IL29992A - Novel phosphorothiolates - Google Patents

Description

NOVEL PH0SPH0R0THI0LATE3 1I0¥EL niOOniOROTIIIOIiATEa Abstract of the Disclosure Phosphorothiolates represented by the formula,-: (having 3 to 4 carbon atoms ) wherein R is an alkyl; A is an alkyl( haloalkyl^ alkenyl, alkinyl, alkylthioalkyl, phenylthioalkyl, g thaiimidoa-bkyi fthe radicals X which may be the same or different are \ or phenylalkyl; ii-i&'hydrogen, a halogen or an alkyl; and n is an integer of 1 to 5, are obtained by (1 ) reacting sodium or potassium hydrosulfide with a compound represented by the formula, wherein R, X and n have the same significances as mentioned above, to prepare a thiophosphate represented by the formula, wherein R, X and n have the same significances as mentioned above; and M is an alkali metal, and then ( 2 ) reacting said thiophosphate with a halide represented by the formula, Y - A wherein A has the same significance as mentioned above; and Y is a halogen.

The phosphorothiolates have insecticidal and fungicidal activities.

This invention relates to novel phosphorothiolates having insecticidal and fungicidal activities, to a process for preparing the same, and to insecticidal and fungicidal compositions containing the same.

Further the present invention relates to novel thiophosphate, and method for producing the same.

At present, organophosphorous compounds such as 0, 0-dimethyl-0-4-nitrophenylphosphorothioate and organo- mercury preparations are extensively used as insecticides and fungicides. However, the use thereof has come into question due to their toxicities to mammals. Further it is difficult to control agricultural injurious insects, sanitary injurious insects and agricultural fungi by using a composition containing only one active ingredient.

The present inventors found that novel phosphoro- thiolates having insecticidal activities capable of completely and advantageously controlling agricultural injurious insects and sanitary injurious insects have been produced by reacting a novel thiophosphate with a halide. As to insecticidal activities, these phosphorothiolates were as strong as 0,0-dimethyl-0-3-methyl-4-nitrophenyl phosphorothioate and 0,0-dimethyl-0-4-nitrophenyl phosphorothioate and were successfully applicable to a wide variety of injurious insects. That is, they not only had prominent effects on rice crop injurious insects such as rice stem borers, leaf hoppers and plant hoppers but also showed marked activities' towards injurious insects belonging to the order of Coleoptera, Lepidoptera and Diptera and •towards plant parasitic nematodes. The characteristics of the above phosphorothiolates are such that they showed towards mites as high as several times the effects of existing mitecides, and that they displayed marked activities towards beetles such as red bean bettles and rice weevils, as well.

Further, the present inventors found that the said phosphorothiolates had effects on various rice diseases and, particularly on rice blast, and that they had more excellent effects than those of commercially available fungicides. In addition, they showed prominent effects of controlling Helminthosporium leaf spot and rice sheath blight.

These phosphorothiolates have both insecticidal and fungicidal actions and hence can control both injurious insects and plant diseases. This is an excellent feature which has never been attained heretofore.

The above-mentioned phosphorothiolates, however, show no such strong and acute toxicities as seen in 0,0-dimethyl-0-4-nitrophenyl phosphorothioate, and contain no such poisonous heavy metal as mercury, and therefore are low toxic. Accordingly, they have great advantages in application.

Summary of the Invention: An object of the present invention is to provide novel phosphorothiolates having both insecticidal and fungicidal activities.

Another object is to provide a process for preparing novel phosphorothiolates having insecticidal and fungicidal activities.

A further object is to provide novel thiophosphates and a process for producing the same.

Furthermore it is an object of the present invention to provide insectieidal- and fungicidal compositions containing novel phosphorothiolates.

Other objects will become clear from the description that follows.

In order to achieve the above objects, the present invention provides phosphorothiolates represented by the formula, wherein R is an alkyl having up to 5 carbon atoms; A is an 3 to 4/ alkyl having l¾p to 10 carbon atoms, haloalkyl having up to 3 carbon atomo> alkenyl having up to 4 carbon. atoms, alkinyl having up to 4 carbon atoms, alkylthioalkyl having up to 6 carbon atoms, phenylthioalkyl having up to 9 carbon atoms, or phenylalkyl having up to 10 carbon atoms; X is hydrogen, a halogen or an alkyl having up to 5 carbon atoms; and n is an integer of 1 to 5.

The present invention further provides a process for preparing phosphorothiolates represented by said formula -[i], characterized by reacting a thiophosphate represented by the formula, M [IT] wherein R, X and n have the same significances as mentioned above; and M is an alkali metal, with a halide represented by the formula, Y . A [V] wherein Y is a halogen; and A has the same significance as in the case of formula [i].

Furthermore the present invention provides thiophosphates represented by the formula [iv] .

Still further the present invention provides a process for producing thiophosphates represented by the formula [iv] , characterized by reacting an 0,0-dialkyl-O-phenylphosphorothionate represented by the formula, wherein R, X and n have the same significances as mentioned above, with an alkali hydrosulfide represented by the formula, M · SH ■ [ill] wherein M has the same significance as mentioned above, to prepare a thiophosphate represented by the aforesaid formula [iv] .

The present invention still further provides a process for producing phosphorothiolates represented by said formula [i] , characterized by reacting an 0,0-dialkyl-O-phenylphosphorothionate represented by the formula, wherein R, X and n have the same significances as mentioned above, with an alkali hydrosulfide represented by the formula, M · SH [ill] wherein M has the same significance as mentioned above, to prepare a thiophosphate represented by the aforesaid formula [iv] , and then reacting said thiophosphate with a halide represented by the aforesaid formula [v].

The invention still further provides an insecticidal and fungicidal composition comprising an effective insecticidal and fungicidal amount of a compound represented by the aforesaid formula [i] , and an inert carrier.

All the phosphorothiolates represented by the formula [i and all the thiophosphates represented by the formula [iv] are novel compounds.

In the present invention, the preparation of the phosphorothiolates of the formula [i] by reaction of the thiophosphates of the formula [iv] with the halides of the formula [v] is carried out in the following manner: The thiophosphate of the formula [iv] is added to a solvent. To this reaction mixture is added the halide of the formula [v] , and the mixture is allowed to react.

In this reaction, the order of addition is not so important. The halide is used in an amount of 0.9 to 1.5 moles per mole of the thiophosphate. The solvent may be freely selected from common solvents. Generally, however, solvents relatively high in polarity such as, for example, water, alcohols, alkoxyalcohols, ketones, dimethylformamide, dimethyl sulfoxide, acetonitrile, etc. give favorable results, and the use of solvents capable of dissolving both the starting materials, i.e. thiophosphates and halides, is preferable. As the thiophosphate, any of those prepared according to the method described afterwards may be used, regardless of whether they have been, isolated or not. The conditions of the above condensation reaction greatly vary depending on the kind of starting materials and solvent employed.

Generally, however, the reaction is effected at room temperature to about 150°C. for a period of 30 minutes to 10 hours. If desired, the halide, which is one starting material, is used in excess and is reacted with the other starting material thiophosphate, without using solvent, whereby the yield is increased, in some cases.

After the condensation reaction, the reaction product is subjected to ordinary after-treatments to obtain the desired phosphorothiolate of the formula [i] .

Several examples of typical phosphorothiolates belonging to the present invention are shown below. 0 ( ) CH, 3CH2C1H - S - PI - 0 CI CH, OC2H 0 32 CH2 = CHCH2 - S - P - 0-^^-CH3 OC2H5 Cl 0 (Sec) - s - p - o- °4H9 2"5 OC2H5 0 (Sec).C4Hg - S - P - 0-Q-CH cH OC2H5 0C Hc 2 5 OC2H5 0 H9 OC2H5 CH, - 1i8 ~ In the present invention, the thiophosphates represented by the formula [iv] and used as a starting material in the above-mentioned reaction are prepared in the following manner: A solution of an alkali hydrosulfide represented by the formula [ill] is prepared by using as a solvent a hydrated or anhydrous alcohol, alkoxyalcohol, dimethyl-formamide, dimethyl sulfoxide, or a mixture thereof.

As the alkali hydrosulfide, there may also be used one which has been synthesized by reacting hydrogen sulfide with an alkali alcoholate or an alkali hydroxide in the above-mentioned solvent. Alternatively, a crystalline alkali hydrosulfide or an aqueous alkali hydrosulfide solution relatively high in concentration may also be used. The thus obtained alkali hydrosulfide solution is reacted with a phosphorothionate represented by the formula [il] . The reaction conditions vary depending on the kinds of starting materials and solvent employed. Generally, however, the reaction is effected at a temperature of 50° - 200°C. for a period of 30 minutes to 10 hours.

After the reaction, the reaction mixture is filtered and then the solvent used and a by-produced mercaptan represented by RSH, wherein R has the same significance as mentioned previously, are removed by distillation, whereby a thiophosphate represented by the formula [iv] can be isolated as crystals. For use in the subsequent reaction with a halide of the formula [v], the thiophosphate in the above manner may be employed, in general, in a liquid form without being isolated. The by-product mercaptan may be removed from the reaction mixture also during the course of the reaction.

The phosphorothionate of the formula [il] , which is used as one starting material, is a known compound and is obtained according to a method disclosed in, for example, German Patent 814,152.

The alkali hydrosulfide is used in an amount of 1 or more moles, preferably 1.1 - 1.2 moles, per mole of the phosphorothionate. The amount of solvent to be employed varies depending on the kind of starting material, but is ordinarily 0.5 to 5 times, preferably 1 to 3 times, the weight of the phosphorothionate.

The thiophosphates of the formula [iv] , which are prepared according to the above procedures, are high in purity even at a crude state, e.g. 90 and more, and are obtained in favorable yields, e.g. 90$ and more. .

Several examples of the starting materials employed in practising the present invention, i.e. 0,0-dialkyl-O-phenyl-phosphorothionates, hydrosulfides and halides, are raised below.

Examples of the phosphorothionate represented by the formula [il] are as follows: 0,0-Dimethyl-O-phenyl-thionophosphate. 0, 0-Diethyl-O-phenyl-thionophosphate. 0,0-Dipropyl-O-phenyl-thionophosphate. 0, O-Diisopropyl-O-phenyl-thionophosphate. 0,0-Di(n)-butyl-0-phenyl-thionophosphate. ,0-Diethyl-0-4-chlorophenyl-thionophosphate. ' , O-Diethyl-0-3-chlorophenyl-thionophosphate. , 0-Diethyl-0-2-chlorophenyl-thionophosphate.

, O-Diethyl-0-2 , 3-dichlorophenyl-thionophosphate.

, O-Diethyl-0-2, 4-dichlorophenyl-thionophosphate.

, O-Diethyl-0-2, 5-dichlorophenyl-thionophosphate.

,O-Diethyl-0-2, 6-dichlorophenyl-thionophosphate.

, O-Diethyl-0-2, 4, 6-trichlorophenyl-thionophospha e.

, O-Diethyl-0-2 ,4, 5-trichlorophenyl-thionophosphate.

, O-Di(n)-propyl-0-4-chlorophenyl-thionophosphate.

,O-Di( )-propyl-O-2-chlorophenyl-thionophosphate.

,O-Di(n)-butyl-O-4-chlorophenyl-thionophosphate.

, O-Di( )-butyl-O-2-chlorophenyl-thionophosphate.

,O-Diethyl-O-4-methylphenyl-thionophosphate . , 0-Diethyl-0-3-methylphenyl-thionophosphate.

, O-Diethyl-O-2-methylphenyl-thionophosphate.

,O-Diethyl-0-2 , 3-dimethylphenyl-thionophosphate.

, O-Diethyl-0-2, 4-dimethylphenyl-thionophosphate.

,O-Diethyl-0-2, 5-dimethylphenyl-thionophosphate.

,O-Diethyl-0-2 , 6-dimethylphenyl-thionophosphate.

,O-Diethyl-0-3 , 4-dimethylphenyl-thionophosphate.

, O-Diethyl-0-3, 5-dimethylphenyl-thionophosphate.

,O-Diethyl-0-2 , 3, 5-trimethylphenyl-thionophosphate.

, O-Diethyl-0-2 , 4, 5-trimethylphenyl-thionophosphate, , O-Diethyl-0-2, 4, 6-trimethylphenyl-thionophospha e.

, O-Diethyl-0-2,3,5, 6-tetramethylphenyl-thionophosphate. , O-Diethyl-O-4-ethylphenyl-thionophosphate.

,O-Diethyl-O-3-ethylphenyl-thionophosphate.

, O-Diethyl-0-3-(iso)-propyl-4-methylphenyl-thionophosphate. , O-Diethyl-0-2-(n)-propylphenyl-thionophosphate. 0 O-Diethyl-0-2-(iso)-propylphenyl-thionophosphate 0 O-Diethyl-0-3-(iso)-propylphenyl-thionophosphate. 0, O-Diethyl-0-4-(iso)-propylphenyl-thionophosphate. 0,O-Diethyl-0-4-(tert)-butylphenyl-thionophosphate. 0, O-Diethyl-0-2-(tert)-butylphenyl-thionophosphate. 0, O-Diethyl-0-2-(sec )-butylphenyl-thionophosphate. 0, O-Diethyl-0-3-(sec)-butylphenyl-thionophosphate. 0, O-Diethyl-0-4-(sec )-butylphenyl-thionophosphate. 0,O-Di(n)-propyl-0-4-methylbutyl-thionophosphate. 0,0-Di(n)-propyl-0-2-methylphenyl-thionophosphate. 0, O-Di(n)-butyl-0-4-methylphenyl-thionophosphate. 0,O-Diethyl-0-2,3,4,5, 6-pentachlorophenyl-thionophosphate. 0, O-Diethyl-0-4-(tert)-amylphenyl-thionophosphate. 0,O-Diethyl-0-4-(sec)-amylphenyl-thionophosphate* 0, 0-Diethyl-0-2-methyl-4-(iso )-propylphenyl- thionophosphate. 0, 0-Diethyl-0-2-bromo-4, 5-dimethylphenyl-thionophosphate, 0,O-Diethyl-0-2, 4-dichloro-3, 4-dimethylphenyl- thionophosphate. 0, O-Diethyl-0-3, 5-dimethyl-4-chlorophenyl-thionophosphate. 0,0-Diethyl-0-3-methyl-4-chlorophenyl-thionophosphate.

Examples of the hydrosulfides are potassium and sodium hydrosulfides.

Examples of the halides are ethyl chloride, propyl chloride, iso-propyl bromide, n-butyl bromide, sec-butyl bromide, iso-butyl bromide, n-amyl bromide, iso-amyl bromide, n-octyl bromide, n-decyl bromide, chlorobromomethane, l-chloro-2-bromoethane, l-chloro-3-bromopropane, allyl chloride, methallyl chloride, propalgyl bromide, 2-chloro-ethyl ethyl thioether, 2-chloroethyl phenyl thioether, N-chloromethyl phthalimide, 1-phenylethyl chloride, 2- phenylethyl chloride, 3-phenylpropyl bromide, 1-phenylpropyl bromide, and 2-phenylpropyl bromide.

The phosphorothiolates represented by the formula [i] , which are obtained in the above manner, are low in toxicity to warm-blooded animals and hence can be safely used. Moreover, they may be formulated into insecticidal and fungicidal compositions, which are high in effect of controlling injurious insects and plant diseases, and thus are markedly useful in various fields as chemicals for agriculture, horticulture, environment sanitation and stock raising.

In actual application, the compounds of the present invention may be used either independently without the incorporation of other ingredients, or in admixture with carriers, for easier use as insecticidal and fungicidal chemicals. Ordinarily, they are formulated into optional forms such as emulsifiable concentrates, wettable powders, oil sprays, dusts, ointments, granules, aerosols and fumigants, like in the case of common organic phosphorus preparations, according to procedures thoroughly known to those skilled in the art, without necessitating any special conditions. Thus, they can be put into practical uses in any desired forms by use of suitable carriers.

Further, the present compounds can be used in admixture with one or more of other chemicals to make the effects thereof broader and stronger. For example, they may be used in admixture with organophosphorus insecticides such as 0,0-dimethyl-0-3-methyl- -nitrophenyl phosphorothioate and 0,0-dimethyl-S-(N-raethylcarbamoyl)methyl phosphorodi-thioate; organochlorine preparations such as $"-1,2,3,4,5,6-hexa'chlorocyclohexane and l,l,l-trichloro-2,2-bis(p-chlorophenyl ) ethane ; carbamate insecticides such as 3,4-dimethylphenyl-N-methylcarbamate and l-naphthyl-N-methylcarbamate; pyrethroid insecticides such as allethrin and phthalthrin; organochlorine fungicides such as pentachlorobenzyl alcohol and pentachlorobenzaldoxime; organosulfur fungicides; and organoarsenic fungicides.

In addition, they are easily miscible with mitecides, herbicides, fertilizers, plant growth controlling agents, synergistics, attractants, repellents and the like, and hence can be formulated into multipurpose compositions, whereby synergistic effects due to mixing may be expected . depending on combinations.

In order to clarify the excellent characteristics and effects of the present compounds, typical test results are' shown in the following test examples, in which the ■ figures in parentheses are the numbers of the compounds mentioned previously.

Test Example 1 A mottled kidney plant at the 2 leaves-stage, which had elapsed 20 days after sowing, was parasitized with a large number of carmine ( Tetrany.chus telarius Linn ).

The leaves of said plant parasitized with the mites were individually dipped for 1 minute in each of solutions prepared by diluting with water the present compounds (1) and (2) in the form of wet>table powders. Subsequently, water was given so as not to wither the leaves. After 48 299S2/2 hours, the alive ana dead of th© mites ware observed. From the mortality f the mites, Ι?50 values vera calculated to obtain the results as eat forth in fable 1. 2 29992, faff* ¾WBTflr¾ ¾ Acute toxicity to aloes An <muluion prepared by dilutin with water the present compound (2) in the fore of en enuleifiafclo concentrate vae orally adninletered to Ma e aloe of about 20 g. in body-weigh « Prom the alive and dead of the mice during 48 hours* U)^Q value vae calculated to obtaint *he reeulte ae ehowft in Table 2· fable 2 Compound ; £Ρ¾ά (¾g/kg) <2) O-^Bthyl-O-p-nitrophenyl bensenephoaphorothioate OyO-Dimethyl-O-^-iiitrophenyl phoophorotliloae Test Example 3 < Potted mottled kidney bean plants at the 2 leaves- stage, which had elapsed 20 days after sowing, were parasitized with a large number of carmine mite (Tetranychus telarius Linne" ) . The plants were individually dusted by use of a bell jar duster with each 4 kg/10 ares of the present compounds (2), (4) and (5) in the form of dusts. After the dusting, the plants were parasitized on different days with carmine mite (Tetranychus telarius Linnd) and the ratios of killed mites individually from after 48 hours were investigated to obtain the results as shown in Table 3.

Table 3 Test Example 4 A rice plant at the tillering stage was grown in a Wagner pot. Onto the rice plant were adhered and encroached eggs of rice stem borers (Chilo suppressalis Walker) immediately before hatching. After 3 days, the rice plant was sprayed with 6 cc. per pot of a solution prepared by diluting with water to 2,000 times the present compounds (2) in the form of a wettable powder. After allowing the rice plant to stand for an additional 3 days, the rice stem was broken and examined, and the alive and dead of the borers were observed to calculate the mortality thereof. The result was as shown in Table 4.

Table 4 Test Example 5 A field, in which soybean plants at the flowering stage were being parasitically damaged with a large number of carmine mites (Tetranychus telarius Linn^), was divided 2 into sections of each 33 m . These sections were individually sprayed with 100 ares of an emulsion prepared by diluting with water to 2,000 times the present compound (2) in the form of an emulsifiable concentrate. After 3 days, 30 soybean leaves were sampled from individual sections, and the alive and dead of the mites were observed to calculate the mortality thereof. The results are shown in Table 5.

Table 5 Test Example 6 Curative effects on rice blast: Rice plants (variety: WASEASAHI), which had been cultivated to the 3 leaves-stage individually in a flower pot of 9 cm. in diameter, were sprayed and inoculated with a spore suspension of rice blast fungi (Pyricularia oryzae). After 1 day, each 7 ml. per pot of test chemical solutions at given concentrations were individually applied to the rice plants. After incubation of 3 days, the number of spots generated was counted to investigate the fungicidal effect of each test chemical, whereby the results as shown in Table 6 were obtained.

Table 6 * Control chemicals.

In Table 6, the curative value was calculated according to the following equation: Number of spots of Number of Spots of Curative _ non-treated area ~ treated area ^QO value ~ Number of spots of non-treated area Test Example 7 Mottled kidney bean plants at the 2 leaves-stage, which had elapsed 20 days after sowing were parasitized with a large number of carmine mites (Tetranychus telarius Linn^). The leaves of said plants parasitized with the mites were individually dipped for 1 minute in each of solutions prepared by diluting with water the present compounds (10), (11), (13), (14) and (15) in the form of wettable powders.

Subsequently, water was added so as not to wither the leaves. After 48 hours, the alive and dead of the mites were observed. From the mortality of the mites, values were calculated to obtain the results as shown in Table 7.

Table 7 : Compound : : diluted : : times) : : do) 6,000,000 J I en) ; ! 256,000 J ; («) , I 1,000.000 : ; (n , ; 3#ooo,ooo : ; <15> ; : ,ooo,ooo i ; <85> ! : 17,000,000 ; (86) ! : 5o,ooo : ; (67) : 2,000,000 I : (88) 3,000,000 ; I (8 ) : 6,000,000 I I 0,0~Dimethyl-3-( N-meth l- 500,000 : ; carbamoyl)methyl • phosphor odithioate I Ethyl-l^l+'-^chlorobenzilate ' 100,000 ϊ 2.,3-p-Dioxane S,8-bis-(0,0- ** 1,000,000 I : diethyl phosphor odithioate) Test Example 8 Dipping effects o adzuki bean weevils: Adzuki "bean weevils (Callosobruchus chinensis Linne) within one day after emergence were dipped for 1 minute in each of emulsions prepared "by diluting with water the present compounds (9) to ( 2) and (fi+) to(l6) i the orm of emulsif iable concentrates. Excess liquid on the surfaces of the weevil was removed on a filter paper.

After 2k hours, the alive and dead of the weevils were observed, and values were calculated to obtain the results as shown in Tabl 8.

Acuta toxicity to mioei Εϋ-ulaione prepared by diluting vlth water the present cowpouiide (I4)f (10), (20) and (22) in th« form of efitulalfiable concentratoa war* orally aclBlnietered individually to aale aloe of about 20 g. in body weig , rm the alive and dead of the tfiloe after 46 houra, LD^Q values were calculated according to Richfield Method to obtain the re a e aft ahowri in Table 9. - (9) 200,000 (10) ^300,000 (m 105,000 (12) 160,000 (14) 115,000 (15) 210,000 (16) 350,000 (85) 410,000 ) 120,000 (67) 270,000 490,000 (09) 600,000 0»0-i*othl-0-5-Metl\l-4- 55,000 iiitrophenyl phoephorothloate 0,000 ethoxyethl) plioephorolithloote ,000 plioaylpiioo ouohlorat© 01 (Compound o larael Patent 15420) CI 01 »· ,-0 5*000 Compound LD50 (mg/kg) (14) 80 (18) 100 (20) 121 (22) 500 0-Ethyl-O-p-nitrophenyl 16 phenylphbsphonothiorate 0, O-Dimethyl-O-4-nitrophenyl 5 phosphorothioate Test Example 10 Potted mottled kidney bean plants at the 2 leaves-stage, which had elapsed 20 days after sowing, were parasitized with a large number of carmine mite (Tetranychus teralius Linne). The plants were individually dusted b use of a bell jar duster with each 4 kg/10 ares of the present compounds (9), (13), (23), (24) and (30) in the form of dusts. After the dusting, the plants were parasitized on different days with the mites, and the ratios of killed mites individually from after 48 hours were investigated to obtain the results as shown in Table 10.

Table 10 Test Example 11 Rice plants at the tillering stage were individually grown in Wagner pots. Onto the rice plants were adhered and encroached eggs of rice stem borers (Chilo suppressalis Walker) immediately before hatching. After 3 days, the rice plants were individually sprayed with each 6 cc. per pot of solutions prepared by diluting with water to 2,000 times the present compounds (11), (14), (15) and (31) in the form of wettable powders. After allowing the rice plants to stand for additional 3 days, the rice stems were broken and examined, and the alive and dead of the borers were observed to calculate the mortality thereof.

The results were as shown in Table 11.

A Table 11 Test Example 12 Well water was charged into a 500 cc. beaker.

Into the water, full grown larvae of northern house mosquitoes (Culex pipiens pallens Coquillett) were liberated, and the present compounds (12), (16), (17), (23), (25), (26), (27), (29) and (30) in the form of granules were individually charged. After 24 hours, the alive and dead of the mosquito larvae were observed and, from the mortality thereof, values were calculated to obtain the results as shown in Table 12.

Table 12 Test Example 13 A field, in which soybean plants at the flowering stage were being parasitically damaged with a large number of carmine mites (Tetranychus terarius Linne), was divided 2 into blocks of each 33 m · These blocks were individually sprayed with each 100 -/10 ares of emulsions prepared by diluting with water to 2,000 times the present compounds (12), (16), (17), (21), (23), (25), (26), (27), (28), (29), (32), (33) and (34) in the form of emulsifiable concentrates. After 3 days, 30 soybean leaves were sampled from individual sections, and the alive and dead of the mites were observed to calculate the mortality thereof. The results are shown in Table 13.

Table 13 Test Example 14 Curative effect on rice blast: Rice plants (variety: WASEASAHI), which had been cultivated to the 3 leaves-stage individually in flower pots of 9 cm in diameter, were sprayed and inoculated with a spore suspension of rice blast fungi (Pyricularia oryzae) .

After one day, each 7 ml. per pot of test chemical solutions at given concentrations were individually applied to the rice plants. After incubation of 4 days, the number of spots generated was counted to investigate the fungicidal effect of each test chemical, whereby the results as shown in Table 14 were obtained.

Table 14 Active ingredient Compound concentration Curative (p.p.m. ) Value (11) 1,000 87.1 (14) 1,000 86.4 (19) 1,000 89.3 (23) 1,000 99.5 (24) 1,000 90.8 (25) 1,000 92.7 (26) 1,000 89.5 (34) 1,000 97.2 Control: 0, O-Diethyl-S- 1,000 78.6 benzyl-phosphorothioate (trade name: Kitazin) Control : Phenylmercuric 30 47.7 acetate Non-treatment 0 0 The curative value was calculated according to the equation shown in Test Example 6.

Test Example 15 Insecticidal effects on Small brown plant hopper (Laoclelphex striatellus Fallen) Rice seedlings (15-20 cm in height), which had elapsed 15 days after germination, were individually dipped for 1 minute in emulsions prepared by diluting with water to given concentrations the present compounds (10), (14), (19), (23) and (31) in the form of emulsifiable concentrates. After air-drying, the rice seedlings were individually charged into test glass tubes, and 20-30 plant hoppers (Laodelphax striatellus Pallin) were liberated in each tube,V-~ and the tube was covered with gauze. After 24 hours, the alive and dead of the plant hoppers were observed to calculate the mortality thereof. From the mortality, values were calculated to obtain the results as shown in Table 15.

Table 15 Test Example 16 Mottled kidney bean plants at the 2 leaves-stage, which had elapsed 20 days after sowing, were parasitized with a large number of carmine mites (Tetranychus terarius Linne"). The leaves of said plants parasitized with the mites were individually dipped for 1 minute in each of solutions prepared by diluting with water the present compounds (35) to (37), (41) to (44) and (46) - (57) in the form of wettable powders. Subsequently, water was added so as not to wither the leaves. After 48 hours, the alive and dead of the mites were observed. From the mortality of the mites, values were calculated to obtain the results as shown in Table 16.

Table 16 Test Example 17 Mottled kidney bean plants at the 2 leaves-stage, which had elapsed 20 days after sowing, were parasitized with a large number of carmine mites (Tetranychus telarius Linne). The leaves of said plants paracitized with the mites were individually dipped for 1 minute in each of solutions prepared by diluting with water the present 'V compounds (58) to (62), (64), (67) and (69) in the form of wettable powders. Subsequently, water was added so as not to wither the leaves. After 48 hours, the alive and dead of the mites were observed. From the mortality of the were calculated to obtain the results shown in Table 17.

Table 17 Test Example 18 Dipping effects on Adzuki bean weevils: Adzuki bean weevils (Callosobruchus chinensis Linn^) within 1 day after emergence were dipped for 1 minute in each of emulsions prepared by diluting with water the present compounds (58), (60) and (61) in the form of emulsifiable concentrates. Excess' liquid on the surfaces of the weevils was removed on a filter paper. .

After 24 hours, the alive and dead of the weevils were observed, and values were calculated to obtain the results as shown in Table 18.

Table 18 Test Example 19 Potted mottled kidney bean plants at the 2 leaves-stage, which had elapsed 20 days after sowing, were parasitized with a large number of carmine mites (Tetranychus telarius Linn£). The plants were individually dusted by use of a bell jar duster with each 4 kg/10 ares of the present compounds (58) to (66) in the form of dusts. After the dusting, the plants were parasitized on different days with the mites, and the ratios of killed mites individually from after 48 hours were investigated to obtain the results as shown in Table 19.

Table 19 Test Example 20 Rice plants at the tillering stage were individually grown in Wagner pots. Onto the rice plants were adhered and encroached eggs of rice stem borers (Chilo suppressalis Walker) immediately before hatching.

After 3 days, the rice plants were individually sprayed with each 6 cc. per pot of solutions prepared by diluting with water to 2,000 times the present compounds (58) to (62), (65) and (68) in the form of wettable powders. After allowing the rice plants to stand for additional 3 days, the rice stems were broken and examined, and the alive and dead of the borers were observed to calculate the mortality thereof. The results were as shown in Table 20.

Table 20 Test Example 21 Mottled kidney bean plants at the 2 leaves-stage, which had elapsed 20 days after sowing, were parasitized with a large number of carmine mites (Tetranychus telarius Linn£). The leaves of said plants parasitized with the mites were individually dipped for 1 minute in each of solutions prepared by diluting with water the present compounds (65) and (76) to (84) in the form of wettable powders. Subsequently, water was added so as not to wither the leaves. After 48 hours, the alive and dead of the mites were observed. Prom the mortality of the mites, LC^Q values were calculated to obtain the results as shown in Table 21.

Table 21 ½ The present invention is illustrated below with reference to examples, but it is needless to say that the examples are merely illustrative and the present invention is by no means limited only to these examples.

Example 1 6.7 g. (0.12 mole) of potassium hydroxide was dissolved in 50 ml. of ethyl alcohol. The solution was saturated with hydrogen sulfide to form an ethyl alcohol solution of potassium hydrosulfide. To this solution, 29.6 g. (0,12 mole) of 0,0-diethyl-O-phenylthionophosphate • - 1 was added, and the mixture was refluxed with stirring for 4 hours. After cooling to room temperature, the mixture was charged with 16.4 g. (0.12 mole) of n-butyl bromide, and was then refluxed with stirring for 5 hours. After removing the 5 solvent by distillation, the residue was charged with toluene, was washed with 5 sodium carbonate and was then washed several times with water, and the toluene layer was dried with anhydrous sodium sulfate. Subsequently, toluene was removed by reduced pressure distillation to obtain 27.0 g. of a pale yellow, oily 0-ethyl-O-phenyl-S-n-butyl phosphorothiolate, n^° 1.5125; yield 82.1 .

Elementary, analysis for i Calculated Pound Example 2 6.7 g. (0.12 mole) of potassium hydroxide was dissolved in 50 ml. of ethyl alcohol. The solution was saturated with hydrogen sulfide to form an ethyl alcohol 0 solution of potassium hydrosulfide . To this solution, 29.6 g. (0.12 mole) of 0, 0-diethyl-O-phenyl-thionophosphate was added, and the mixture was refluxed with stirring for 4 hours. After removing ethyl alcohol by reduced pressure distillation, the deposited crystals were suspended in ether, 5 filtered and dried to obtain 28.0 g. of white crystals, yield 91.0 ; m.p. 140°C. .6 g. (0.1 mole) of the thus obtained thiophosphate was dissolved in 100 ml. of ethyl alcohol.

To this solution, 14.3 g. (0.1 mole) of l-chloro-2-bromoethane was added at room temperature, and the mixture was refluxecfc' with stirring for 7 hours.

Thereafter, the reaction mixture was treated in the same manner as in Example 1 to obtain 20.0 g. of a pale yellow, oily 0-ethyl-0-phenyl-S-2-chloroethyl-phosphpro-thiolate, n^8 1.5324; yield 71.2%.

Elementary analysis for : Calculated Found P { ) 11.03 11.24 S { ) 11.42 11.71 ClW 12.63 12.51 Example 3 .6 g. (0.1 mole) of a potassium salt of 0-ethyl-O-phenylphosphorothioate, which had been prepared in the same manner as in Example 2, was dissolved in 100 ml. of ethyl alcohol. To the solution, 12.1 g. (0.1 mole) of allyl bromide was added at room temperature, and the mixture was stirred at 60° - 70°C. for 3 hours. Thereafter, the mixture was treated in the same manner as in Example 1 to obtain 25.1 g. of a pale yellow oily 0-ethyl-O-phenyl-S-allyl-phosphorothiolate, n^° 1.5310; yield 97.3 .

Elementary analysis for C-^H-^O^PS : Calculated Found P (%) 11.99 11.87 S {%) 12.41 12.68 Example 4 24.0 g. (0.1 mole) of a sodium salt of O-ethyl-0-phenylphosphorothioate, which had been prepared in the same manner as in Example 2, was dissolved in 100 ml. of ethyl alcohol. To the solution, 18.5 g. (0.1 mole) of bromide was added at room temperature. Further, a catalytic amount of potassium iodide was added thereto. Subsequently, the mixture was refluxed with stirring for 5 hours and was then treated in the same manner as in Example 1 to obtain 29.2 g. of a pale yellow, oily 0-ethyl-0-phenyl-S-2-phenyl-ethyl-phosphorothiolate, n^ 1.5567; yield 90.6 .

Elementary analysis for Calculated Found P (#) 9.61 9.60 S (J6) 9.95 10.21.

Example 5 .6 g. (0.1 mole) of a potassium salt of 0-ethyl-O-phenyl-phosphorothioate, which had been prepared in the same manner as in Example 2, was dissolved in 100 ml. of ethyl alcohol. To the solution, 17.3 g. (0.1 mole) of 2-phenylthioethyl chloride was added at room temperature.

Further, a catalytic amount of potassium iodide was added thereto. Subsequently, the mixture was refluxed with stirring for 5 hours and was then treated in the same manner as in Example 1 to obtain 33.1 g. of a pale yellow, oily 0-ethyl-0-phenyl-S-2-phenylthioethyl-phosphorothiolate, nj 1.5790; yield 93.3$.

Elementary analysis for : Calculated Found P W 8.74 8.49 S ($) 18.09 18.22. 2¾992/2 gxanrole 6 6.7 g. (0.12 nolo) of potassium hydroxide was dissolved in 50 ml. of ethyl alcohol. The (solution was saturated with hydrogen sulfide to for* an ethyl alcohol solution of potassium hydroaulfid*. So this solution, 51.2 g« (0*12 mole) o 0,0-diethyl~0-4-ra»thyl-phonylthlonophoaphate was added, and the mixture w s rofluxed with stirring for $ hours. After cooling to room temperature, the mixture was charged with 22.2 g. (0.12 mole) Of 2-phonylothyl bromide and further with a catalytic amount of potassium iodide* Subsequently, the mixture was rofluxed with stirring for 5 hours* Afte removing the solvent from the reaction mixture by distillation, the residue was -' charged with toluene, was washed with sodium carbonate and was then washed several times with water, and the toluene layer was dried with anhydrous sodium sulfate.

Subsequently, toluene was removed by reduced pressure distillation to obtain 34.4 g. of a pale yellow, oily 0-ethyl-0-4-methylphenyl-S-2-phenylethyl-phosphorothiolate, n^5 1.5536; yield 85.2%.

Elementary analysis for (^γί^Ο^Ρδ : Calculated Found P W 9.21 9.18 S (96) 9.53 9.74 Example &J 6.7 g. (0.12 mole) of potassium hydroxide was dissolved in 50 ml. of ethyl alcohol. The solution was saturated with hydrogen sulfide to form an ethyl alcohol solution of potassium hydrosulfide. To this solution, 36.2 g. (0.12 mole) of 0,0-diethyl-0-4-(tert )butylphenyl-thionophosphate was added, and the mixture was refluxed with stirring for 6 hours. After cooling to room temperature, the mixture was charged with 22.2 g. (0.12 mole) of 2-phenylethyl bromide and a catalytic amount of potassium iodide, and was then refluxed with stirring for 7 hours.

Subsequently, the mixture was treated in the same manner as in Example 1 to obtain 37.6 g. of a pale yellow, oily 0-ethyl-0-4- ( tert ) -butylphenyl-S-2-phenylethyl phosphorothiolate, 1.5412; yield 82.7$.

Elementary analysis for V- Calculated Found P { ) 8.18 8.18 Example 8 28.4 g. (0.1 mole) of a potassium salt of 0-ethyl-0-3 , 4-dimethylphenyl phosphorothioate, which had been prepared in the same manner as in Example 1, was dissolved in 100 ml. of water. To the solution, 18.5 g. (0.1 mole) of 2-phenyl-ethyl bromide and a catalytic amount of potassium iodide was added, and the mixture was stirred at 80°C. for 5 hours.

Subsequently, the reaction mixture was treated in the same manner as in Example 1 to obtain 31.3 g. of a brown, oily O-ethyl-0-3 , 4-dimethylphenyl-S-2-phenylethyl-phosphoro-thiolate, n^8 1.5530; yield 89.2 .

Elementary analysis for C^gB^jO^PS : Calculated . Found P (%) 8.84 8.67 S { ) 9.15 9.18 Example i£) 6.7 g. (0.12 mole) of potassium hydroxide was dissolved in 50 ml. of ethyl alcohol. The solution was saturated with hydrogen sulfide to form an ethyl alcohol solution of potassium hydrogen sulfide. To this solution, 31.2 g. (0.12 mole) of 0, 0-diethyl-0-3-methylphenyl-thionophosphate was added, and the mixture was refluxed with stirring for 6 hours. After cooling to room temperature, the mixture was charged with 22.2 g. (0.12 mole) of 2-phenylethyl bromide and was then refluxed with stirring ' for 5 hours. Subsequently, the reaction mixture was treated in the...same manner as in Example 1 to obtain 32.8 g. of a pale yellow, oily O-e-thyl-0-3-methylphenyl-S-2-phenylethyl phosphorothiolate, n 1.5522; yield 81.3 .

Elementary analysis for C^I^O^S : ' " Calculated Found P (%) ' 9.21 9.22 S W 9.53 9.71 Example llO 6.7 g. (0.12 mole) of potassium hydroxide was dissolved, in 50- ml... -of ethyl . alcohol. The solution was saturated with hydrogen, sulfide to form an ethyl, alcohol solution of potassium hydroxide. To this solution, 33.7 g. (0.12 mole) of 0,0-diethyl-0-4-chlorophenyl-thionophosphate was added, and the mixture was refluxed with stirring for 4 hours. After removing ethyl alcohol by reduced pressure distillation, deposited crystals were suspended in ether, filtered and dried to obtain 32.2 g. of white crystals, yield 92.3 ; m.p. 154° - 156°C. 29.1 g. (0.1 mole) of the thus obtained thiophosphate was dissolved in 100 ml. of water. To the solution, 18.5 g. (0.1 mole) of 2-phenylethyl bromide was added at room temperature, and the mixture was stirred at 80°C. for 5 hours. Subsequently, the reaction mixture was treated in the same manner as in Example 1 to obtain 33.5 g.. of a pale yellow, oily 0-ethyl-0-4-chlorophenyl-S-2-phenylethyl phosphorothiolate, ηπ 1.5610; yield 94.0 .

Elementary analysis for 0η ΛΗη pC10,PS : V- Calculated Found S (#) 8.99 8.90 CI (#) .94 10.14 Example ¾2 \\ A mixture comprising 30.5 g. of a potassium salt of 0-ethyl-0-3-methyl-4-chlorophenyl-phosphorothioate, which had been prepared in the same manner as in Example 1, 100 ml. of ethanol and 18.5 g. of 2-phenylethyl bromide was refluxed for 5 hours and was then subjected to ordinary after-treatments to obtain a pale yellow, oily O-ethyl-0-3-methyl-4-chlorophenyl-S-2-phenylethyl-phosphorothiolate, n^11.5568; yield 93#.

Elementary analysis for : Calculate p w 8.37 s W 8.64 oi { ) 8.58 Example ¾ |2, 27.5 g. (0.1 mole) of a sodium salt of 0-ethyl-O-2-chlorophenyl-phosphorothioate, which had been obtained in the same manner as in Example 1, was dissolved in 100 ml. of ethyl alcohol. To the solution, 18.5 g. (0.1 mole) of 2-phenylethyl bromide and a catalytic amount of potassium iodide were added at room temperature, and the mixture was refluxed with stirring for 5 hours. Subsequently, the reaction mixture was treated in the same manner as in Example 1 to obtain 32.5 g. of a pale yellow, oily O-ethyl-^" 0-2-chlorophenyl-S-2-phenylethyl phosphorothiolate, 1.5613; yield 91.2%.

Elementary analysis for C-, ,-H-, oClO^ S : Calculated Found P ( ) 8.68 8.80 S { ) 8.99 9.22 Example 344"5 6.7 g. (0.12 mole) of potassium hydroxide was dissolved in 50 ml. of ethyl alcohol. The solution was saturated with hydrogen sulfide to form an ethyl alcohol solution of potassium hydrosulfide. To this solution, 37.8 g. (0.12 mole) of 0,0-diethyl-0-2,4-dichlorophenyl-thionophosphate was added, and the mixture was refluxed with stirring for 4 hours. After cooling to room temperature, the mixture was charged with 22.2 g. (0.12 mole) of 2-phenylethyl bromide and was then refluxed with stirring for 4 hours. Subsequently, the reaction mixture was treated in the same manner as in Example 1 to obtain 40.5 g. of a pale yellow, oily O-ethyl-0-2 , 4-dichlorophenyl-S-2-phenylethyl-phosphorothiolate, nj 1.5678; yield 86.2 .

Elementary analysis for : Calculated Found P W 7.92 7.85 s ( ) 8.19 8.33 CI (*) 18.12 17.93 Examples -fc5-!?g According to Examples 1-14, the compounds set forth in the table below were synthesized. wherein A is a phenylethyl group.

Provided that the starting materials, salts of 0-alkyl-O-substituted phenyl-phosphorothioates, were synthesized in the manner similar to that as in Example 11.

Example 9532 V (0.12 mole) of potassium hydroxide was dissolved in 50 ml. of ethyl alcohol. The solution was saturated with hydrogen sulfide to form an ethyl alcohol solution of potassium hydrosulfide. To this solution, 31.2 g. (0.12 mole) of 0, 0-diethyl-0-4-methylphenyl thionophosphate was added, and the mixture was refluxed with stirring for 5 hours. After removing ethyl alcohol from the reaction liquid by reduced pressure distillation, deposited crystals were suspended in ether, filtered and dried to obtain 29.2 g. of a potassium salt of O-ethyl-0-4-methylphenyl phosphorothioate, yield 90.1 ; m.p. 157° -160°C. 27.0 g. (0.1 mole) of this thiophosphate was dissolved in 100 ml. of acetone. To the solution, 7.7 g. (0.1 mole) of allyl chloride was added at room temperature, and the mixture was refluxed with stirring for 3 hours. After removing the solvent by distillation, the residue was charged with toluene, was washed with $ sodium carbonate and was washed several times with water, and then the toluene layer was dried with anhydrous sodium sulfate. Subsequently, toluene was removed by reduced pressure distillation to obtain 25.4 g. of a pale yellow, oily 0-ethyl-0-4-methylphenyl-S-allyl-phosphorothiolate, n-27.5 1.5235; yield 93.3$.

Elementary analysis for C^H^O^S : Calculated Found S (*) 11.77 12.00 Example 433 27.0 g. (0.1 mole) of a potassium salt of 0-ethyl- 0-4-methylphenyl-phosphorothioate, which had been prepared 3a in the same manner as in Example 53, was dissolved in 100 ml. of ethyl alcohol. To the solution, 13.7 g. (0.1 mole) of sec-butyl bromide was added at room temperature, and the mixture was refluxed with stirring for 7 hours. Subsequently, the reaction mixture was treated in the same manner as in Example 33 to obtain 20.3 g. of a pale yellow, oily 0-ethyl-0-4-methylphenyl-S-(sec)-butyl-phosphorothiolate, 1.5101; yield 70.5 .

Elementary analysis for C^I^O^S : Calculated Found .74 10.57 S W 11.12 11.31 Example ¾ 27.0 g. (0.1 mole) of a potassium salt of 0-ethyl-0-4-methylphenyl phosphorothioate, which had been prepared in the same manner as in Example 53, was dissolved in 100 ml. of ethyl alcohol. To the solution, 11.9 g. (0.1 mole) of propargyl bromide was added, and the mixture was stirred at 60° - 70°C. for 4 hours. Subsequently, the reaction mixture was treated in the same manner as in Example 33 to obtain 24.9 g. of a pale brown, oily 0-ethyl-0-4-methylphenyl-S-propargyl phosphorothiolate, n^ 1.5285; yield 92.1$.

Elementary analysis for ϋ-^Η-^Ο^Ρδ : Calculated Found P { ) 11.46 11.50 A s ( ) 11.86 11.93.

Example ^ "55" 0,O-Diethyl-0-4-(tert)-butylphenyl thionophosphate was treated in the same manner as in Example to prepare 5 white crystals of a potassium salt of 0-ethyl-0-4-(tert )- butylphenyl phosphorothioate, yield 9315?°', m.p. 178° - 181°C. 31.2 g. (0.1 mole) of this thiophosphate was dissolved in 100 ml. of ethyl alcohol. To the solution, 12.1 g. (0.1 mole) of allyl bromide was added, and the 0 mixture was stirred at 60° - 70°C. for 3 hours. Subsequently, the reaction mixture was treated in the same manner as in Example 33 to obtain 29.7 g. of a yellow, oily O-ethyl-0- 4-(tert)-butylphenyl-S-allyl phosphorothiolate, ^ 1.5179; yield 94.4/°.

Elementary analysis for C-j^i^O^PS : Calculated Found P ( ) 9.85 9.79 S { ) 10.20 10.37 Example 3^ 6.7 g. (0.12 mole) of potassium hydroxide was dissolved in 50 ml. of ethyl alcohol. The solution was saturated with hydrogen sulfide to form an ethyl alcohol solution of potassium hydrosulfide. To this solution, 32.9 g. (0.12 mole) of 0,0-diethyl-0-3, 4-dimethylphenyl- 25 thionophosphate was added, and the mixture was refluxed with stirring for 7 hours.. After cooling to room temperature, the mixture was charged with 16.4 g. (0.12 mole) of sec-butyl bromide and a catalytic amount of potassium iodide, and was then refluxed with stirring for 9 hours. Subsequently, reaction mixture was treated in the same manner as in Example 33 to obtain 26.7 g. of a pale brown, oily O-ethyl-0- , 4-dimethylphenyl-S- ( sec )-butyl phosphorothiolate, n^6 1.5148; yield 73.6%.

Elementary analysis for C-^H^O^PS: Calculated Found S (%) 10.60 10.33 Example 38 ¾7 0, O-Diethyl-0-3, 4-dimethylphenyl-thionophosphate was treated in the same manner as in Example ¾ to prepare white crystals of a potassium salt of O-ethyl-0-3,4-dimethylphenyl-phosphorothioate, yield 90.5$; m.p. 170° -172°C. 28.4 g. (0.1 mole) of this thiophosphate was dissolved in 100 ml. of ethyl alcohol. To the solution, 14.3 g. (0.1 mole) of l-chloro-2-bromoethane was added, and the mixture was refluxed with stirring for 10 hours. Subsequently, the reaction mixture was treated in the same manner as in Example 33 to obtain 22.0 g.. of a pale brown, oily O-ethyl-0-3 , 4-dimethylphenyl-S-2-chloroethyl-phosphorothiolate, n^9,5 1.5330; yield 71.1 .

Elementary analysis for C-.9Ηη oC10-,PS : Calculated Found P (*) 10.03 10.26 s 10.38 10.41 CI (*) 11.48 11.28 Example 38 26.8 g.- (0.1 mole) of a sodium salt of O-ethyl-0-3, 4-dimethylphenyl-phosphorothioate, which had been prepared in the same manner as in Example 55, was dissolved in 100 ml. of acetone. To the solution, 7.7 g. (0.1 mole) of allyl chloride was added, and the mixture was refluxed with stirring for 3 hours. Subsequently, the reaction mixture was treated in the same manner as in Example 33 to obtain 27.5 g. of a pale brown, oily 0-ethyl-0-3,4-dimethyl-phenyl-S-allyl-phosphorothiolate, n^9,5 1.5270; yield 96.0$. Elementary analysis for C-^H-^O^PS: Calculated Found P (%) 10.82 10.87 S { ) 11.20 11.42.

Example 27.0 g. (0.1 mole) of a potassium salt of 0-ethyl-0-3-methylphenyl-phosphorothioate, which had been prepared in the same manner as in Example 33, was dissolved in 100 ml. of water. To the solution, 14.3 g. (0.1 mole) of 1-chloro-2-bromoethane was added, and the mixture was stirred at 70° - 80°C. for 6 hours. Subsequently, the reaction mixture was treated in the same manner as in Example 33 to obtain 21.1 g. of a pale yellow, oily 0-ethyl-0-3-methylphenyl-S-2-chloroethyl-phosphorothiolate, n^ 1.5260; yield 71.5%.

Elementary analysis for : Calculated Pound (*) 10.51 10.53 (*) 10.88 11.02 w 12.03 11.81.

Example 27.0 g. (Ό.1 mole) of a potassium salt of 0-ethyl- 0-3-methylphenyl-phosphorothioate, which had been prepared in the same manner as in Example 33, was dissolved in 100 ml. of ethyl alcohol. To the solution, 12.1 g. (0.1 mole) of all l bromide was added, and the mixture was stirred at 60° - 70°C. for 3 hours. Subsequently, the reaction mixture was treated in the same manner as in Example 33 to obtain 25.6 g. of a pale yellow, oily 0-ethyl-0-3-methylphenyl-S-allyl-phosphorothiolate, ¾ 27 5 1.5235; yield 94.1$.

Elementary analysis: Calculated Found S W 11.77 12.01 Example 4-2 †1 27.0 g. (0.1 mole) of a potassium salt of 0-ethyl-0-3-methylphenyl-phosphorothioate, which had been prepared in the same manner as in Example 33, was dissolved in 100 ml. of ethyl alcohol. To the solution, 13.7 g. (0.1 mole) of sec-butyl bromide was added, and the mixture was refluxed with stirring for 5 hours. Subsequently, the reaction mixture was treated in the same manner as in Example 33 to obtain 21.4 g. of a pale brown, oily 0-ethyl-0-3-methylphenyl-S-(sec)-butyl-phosphorothiolate, nj^ 1.5077; yield 74.1$.

Elementary analysis for C-^f^O^PS : Calculated Pound P (%) 10.74 10.81 S { o) 11.12 11.32 Example 3 2> 6.7 g. (0.12 mole) of potassium hydroxide was dissolved in 50 ml. of ethyl alcohol. The solution was saturated with hydrogen sulfide to form an ethyl alcohol solution of potassium hydrosulfide. To this solution, 33.7 g. (0.12 mole) of 0,0-diethyl-0-4-chlorophenyl-thionophosphate was added, and the mixture was refluxed with stirring for 4 hours. After cooling to room temperature, the mixture was charged with 14.5 g. (0.12 mole) of allyl bromide and was stirred at 60° - 70°C. for 3 hours. After removal of the solvent, the residue was charged with toluene, was washed with sodium carbonate and was then washed several times with water, and the toluene layer was dried with anhydrous sodium sulfate. Subsequently, toluene was removed by reduced pressure distillation to obtain 30.6 g. of a pale yellow, oily 0-ethyl-0-4-chlorophenyl-S-allyl-phosphorothiolate, n^7 1.5370; yield 87.0 .

Elementary analysis for C^H^CIO^PS : Calculated Found P (*) 10.58 10.65 s (*) 10.95 11.21 CI 12.11 12.03 Example 44 t†2> 29.1 g. (0.1 mole) of a potassium salt of 0-ethyl-0-4-chlorophenyl phosphorothioate, which had been obtained in the same manner as in Example 3§, was dissolved in 100 ml. of ethyl alcohol. To the solution, 13.7 g. (0.1 mole) of sec-butyl bromide and a catalytic amount of potassium iodide were added at room temperature, and the mixture was refluxed with stirring for 7 hours. Subsequently, the reaction mixture was treated in the same manner as in Example 33 to obtain 24.2 g. of a pale yellow, oily 0-ethyl-0-4-chloro- 2^ phenyl-S-sec-butyl phosphorothiolate, n^ 1.5221; yield 78.5 .

Elementary analysis for : Calculated Found P ('*) 10.03 10.25 S { ) 10.38 10.43 CI {%) 11.48 11.58 Example 4 - 29.1 g. (0.1 mole) of a potassium salt of 0-ethyl-0-4-chlorophenyl-phosphorothioate, which had been prepared in the same manner as in Example 31Jr, was dissolved in 100 ml. of ethyl alcohol. To the solution, 14.3 g. (0.1 mole) of 2-chloro-l-bromoethane was added at room temperature, and the mixture was refluxed with stirring for 7 hours.

Subsequently, the reaction mixture was treated in the same manner as in Example 33 to obtain 22.2 g. of a pale yellow, oily 0-ethyl-0-4-chlorophenyl-S-2-chloroethyl-phosphoro-thiolate, nj 1.5332; yield 70.3%.

Elementary analysis for 0Ί ηΗΊ -^ClpO^PS : Calculated Found p W 9.83 10.05 s W 10.17 10.41 ci W 22.50 22.20 Example -645 6.7 g. (0.12 mole) of potassium hydroxide was dissolved in 50 ml. of ethyl alcohol. The solution was saturated with hydrogen sulfide to form an ethyl alcohol " solution of potassium hydrosulfide. To this solution, 33.7 g. (0.12 mole) of 0,0-diethyl-0-2-chlorophenyl-thionophosphate was added, and the mixture was refluxed with stirring for 4 hours. After cooling to room temperature; the mixture was charged with 9.2 g. (0.12 mole) of allyl chloride and was then stirred at 60° - 70°C. for 3 hours. Subsequently,- the reaction mixture was treated in the same manner as in Example 33 to obtain 31.0 g. of a pale yellow, oily 0-ethyl-0-2-chlorophenyl-S-allyl-phosphorothiolate, np9,5 1.5370; yield 88.2 .

Elementary analysis for C-, ·,ΗΊ AC10,PS : Calculated Found P ( ) 10.58 10.66 s (%) 10.95 11.21 CI 12.11 12.19 Example 41 0,0-Diethyl-0-2-chlorophenyl-thionophosphate treated in the same manner as in Example ¾ to prepare white crystals of a potassium salt of 0-ethyl-0-2-chlorophenyl-phosphorothioate, yield 94.3 , m.p. 184° - 186°C. 29.1 g. (0.1 mole) of this thiophosphate was dissolved in 100 ml. of ethyl alcohol. To the solution, 13.7 g. (0.1 mole) of sec-butyl bromide was added at room temperature, and the mixture was refluxed with stirring for 7 hours.

Subsequently, the reaction mixture was treated in the same 33 manner as in Example 55 to obtain 23.0 g. of a pale brown, oily 0^ethyl-0-2-chlorophenyl-S-sec-butyl-phosphorothiolate, ¾91.5215; yield 74.6 .

Elementary analysis for Cn Ηη oC10,PS : Calculated Found P ( ) 10.03 10.28 s (*) 10.38 10.52 01 11.48 . 11.44 Example 48 ·? 27.5 g. (0.1 mole) of a sodium salt of O-ethyl-0- 2-chlorophenyl-phosphorothioate, which had been prepared in 32, the same manner as in Example 5f , was dissolved in 100 ml. of acetone. To the solution, 11.9 g. (0.1 mole) of propargyl bromide was added at room temperature, and the mixture was refluxed with stirring for 3 hours. Subsequently, the 32 mixture was treated in the same manner as in Example to obtain 26.7 g. of a pale yellow, oily 0-ethyl-0-2-chloro- 2Q phenyl-S-propar yl phosphorothiolate, n^ 1.5420; yield 91.7 .

Elementary analysis for C-,ηΗ·, ,,C10,PS: Calculated Found P 10.63 10.70 s (#) 11.03 11.12 CI (*) 12.19 12.15 Example 48 0, O-Diethyl-0-2 , 4-dichlorophenyl-thionophosphat< was treated in the same manner as in Example 35 to obtain white crystals of a potassium salt of O-ethyl-0-2 , 4-dichlorophenyl-phosphorothioate, yield 96.2 ; m.p. 173° -175°C. 32.5 g. (0.1 mole) of this thiophosphate was dissolved in 100 ml. of acetone. To the solution, 7.7 g. (0.1 mole) of allyl chloride was added at room temperature, and the mixture was refluxed with stirring for 3 hours.

Subsequently, the mixture was treated in the same manner as in Example 33 to obtain 29.6 g. of a pale yellow, oily O-ethyl-0-2 , 4-dichlorophenyl-S-allyl phosphorothiolate, n^7*5 1.5460; yield 90.6 .

Elementary analysis for Cn ηΗΊ ,ΟΙ^Ο,ΡΘ : Calculated Pound P ( %) 9.47 9.54 s (*) 9.80 9.68 CI 21.67 21.50.

Example gff - -9 32.5 g. (0.1 mole) of a potassium salt of 0-ethyl-0-2,4-dichlorophenyl-phosphorothidate, which had been prepared in the same manner as in Example 9≤5, was dissolved in 100 ml. of water. To the solution, 10.9 g. (0.1 mole) of bromoethane was added at room temperature, and the mixture was stirred at 50° - 60°C; fOr 4 hours. Subsequently, the 32 mixture was treated in the same manner as in Example 35 to obtain 26.7 g. of a pale yellow oily O-ethyl-0-2,4-dichlbrbphenyl-S-ethyl-phospho'rothiolate, n-^ 1.5380; yield 84; 7%.

Elementary analysis for : Calculated Pound CI ( ?°) 22.50 22.57.

Example 5ί> 32.5 g. (0.1 mole) of a potassium salt of 0-ethyl- 0-2, 4-dichlorophenyl-phosphorothioate, which had been prepared 32. in the same manner as in Example ·¾$, was dissolved in 100 ml. of ethyl alcohol. To the solution, 13.7 g. (0.1 mole) of sec-butyl bromide was added at room temperature, and the mixture was refluxed with stirring for 7 hours. Subsequently, the mixture was treated in the same manner as in Example 33 to obtain 26.5 g. of a pale yellow, oily 0-ethyl-0-2,4-dichloro- 27 phenyl-S-sec-butyl-phosphorothiolate, n^ 1.5304; yield 77.1$. Elementary analysis for C-.9Ηη 7C1~0,PS : Calculated Found P 9.02 9.13 s (*) 9.34 9.26 CI (#) 20.66 20.73 Example gg¾4- 29.I g. of a potassium salt of O-ethyl-0-4-chlorophenyl-phosphorothiolate, which had been prepared in 32 the same manner as in Example was dissolved in 50 ml. of water. The solution was heated to 50°C, and then 12·. 5 g. of 2-chloroethyl-ethylthioether was added dropwise thereto over a period of 1 hour. After the dropwise addition, the mixture was heated with stirring at 70°C. for 4 hours, was charged with 100 g. of toluene and was then separated. 3S Subsequently, the same after-treatments as in Example ¾ were effected to obtain a pale yellow, oily 0-ethyl-0-4-chloro-phenyl-S-2-ethylthio-ethyl-phosphorothiolate, ^ 1. 5467 ; yield 92.0^.

Elementary analysis for : Calculated Pound P W . 9.10 9.61 s (*) 18.50 19.20 CI (*) 10.43 10.11 Example ¾ A mixture comprising 28.4 g. of a potassium salt of O-ethyl-0-3 , 4-dimethylphenyl-phosphorothioate, which had been prepared in the same manner as in Example 33, 100 ml. of ethanol, and 17.3 g. of 2-chloroethylphenyl-thioether was treated in the same manner as in Example 33 to obtain a yellow, oily 0-ethyl-0-3 , 4-dimethyl-S-2-phenylthioethyl-phosphorothiolate, yield 86$.

Elementary analysis for C^H^O^I^ : Calculated Found P (%) 8.12 8.38 S {) 16.75 17.05 Example Sfr 5"3 A mixture comprising 32.5 g. of a potassium salt of O-ethyl-0-2 , 4-dichlorophenyl-phosphorothioate, which had been prepared in the same manner as in Example 53, 100 ml. of ethanol, and 19.6 g. of N-chloromethyl-phthalimide was refluxed for 5 hours. Subsequently, the mixture was subjected to ordinary after-treatments to obtain a pale yellow, oily O-ethyl-0-2 , 4-dichlorophenyl-S-N-phthalimide-methyl-phosphorothiolate, yield 83 .

Elementary analysis for C 7Hn ,C1~N0,-PS : Calculated Found P ( f ) 6.95 7.13 S ( f>) 7.17 7.26 CI ( f>) 15.92 15.40 N (%) 3.14 3.03 Example 5 54- A mixture comprising 31.9 g. of a potassium salt of O-ethyl-0-3, 5-dimethyl-4-chlorophenyl-phosphorothioate, which had been prepared in the same manner as in Example 33» 50 ml. of ethanol, 50 ml. · of water and 13.7 g. of sec-butyl bromide was reacted at 60°C. for 10 hours. Subsequentl the mixture was subjected to ordinary after-treatments to obtain a pale yellow, oily substance of O-ethyl-0-3, 5-dimethyl-4-chlorophenyl-S-sec-butyl phosphorothiolate, yield 57%.

Elementary analysis for C-, AH C10,PS : Calculated Pound Example 32.5 g. (0.1 mole) of a potassium salt of 0-ethyl-0-2, 4-dichlorophenyl-phosphorothioate, which^had been prepared in the same manner as in Example 35, was dissolved in 100 ml. of ethyl alcohol. To the solution, 15*1 g. (0,1 mole) of isoamyl bromide and a catalytic amount of potassium iodide were added,, and the mixture was refluxed with stirring for 6 hours. Subsequently, the mixture was treated in the same manner as in Example 5^ to obtain 27.4 g. of a pale yellow, oily O-ethyl-0-2, 4-dichlorophenyl-S-isoamyl-phosphorothiolate, n^11.5242; yield 76.7 .

Elementary analysis for Calculated Found P { ) 8.67 8.91 S W 8.97 9.23 CI (%) 19.85 19.83.

Examples ^=Θ gk-E¾ ¾SL 5*5" According to Examples 3*3 to ^&, compounds shown in the table below were synthesized.

Provided that the starting materials, salts of 0-alkyl-0-substituted phenyl phosphorothioates, were synthesized in entirely the same manner as in Example 33. The results of synthesis are shown in the table.

Several ..processes...!or the formulation of th.e V present compounds are exemplified, below.

Example &5 Formulation of emulsifiable concentrates: Each of the compounds shown in the table below is thoroughly mixed with the solvent and emulsifier, in this order, in the proportions set forth in the table, whereby a homogeneous emulsifiable concentrate is obtained. In application, the emulsifiable concentrate is diluted with water, and the emulsion is sprayed.

Example Formulation of wettable powders: 40 Parts of the compound (5) is thoroughly mixed with 5 parts of emulsifier (Higher alcohol sodium sulfonate type).. The mixture is added dropwise to 55 parts of 200 mesh talc under thorough stirring in a mortar and is kneaded therewith, whereby a wettable powder is obtained. In application, the wettable powder is diluted with water, and the solution is sprayed.

Example ¾? 31 Each of the compounds shown in the table below is dissolved in a small amount of acetone and is thoroughly mixed with 200 mesh talc in proportions set forth in the table. Subsequently, acetone is removed by volatilization, whereby a dust is obtained.

In application, the dust is dusted as such.

Example ΒΒ<¾ Formulation of granules: Each of the compounds shown in the table below is mixed with the binder and extender, in this order, in the proportions set forth in the table. The mixture is kneaded with a small amount of water, is formed into granules by means of a granulator and is then dried, whereby a granule is obtained. In application, the granule is sprinkled as such.

Claims (1)

V Claims

1. Phosphorothiolates represented by the formula, wherein R is an alkyl having up to 5 carbon atoms; A is an 3 to 4 alkyl having ¾p to 10 carbon atoms, haloalkyl having up to. 3 oar-bon atomo, alkenyl having up to 4 carbon atoms, alkinyl having up to 4 carbon atoms, alkylthioalkyl having up to 6 carbon atoms, phenylthioalkyl having up to 9 carbon atoms, •phthalimidoalkyl .ha ing up. to-11- carbon"- a-faoae or phenylalkyl having up to 10 carbon atoms; X is hydrogen, a halogen or an alkyl having up to 5 carbon atoms; and n is an integer of 1 to 5. A process for preparing phosphorothiolates represented by the formula, wherein R is an alkyl having up to 5 carbon atoms; A is an alkyl having/up to 10 carbon atoms, haloalkyl having up to ■3 carbon a oms., alkenyl having up to 4 carbon atoms, alkinyl having up to 4 carbon atoms, alkylthioalkyl having up to 6 carbon atoms, phenylthioalkyl having up to 9 carbon atoms, F^t^p"1 imi^oq^k l having UP- o 11 oarbo-Sr atome- or phenylalkyl having up to 10 carbon atoms; X is hydrogen, a halogen or an alkyl having up to 5 carbon atoms; and n is an integer of 1 to 5 characterized by reacting a thiophosphate represented by the formula, wherein R, X and n have the same significances as mentioned above; and M is an alkali metal, with a halide represented by the formula, wherein A has the same significance as mentioned above; and Y is a halogen. Λ proc for produoing thiophosphates repress as mentioned by the formula, k. A process for preparing phosphorothiolates represented by the formula, wherein R is an alkyl having up to 5 carbon atoms; A is an 3 to 4 alkyl having up to 10 carbon atoms, -haloalkyl having up to 3- oar on. atome-y alkenyl having up to 4 carbon atoms, alkinyl having up to 4 carbon atoms, alkylthioalkyl having up to 6 carbon atoms, phenylthioalkyl having up to 9 carbon atoms, pta hn.1 imirinnlVyl ha.v¾rg 1p ■ +-^—Π nn >ift« -ojMiii». or phenylalkyl having up to 10 carbon atoms; X is hydrogen, . a halogen or an alkyl having up to 5 carbon atoms; and n is an integer of 1 to 5, characterized by reacting an 0,0-dialkyl-O-phenyl phosphorothionate represented by the formula, wherein R, X and n have the same significances as mentioned * » » r above, with an alkali hydrosulfide represented by the formula, M · SH f wherein M is an alkali metal, to form a thiophosphate represented by the formula, wherein R, M, X and n have the same significances as mentioned above, and then reacting said thiophosphate with a halide represented by the formula, wherein A has the same significance as mentioned above; and Y is a halogen atom. An insecticidal and fungicidal composition comprising an inert carrier and, as an active ingredient, an effective amount of a phosphorothiolate represented by the formula, wherein R is an alkyl having up to 5 carbon atoms; A is an 3 to 4/ alkyl having jap to 1Q- carbon atoms, haloalkyl having up to ■3 carbon atoao¾ alkenyl having up to 4 carbon atoms, alkinyl having up to 4 carbon atoms, alkylthioalkyl having up to 6 carbon atoms, phenylthioalkyl having up to 9 carbon atoms, or phenylalkyl having up to 10 carbon atoms; X is hydrogen, a halogen or an alkyl having up to 5 carbon atoms; and n is an integer of 1 to 5. fl . An insecticidal and fungicidal composition according 4 to Claim wherein the composition is in a form of emulsifi-able concentrate, wettable powder, oil spray, dust, ointment, granule, aerosol or fumigant.