Phosphoryl phenylenediamines

The present invention relates to novel phenylenediamine compounds and their production and use.
The said phenylenediamine compounds are representable by the formula: ##SPC3##
Wherein R.sub.1 is a lower alkyl group or a phenyl group which may bear one to five substituents, R.sub.2 is a lower alkyl group, A is an alkyl group, an alkenyl group, an alkynyl group, a haloalkyl group, a phenyl group, a cyanoalkyl group, a lower alkylthioalkyl group, a haloalkenyl group, a lower alkoxyalkyl group, a lower alkoxycarbonylalkyl group, a lower alkylcarbamoylalkyl group or a phenylalkyl group which may bear one to five substituents on the benzene ring and X is an oxygen atom or a sulfur atom.
The term "lower" as herein used is intended to mean the one having not more than 8 (preferably not more than 5) carbon atoms. Any of the hydrocarbon residues or moieties such as alkyl, alkenyl or alkynyl may be a lower (C.sub.1 -C.sub.8) or higher (C.sub.8 -C.sub.30) one, when used without the term lower. The term "halogen" includes chlorine, bromine, iodine and fluorine. Examples of the substituents which may be present on the benzene ring are lower alkyl, lower alkoxy, lower alkylthio, nitro, cyano, halogen, lower alkylenedioxy, etc. Particularly preferred are lower alkyl, lower alkylthio, nitro, cyano and halogen for the substituents on the phenyl group represented by the symbol R.sub.1 and lower alkyl, lower alkoxy, nitro, halogen and lower alkylenedioxy for the substituents on the phenyl group in the phenylalkyl group represented by the symbol A.
The phenylenediamine compounds [I] show a strong antimicrobial activity against a wide variety of microorganisms, particularly phytopathogenic bacteria and fungi including Piricularia oryzae, Cochliobolus miyabeanus, Pellicularia sasakii, Sphaerotheca fulginea, Botrytic cinerea, Alternaria kikuchiana, Alternaria mali, Glomerella cingulata, Pythium aphanidermatum, Pellicularia filamentosa, Corticium rolfsii, Sclerotinia sclerotiorum, Aspergillus niger, Xanthomonas oryzae, Diaporthe citri, Colletotrichum lagenarium and Fusarium oxysporum f. lycopersici, which cause plant diseases on crop plants, vegetables, flowers, fruit trees, etc. Advantageously, they exhibit an extremely low toxicity on mammals and do not cause any serious chemical injury on plants. In view of the meritorious characteristics as above, they are quite useful as pesticides which can prevent and control two or more kinds of plant diseases simultaneously.
According to the present invention, the phenylenediamine compounds [I] can be produced by reacting an amidophosphoric ester of the formula: ##SPC4##
wherein R.sub.1, A and X are each as defined above with an alkoxycarbonyl isothiocyanate of the formula: ##EQU2## wherein R.sub.2 is as defined above.
The starting amidophosphoric ester [II] may be produced, for instance, by either one of the procedures as shown in the following scheme: ##SPC5##
wherein R.sub.3 is a lower alkyl group, M is an alkali metal atom, Z is a halogen atom and R.sub.1, A and X are each as defined above.
Examples of the amidophosphoric ester [II] are as follows:
O,s-dimethylphosphoryl-o-phenylenediamine;
O,s-diethylphosphoryl-o-phenylenediamine;
O-methyl-S-ethylphosphoryl-o-phenylenediamine;
O-ethyl-S-methylphosphoryl-o-phenylenediamine;
O-methyl-S-n-propylphosphoryl-o-phenylenediamine;
O-methyl-S-n-butylphosphoryl-o-phenylenediamine;
O-ethyl-S-n-propylphosphoryl-o-phenylenediamine;
O-ethyl-S-isopropylphosphoryl-o-phenylenediamine;
O-ethyl-S-n-butylphosphoryl-o-phenylenediamine;
O-ethyl-S-sec.-butylphosphoryl-o-phenylenediamine;
O-ethyl-S-n-amylphosphoryl-o-phenylenediamine;
O-ethyl-S-benzylphosphoryl-o-phenylenediamine;
O-ethyl-S-p-chlorobenzylphosphoryl-o-phenylenediamine;
O-ethyl-S-p-tert.-butylbenzylphosphoryl-o-phenylenediamine;
O-ethyl-S-p-bromobenzylphosphoryl-o-phenylenediamine;
O-ethyl-S-p-nitrobenzylphosphoryl-o-phenylenediamine;
O-methyl-S-benzylphosphoryl-o-phenylenediamine;
O-methyl-S-2-phenethylphosphoryl-o-phenylenediamine;
O-ethyl-S-2-phenethylphosphoryl-o-phenylenediamine;
O-ethyl-S-3-phenylpropylphosphoryl-o-phenylenediamine;
O-ethyl-S-2-methylthioethylphosphoryl-o-phenylenediamine;
O-ethyl-S-2-chloroethylphosphoryl-o-phenylenediamine;
O-ethyl-S-cyanomethylphosphoryl-o-phenylenediamine;
O-ethyl-S-2-ethoxyethylphosphoryl-o-phenylenediamine;
O-ethyl-S-ethoxycarbonylmethylphosphoryl-o-phenylenediamine;
O-ethyl-S-methoxycarbonylmethylphosphoryl-o-phenylenediamine;
O-ethyl-S-allylphosphoryl-o-phenylenediamine;
O-methyl-S-alloylphosphoryl-o-phenylenediamine;
O-ethyl-S-2-bromopropenylphosphoryl-o-phenylenediamine;
O-ethyl-S-methallylphosphoryl-o-phenylenediamine;
O-ethyl-S-propargylphosphoryl-o-phenylenediamine;
O-methyl-S-proparagylphosphoryl-o-phenylenediamine;
O-ethyl-S-phenylphosphoryl-o-phenylenediamine;
O-methyl-S-p-tolylphosphoryl-o-phenylenediamine;
O-methyl-S-2,4,5-trichlorophenylphosphoryl-o-phenylenediamine;
O-ethyl-S-p-chlorophenylphosphoryl-o-phenylenediamine;
O-ethyl-S-p-nitrophenylphosphoryl-o-phenylenediamine
O-phenyl-S-methylphosphoryl-o-phenylenediamine;
O-p-Tolyl-S-methylphosphoryl-o-phenylenediamine;
O-p-Chlorophenyl-S-ethylphosphoryl-o-phenylenediamine;
O-p-Nitrophenyl-S-methylphosphoryl-o-phenylenediamine;
O-p-Methylthiophenyl-S-ethylphosphoryl-o-phenylenediamine;
O-p-Cyanophenyl-S-ethylphosphoryl-o-phenylenediamine;
O-phenyl-S-phenylphosphoryl-o-phenylenediamine;
O,s-dimethylthiophosphoryl-o-phenylenediamine;
O,s-diethylthiophosphoryl-o-phenylenediamine;
O-methyl-S-ethylthiophosphoryl-o-phenylenediamine;
O-ethyl-S-methylthiophosphoryl-o-phenylenediamine;
O-methyl-S-n-propylthiophosphoryl-o-phenylenediamine;
O-methyl-S-n-butylthiophosphoryl-o-phenylenediamine;
O-ethyl-S-n-propylthiophosphoryl-o-phenylenediamine;
O-ethyl-S-isopropylthiophosphoryl-o-phenylenediamine;
O-ethyl-S-n-butylthiophosphoryl-o-phenylenediamine;
O-ethyl-S-sec.-butylthiophosphoryl-o-phenylenediamine;
O-ethyl-S-n-amylthiophosphoryl-o-phenylenediamine;
O-ethyl-S-benzylthiophosphoryl-o-phenylenediamine;
O-ethyl-S-p-chlorobenzylthiophosphoryl-o-phenylenediamine;
O-ethyl-S-p-tert.-butylbenzylthiophosphoryl-o-phenylenediamine;
O-ethyl-S-p-bromobenzylthiophosphoryl-o-phenylenediamine;
O-ethyl-S-p-nitrobenzylthiophosphoryl-o-phenylenediamine;
O-methyl-S-benzylthiophosphoryl-o-phenylenediamine;
O-methyl-S-2-phenethylphosphoryl-o-phenylenediamine;
O-ethyl-S-2-phenethylphosphoryl-o-phenylenediamine;
O-ethyl-S-3-phenylpropylthiophosphoryl-o-phenylenediamine;
O-ethyl-S-2-methylthioethylphosphoryl-o-phenylenediamine;
O-ethyl-S-2-chloroethylthiophosphoryl-o-phenylenediamine;
O-ethyl-S-cyanomethylthiophosphoryl-o-phenylenediamine;
O-ethyl-S-2-ethoxyethylthiophosphoryl-o-phenylenediamine;
O-ethyl-S-ethoxycarbonylmethylthiophosphoryl-o-phenylenediamine;
O-ethyl-S-methoxycarbonylmethylthiophosphoryl-o-phenylenediamine;
O-ethyl-S-allylthiophosphoryl-o-phenylenediamine;
O-methyl-S-allylthiophosphoryl-o-phenylenediamine;
O-ethyl-S-2-bromopropenylthiophosphoryl-o-phenylenediamine;
O-ethyl-S-methallylthiophosphoryl-o-phenylenediamine
O-ethyl-S-propargylthiophosphoryl-o-phenylenediamine;
O-methyl-S-propargylthiophosphoryl-o-phenylenediamine;
O-ethyl-S-phenylthiophosphoryl-o-phenylenediamine;
O-methyl-S-p-tolylthiophosphoryl-o-phenylenediamine;
O-methyl-S-2,4,5-trichlorophenylthiophosphoryl-o-phenylenediamine;
O-ethyl-S-p-chlorophenylthiophosphoryl-o-phenylenediamine;
O-ethyl-S-p-nitrophenylthiophosphoryl-o-phenylenediamine;
O-phenyl-S-methylthiophosphoryl-o-phenylenediamine;
O-p-Tolyl-S-methylthiophosphoryl-o-phenylenediamine;
O-p-Chlorophenyl-S-ethylthiophosphoryl-o-phenylenediamine;
O-p-Nitrophenyl-S-methylthiophosphoryl-o-phenylenediamine;
O-p-Methylthiophenyl-S-ethylthiophosphoryl-o-phenylenediamine;
O-p-Cyanophenyl-S-ethylthiophosphoryl-o-phenylenediamine;
O-phenyl-S-phenylthiophosphoryl-o-phenylenediamine, etc.
Examples of the alkoxycarbonyl isothiocyanate [III] are methoxycarbonyl isothiocyanate, ethoxycarbonyl isothiocyanate, etc.
The reaction may be carried out by treatment of the amidophosphoric ester [II] with the alkoxycarbonyl isothiocyanate [III] in a non-polar solvent (e.g. benzene, toluene) at room temperature or while heating (preferably at a temperature of about 10.degree. to 100.degree.C), favorably under stirring to give the objective phenylenediamine compound [I] in an excellent yield.
Examples of the thus produced phenylenediamine compound [I] are shown in Table 1.
Table 1__________________________________________________________________________Compound Chemical M.P.No. structure (.degree.C)__________________________________________________________________________ SO .parallel..parallel. NHCNHCOCH.sub.31 153-153.5 OCH.sub.3 NHP.angle. .parallel. OSCH.sub.3 SO .parallel..parallel. NHCNHCOCH.sub.32 124-125 OC.sub.2 H.sub.5 NHP.angle. .parallel. OSCH.sub.3 SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.53 115-116 OCH.sub.3 NHP.angle. .parallel. OSCH.sub.3 SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.54 121-122 OC.sub.2 H.sub.5 NHP.angle. .parallel. OSCH.sub.3 SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.55 142.5 OCH.sub.3 NHP.angle. .parallel. OSC.sub.2 H.sub.5 SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.56 152.5-153 OCH.sub.3 NHP.angle. .parallel.- OSC.sub.3 H.sub.7 (n) SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.57 135-135.5 OCH.sub.3 NHP.angle. .parallel. OSCH.sub.2 C.tbd.CH SO .parallel..parallel. NHCNHCOCH.sub.38 160-161 OC.sub.2 H.sub.5 NHP.angle. .parallel. OSC.sub.2 H.sub.5 SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.59 162 OC.sub.2 H.sub.5 NHP.angle. .parallel. OSC.sub.2 H.sub.5 SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.510 162-162.5 OC.sub.2 H.sub.5 NHP.angle. .parallel. OSC.sub.3 H.sub.7 (n) SO .parallel. .parallel. NHCNHCOC.sub.2 H.sub.511 158-158.5 OC.sub.2 H.sub.5 NHP.angle. .parallel. OSC.sub.3 H.sub.7 (iso) SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.512 156-156.5 OC.sub.2 H.sub.5 NHP.angle. .parallel. OSC.sub.4 H.sub.9 (n) SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.513 152.5-153.5 OC.sub.2 H.sub.5 NHP.angle. .parallel. OSC.sub.5 H.sub.11 (n) SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.514 151-152 OC.sub.2 H.sub.5 NHP.angle. .parallel. OSC.sub.4 H.sub.9 (sec) SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.515 151-151.5 OC.sub.2 H.sub.5 NHP.angle. .parallel. OSCH.sub.2 CH=CH.sub. 2 SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.516 143-145 OC.sub.2 H.sub.5 NHP.angle. .parallel. OSCH.sub.2 C.tbd.CH SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.517 149-149.5 OC.sub.2 H.sub.5 CH.sub.3 NHP.angle. .parallel. OSCH.sub.2 C=CH.sub.2 SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.518 161-161.5 OC.sub.2 H.sub.5 NHP.angle. .parallel. OSCH.sub.2 ---- SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.519 181-182 OC.sub.2 H.sub.5 NHP.angle. .parallel. OSCH.sub.2 ---- SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.520 140-142 OC.sub.2 H.sub.5 NHP.angle. .parallel. OSCH.sub.2 ---- SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.521 134-134.5 OC.sub.2 H.sub.5 NHP.angle. .parallel. OSCH.sub.2 CH.sub.2 -- SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.522 115-116 OC.sub.2 H.sub.5 NHP.angle. .parallel. OSCH.sub.2 COOC.sub.2 H.sub.5 SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.523 168 OC.sub.2 H.sub.5 NHP.angle. .parallel. OSCH.sub.2 CH.sub.2 SCH.sub.3 SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.524 155.5-156 OC.sub.2 H.sub.5 NHP.angle. .parallel. OSCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5 SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.525 163-163.5 OC.sub.2 H.sub.5 NHP.angle. .parallel. OSCH.sub.2 ---- SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.526 157.5-158 OC.sub.2 H.sub.5 NHP.angle. .parallel. OSCH.sub.2 ---- SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.527 161-162 OC.sub.2 H.sub.5 NHP.angle. .parallel. OSCH.sub.2 ---- SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.528 173.5-174 OC.sub.2 H.sub.5 NHP.angle. .parallel. OSCH.sub.2 ---- SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.529 160.5-161 OC.sub.2 H.sub.5 NHP.angle. .parallel. OSCH.sub.2 ---- SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.530 161-161.5 OC.sub.2 H.sub.5 NHP.angle. .parallel. OSCH.sub.2 SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.531 144.5-145 OC.sub.2 H.sub.5 NHP.angle. .parallel. OSCH.sub.2 SCH.sub.3 SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.532 161.5-162 OC.sub.2 H.sub.5 NHP.angle. .parallel. OSCH.sub.2 ---- SO .parallel..parallel. NHCNHCOCH.sub.333 161.5-162 OCH.sub.3 NHP.angle. .parallel. OSCH.sub.2 ---- SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.534 78-79 OC.sub.2 H.sub.5 NHP.angle. .parallel. OSCH.sub.2 COOC.sub.3 H.sub.7 (iso) SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.535 161-161.5 OC.sub.2 H.sub.5 NHP.angle. .parallel. OSC.sub.5 H.sub.11 (iso) SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.536 127-127.5 OC.sub.2 H.sub.5 NHP.angle. .parallel. OSC.sub.6 H.sub.13 (n) SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.537 120-121 OC.sub.2 H.sub.5 NHP.angle. .parallel. OSC.sub.7 H.sub.15 (n) SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.538 114-114.5 OC.sub.2 H.sub.5 NHP.angle. .parallel. OSC.sub.8 H.sub.17 (n) SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.539 108-108.5 OC.sub.2 H.sub.5 NHP.angle. .parallel. OSC.sub.9 H.sub.19 (n) SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.540 155-155.5 OC.sub.2 H.sub.5 NHP.angle. .parallel. OSCH.sub.2 ---- SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.541 161-161.5 OC.sub.2 H.sub.5 NHP.angle. .parallel. OSCH.sub.2 SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.542 133-134 OC.sub.2 H.sub.5 NHP.angle. .parallel. OSCH.sub.2 ---- SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.543 165.5-166.5 OC.sub.2 H.sub.5 NHP.angle. .parallel. OSCH.sub.2 ---- SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.544 184-185 OC.sub.2 H.sub.5 NHP.angle. .parallel. OSCH.sub.2 ---- SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.545 160-161.5 OC.sub.2 H.sub.5 NHP.angle. .parallel. OSCH.sub.2 ---- SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.546 101-101.5 OC.sub.2 H.sub.5 NHP.angle. .parallel. OSC.sub.10 H.sub.21 (n) SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.547 94.5-95.5 OC.sub.2 H.sub.5 NHP.angle. .parallel. OSC.sub.11 H.sub.23 (n) SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.548 92-92.5 OC.sub.2 H.sub.5 NHP.angle. .parallel. OSC.sub.12 H.sub.25 (n) SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.549 141-142 OC.sub.2 H.sub.5 NHP.angle. .parallel. OSCH.sub.2 SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.550 158-160 OC.sub.2 H.sub.5 NHP.angle. .parallel. OSCH.sub.2 -- SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.551 139-140 OC.sub.2 H.sub.5 NHP.angle. .parallel. OSCH.sub.2 ---- SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.552 180.5-181 OC.sub.2 H.sub.5 NHP.angle. .parallel. OSCH.sub.2 ----- SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.553 153-154 OC.sub.2 H.sub.5 NHP.angle. .parallel. OSCH.sub.2 ---- SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.554 93.5-94.5 OC.sub.2 H.sub.5 NHP.angle. .parallel. OSC.sub.16 H.sub.33 (n) SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.555 98-98.5 OC.sub.2 H.sub.5 NHP.angle. .parallel. OSCH.sub.2 COOC.sub.4 H.sub.9 (iso) SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.556 136-136.5 OCH.sub.3 NHP.angle. .parallel. OSC.sub.4 H.sub.9 (n) SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.557 152.5-153.5 OCH.sub.3 NHP.angle. .parallel. OSC.sub.6 H.sub.13 (n) SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.558 133-135 OCH.sub.3 NHP.angle. .parallel. OSCH.sub.2 ---- SO .parallel..parallel. NHCNHCOCH.sub.359 160-160.5 OCH.sub.3 NHP.angle. .parallel. OSC.sub.25 4 H.sub.9 (n) SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.560 92.5-93.5 OC.sub.2 H.sub.5 NHP.angle. .parallel. OSC.sub.14 H.sub.29 (n) SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.561 40-43 OC.sub.2 H.sub.5 NHP.angle. .parallel. OSC.sub.18 H.sub.37 (n) SO .parallel..parallel. NHCNHCOC.sub.2 H.sub.562 138-140 OCH.sub.3 NHP.angle. .parallel. OSCH.sub.2 ----__________________________________________________________________________
Some practical procedures for the preparation of the phenylenediamine compounds [I] are shown in the following Examples.

EXAMPLE 1
To a suspension of o-phenylenediamine (0.1 mol) in 20% aqueous solution of sodium hydroxide, O,O-dimethylthio-phosphoryl chloride (0.1 mol) is dropwise added at room temperature, and stirring is continued for a while. When the reaction mixture is made acidic, it is extracted with benzene. The benzene extract is washed with water and dried. On removal of the benzene by distillation under reduced pressure, there is obtained O,O-dimethylthiophosphoryl-o-phenylenediamine (M.P. 71.degree. - 72.degree.C) in a yield of 85%.
EXAMPLE 2
O,O-Diethylthiophosphoryl-o-phenylenediamine (0.1 mol) prepared as in Example 1 is dropwise added to a solution of sodium hydrosulfide (0.1 mol) in methylcellosolve. The resulting mixture is kept at 105.degree. to 110.degree.C for 5 hours and then the methylcellosolve is distilled off. To the residue, benzene and water are added, and the water layer is separated from the benzene layer, washed with benzene and concentrated. The resulting sodium salt is dissolved in ethanol, an equimolar amount of ethyl iodide is added thereto and the resultant mixture is maintained at 80.degree.C for 1 hour. After removal of the ethanol, the residue is extracted with benzene and the benzene extract is washed with water, dried and concentrated to give O,S-diethylphosphoryl-o-phenylenediamine (M.P. 60.degree. - 62.degree.C) in a yield of 81%. This product is dissolved in benzene, and an equimolar amount of ethoxycarbonyl isothiocyanate is added thereto. The precipitated crystals are collected by filtration to give N-O,S-diethylphosphoryl-N'-ethoxycarbonylthioureido-o-phenylenediamine (M.P. 162.degree.C) in a yield of 95%.
EXAMPLE 3
To a solution of o-phenylenediamine (0.1 mol) in ether, O-ethyl-S-n-propylphosphoryl chloride (0.1 mol) is added, and triethylamine (0.1 mol) is dropwise added thereto at a temperature below 10.degree.C. The resulting mixture is stirred at room temperature for 3 hours. The reaction mixture is washed with water and the ether is distilled off. The resultant brown oil is dissolved in benzene, an equimolar amount of ethoxycarbonyl isothiocyanate is added thereto, and the resultant mixture is allowed to stand overnight. The precipitated crystals are collected by filtration and recrystallized from a mixture of benzene and n-hexane to give N-O-ethyl-S-n-propylphosphoryl-N'-ethoxycarbonylthio-ureido-o-phenylenediamine (M.P. 162.degree. - 162.5.degree.C) in a yield of 85%.
EXAMPLE 4
O-Ethyl-S-ethoxycarbonylmethylphosphoryl-o-phenylenediamine (0.1 mol) prepared as in Example 2 is dissolved in a small amount of benzene, and an equimolar amount of ethoxycarbonyl isothiocyanate is added thereto. After several minutes, there are precipitated crystals, which are collected by filtration to give N-O-ethyl-S-ethoxycarbonylmethylphosphoryl-N'-ethoxycarbonyl-thioureido-o-phenylenediamine (M.P. 115.degree. - 116.degree.C) in a yield of 93%.
In the same manner as above, other phenylenediamine compounds as shown in Table 1 can be produced.
As the pesticide, the phenylenediamine compound [I] may be used alone. For the practical use, however, it is usually extended with a suitable carrier or diluent, if desired, by the aid of any emulsifier to formulate a preparation as conventionally employed in this art field such as pellets, dust, wettable powder or emulsifiable concentrate.
Examples of the solid carrier or diluent are talc, bentonite, clay, kaolin, diatomaceous earth, vermiculite, calcium hydroxide, etc. Examples of the liquid carrier or diluent are benzene, alcohols, acetone, xylene, dioxane, methylnaphthalene, cyclohexane, etc. As the emulsifier, there may be employed alkylsulfates, alkylsulfonates, arylsulfonates, polyethyleneglycol ethers, polyvalent alcohol esters and the like.
When desired, the preparation may contain any other active ingredient such as a fungicide, an insecticide, a lanatocide, a herbicide or a fertilizer.
Some specific embodiments of the preparation comprising the phenylenediamine compound [I] as the active ingredient are shown in the following Examples wherein parts and % are by weight.
EXAMPLE A
Dust
The phenylenediamine compound [I] (e.g. Compound No. 1 in Table 1) (2 parts) and clay (98 parts) are pulverized and mixed well to make a dust comprising the active ingredient in a concentration of 2%. The dust may be applied as such or admixed with soil on use.
EXAMPLE B
Dust
The phenylenediamine compound [I] (e.g. Compound No. 4 in Table 1) (3 parts) and talc (97 parts) are pulverized and mixed well to make a dust comprising the active ingredient in a concentration of 3%. The dust may be applied as such or admixed with soil on use.
EXAMPLE C
Wettable powder
The phenylenediamine compound [I] (e.g. Compound No. 9 in Table 1) (50 parts), a wetting agent (alkylbenzenesulfonate) (5 parts) and diatomaceous earth (45 parts) are pulverized and mixed well to make a wettable powder comprising the active ingredient in a concentration of 50%. The wettable powder may be diluted with water and then applied on use.
EXAMPLE D
Emulsifiable concentrate
The phenylenediamine compound [I] (e.g. Compound No. 20 in Table 1) (10 parts), an emulsifier (polyoxyethylene phenylphenol ether) (10 parts) and dimethylsulfoxide (80 parts) are mixed well to make an emulsifiable concentrate comprising the active ingredient in a concentration of 10%. The emulsifiable concentrate may be applied as such or after dilution with water on use.
EXAMPLE E
Pellets
The phenylenediamine compound [I] (e.g. Compound No. 3 in Table 1) (5 parts), clay (93.5 parts) and a binding agent (polyvinyl alcohol) (1.5 parts) are pulverized and mixed well. The resulting mixture is kneaded with water, pelletized and dried to give pellets comprising the active ingredient in a concentration of 5%. The pellets may be applied as such on use.
EXAMPLE F
Composite dust
The phenylenediamine compound [I] (e.g. Compound No. 47 in Table 1) (2 parts), O-n-butyl-S-ethyl-S-benzyl-phosphorodithiolate (1.5 parts) and clay (96.5 parts) are pulverized and mixed well to make a dust comprising the active ingredients in a concentration of 3.5%. The dust may be applied as such on use.
EXAMPLE G
Composite dust
The phenylenediamine compound [I] (e.g. Compound No. 4 in Table 1) (2 parts), Kasugamycin (0.1 part), O,O-dimethyl-O-(3-methyl-4-nitrophenyl)phosphorothioate (2 parts), 3,4-dimethylphenyl-N-methylcarbamate (1.5 parts) and clay (95 parts) are pulverized and mixed well to make a dust comprising the active ingredients in a concentration of 5%. The dust may be applied as such on use.
EXAMPLE H
Composite dust
The phenylenediamine compound [I] (e.g. Compound No. 22 in Table 1) (2 parts), N-(3',5'-dichlorophenyl)succinimide (1.5 parts), O,O-dimethyl-O-(3-methyl-4-nitrophenyl)phosphorothioate (2 parts), 3,4-dimethylphenyl-N-methylcarbamate (1.5 parts) and clay (93 parts) are pulverized and mixed well to make a dust comprising the active ingredients in a concentration of 7%. The dust may be applied as such on use.
EXAMPLE I
Composite wettable powder
The phenylenediamine compound [I] (e.g. Compound No. 5 in Table 1) (30 parts), zinc ethylenebisdithiocarbamate (10 parts), 1,2-bis[(3-methoxycarbonyl)thioureido]benzene (10 parts), calcium alkylbenzenesulfonate (5 parts) and diatomaceous earth (45 parts) are pulverized and mixed well to make a wettable powder comprising the active ingredients in a concentration of 50%. The wettable powder may be diluted with water and then applied on use.
The following test data support that the phenylenediamine compounds [I] have a more excellent antimicrobial activity than known commercially available pesticides and are effective in preventing and controlling multi plant diseases:
Test 1
Growth inhibitory effects on microorganisms
The growth inhibitory potency of the phenylenediamine compounds [I] on five kinds of phytopathogenic microorganisms was examined according to the agar dilution method. The evaluation was made on the following criteria:
A. complete inhibition at a concentration of 50 ppm
B. inhibition to less than 5% at a concentration of 50 ppm in comparison with the control (untreated)
C. inhibition to less than 10% at a concentration of 50 ppm in comparison with the control
D. inhibition to less than 20% at a concentration of 50 ppm in comparison with the control
E. inhibition to less than 50% at a concentration of 50 ppm in comparison with the control
F. no inhibition at a concentration of 50 ppm
The results are shown in Table 2 wherein the abbreviations have the following meanings:
Cm -- Cochliobolus miyabeanus
Gc -- Glomerella cingulata
Ss -- Sclerotinia sclerotiorum
Cl -- Colletotrichum lagenarium
Bc -- Botrytis cinerea
Table 2______________________________________Compound No. Test microorganism Cm Gc Ss Cl Bc______________________________________ 1 A A B A A 2 B A A A B 3 B A A A A 4 A A A A A 5 C A A A A 7 B A A A B 8 B B A A A 9 B A A A A 10 C A A A A 14 B A B A A 19 B A B A A 20 A A B A B 23 B A B A B 24 B A A A B 25 B A B A B 27 B A A A B 28 A A A A B 29 B B A A A 30 B A A A B 32 A A B A A 33 B A B A A 36 B A B A A 39 C A B A B 40 B A B A A 43 B A A A B 44 B A A A B 45 B A A A B 49 B A A A B 50 B A A A A 51 B A A A A 53 B A A A A 55 B A A A B______________________________________
Test 2
Growth inhibitory effects on microorganisms
The growth inhibitory potency of the phenylenediamine compounds [I] on nine kinds of phytopathogenic microorganisms was examined according to the agar dilution method. The evaluation was made on the following criteria:
A. complete inhibition at a concentration of 25 ppm
B. inhibition to less than 10% at a concentration of 25 ppm
C. inhibition to less than 20% at a concentration of 25 ppm
The results are shown in Table 3 wherein the abbreviations have the following meanings:
Dc -- Diaporthe citri
Ps -- Pellicularia sasakii
Po -- Pyricularia oryzae
Xo -- Xanthomonas oryzae
Fol -- Fusarium oxysporum f. lycopersici
Gc, Ss, Bc, Cl -- Same as in Test 1.
Table 3______________________________________Compound No. Test microorganism Gc Ss Dc Ps Cl Bc Po Xo Fol______________________________________1 A A A A A A A B A2 A A A B A A A A B3 A A A A A A A C B4 A A A A A A A A A5 A A A B A A A B A6 A A A B A A A C B7 A A A A B A A C A8 A A A A A A A A A9 A A A A A A A C A11 A A A B A A A C A16 A A A B B A A B B31 A A A A A B A C A32 A A A B A A B C A33 A A A A A A A B B34 A A A A A A A B B35 A A A A B A B A A41 A A A A A A B B A47 A A A A B A B A B51 A A A B A A A C A56 A A A A A B B C A62 A A A A A A A B B______________________________________
Test 3
Rice blast controlling effects
The test compound in the form of an emulsifiable concentrate preparation was applied to rice plants cultured in pots of 9 cm in diameter and grown up to the five leaved stage at a rate of 10 ml of the preparation per pot by the use of a spray gun. After 24 hours, the plants were sprayed to inoculate thereon with a spore suspension of Pyricularia oryzae cultured in an oatmeal medium. The plants were placed in a room of high humidity at 26.degree.C. Three days thereafter, the degree of damage was determined based on the percentage of the infectious area, and the degree of damage and the degree of disease-preventing effect were calculated according to the following equations, respectively: ##EQU3## wherein the infectious index was determined by the following criteria:
Infectious index Infectious state______________________________________0 No infectious spot1 Infectious spots only at or around the inoculated place2 Infectious spots in about one fifth of the inoculated leaf3 Infectious spots in about two fifths of the inoculated leaf4 Infectious spots in about three fifths of the inoculated leaf5 Infectious spots in four fifths or more of the inoculated leaf______________________________________ ##EQU4##
The results are shown in Table 4 wherein the commercially available fungicide is O,O-diisopropyl-S-benzyl-thiophosphate.
Table 4______________________________________Compound Con- Degree of Degree of ChemicalNo. centra- damage disease- injury tion (%) preventing (ppm) effect______________________________________ 1 500 0 100 None 3 500 1.0 99 " 4 500 0 100 " 6 500 2.0 98 "12 500 3.5 96 "13 500 4.0 96 "15 500 3.5 96 "20 500 0 100 "21 500 0 100 "22 500 1.0 99 "26 500 1.0 99 "34 500 1.0 99 "37 500 2.0 98 "41 500 3.0 97 "46 500 3.0 97 "48 500 0 100 "51 500 4.0 96 "55 500 2.0 98 "58 500 3.5 96 "59 500 1.0 99 "Commercial-ly availa- 200 5.5 94 "ble fungi-cideUntreated -- 100.0 -- "______________________________________
Test 4
Rice blast controlling effects (in field)
Rice plants were cultured in the field (each plot having an area of 1 m.sup.2) and, when grown up to the three to four leaved stage, straw infected with Pyricularia oryzae was placed between the stems for inoculation. When initial infectious spots were recognized, the test compound in the form of a dust preparation was sprayed on the rice plants at a rate of 4 kg per 10 are. After 7 days, the second application was carried out in the same manner as above. Ten days after the second application, the first observation was made on 25 stocks in each of the plots. The second and third observations were made at intervals of 10 days. The results are shown in Table 5 wherein the commercially available fungicides A and B are 4,5,6,7-tetrachlorophthalide and O,O-diisopropyl-S-benzyl-thiophosphate.
Table 5__________________________________________________________________________Compound Concentra- Rate of infectious area ChemicalNo. tion in average (%) injury 1st 2nd 3rd__________________________________________________________________________ 4 3 % (dust) 9.69 20.95 30.85 NoneCommerciallyavailable 3 % (dust) 12.91 13.40 20.97 "fungicide ACommerciallyavailable 48 % (emulsion)* 15.81 29.89 70.95 "fungicide BUntreated -- 32.35 63.35 92.22 "__________________________________________________________________________ *Applied in a rate of 150 liters per 10 are.
Test 5
Sheath blight controlling effects
The test compound in the form of a wettable powder preparation was applied to rice plants cultured in pots of 9 cm in diameter and grown up to 60 cm tall at a rate of 10 ml of the preparation per pot by the use of a spray gun. After 24 hours, a mycelium-disc-inoculum (5 mm in diameter) of Pellicularia sasakii cultured on PS synthetic medium was inoculated on the sheath, and the plants were placed into a room at 28.degree.C. Four days thereafter, the infectious state at the sheath was observed, and the size of the diseased spot was measured. The degree of damage and the degree of disease-preventing effect of the test compound were calculated according to the following equations, respectively: ##EQU5## wherein the infectious index was determined on the following criteria:
Infectious index Infectious state______________________________________0 No infectious spots on sheath1 Infectious spot-like parts2 Infectious spots of less than 3 cm in size3 Infectious spots of not less than 3 cm in size______________________________________Degree of disease-preventing effect = Degree of damage in Degree of damage in( ) - ( ) untreated plot treated plotDegree of damage in untreated plot______________________________________
The results are shown in Table 6 wherein the commercially available fungicide is a 3.0% solution of polyoxin PS.
Table 6______________________________________Compound Con- Degree of Degree of ChemicalNo. centra- damage disease- injury tion (%) preventing (ppm) effect______________________________________ 1 500 0 100 None 2 500 0 100 " 3 500 0 100 " 4 500 0 100 " 5 500 0 100 " 6 500 0 100 " 9 500 0 100 "15 500 0 100 "20 500 0 100 "21 500 0 100 "22 500 0 100 "24 500 0 100 "30 500 1.8 98 "31 500 1.8 98 "32 500 0 100 "34 500 0 100 "35 500 0 100 "36 500 0 100 "-37 500 0 100 "-38 500 0 100 "-39 5 00 0 100 "-40 500 0 100 "-42 500 3.6 194 "46 500 0 100 "47 500 0 100 "48 500 0 100 "49 500 1.8 98 "56 500 0 100 "59 500 0 100 "Commercial-ly availa- 1000* 4.8 95 "ble fungi-cideUntreated -- 100.0 --"______________________________________ *1000 fold dilution.
Test 6
Controlling effects on bacterial leaf spot of rice
Two loopfuls of a spore suspension of Xanthomonas oryzae were applied to the second leaf of rice plants cultured in pots of 9 cm in diameter and grown up to the five leaved stage for inoculation. After 24 hours and 48 hours, the test compound in the form of a wettable powder preparation was applied to the plants. On the 7th day from the inoculation, observation was made, and the degree of damage was calculated as in test 5. The results are shown in Table 7 wherein the commercially available fungicide is a 10% wettable powder preparation of phenazin-5-oxide.
Table 7______________________________________Compound Con- Number Degree of ChemicalNo. centra- of damage injury tion leaves (%) (ppm)______________________________________ 7 1000 30 10.0 None12 1000 30 10.0 "18 1000 30 16.7 "50 1000 30 13.3 "51 1000 30 9.6 "58 1000 30 16.7 "Commercial-ly availa-ble funci- 1000* 30 26.7 "cideUntreated -- 40 97.5 "______________________________________ *1000 fold dilution.
Test 7
Powdery mildew controlling effects
The test compound in the form of an emulsifiable concentrate preparation was applied to seed leaves of cucumbers cultured in pots of 9 cm in diameter and having nipped off the first leaf when developed at a rate of 7 ml of the concentrate per pot by the use of a spray gun. After 24 hours, a spore suspension of Sphaerotheca fuliginea was sprayed on the plants, and the pots were left in a room at 28.degree.C in a humidity of 60 to 80% for 14 days. Then, the infectious state of the seed leaves was observed, and the degree of damage and the degree of disease-preventing effect were calculated according to the following equations, respectively: ##EQU6## wherein the infectious index was determined by the following criteria:
Infectious index Infectious state______________________________________0 No infectious spot1 Infectious spots only at or around the inoculated place2 Infectious spots in about one fifth of the inoculated seed leaf3 Infectious spots in about two fifths of the inoculated seed leaf4 Infectious spots in about three fifths of the inoculated seed leaf5 Infectious spots in four fifths or more of the inoculated seed leaf______________________________________Degree of disease-preventing effect = No. of infectious No. of infectious( ) - ( ) spots in untreated plot spots in treated plot .times.100Number of infectious spots in untreated plot______________________________________
The results are shown in Table 8 wherein the commercially available fungicide is a 25% wettable powder preparation of S,S-6-methylquinoxaline-2,3-diyldithiocarbonate.
Table 8______________________________________Compound Con- Degree of Degree of ChemicalNo. centra- damage disease- injury tion (%) preventing (ppm) effect______________________________________ 1 500 0 100 None 2 500 0 100 " 3 500 0 100 " 4 500 0 100 " 5 500 0 100 " 6 500 0 100 " 7 500 0 100 " 8 500 0 100 " 9 500 0 100 "11 500 0 100 "12 500 0 100 "13 500 0 100 "14 500 0 100 "15 500 0 100 "16 500 0 100 "17 500 0 100 "18 500 0 100 "20 500 0 100 "21 500 0 100 "22 500 0 100 "23 500 0 100 "24 500 0 100 "25 500 0 100 "26 500 0 100 "29 500 0 100 "30 500 0 100 "32 500 7.6 92 "35 500 7.0 93 "36 500 4.8 95 "37 500 6.6 93 "38 500 7.6 92 "39 500 0 100 "41 500 7.6 92 "42 500 4.0 96 "44 500 7.6 92 "46 500 4.8 95 "47 500 1.7 98 "48 500 2.6 97 "49 500 0 100 "50 500 9.2 91 "51 500 4.8 95 "53 500 6.6 93 "54 500 1.7 98 "55 500 6.6 93 "56 500 7.6 92 "57 500 0 100 "58 500 4.8 95 "59 500 6.6 93 "60 500 0 100 "Commercial-ly availa- 200 10.8 87 "ble fungi-cideUntreated -- 100.0 -- "______________________________________
Test 8
Controlling effects on anthracnose of cucumber
The test compound in the form of an emulsifiable concentrate preparation was applied to the seed leaves of cucumbers cultured in pots of 9 cm in diameter at a rate of 7 ml per pot by the aid of a spray gun. After 24 hours, a spore suspension of Colletotrichum lagenarium cultured on potato agar medium was sprayed on the plants, and the pots were left in a room at 20.degree.C in a humidity of 95%. Five days thereafter, the infectious state of the seed leaves was observed, and the degree of damage and the degree of disease-preventing effect were calculated as in Test 7.
The results are shown in Table 9 wherein the commercially available fungicide is a 80% wettable powder preparation of N-trichloromethylthio-4-cyclohexene-1,2-dicarboximide.
Table 9______________________________________Compound Con- Degree of Degree of ChemicalNo. centra- damage disease- injury tion (%) preventing (ppm) effect______________________________________ 1 200 0 100 None 3 200 0 100 " 5 200 0 100 " 7 200 1.9 98 " 9 200 0 100 "10 200 0 100 "12 200 0 100 "13 200 0 100 "14 200 0 100 "15 200 0 100 "17 200 0 100 "19 200 0 100 "21 200 0 100 "23 200 1.9 98 "24 200 0 100 "25 200 3.8 96 "26 200 0 100 "27 200 7.6 92 "28 200 1.9 98 "29 200 5.7 94 "30 200 0 100 "31 200 0 100 "33 200 3.8 96 "35 200 3.8 96 "36 200 1.9 98 "40 200 0 100 "41 200 0 100 "43 200 1.9 98 "44 200 0 100 "45 200 0 100 "48 200 0 100 "49 200 0 100 "50 200 3.8 96 "51 200 0 100 "52 200 1.9 98 "53 200 1.9 98 "57 200 0 100 "60 200 3.8 96 "Commercial-ly availa- 200 25.6 73 "ble fungi-cideUntreated -- 98.2 -- "______________________________________
Test 9
Cucumber bacterial blight controlling effects
In pots of 9 cm in diameter, field soil was filled, and soil infected with Rhizoctonia solani was placed thereon in an amount of 10 ml per pot. The test compound in a wettable powder preparation was diluted with water and poured in the pots at a rate of 9 ml per pot. After 4 hours, ten seeds of cucumber were sowed in each pot. Five days thereafter, the infectious state was observed, and the percentage of healthy seedlings was calculated according to the following equation: ##EQU7##
The results are shown in Table 10 wherein the commercially available fungicide is pentachloronitrobenzene.
Table 10______________________________________Compound Concen- Percentage of ChemicalNo. tration healthy injury (ppm) seedlings (%)______________________________________ 1 500 100.0 None 2 500 90.0 " 3 500 100.0 " 4 500 100.0 " 5 500 86.7 " 7 500 100.0 " 8 500 90.0 "16 500 93.4 "20 500 86.7 "22 500 100.0 "31 500 100.0 "32 500 86.7 "34 500 100.0 "46 500 93.4 "47 500 86.7 "54 500 93.4 "55 500 90.0 "57 500 93.4 "Commerciallyavailable 500 76.7 "fungicideUntreated -- 96.7 "______________________________________
Test 10
Fusarium wilt controlling effects
In pots of 9 cm in diameter, field soil was filled, and soil infected with Fusarium oxysporum f. raphani was placed thereon in an amount of 10 ml per pot. The test compound in a wettable powder preparation was diluted with water and poured in the pots at a rate of 18 ml per pot. Then, 20 seeds of radish were sowed in each pot. After 3 weeks, the infectious state was observed, and the percentage of healthy seedlings was calculated as in Test 9.
The results are shown in Table 11 wherein the commercially available fungicide is a 80% wettable powder preparation of N-trichloromethylthio-4-cyclohexene-1,2-dicarboximide.
Table 11______________________________________Compound Concen- Percentage of ChemicalNo. tration healthy injury (ppm) seedlings (%)______________________________________ 1 500 100.0 None 3 500 88.7 " 4 500 100.0 " 5 500 100.0 " 6 500 94.4 " 9 500 90.8 "10 500 100.0 "11 500 100.0 "12 500 94.4 "18 500 94.4 "24 500 100.0 "47 500 98.0 "52 500 88.7 "53 500 88.7 "58 500 98.0 "60 500 94.4 "Commerciallyavailable 500 72.0 "fungicideUntreated -- 100.0 "______________________________________

Number	Name	Date	Kind
3767734	Mihailovski et al.	Oct 1973
3776942	Miller et al.	Dec 1973

Phosphoryl phenylenediamines

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