Combating arthropods with N-(O-ethyl-S-n-propyl-thiophosphoryloxy)-naphthalimides

N-(O-Ethyl-S-n-propyl-(di)thiophosphoryloxy)-naphthalimides of the formula ##STR1## in which X is oxygen or sulphur, which possess arthropodicidal properties.

The present invention relates to and has for its objects the provision of 
particular new N-(O-ethyl-S-n-propyl-thiophosphoryloxy)-naphthalimides 
which possess arthropodicidal properties, active composition 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, with 
other and further objects becoming apparent from a study of the within 
specification and accompanying examples. 
It is known that certain N-(O,O-dialkylphosphoryloxy)-naphthalimides, for 
example N-(O,O-diethyl-phosphoryloxy)-naphthalimide, possess insecticidal 
properties (see J. Econ. Entomol. 55 (1962), 142-43). 
The action of these compounds is however not always satisfactory, 
especially when low amounts and low concentrations of active compound are 
used. 
The present invention now provides, as new compounds, the 
N-(O-ethyl-S-n-propyl-(di-)thiophosphoryloxy)-naphthalimides of the 
general formula 
##STR2## 
in which X represents oxygen or sulphur. 
Surprisingly, the 
N-(O-ethyl-S-n-propyl-(di)-thiophosphoryloxy)-naphthalimides according to 
the invention exhibit a better activity in combating pests, in particular 
a better insecticidal action, than the corresponding compounds, known from 
the prior art, of analogous structure and of the same type of action. The 
products according to the present invention thus represent a valuable 
enrichment of the art. 
The invention also provides a process for the preparation of an 
N-(O-ethyl-S-n-propyl-(di)-thiophosphoryloxy)-naphthalimide of the general 
formula (I), in which an O-ethyl-S-n-propyl-(di)-thiophosphoric acid 
diester halide of the general formula 
##STR3## 
in which X represents oxygen or sulphur and 
Hal represents chlorine or bromine, especially chlorine, 
is reacted with naphthaloxime, of the formula 
##STR4## 
if appropriate in the presence of an acid acceptor and, if appropriate, in 
the presence of a diluent. 
If, for example, O-ethyl-S-n-propyl-dithiophosphoric acid diester chloride 
and naphthaloxime are used as starting materials, the reaction of these 
compounds can be outlined by the following equation: 
##STR5## 
The following may be mentioned as examples of the 
O-ethyl-S-n-propyl-(di)-thiophosphoric acid diester halides (II) to be 
used as starting materials: O-ethyl-S-n-propylthiolphosphoric acid diester 
chloride and O-ethyl-S-n-propyl-dithiophosphoric acid diester chloride. 
These compounds are already known. 
Naphthaloxime (III), to be used as the other starting compound, is also 
known. 
The process for the preparation of the 
N-(O-ethyl-S-n-propyl-(di)-thiophosphoryloxy)-naphthalimides according to 
the invention is preferably carried out in the presence of a suitable 
solvent or diluent. Virtually any of the inert organic solvents can be 
used for this purpose. These include, as preferences, aliphatic and 
aromatic, optionally chlorinated, hydrocarbons, such as petrol, benzene, 
toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, 
chlorobenzene and o-dichlorobenzene; ethers, such as diethyl ether, 
dibutyl ether, tetrahydrofuran and dioxane; ketones, such as acetone, 
methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone; 
nitriles, such as acetonitrile and propionitrile; and carboxylic acid 
amides, such as dimethylformamide. 
Any of the customary acid-binding agents can be used as the acid acceptor. 
Alkali metal carbonates and alkali metal alcoholates, such as sodium 
carbonate and potassium carbonate, sodium methylate and ethylate and 
potassium methylate and ethylate, have proved particularly suitable, as 
have aliphatic, aromatic or heterocyclic amines, for example 
triethylamine, trimethylamine, dimethylaniline, dimethylbenzylamine and 
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 80.degree. C. The process according to 
the invention is in general carried out under normal pressure. 
To carry out the process according to the invention, the starting materials 
are usually employed in equimolar amounts. An excess of one or other 
reactant offers no significant advantages. The reaction is in general 
carried out in a suitable diluent, in the presence of an acid acceptor, 
and the reaction mixture is stirred for one or more hours at the required 
temperature. The reaction mixture is then poured into water and is 
slightly acidified, if necessary, and the product which has crystallized 
out is filtered off. The product is characterized by the melting point. 
The N-(O-ethyl-S-n-propyl-(di)-thiophosphoryloxy)-naphthalimides according 
to the invention are distinguished by a very good activity against insects 
which damage plants. They can therefore be employed successfully as 
pesticides in plant protection. 
Because of their good activity against ectoparasites, the compounds 
according to the invention can also be used in the veterinary medicine 
field. 
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, 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 
abovementioned 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 aurantii, 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. 
The active compounds can be converted into 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, 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 may be produced in known manner, for example by mixing 
the active compounds with extenders, that is to say liquid or liquefied 
gaseous or solid diluents or carriers, optionally with the use of 
surface-active agents, that is to say emulsifying agents and/or dispersing 
agents and/or foam-forming 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 or alkyl 
naphthalenes, chlorinated aromatic or chlorinated aliphatic hydrocarbons, 
such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic 
or alicyclic hydrocarbons, such as cyclohexaneor 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 halogenated hydrocarbons as well as butane, 
propane, nitrogen and carbon dioxide. 
As solid carriers there may be 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. As solid carriers 
for granules there may be used crushed and fractionated natural rocks such 
as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic 
granules of inorganic and organic meals, and granules of organic material 
such as sawdust, coconut shells, corn cobs and tobacco stalks. 
As emulsifying and/or foam-forming agents there may be used non-ionic and 
anionic emulsifiers, such as polyoxyethylene-fatty acid esters, 
polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycol 
ethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well as 
albumin hydrolysis products. Dispersing agents include, for example, 
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 or 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 from 0.5 to 90 percent by weight. 
The active compounds according to the invention may be used in the form of 
their formulations of the types that are commercially available 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 may be employed in a customary manner approprirate for the 
particular 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. 
In the veterinary field, the active compounds according to the invention 
may be used in a known manner, such as orally in the form of, for example, 
tablets, capsules, drenches and granules; dermally by means of, for 
example, dipping, spraying, pouring-on, spotting-on and powdering; and 
parenterally, for example by means of injections. 
The present invention also provides an arthropodicidal composition 
containing as active ingredient a compound of the present invention in 
admixture with a solid or liquefied gaseous diluent or carrier or in 
admixture with a liquid diluent or carrier containing a surface-active 
agent. 
The present invention also provides a method of combating arthropods 
(especially insects) which comprises applying to the arthropods, or to a 
habitat thereof, a compound of the present invention alone or in the form 
of a composition containing as active ingredient a compound of the present 
invention in admixture with a diluent or carrier. 
The present invention also provides a method of freeing or protecting 
domesticated animals from ectoparasitical insects which comprises applying 
to said animals a compound according to the present invention, in 
admixture with a diluent or carrier. 
The present invention further provides crops protected from damage by 
arthropods by being grown in areas in which immediately prior to and/or 
during the time of the growing a compound of the present invention was 
applied alone or in admixture with a diluent or carrier. 
It will be seen that the usual methods of providing a harvested crop may be 
improved by the present invention. 
The present invention further provides domesticated animals whenever freed 
or protected from ectoparasitical insects by the application to said 
animals of a compound according to the present invention, in admixture 
with a diluent or carrier.

The preparation of the novel compounds is shown in the following 
illustrative examples: 
EXAMPLE 1 
##STR6## 
53.3 g (0.25 mol) of naphthaloxime were dissolved in 200 ml of 
dimethylformamide and 30 g (0.3 mol) of triethylamine were added. 50.6 g 
(0.25 mol) of O-ethyl-S-n-propyl-thiolphosphoric acid ester chloride were 
added dropwise to this mixture at 20.degree. to 30.degree. C. internal 
temperature. The reaction mixture was stirred for a further hour and was 
then poured into 1 lit of ice-water. The batch was rendered acid to Congo 
Red and the product was filtered off, washed until netural and dried. 
After recrystalli ing the crude product from isopropanol, 57 g (60% of 
theory) of N-(O-ethyl-S-n-propyl-thiophosphoryloxy)-naphthalimide were 
obtained. Melting point: 145.degree. C. 
EXAMPLE 2 
##STR7## 
44 g (0.2 mol) of O-ethyl-S-n-propyl-thiono-thiolphosphoric acid diester 
chloride were rapidly added dropwise to a solution of 41 g (0.2 mol) of 
naphthaloxime and 22 g (0.22 mol) of triethylamine in 100 ml of 
dimethylformamide. In the course thereof, the internal temperature rose 
from about 25.degree. to 55.degree. C. The reaction mixture was stirred 
for a further hour and was then poured into water, the batch was stirred 
thoroughly and the product was filtered off and dried. 75 g (95% of 
theory) of N-(O-ethyl-S-n-proply-dithiophosphorlyoxy)-naphthalimide were 
obtained. Melting point: 135.degree. C. 
The insecticidal activity of the compounds of this invention is illustrated 
by the following examples wherein the compounds according to the present 
invention are each identified by the number (given in brackets) from 
Example 1 or 2. 
EXAMPLE 3 
Myzus test 
Solvent: 3parts 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 plants (Brassica oleracea) which had been heavily infested with 
peach aphids (Myzus persicae) were treated by being dipped into the 
preparation of active compound of the desired concentration. 
After the specified periods of time, the degree of destruction was 
determined as a percentage: 100% meant that all of the aphids were killed 
whereas 0% meant that none of the aphids were killed. 
In this test, for example, compound 1 showed a superior activity compared 
to the prior art. 
EXAMPLE 4 
Plutella test (long-term action after spraying) 
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 plants (Brassica oleracea), which were about 10-15 cm high, were 
sprayed with the desired preparation of the active compound until dripping 
wet. 
After the specified periods of time the plants were infested with 
caterpillars of the diamond-back moth (Plutella maculipennis). The 
destruction in % was determined at intervals of 3 days. 100% meant that 
all the caterpillars had been killed; 0% meant that none of the 
caterpillars had been killed. 
In this test, for example, compound 1 showed a superior activity compared 
to the prior art. 
EXAMPLE 5 
Test with parasitic fly larvae 
Emulsifier: 80 parts by weight of alkylaryl polyglycol ether 
To produce a suitable preparation of active compound, 20 parts by weight of 
the active compound in question were mixed with the stated amount of the 
emulsifier and the mixture thus obtained was diluted with water to the 
desired concentration. 
About 20 fly larvae (Lucilia cuprina, res.) were introduced into a test 
tube which contained about 3 ml of a 20% strength suspension of egg yolk 
powder in water, and which was fitted with a cottonwool plug of 
appropriate size. 0.5 ml of the active compound preparation was placed on 
this egg yolk powder suspension. After 24 hours, the degree of destruction 
was determined. 
In this test, for example, compound 1 showed a superior action compared to 
the prior art. 
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.