Phosphoric acid esters of coumarins
United States Patent [1 1 Oswald et al.  
 [451 Apr. 8, 1975 PHOSPHORIC ACID ESTERS OF COUMARINS [75] Inventors: Alexis A. Oswald, Mountainside;  
 Paul L. Valint, Woodbridge, both of [73] Assignee: Ciba-Geigy AG, Basel, Switzerland [22] Filed: Feb. 1, 1973 [2]] Appl. No.: 328,588  
 [30] Foreign Application Priority Data Feb. I 1972 Switzerland l498/72 [52] US. Cl. 260/343.2 P; 424/203; 424/200; 424/214; 260/283 P; 260/940; 260/930; 260/956; 260/979 [51] Int. Cl C07d 7/26 [58] Field of Search 260/343.2 P  
 [56] References Cited UNITED STATES PATENTS 3.067.210 lZ/l962 Schr&#39;tlder 260/343.2 3.3()9 37| 3/I967 Curry et al 2610/3432 Prinmry E.\&#39;aminer-.lohn M. Ford Attorney. Agent. or FirmFrederick H. Rabin [57] ABSTRACT Thiolphosphoric acid esters of the formula wherein R represents methyl or ethyl,  
 R represents propyl or butyl,  
 R is a substitued phenyl radical selected from the group consisting of compounds having the formula:  
 R represents allyl. methallyl, CH CN. or  
 2 Claims, N0 Drawings 1 PHOSPHORIC ACID ESTERS OF COUMARINS The present invention relates thiolphosphoric acid esters, to processes for their production. and to their use in the control of pests.  
  Substituted phenyl esters of dialkyl thionophosphoric acid, of the formula (RO) P(S)OR&#39;, represent a very important class of known pesticides. For example. among the phenyl compounds substituted with divalent Z-acryloyloxy groups to form the fused benzopyranyl ring are Potasan is an insecticide described in German Pat. No.  
 8l4,297. Co-Ral was first described in German Pat.  
 No. 881,194 and is employed as a pesticide in veterinary medicine. The use of such thionophosphoric acid esters is limited by their generally high toxicity towards warm-blooded animals and their lack of activityagainst certain pests. It was surprisingly found in the present invention that certain novel thiolphosphoric acid esters, structurally related to these known esters, have a reduced toxicity and broadened pesticidal spectrum.  
  The unsymmetrically substituted O.S-dialkyl thiolphosphoric acid esters disclosed in the present invention have the formula f P-O-R k wherein R represents methyl or ethyl, R represents propyl or butyl.  
 R represents allyl, methallyl, -CH CN, or  
 R represents hydrogen, halogen, C C --alkyl, ni-  
 tro. cyano, methylmercapto or carbalkoxy,  
 R represents hydogen, halogen, C C -alkyl or COCH 5 X represents oxygen or sulphur, and m and n each denote the number 1 or 2.  
 By halogen is meant fluorine, chlorine, bromine and- /or iodine, particularly however chlorine.  
 The alkyl groups applicable for formula I can be are: methyl, ethyl, n-propyl, isopropyl, n-, i-, sec.- tert.- butyl. n-pentyl, and isomers thereof.  
  From the viewpoint of the unexpected properties of the novel compositions, the choice of the alkyl groups R, and R is most critical. in the related prior art compositions, the alkyl groups (R) are generally identical and equal methyl or ethyl. In the present compounds R is methyl or preferably ethyl and R is propyl or butyl. Among the R groups, the n-propyl and primary i-butyl are preferred. The optimum choice is the O-ethyl S-npropyl substitution which leads to compounds of decreased toxicity and at the same time increased activity. This finding is in contrast to the structure-biological property correlations observed in the field of the phenyl esters of 0,0-dialkyl thionophosphates wherein the O-ethyl group attributes high toxicity and the O-npropyl substitution reduces the pesticidal activity. For reference, see Volume 1 of the monograph, Chemie der Pflanzenshutz und Schadlingsbekampfungsmittel edited by R. Wegler and published by Springer Verlag. New York in 1970. pages 306-324.  
  An example of the unexpected change of properties is O-ethyl S-n-propyl 0&#39;-3-chloro-4-methyl Z-exo-ZH- l -benzopyran-7-yl thiolphosphate,  
 a compound closely related to Co-Ral which shows a high activity against mites and aphids which is completely absent in the ease of Co-Ral.  
 Compounds of formula I preferred because of their properties unexpected biological wherein R represents ethyl, R represents n-propyl R represents are compounds branched or straight chain. Examples of such groups 3 4 R represents allyl. -CH CN or wherein R is n-propyl or i-butyl, R is hydrogen or methyl. R and R are hydrogen, chlorine, bromine. H C H From the phenyl compounds substituted to form a O P 2 5 quinoline ring system, the preferred thiolphosphate 5 compounds have no other substituents on the ring. 50-11. (n)  
  5 l 0 R represents hydrogen. chlorine. bromine. cyano. C H O methylmercapto. nitro or methyl. P-O I R represents hydrogen, methyl or COCH;,. 0 2  
 X represents oxygen or sulphur. and m and n each represent the number 1 or 2. Specifically. preferred types of compounds are those of the formula 5 CH CH=CH where n R 18 n-propyl or i-butyl.  
  2 2 Particularly preferred compounds, however, are compounds of formula I wherein P Q R R. represents ethyl.  
 7 R represents n-propyl.  
 (n) 3 7 R represents 0\ wherein R ischlorine or bromine. R. is hydrogen. or {64:1 chlorine. bromine. and  
 ( 5 n CH C H 0&#39;. R represents ally]. CH CN or R 9 (n)C3H- &#39;S LL; 0  
 &#34; sc H (n) 3 wherein R is nitro. methylthio. cyano. and -P 7 It C2 50- k P 0 R represents hydrogen. chlorine or bromine.  
 R CH CN X represents oxygen. and  
  Vii] 40 n represents the number 1 or 2.  
 The compounds of formula I can be produced by the wherein R is n-propyl or i-butyl and following methods:  
  R 0 Y 0 l, 0 oc ir 1 Cl- HO-R c n 0. I L R 2 5 X SR2 2,  
  Z (II) (III)- wherein R is n-propyl of i-butyl.  
  Among the phenyl compounds substituted with the acid-binding I divalent 2-acryloyloxy group to form the fused bena t zopyranyl ring systems specifically preferred are those of the formula R O Y 1 \u 1b) P c1 142021 R R 3 12 1o R 8 R 11 Cho 0 11 R s O The symbols R R R and Y in formulae ll, Ill and IV have the meanings given in the case of formula I, and Me stands for an alkali metal, particularly for sodium or potassium, or for an ammonium group such as.  
 e.g. the group 69 1 a (R Ml,  
 wherein R, represents hydrogen or alkyl.  
 &#39; R 0 Y t l \s 2) .P -01 llO-R R O Y acid-binding l agent P 0R3 R OG  3 Z acid-binding I cl agent P OR MeSR --9 I 01 (v1) (IIIb) The symbols R,. R R and Y in formulae ll, Illa, lllb, V and VI have the meanings given in the case of formula l. and Me stands for an alkali metal, particularly sodium or potassium, or for the group wherein R, represents hydrogen or C. to C, alkyl.  
  R&#39; o s 3a) P 0 R3 (R4)3N (v11) (XI) Dealkylat ion (VIII) V Alkylation R O O l \u 1 (XIII) Dealkylation ih OR KS (IX) R llal (XII) Alk l ylaclon 0R3 The symbols R and R in formulae Vll to Xll have the meanings given in the case of formula I. R stands for an alkyl radical. and Hal for a halogen atom such as chlorine. bromine or iodine, and R is a primary or secondary propyl or butyl radical. and Me in formula Xlll stands for an alkali metal, preferably sodium or potassium.  
  Suitable acid-binding agents are: tertiary amines, e.g., trialkylamines. pyridine, pyridine bases. dialkylanilines; inorganic bases such as hydrides. hydroxides&#34;, carbonates and bicarbonates of alkali metals and alkaline-earth metals.  
  It is sometimes necessary in performing the reactions to use catalysts. such as. e.g., copper or copper chloride. The processes la and lb, 2 and 3a and 3b are carried out at a reaction temperature of between 0 and C, at normal pressure and in solvents or diluents.  
  Suitable solvents or diluents are, e.g., ethers and ethereal compounds, such as diethyl ether, dipropyl ether, dioxane, tetrahydrofuran; amides such as N,N- dialkylated carboxylic acid amides; aliphatic, aromatic as well as halogenated hydrocarbons, especially benzene, toluene, xylenes, chloroform, chlorobenzene; nitriles such as acetonitriles; DMSO, ketones such as acetone, methyl ethyl ketone, and water. A further suitable solvent in the case of processes 3a and 3b is ethanol.  
  The starting materials of formulae ll, V and Vll can be produced by methods analogous to known methods, e.g., those described in Organic Reactions ll&#34;, pp, l to 48.  
  The compounds of formula I have a broad biocidal action, and can be used for the control of diverse plant and aniamal pests. Surprisingly, they have a better action against, for example, larvae of Spodoptera littoralis than analogous compounds from the German Pat. No. l,l64,4()8 have. Furthermore, the compounds of formula I are suitable also for the control of all development stages, such as, e.g., eggs, larvae, pupae, nymphs and adults of insects of the families: Acrididae, Blattidae, Gryllidae, Gryllotalpidae, Tettigoniidae, Cimicidae. Phyrrhocoridae, Reduviidae, Aphididae. Delphacidae, Diaspidae, Pseudococcidae, Chrysomelidae, Coccinellidae, Bruchidae, Scarabaeidae. Dermestidae, Tenebrionidae, Curculionidae. Tineidae, Noctuidae, Lymantriidae, Pyralidae. Galleridae, C ulicidae, Tipulidae, Stomoxydae, Muscidae, Calliphoridae, Trypetidae, Pullicidae. as well as acarids of the families: lxodidae, Argasidae. Tetranychidae. Dermanysidae.  
  The insecticidal or acaricidal action can be substantially broadened and adapted to suit the given circumstances by the addition of other insecticides and/or acaricides. Suitable additives are. for example. the following active substances:  
 ORGANIC PHOSPHORUS COMPOUNDS Bis-0-diethylphosphoric acid anhydride (TEPP) Dimethyl-(2,2.2-trichl0ro-l-hydroxyethyl)- phosphonate (TRICHLORFON) l.2-dibromo-2,Z-dichloroethyldimethylphosphate (NALED) 22-dichlorovinyldimethylphosphate C HLOROVOS) Z-mcthoxycarbamyll -methylvinyldimethylphosphate (MEVINPHOS) Dimethyl-l-methyl-2-(methylcarbamoyl)- vinylphosphate cis (MONOCROTOPHOS) 3-(dimcthoxyphosphinyloxy)-N.N-dimethyl-ciscrotonamide (DICROTOPHOS) 2-chloro-Z-diethylcarbamoyl-l-methylvinyldimethylphosphate (PHOSPHAMIDON) 0 O-diethyl-0(or S)-2-(cthylthio)-ethylthiophosphate (DEMETON) S-ethylthioethyl-0,0-dimethyl-dithiophosphate (THI- OMETON) 0.0-diethyl-S-cthylmercaptomethyldithiophosphate (PHORATE) 0.0-diethyl-S-2-(ethylthio)ethyldithiophosphate (DI- SULFOTON) 0 0-dimethyl-S-2-(ethylsulphinyl)ethylthiophosphate (OXYDEMETON METHYL) 00-dimethyl-S-( l .2-dicarbethoxyethyIdithiophosphatc (MALATHION) 0,0 0.0-tetramethyl-S.S&#39;-methylene-bisdithiophosphate (ETHION) O-ethyl-S,S-dipropyldithiophosphate ().O-dimethyl-S-(N-methyl-N- formylcarbamoylmethyl)-dithiophosphate MOTHION) 0.0-dimethyl-S-(N-methylcarbamoylmethyl)dithiophosphate (DIMETHOATE) (FOR- O,()-dimethyl-O-p-nitrophenylthiophosphate (PA- RATHlON-METHYL) 0,0-diethyl-O-p-nitrophenylthiophosphate (PARA- THION) O-ethyl-0-p-nitrophenylphenylthiophosphate (EPN) 0,0-dimethyl-O-(4-nitro-m-tolyl)thiophosphate (FENITROTHION) 0,0-dimcthyl-0,2,4,5-trichlorophenylthiophosphate (RONN EL) O-ethyl-O,2,4,5-trichlorophenylethylthiophosphate (TRICHLORONATE) 0,0-dimethylO-2,5-dichloro-4-bromophenylthiophosphate (BROMOPHOS) 8 0.0-dimethyl-0-(2,5-dichloro-4-iodophenyl)- thiophosphate (JODOFENPHOS) 4-tert.butyl-Z-chlorophenyl-N-methyl-0- methylamidophosphate (CRUFOMATE) 0.0-dimethyl-O-( 3-methyl-4- methylmercaptophenyl)thiophosphate (FENTH- ION) Isopropylamino-0-ethyl-0-(4-methylmercapto-3- me&#39;thylphenyl)-phosphate 4 0,0-diethyl-0-p-(methylsulphinyl)phenylthiophosphate (FENSULFOTHION) 0-p-(dimethylsulphamido)phenyl-0,0-dimethylthiophosphate (FAMPHUR) 0,0,0,O-tetramethyl-0,0-thiodi-p-phenylenethi0- phosphate O-ethyl-S-phenyl-ethyldithiophosphate 0,0-dimethyl-O-(a-methylbenzyl-3-hydr0xycrotonyl)phosphate 2-chlorol 2,4-dichlorophenyl )vinyldiethylphosphate (CHLORFENVINPHOS) 2-chloro-l-(2,4,5-trichlorophenyl)vinyldimethylphosphate O-[2-chloro-l-(2,5-dichlorophenyl)]vinyl-O 0- diethylthiophosphate Phenylglyoxylonitriloxime-0,0-diethylthiophosphate (PHOXIM) 0,0-diethyl-0-(3-chloro-4-methy]-2-oxo-H-lbenzopyran-7-yl)-thiophosphate (COUMAPHOS) 2,3-p-dioxandithiol-S,S-bis(0,0-diethyldithiophosphate) (DlOXATHlON) 5-[6-chloro-2-oxo-3-benzoxazolinyl)methyl]0.0-  
  diethyldithiophosphate (PHOSALONE) 2-(diethoxyphosphinylimino)-1,3-dithiolane 0,0-dimethyl-S-[ 2-methoxy-l ,3 ,4-thiadiazol-5-( 4H onyl-(4)-methyl]dithiophosphate 0,0-dimethyl-S-phthalimidomethyl-dithiophosphate (IMIDAN) 0,0-diethyl-O-(3,5 6-trichIoro-2-pyridyl)thiophosphate 0O-diethyl-O-2-pyrazinylthiophosphate ZIN) 0.0-diethyl-0-( 2-isopropyl-4-methyl-6-pyrimidyl )thiophosphate (DlAZlNON) 0,0-diethyl-O-( Z-quinoxalyl )thiophosphate 0,0-dimethyl-S-( 4-oxol ,2,3-benzotriazin-3(4H ylmethyl)-dithiophosphate (AZINPHOS- METHYL) 0,0-diethyl-S-( 4-oxol ,2,3-benzotriazin-3( 4H ylmethyl)-dithiophosphate (AZINPHOSETHTYL) S-[(4 6-diamino-s-triazin-2-yl)methyl1-0.0- dimethyldithiophosphate (MENAZON) 0,0-dimethyl-0-( 3-chloro-4-nitrophenyl)thiophosphate (CHLORTHION) 0,0-dimethyl-0(or S)-2-(ethylthioethyUthiophosphate (DEMETON-S-METHYL) 2-(0,0-dimethyl-phosphoryl-thiomethyl)-5-methoxypyrone4-3,4-dichlorobenzyl-triphenylphosphoniumchloride 0.0-diethyl-S-( 2,5-  
  dichlorophenylthiomethyl)dithiophosphate(- PHENKAPTON) 0,0 diethyl-0-(4-methyl-cumarinyl-7-)- v (THIONA- thiophosphate (POTASAN) S-aminobis(dimethylamido)phosphinyl-3-phenyl-1,2,4- triazole(TRlAMlPHOS) N-methyl-S-(0.0-dimethylthiolphosphoryl)-3- thiavaleramide( VAMlDOTHlON) l-methylthio-O-carbamyl-acetaldoxime 3-sec. butylphenyl)-N-phenythio-N- methylcarbamate 2,5-dimethyl-l ,3-dithiolane-2-( O-methylcarbamyl aldoxime) 0-2-diphenyl-N-methylcarbamate 2-( N-methylcarbamyl-oximino )-3-chlorobicycle[2.2.l lheptane 2-( N-methylcarbamyl-oximino bicyclo[2.2.l lheptane 3-isopropylphenylQN-methyl-N-chloroacetalcarbamate 3-ispropylphenyl-N-methylthiomethyl-carbamate O-( 2,2-dimethyl-4-chloro-2,3-dihydro-7- benzofuranyl )-N-methyl-carbamate 0-( 2,2,4-trimethyl-2,3-dihydro-7-benzofuranyl )-N- methylcarbamate O-naphthyl-N-methyl-N-acetal-carbamate 0-5 ,6,7 ,8-tetrahydronaphthyl-N-methyl-carbamate 3-isopropyl-4-methylthio-phenyl-N- methylcarbamate 3,5-dimethyl-4-methoxy-phenyl-N-methylcarbamate 3 ,5-dimethyl-4-methoxy-phenyl-N-methylcarbamate -methoxymethoxy-phenyl-N-methylcarbamate 3-allyloxyphenyl-N-methylcarbamate Z-propargtloxymethoxy-phenyl-N-methyl-carbamate Z-allyloxyphenyl-N-methyl-carbamate 4-methoxycarbonylamino-3-isopropylphenyl-N- methyl-carbamate 3 ,5-dimethyl-4-methoxycarbonylamino-phenyl-N- methyl-carbamatet 2-7-methylthiopropylphenyl-N-methyl-carbamate 3-( a-methyloxymethyl-2-propenyl )-phenyl-N-methyl-carbamate 2-chloro-5-tert.butyl- 4-( methyl-propargylamino-3 .5-xylyl-N-methylcarbamate 4-( meth yl-y-chloroallylamino )-3 ,5-xylyl-N-methylcarbamate 4-( methyl-B-chloroallylamino )-3 ,S-xylyl-N-methylcarbamate l-( B-ethoxycarbonylethyl )-3-methyl-5 -pyrazolyl- N ,N-dimethyl-carbamate 3-methyl-4-( diemthylamino-methylmercaptomethyleneimino )phenyl-N-methylcarbamate l ,3-bis(carbamoylthio)-2-(N,N-dimethy1amino)- propanehydrochloride 5,5-dimethylhydroresorcinoldimethylcarbamate 2-[ethyl-propargylamino]-phenyl-N- methylcarbamate Z-[methyl-propargylamino l-phenyl-N- methylcarbamate 2-[dipropargylamino]-phenyl-N-methylcarbamate 4-[dipropargylamino]-3-tolyl-N-methylcarbamate 4-[dipropargylamino1-3 ,5-xylyl-N-methylcarbamate 2-[allyl-isopropylamino1-phenyl-N-methylcarbamate 3-[allyl-isopropylamino]-phenyl-N-methylcarbamate- CHLORINATED HYDROCARBONS y-hexachlorocylclohexane lGAMMEXANE: LIN- DAN: y HCH] l,2,4,5,6,7,8,8-octachloro-3a,4,7,7atetrahydro-4,7-  
 methyleneindane [CHLORDAN] 1,4,5 ,6,7,8 ,9-heptachloro,3a,4,7,7a-tetrahydor-4,7-  
 methylene indane [HEPTACHLOR] l,2,3,4, l 0, l O-hexachlro-l ,4,4oz,5,8,8a-hexahydro- &#39;endo-l ,4-exo-5,8-dimethanonaphthalene AL- DRIN] l,2,3,4, l 0, l 0-hexachlro-6,7-epoxyl,4,4a,5,6,7,8,8a-octahydro-exo-l ,4-endo-5 ,8- dimethanonaphthalene [DIELDRIN] l 2,3,4,10,l0-hexachloro-5,7-epoxyl,4,4a,5,6,7,8,8a-octahydro-endo-endo-S,8- dimethanonaphthalene [ENDRIN 1.  
  In addition to possing te above mentioned properties, the compounds of formula I are also effective against members of the division Thallaphyta. Some of these compounds thus have a bacteriacidal action. They are particularly effective, however, against fungi, especially against phytopathogenic fungi belonging to the following classes: Oomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Denteromycetes. The compounds of formula I have moreover a fungitoxic action in the case of fungi which attack plants from the soil. Furthermore, the new active substances are suitable for the treatment of seeds, fruits, tubers, and so forth, to obtain protection against fungus infections. The compounds of formula I are suitable also for the control of phytopathogenic nematodes.  
  The compounds of formula i can be used aon their own or together with suitable carriers and/or additives. Suitable carriers and additives may be solid or liquid, and correspond to the substances common in formulation practice, such as, e.g., natural and regenerated substances, solvents, dispersing agents, wetting agents. adhesives, thickeners, binders and /or fertilisers.  
  For application, the compounds of formulat I can be process into the form of dust, emulsion concentrates. granulates, dispersions, sprays, or solutions, the formulation of these preparations being effected in a manner commonly known in practice. Also to be mentioned are cattle dips and spray races, in which aqueous preparations are used.  
  The agents according to the invention are produced in a manner known per se by the intiamate mixing and- /or grinding of active substances of formula I with the suitable carriers, optionally with the addition of dispersing agents or solvents which are iert to the active substances. The active substances can be obtained and used in the following preparation forms: solids preparations:  
 dusts, scattering agents, granulates,  
 coated granulates, impregnated granultes and ho,ogenous granulates; liquid preparations:  
 a. water dispersible active substance concentrates:  
 wettable powders, pastes, emulsions;  
 b. solutions.  
  The solid preparations (dusts, scattering agents) are producined by the mixing of the active substances with solid carriers. Sutiable carriers are, e.g., kaolin, talcum, bole, loess, chalk, limetstone, ground limestone, attapulgiite, dolomite, diatomaceous earth, precipitated silicic acid, alkaline-earth silicates, sodium and potassium aluminium silicates, sodium and potassium aluminium silicates (feldspar and mica), calcium and magnesium sulphates, magnesium oxide, ground synthetic materials, fertilsers such as ammonium sulphate, am-  
 monium phosphate, ammonium nitrate, urea, ground vegtable products such as bran, bark dust, sawdust, ground nutshells, cellulose powder, residues of plant extractions, active charcoal, etc., alone or in admixture with each other.  
  Granulates can be very easily prepared by a process in which an active substance of formula I is dissolved in an organic solvent the thus obtained solution applied to a granulated mineral, e.g., attapulgite, Sio. granicalcium, bentonite, etc., and the organic solvent then evaporated off.  
  It is possible also to produce polymer granulates; in this case the active substances of formula I are mixed with polymersable compounds (urea/formaldehyde, or others); polymerisation is then carefully carried out in a manner which leaves the active substances unaffected, and granulation performed actually during the gel forming processs. It is more favorable, however, to impregnate finished porous polymer granulates (urea/ formaldehydre, polyacrylonitrile, polyester and others), having a specific surface area and a favourable predeterminable absorption/desorption ratio, with the active substances, e.g., in the form of their solutions (in a low-boling solvent), and to then remove the solvent. Polymer granulates of this kind can be also sprayed in the form of microgranulates, having bulk weights of preferably 300 g/litre to 600 g/litre, with the aid of spray apparatus. Spraying can be carried out over extensive areas of useful plant crops by the use of aeoplanes.  
  Granulates can also be obtianed by the compacting of the carrier material with the active substances and additives. and a susequent reducing operation.  
  Moreover, it is possible to add to therse mixtures additives stabilixing the active subatnaces which improve, e.g., the adhesives of the active substances on plants and parts of plants (adhesives and agglutinants), and/or ensure a better wettability (wetting agents) as well as dispersibility (dispersing agents).  
  The following substances are, for example, sutiable; olein/lime mixture, cellulose drivatives (methyl cellulose, carboxymethyl cellulose), hydroxyethylene glycol etheres of monoalkyl and diakul phenols having to ethylene oxide radicals per molecule and 8 to 9 carbon atoms in the alkyl radical, lignin-sulphonic acid, the alkli metal and alkaline-earth metal salts thereof. polyethylene glycol ethers (carbowaxes), fatty alcohol polyglycol ethers having 5to ethylene oxide radicals per molecule and 8 to 18 carbon atoms in te fatty alcohol moiety, condensation products of ethylene oxide, propylene oxide, polyvinylpyrrolidones, polyvinyl alcohols, condensation products of urea and formaldehyde. as well as latex products.  
  Water-dispersible concentrates, are agents which can be diluted with water to obtain any desired concentration. They consist of active substance. Carrier, optionally additives which stabilise the active substance, surface-active substances. and anti-foam&#39;agents and, otpinally, solvents.  
  The wettable powders and pastes are obtained by the mixing and grinding of the active substances with disipersing agents and pulverulent carriers, in suitable devices, until homogeneity is obtained. Sutiable carries are, e.g., those previously mentioned in the case of solid preparations. It is advantageous in some cases to use mixtures of different carriers. As dispersing agents it is possible to use, e.g.,: condensation products f sulphonated napthalene and sulphonated naphthalene derivatives with formaldehde, condensation products of napthalene or of naphthalenesulphonic acids with phenol and formaldehyde, as well as alkali, ammonium and alkaline-earth metal salts of ligninsulphonic acid, also alkylarylsulphonates, alkali metal salts and alkalineearth metal salts of dibutyl naphthalenesulphonic acid, fatty alcohol sulphates such as salts of sulphated fatty alcohol glycol ethers, the sodium salt of oleyl methyl tauride, ditertiary ethylene glycols, dialkyl dilauryl ammonium chloride, and fatty acid alkali-metal and alkaline-earth metal salts.  
 Sutiable anti-foam agents are, e.g., silicones.  
  The acctive substances are so mixed, ground, sieved and strained with the above mentioned additives that theh solid constituent in the case of wettable powders has a particle size not exceeding 0.02 to 0.04 mm, and  
 in the case of pastes not exceeding 0.03 mm. For the preparation of emulsion concentrates and pastes, dispersing agents are used such as those mentioned in the preceding paragraphs, orgainic solvents and water. Suitable solvents are, e.g. alcohols, benzene, xylene, toluene, dimethylsulphoxide, and mineral oil fractions boiling in the range of 120 to 350C. The solvents must be practically odourless, noaphytotoxic. and inert to the active substances.  
  Furthermore, the agents according to the invention can be used in the form of solutions. For this purpose. the active substance, or several active substances, of the general formulal is dissolved in suitable organic solvents, solvent mixtures, or water. As organic solvents itis possible to use aliphatic and aromatic hydrocarbons, their chlorinated derivatives, alkylnaphthalenes, mineral oils on their own or in admixture with each other.  
  The content of active substance in the above described agents is between 0.1 and percent; it is to be mentioned in this connection that in the case of application of the agents from an aeroplane, or by means of some other suitable application devices. concentrations of up to 99.5 percent can be used. or even the pure active substance.  
  The active substances of formula I can be prepared, e.g., as follows:  
 DUSTS The following substances are used for the preparation of a) a 5 percent dust, and b) a 2 percent 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 percent granulate:  
 5 parts of active substance.  
 0.25 parts of epichlorhydrin,  
 0.25 parts of cetyl polyglycol ether,  
 3.50 parts of polyethylene glycol,  
 91 part of kaolin (particle size 0.3 0.8 mm).  
  The active substance is mixed with epichlorhydrin and dissolved with 6 parts of acetone; the polyethylene glycol and cetyl polyglycol ether are then added. The thus obtained solution is sprayed on to kaolin, and the acetone subsequently evaporated in vacuo.  
 WETTABLE POWDER The following constituents are used for the preparation of a) a 40 percent. b) and c) a 25 percent. and d) a 10 percent wettable powder:  
 a. 40 parts of active substance.  
  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-polyoxyethyleneethanol.  
 1.7 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1),  
 8.3 parts of sodium aluminium silicate.  
 16.5 parts of kieselguhr.  
 46 parts of kaolin.  
 d. 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. the mixture being then ground in the appropriate mills and rollers. Wettable powders are obtained which can be diluted with water to give suspensions of any desired concentration.  
 EM U LSlFlABLE CONCENTRATES The following substances are used to produce a) a 10 percent and b) a percent emulsifiable concentrate:  
 a. 10 parts of active substance. 3.4 parts of epoxidised vegetable oil. 13.4 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 an alkylarylsulphonate/fatty alcoholpolyglycol ether mixture 5 parts of dimethylformamide. 57.5 parts of xylene. From these concentrates it is possible to produce, by  
 10 dilution with water, emulsions of any desired concentration.  
 SPRAY The following constituents are used to prepare a 5 15 percent spray:  
 EXAMPLE I O-Ethyl-S-n-propyl-O-( 2-allyl-4-chlorophenyl thiolphosphate An amount of 10.12 g of triethylamine is added to a solution of 16.86 g of 2-allyl-4-chlorophenol (B.P. 133C/16 Torr) in ml of benzene. An addition is then made dropwise at 10-l 5C. with continuous stirring. of 20.3 g of O-ethyl-S-n-propylthiolphosphoric acid chloride; stirring is subsequently continued for 12 hours at room temperature. The mixture is washed with water. with a 3 percent Na CO solution. and again with water. and dried over anhydrous sodium sulphate. The benzene is distilled off and the residue purified by means of molecular distillation. There is thus obtained the compound of the formula C H O O 2 5 n 12 (n)L l&#39;l S having a refraction of =l.5306 and a B.P. of 124C/O.l Torr.  
  The following compounds too are obtained in an analogous manner:  
 0 CHZCN n 1 5262 CH2CH=CH2 2o 9 1}. n 1.5205 oo A. Insecticidal stomach poison action Cotton and potato plants were sprayed with a 0.05 percent aqueous active-substance emulsion (obtained from a 10 percent emulsifiable concentrate).  
  After the drying of the obtained coating, Spodoptera litoralis or Heliothis virescens larvae L, were placed onto the cotton plants. and Colorada beetle larvae 7 (Leptinotarsa decemlineata) onto the potato plants. The test was carried out at 24C with 60 percent relative humidity.  
  The compounds according to Example 1 exhibited in the above test a good insecticidal stomach poison action against Spodoptera litoralis. l-Ieliothis and Leptinotarsa decemlineata larvae.  
 B. Systemic insecticidal action In order to determine the systemic action. rooted bean plants (Vicia faba) were placed into a 0.0l percent aqueous active-substance solution (obtained from a 10 percent emulsifiable concentrate). After a period of 24 hours. bean aphids (Aphis fabae) were placed onto the parts of the plants above the soil. The insects were protected by a special device from the effects of contact and of gas. The test was carried out at 24C with 70 percent relative humidity.  
  In the above tests, the compounds according to Example 1 exhibited a systemic action against Aphis fabae.  
 EXAMPLE 3 Action against Chilo suppressalis Rice plants of the type Caloro were planted. 6 plants per pot. in plastic pots having a top diameter of 17 cm. and grown to a height of ca. 60 cm. Infestation with Chilo suppressalis larvae (L,; 34 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. The evaluation of the insecticidal action was made 10 days after application of the granules.  
  The compounds according to Example I were effective against Chilo suppressalis in the above test.  
 EXAMPLE 4 Action against ticks A. Rhipicephalus bursa In each case, 5 adult ticks or 50 tick larvae were placed into a small glass test tube. and the test tubes then immersed for l to 2 minutes in 2 ml of an aqueous emulsion from a dilution series of I00. l0. 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.  
  An 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 in Test A. tests were carried out with 20 sensitive larvae and OP- resistant larvae. respectively (resistance is with respect to diazinon compatibility).  
  The 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 5 Acaricidal action Phaseolus vulgaris (plants) were infested. 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 running off of the spray liquor. An assessment was made after 2 to 7 days. by examination under a binocular. of the living and of the dead larvae. adults and eggs. and the results expressed in percentages. The treated plants were kept during the holding time in greenhouse compartments at 25C.  
  The compounds according to Example I were effective in the above test against adults. larvae and eggs of Tetranychus urticae.  
 EXAMPLE 6 Action against soil nematodes In order to test the action against soil nematodes the active substances were added, in the concentration stated in each case. to soil infested with root-gallnematodes (Meloidogyne arenaria). and the whole intimately mixed. In the one test series. tomato seedlings were planted immediately afterwards in the thus prepared soil. and in the other test series tomatoes were planted after a waiting time of 8 days.  
  For an assessment of the nematicidal action. the galls present on the roots were counted 28 days after planting and sowing. respectively.  
  The active substances according to Example I exhibited in this test a good action against Meloidogyne arenaria.  
 EXAMPLE 7 Action against Botrytis cinerea on Vicia faba In Petri dishes lined with moist filter paper were placed, in each case. three fully developed, identically large leaves of Vicia faba which had been sprayed until dripping wet with a liquor prepared from the active substance in the form of a 10 percent wettable powder (content of active substance in the liquor 0.1 percent), spraying being effected by means of a spraying apparatus. When the leaves were again dry, they were infested with a freshly prepared, standardized spore suspension of the fungus (concentration: 100,000 spores/ml). and kept for 48 hours in a moist atmosphere at 20C. The leaves exhibited after this period of time firstly point-like spots, which then rapidly spread. The number and size of the areas of infection served as a criterion in the assessment of the effectiveness of the test substance.  
  The compounds according to Example l were effective in the above test against Botrytis cinerea.  
 EXAMPLE 8 O-Ethyl S-n-Propyl O-3-Chloro-4-Methyl 2-Exo-2H-l-Benzopyran-7-yl Thiophosphate 0.0&#39;-Diethyl-O-3-chloro-4-methyl-2-exo-2H- 1 -benzopyran-7-yl thiophosphate (38.25 g., 0.1 mole) and 11.2 g. (0.1 mole) of l.4-di-azabicylo [2.2.2] octane (triethylene diamine) were dissolved in 500 ml. of acetonitrile. The solution was left to stir at ambient temperature for 24 hrs. To the solution. 24.6 g (0.2 mole) of l-bromopropane were added and mixture was heated to 70C for 24 hrs. A solid precipitated which was removed by filtration. The filtrate was concentrated under reduced pressure and the residue was dissolved in 500 ml. of ether. The ether solution was washed with water and 5 percent aqueous sodium bicarbonate and dried over anhydrous magnesium sulfate. The solvent was removed under vacuum (0.1 mm) to give l0.6 g. of residue. The structure of the product was confirmed by nuclear magnetic resonance (nmr) Analyses Calcd. for C H CIO PS: C. 45.57; H, 4.55; P, 7.84: CI. 8.95; Found: C, 47.38: H, 4.85; P. 8.20; CI, 9.06.  
  EXAMPLE 9 Comparative Biological Testing of O-Ethyl S-n-Propyl Thiolphosphate and Related 0,0&#39;-Diethyl Thionophosphate The thiolphosphate described in Example 8 and the related thionophosphate Co-Ral described in the specification were tested as aqueous emulsions containing 100 ppm active compound each using the following methods: Mites, Contact: Potted bean plants infested with the two-spotted spider mite were placed on a turntable and sprayed with a formulation of the test chemical. The plants were held for 5 days and the degree of mite control was rated after 2 days. Mites, Systemic: Bean plants infested with the twospotted mites were treated by applying 20 ml. of the formulated test chemical to the soil. Aphid, Contact: Potted nasturtium plants infested with the bean aphids were placed on a turntable and sprayed with a formulation of the test chemical. The plants were held for 2 days and the degree of aphid control was rated. Results: It was found that the thiolphosphate produced a complete control in all the above tests while no control whatsoever was observed for the thionophosphate.  
 What is claimed is:  
 l. A thiolphosphoric acid ester of the formula RS 0 O wherein R is n-propyl or i-butyl, R is hydrogen or methyl, and each of R and R are hydrogen. chlorine or bromine. 2. Compound according to claim 1 of the formal