a yellow oil having a refractive index 
n.sub.D.sup.25 of 1.4690. 
The following compounds of the formula 
##STR9## 
were synthesized analogously: 
Table 1 
______________________________________ 
Yield Refract- 
Compound R (% of ive 
No. R.sup.1 theory) index: 
______________________________________ 
2 C.sub.2 H.sub.5 
CH.sub.3 33 n.sub.D.sup.23 : 1.4760 
3 iso-C.sub.3 H.sub.7 
iso-C.sub.3 H.sub.7 
99 n.sub.D.sup.23 : 1.4679 
4 iso-C.sub.3 H.sub.7 
CH.sub.3 80 n.sub.D.sup.23 : 1.4700 
5 iso-C.sub.3 H.sub.7 
C.sub.2 H.sub.5 
82 n.sub.D.sup.20 : 1.4689 
6 CH.sub.3 CH.sub.3 56 n.sub.D.sup.22 : 1.4780 
7 CH.sub.3 C.sub.2 H.sub.5 
77 n.sub.D.sup.25 : 1.4727 
______________________________________ 
In the following examples the active compounds according to the present 
invention are identified by the number given in brackets and the known 
comparison compounds are identified as follows: 
##STR10## 
EXAMPLE 2 
Test insects: Blatta orientalis 
Solvent: Acetone 
The active compound was taken up in the solvent in an amount of 2 g per 
liter. The solution so obtained was diluted with further solvent to the 
desired concentrations. 
2.5 ml of the solution of the active compound were pipetted into a Petri 
dish. On the bottom of the Petri dish there was a filter paper with a 
diameter of about 9.5 cm. The Petri dish remained uncovered until the 
solvent had completely evaporated. The amount of active compound per 
m.sup.2 of filter paper varied with the concentration of the solution of 
active compound. About 10 test insects were then placed in the Petri dish 
and it was covered with a glass lid. 
The condition of the test insects was observed 3 days after the 
commencement of the experiments. The destruction, in %, was determined. 
100% denoted that all the test insects had been killed; 0% denoted that no 
test insects had been killed. 
The active compounds, the concentrations of the active compounds, the test 
insects and the results can be seen from the following table: 
Table A 
______________________________________ 
(Blatta orientalis) 
Active com- 
pound con- 
centration Degree of 
Active of the solu- 
destruction 
compound tion in % in % 
______________________________________ 
(B) 0.2 0 
(C) 0.2 0 
(6) 0.2 100 
(7) 0.2 100 
(2) 0.2 100 
(4) 0.2 100 
(1) 0.2 100 
(5) 0.2 100 
(3) 0.2 100 
______________________________________ 
EXAMPLE 3 
Test insects: Sitophilus granarius 
Solvent: Acetone 
The active compound was taken up in the solvent in an amount of 2 g per 
liter. The solution so obtained was diluted with further solvent to the 
desired concentrations. 
2.5 ml of the solution of the active compound were pipetted into a Petri 
dish. On the bottom of the Petri dish there was a filter paper with a 
diameter of about 9.5 cm. The Petri dish remained uncovered until the 
solvent had completely evaporated. The amount of active compound per 
m.sup.2 of filter paper varied with the concentration of the solution of 
active compound. About 25 test insects were then placed in the Petri dish 
and it was covered with a glass lid. 
The condition of the test insects was observed 3 days after the 
commencement of the experiments. The destruction, in %, was determined. 
100% denoted that all the test insects had been killed; 0% denoted that no 
test insects had been killed. 
The active compounds, the concentrations of the active compounds, the test 
insects and the results can be seen from the following table: 
Table 3 
______________________________________ 
(Sitophilus granarius) 
Active com- 
pound con- 
centration Degree of 
Active of the solu- 
destruction 
compound tion in % in % 
______________________________________ 
(B) 0.2 100 
0.02 80 
(C) 0.2 0 
(2) 0.02 100 
0.002 100 
(4) 0.02 100 
0.002 60 
(1) 0.02 100 
0.002 100 
(5) 0.02 100 
0.002 50 
(3) 0.02 100 
0.002 50 
______________________________________ 
EXAMPLE 4 
Plutella test 
Solvent: 3 parts by weight of acetone 
Emulsifier: 1 part by weight of alkylaryl polyglycol ether 
To produce a suitable preparation of active compound, 1 part by weight of 
the active compound was mixed with the stated amount of solvent containing 
the stated amount of emulsifier and the concentrate was diluted with water 
to the desired concentration. 
Cabbage leaves (Brassica oleracea) were sprayed with the preparation of the 
active compound until dew moist and were then infested with caterpillars 
of the diamond-back moth (Plutella maculipennis). 
After the specified periods of time, the degree of destruction was 
determined as a percentage: 100% meant that all the caterpillars were 
killed whereas 0% meant that none of the caterpillars were killed. 
The active compounds, the concentrations of the active compounds, the 
evaluation times and the results can be seen from the following table: 
Table 4 
______________________________________ 
(Plutella test) 
Active com- 
Degree of 
pound con- destruction 
Active centration in % after 
compound in % 3 days 
______________________________________ 
(B) 0.1 100 
0.01 0 
(6) 0.1 100 
0.01 100 
(2) 0.1 100 
0.01 100 
(4) 0.1 100 
0.01 100 
(7) 0.1 100 
0.01 100 
(1) 0.1 100 
0.01 100 
(5) 0.1 100 
0.01 100 
(3) 0.1 100 
0.01 100 
______________________________________ 
EXAMPLE 5 
Tetranychus test (resistant) 
Solvent: 3 parts by weight of acetone 
Emulsifier: 1 part by weight of alkylaryl polyglycol ether 
To produce a suitable preparation of active compound, 1 part by weight of 
the active compound was mixed with the stated amount of solvent and the 
stated amount of emulsifier and the concentrate was diluted with water to 
the desired concentration. 
Bean plants (Phaseolus vulgaris) which were heavily infested with the 
two-spotted spider mite (Tetranychus urticae) in all stages of development 
were sprayed with the preparation of the active compound until dripping 
wet. 
After the specified periods of time, the degree of destruction was 
determined as a percentage: 100% meant that all the spider mites were 
killed whereas 0% meant that none of the spider mites were killed. 
The active compounds, the concentrations of the active compounds, the 
evaluation times and the results can be seen from the following table: 
Table 5 
______________________________________ 
(Tetranychus test) 
Active com- 
Degree of 
pound con- destruction 
Active centration in % after 
compound in % 2 days 
______________________________________ 
(A) 0.1 98 
0.01 0 
(6) 0.1 99 
0.01 80 
(2) 0.1 99 
0.01 60 
(7) 0.1 99 
0.01 50 
______________________________________ 
It will be appreciated that the instant specification and examples are set 
forth by way of illustration and not limitation, and that various 
modifications and changes may be made without departing from the spirit 
and scope of the present invention.