Novel N-containing heterocyclic ring-substituted O-arylphosphate derivatives, the preparation thereof and insecticides acaricides and nematicides containing said derivatives are provided. The O-arylphosphate derivatives have the general formula: ##STR1## wherein A is --CH or nitrogen, X is hydrogen, a halogen or trifluoromethyl; Y is oxygen, S(O)n (wherein n is an integer of from 0 to 2) or NR.sup.2 (wherein R.sup.2 is hydrogen or a lower alkyl); Z is oxygen or sulfur; R and R.sup.1 independently are a lower alkoxy or lower alkylthiol; and B is hydrogen, a halogen or a lower alkyl. The O-arylphosphate derivatives have an excellent insecticidal acaricidal and nematocidal action.

BACKGROUND OF THE INVENTION 
(1) Field of the Invention 
This invention relates to a novel N-containing heterocyclic 
ring-substituted O-arylphosphate derivative, a process for preparation 
thereof, and an insecticide, acaricide and nematicide (hereinafter 
referred to as "insecticide) containing said derivative as an active 
ingredient. 
(2) Description of the Prior Art 
Hitherto, a variety of insecticides have been developed and put into 
practice, and some of these insecticides have contributed to increase the 
productivity of agricultural and horticultural crops. 
Pyridine-substituted O-arylphosphate derivatives have been known (see U.S. 
Pat. No. 4,080,443 and Japanese Patent Laid-Open Pub. No. 6424/78). The 
pyridine-based phosphate derivatives have been found unsatisfactory with 
respect to insecticidal action and the like. 
Thus, novel insecticides having higher insecticidal activity are now 
desired in this field. 
The present inventors have made intensive researches on insecticidal 
activities of many heterocyclic compounds in order to develop novel and 
useful insecticides and have unexpectedly found that novel O-arylphosphate 
derivatives having a quinolyl or quinoxalyl group as the heterocyclic ring 
exhibit excellent insecticidal actions. 
The O-arylphosphate derivatives having a quinolyl or quinoxalyl group are 
novel compounds, which have not yet been disclosed in literature and have 
been prepared for the first time by the present inventors so far as they 
know. 
SUMMARY OF THE INVENTION 
An object of this invention is to provide novel O-arylphosphate derivatives 
which have an N-containing heterocyclic ring in their structure and 
exhibit excellent insecticidal activities. 
Another object of this invention is to provide a process for preparing 
novel O-arylphosphate derivatives having an N-containing heterocyclic 
ring. 
A further object of this invention is to provide novel and useful 
insecticides. 
Other objects of this invention will be apparent from the description 
below. 
DETAILED DESCRIPTION OF THE INVENTION 
The compounds according to the invention have the general formula (I): 
##STR2## 
wherein A represents --CH or nitrogen; X represents hydrogen, a halogen or 
trifluoromethyl; Y represents oxygen, S(O)n (wherein n is an integer of 
from 0 to 2) or NR.sup.2 (wherein R.sup.2 is hydrogen or a lower alkyl); Z 
represents oxygen or sulfur; R and R.sup.1 independently represent a lower 
alkoxy or lower alkylthio; and B represents hydrogen, a halogen or a lower 
alkyl. 
Preferred R.sup.2 as the lower alkyl is a straight or branched C.sub.1 
-C.sub.4 alkyl group, especially methyl. 
The alkyl moiety in R or R.sup.1 is preferably a straight or branched 
C.sub.1 -C.sub.4 alkyl group such as methyl, ethyl, propyl or butyl, more 
preferably ethyl or propyl. 
Preferred B as the lower alkyl is a straight or branched C.sub.1 -C.sub.4 
alkyl group, and more preferably methyl. 
The halogen for X or B is preferably fluorine, chlorine or bromine. 
Preferred compounds according to the invention have the general formula 
(IA): 
##STR3## 
wherein X, A, Y, Z, R and R.sup.1 have the same meanings as above, or the 
general formula (IB): 
##STR4## 
wherein X and Z have the same meanings as above; B' represents a halogen 
or a lower alkyl, and preferably a C.sub.1 -C.sub.4 alkyl; and R.sup.3 and 
R.sup.4 independently represent a lower alkyl, preferably a C.sub.1 
-C.sub.4 alkyl. 
Of the compounds of the formula (IA), more preferred are those having the 
general formula (IA)': 
##STR5## 
wherein X, Z, R.sup.3 and R.sup.4 have the same meanings as above. 
Compounds of particular importance of the formula (IA)' are those 
wherein 
X is hydrogen, chlorine, fluorine, bromine or trifluoromethyl; 
Z is oxygen or sulfur, especially oxygen; 
R.sup.3 is ethyl; and 
R.sup.4 is a propyl, especially n-propyl. 
The compounds of the formula (IA)' are exemplified by the following: 
O-ethyl S-n-propyl O-[4-(quinoxalyl-2-oxy)phenyl]thiophosphate, 
##STR6## 
O-ethyl S-n-propyl O-[3-(6-chloroquinoxalyl-2-oxy)phenyl]thiophosphate, 
##STR7## 
O-ethyl S-n-propyl O-[4-(6-chloroquinoxalyl-2-oxy)phenyl]thiophosphate, 
##STR8## 
O-ethyl S-n-propyl O-[2-(6-chloroquinoxalyl-2-oxy)phenyl]thiophosphate, 
##STR9## 
O-ethyl S-n-propyl O-[4-(6-fluoroquinoxalyl-2-oxy)phenyl]thiophosphate, 
##STR10## 
O-ethyl S-n-propyl 
O-[4-(6-trifluoromethylquinoxalyl-2-oxy)-phenyl]thiophosphate, 
##STR11## 
O-ethyl S-n-propyl O-[4-(7-bromoquinoxalyl-2-oxy)phenyl]thiophosphate. 
##STR12## 
Compounds of particular importance among the compounds of the formula (IB) 
are those 
wherein 
X is hydrogen, chlorine, bromine or trifluoromethyl; 
B' is chlorine, bromine or methyl, 
Z is oxygen or sulfur, especially oxygen; 
R.sup.3 is ethyl, and 
R.sup.4 is a propyl, especially n-propyl. 
The compounds of the formula (IB) are exemplified by the following: 
O-ethyl S-n-propyl 
O-[2-chloro-4-(7-bromoquinoxalyl-2-oxy)phenyl]thiophosphate, 
O-ethyl S-n-propyl O-[2-bromo-4-(quinoxalyl-2-oxy)phenyl]thiophosphate, 
O-ethyl S-n-propyl 
O-[3-chloro-4-(7-bromoquinoxalyl-2-oxy)phenyl]thiophosphate, 
O-ethyl S-n-propyl 
O-[2-methyl-4-(6-trifluoromethylquinoxalyl-2-oxy)phenyl]thiophosphate, 
O-ethyl S-n-propyl O-[2-bromo-4-(quinoxalyl-2-oxy)phenyl]dithiophosphate, 
O-ethyl S-n-propyl O-[2 or 
4-chloro-5-(6-chloroquinoxalyl-2-oxy)phenyl]thiophosphate, 
O-ethyl S-n-propyl 
O-[6-methyl-5-(6-chloroquinoxalyl-2-oxy)phenyl]thiophosphate. 
Incidentally, by the term "N-containing heterocyclic ring-substituted 
O-arylphosphate derivatives" used herein is meant the compounds 
represented by the general formulae given above, or shown by the 
above-mentioned chemical names. 
The compounds of the formula (I) may be generally synthesized according to 
the following reaction method; 
##STR13## 
wherein A, X, Y, Z, R, R.sup.1 and B have the same meanings as above. 
Namely, the compounds of the formula (I) can be prepared by reacting 
monochloride of a phosphate derivative of the formula (II) with a phenol 
derivative of the formula (III) in an organic solvent in the presence of 
an acid acceptor. The reaction time is usually 30 minutes to 5 hours, 
preferably 1 to 3 hour. The reaction temperature is usually in the range 
of from 5.degree. to 60.degree. C., preferably 30.degree. to 50.degree. C. 
The organic solvent to be used may be benzene, acetonitrile, methyl ethyl 
ketone, chloroform, methylene chloride, dimethylsulfoxide and the like. 
The acid acceptor to be used may be triethylamine, pyridine, potassium 
carbonate, potassium t-butoxide and the like. 
After completion of the reaction, the reaction mixture is poured into cold 
water and extracted with an appropriate organic solvent. The organic layer 
is washed with water and dried. The organic solvent is then distilled off 
to give a crude product. Purification of the resulting crude product by 
column chromatography, gives a substantially pure compound of the formula 
(I). 
The monochlorides of phosphate derivative of the formula (II) are known 
compounds and can be prepared by known methods. For example, an 
O,S-dialkylphosphorochloride thiolate (i.e. a compound of the formula 
(II), wherein R is a lower alkoxy, R.sup.1 is a lower alkylthio and Z is 
oxygen) can be synthesized by the method disclosed in Japanese Patent 
Publication No. 86/1977 and German Patent Publication No. 2635931. 
Moreover, an O,S-dialkylphosphorochloride dithiolate (i.e. a compound of 
the formula (II), wherein R is a lower alkoxy, R.sup.1 is a lower 
alkylthio and Z is sulfur) can be synthesized by the method disclosed in 
Japanese Patent Laid Open Publication No. 125127/77. 
The phenol derivatives of the formula (III) wherein Y is oxygen can be 
synthesized by the method similar to that disclosed in Japanese Patent 
Laid Open Publication No. 51454/81. Also, the phenol derivatives of the 
formula (III) wherein Y is NR.sup.2 can be prepared by the method similar 
to that of Japanese Patent Laid Open Publication No. 57770/81. Synthesis 
of the phenol derivatives of the formula (III) wherein Y is S(O)n will be 
described below in Synthesis Example 3. 
The compound of the formula (I) wherein B is hydrogen, and one of R and 
R.sup.1 is a lower alkoxy and the other is a lower alkylthio may also be 
synthesized through the following reaction scheme: 
##STR14## 
wherein A, X and Y have the same meanings as above; Hal represents a 
halogen atom such as chlorine, bromine and iodine; M represents an alkali 
metal such as potassium and sodium; and R.sup.3 and R.sup.4 have the same 
meaning as defined for formula (IB). Namely, the compound of the formula 
(IC) can be obtained in a good yield by reacting a thiophosphate salt of 
the formula (IV) with an appropriate lower alkyl halide. 
The compounds of the present invention thus obtained are exceedingly useful 
as agents for controlling and combating sanitary insect pests as well as 
agricultural and horticultural insect pests which damage paddy-rice 
plants, vegetables, fruit trees, cotton plants and other crops and 
flowering plants, insect pests of forest and insect pests in stored crops. 
In accordance with the present invention are provided insect 
pests-combating agents which are suitable to apply an effective amount of 
the present compounds onto the locus of insect pests. 
The locus of insect pests herein means any place which insect pests 
inhabit, and includes, for example, soil, atmosphere, water, food, plants, 
fertilizers, inactive materials, and stored good such as cereals. 
Typical pests to which the compounds of the present invention are 
applicable are exemplified in the following, but the application of the 
present invention is not restricted to these pests, or merely to insect 
pests, as shown in Test Example 5 (acaricidal action on mites) and Test 
Example 6 (nematicidal action on nematodes). 
Sanitary insect pests: 
housefly (Musca domestica), mosquito (Culex spp., Aedes spp., Anopheles 
spp.) cockroach (Periplaneta spp., Blattella spp.) 
Agricultural and horticultural insect pests: 
(Insect pests of rice) 
rice stem borer (Chilo suppressalis), 
rice leaf beetle (Oulema oryzae), 
ricewater weevil (Lissothoptrus oryzophilus), 
rice leaf miner (Agromyza oryzae), 
smaller rice leaf miner (Hydrellia griseola), 
small brown planthopper (Laodelphax striatellus), 
white-backed rice planthopper (Sogatella furcifera), 
brown rice planthopper (Nilaparvata lugens), 
green rice leafhopper (Nephotettix cincticeps) 
(Vegetable pests) 
cabbage armyworm (Mamestra brassicae), 
tobacco cutworm (Spodoptera litura), 
common white (Pieris rapae crucivora), 
diamondback moth (Plutella xylostella), 
28-spotted lady bettle (Epilachna vigintioctopunctata), 
Green peach aphid (Myzus persicae) 
Root-knot nematode (Meloidogyne sp.) 
Root-lesion nematode (Pratylenchus sp.) 
(Insect pest of fruit tree) 
tortrix, Leafrolles (Adoxophyes spp., Archips spp., 
Archippus spp.), 
apple leafminer (Phyllonorycter ringoneella), 
oriental fruit moth (Grapholita molesta), 
peach fruit moth (Carposina niponensis), 
smaller tea tortrix (Adoxophyes orana), 
comstock mealybug (Pseudococcus comstocki) 
Generally, it is preferred that the insecticides according to the present 
invention are applied in a concentration of 0.1 to 10,000 ppm, especially 
0.5 to 2,000 ppm, of an active substance. In the case of aquatic insect 
pests, a liquid insecticide containing an active substance within the 
above concentration range can be applied onto the breeding locus for 
controlling such pests: the insecticidal action is still effective with 
the concentration of the active substance in water outside of the above 
concentration range. 
In applying the compounds of the present invention as insecticides, they 
are generally mixed with suitable carriers such as solid carriers, e.g. 
clay, talcum, bentonite, kaolin, bolus, loess, chalk, limestone, ground 
limestone, attaclay, dolomite, diatomaceous earth, precipitated silica, 
alkaline earth silicates, sodium and potassium aluminium silicates 
(feldspar and mica), secondary calcium phosphate, calcium and magnesium 
sulphates, magnesium oxide, ground synthetic materials etc.; or liquid 
carriers, e.g. water, alcohols (methanol, ethanol, etc.), ketones, ethers, 
aliphatic hydrocarbons, aromatic hydrocarbons (benzene, toluene, xylene, 
etc.,), organic bases, acid amides (dimethyl formamide, etc.), esters, 
nitriles, etc. If desired, the resulting mixture may be further 
supplemented with agents such as emulsifiers, dispersing agents, 
suspending agents, spread, penetrating agents and stabilizers to provide 
practical preparations such as emulsions, oil solutions, wettable powders, 
dusts, granules, pastes, flowables, aerosols, smoking chemicals, 
mosquito-repellent incenses, electric mosquito-repellent and the like. 
Furthermore, it is possible to apply the insecticides of the present 
invention mixed or together with other insecticides, fungicides, 
herbicides, plant-controlling agents, fertilizers and the like in the 
course of preparation or application, if necessary. 
The insecticidal action of the compounds according to the present invention 
can be further enhanced by adding thereto synergists such as piperonyl 
butoxide, octachlorodipropyl ether, N-octylbicycloheptene dicarboxyimide. 
It is also possible to increase the stability of the compounds according to 
the present invention by adding thereto as an antioxidant phenolic 
compounds such as 2,6-di-tert.-butyl-4-methylphenol, 
2,6-di-tert.-butylphenol, amine compounds, or the like.

The present invention will be further explained in detail by way of the 
following synthesis examples, formulation examples and test examples. It 
should be noted, however, that the present invention is not restricted to 
these illustrative examples. 
SYNTHESIS EXAMPLE 1 
O,O-diethyl-O-[4-(6-fluoroquinolyl-2-oxy)phenyl]thiophosphate 
##STR15## 
In 20 ml of dimethylsulfoxide is dissolved 4-(6-fluoroquinolyl-2-oxy)phenol 
(1.3 g), followed by addition thereto under cooling of potassium 
t-butoxide (0.7 g) all at once. Then, O,O-diethylthiophosphoryl chloride 
(1.0 g) is added dropwise to the reaction liquid under cooling. After the 
dropwise addition, the resulting reaction liquid is allowed to stand at 
room temperature for 5 minutes and then diluted with a large amount of 
water to terminate the reaction. 
The reaction mixture is extracted with chloroform. The resulting chloroform 
phase is separated, washed with water, dried over anhydrous sodium 
sulfate, and then concentrated under reduced pressure to give a 
substantially pure product. The resulting product is subjected to 
purification by means of column chromatography to obtain 1.8 g of the 
aimed Compound No. 1 of the present invention as pale yellow liquid. 
N.sub.D.sup.20 =1.5798. 
SYNTHESIS EXAMPLE 2 
O-ethyl S-n-propyl O-[4-(6-fluoroquinoxalyl-2-oxy)phenyl]thiophosphate 
##STR16## 
To 100 ml of chloroform are added 4-(6-fluoroquinoxalyl-2-oxy)phenyl (1.0 
g), O-ethyl S-n-propyl thiophosphoryl chloride (0.7 g) and triethylamine 
(0.4 g), and the resulting solution is heated under reflux for 7 hours. 
The resulting reaction liquid is washed with water, dried and concentrated 
under reduced pressure to give pale red oily residue. The resulting oily 
residue is subjected to purification by means of column chromatography to 
obtain 0.8 g of the compound No. 8 of the present invention as a yellow 
oil. N.sub.D.sup.20 =1.5779 
SYNTHESIS EXAMPLE 3 
O-ethyl S-n-propyl O-[4-(7-bromoquinoxalyl-2-thio)phenyl]dithiophosphate 
##STR17## 
In 300 ml of methylene chloride is dissolved 
4-(7-bromoquinoxalyl-2-thio)anisole (12 g), followed by addition thereto 
under cooling to -78.degree. C. of boron tribromide (25 g). Thereafter, 
the resulting reaction liquid is gradually warmed to room temperature, 
allowed to stand at room temperature for 3 days and then diluted carefully 
with water to terminate the reaction. The methylene chloride phase is 
mixed with 5% NaOH aqueous solution and the aqueous alkaline phase 
separated therefrom is slightly acidified with diluted hydrochloric acid 
to precipitate pale yellow solid. The resulting pale yellow crystals are 
sufficiently dehydrated and dried to obtain 7.6 g of substantially pure 
4-(7-bromoquinoxalyl-2-thio)phenol. (m.p. 191.degree.-194.degree. C.) 
In 50 ml of chloroform are dissolved the phenol obtained in the above (1.3 
g), O-ethyl S-n-propyl dithiophosphoryl chloride (1.1 g) and triethylamine 
(0.6 g) and the resulting chloroform solution is heated under reflux for 7 
hours. The chloroform reaction liquid is then washed with diluted alkaline 
aqueous solution and then with water, dried and concentrated under reduced 
pressure to give substantially pure compound No. 20 of the present 
invention as a pale yellow oil. The resulting product is subjected to 
purification by column chromatography to obtain 1.1 g of pure compound No. 
20 of the present invention as a pale yellow oil. N.sub.D.sup.20 =1.6675 
SYNTHESIS EXAMPLE 4 
O-ethyl S-n-propyl O-[3-(6-chloroquinoxalyl-2-oxy)phenyl]thiophosphate 
##STR18## 
A solution of 3-(6-chloroquinoxalyl-2-oxy)phenol (1.5 g), 
O-ethyl-S-n-propylthiophosphoryl chloride (1.0 g) and triethylamine (0.6 
g) in 100 ml of methylene chloride is heated under reflux for 5 hrs. The 
reaction mixtures is then washed with water, dried and concentrated to 
give pale red, oily residue. The oily residue is purified by means of 
silica gel column chromatography to obtain 1.1 g of substantially pure 
compound No. 22 of the present invention. N.sub.D.sup.20 =1.5963 
In the manner similar to Synthesis Examples 1 to 4, the compounds listed in 
Tables 1, 2 and 3 were synthesized. The physical properties of these 
compounds are also listed in the tables together with those of compounds 
No. 1, 20 and 22. 
TABLE 1 
__________________________________________________________________________ 
Syntheses of the compounds of the formula (Ia): 
##STR19## (1a) 
Compound 
No. X Y Z A R R.sup.1 
Appearance 
N.sub.D.sup.20 
__________________________________________________________________________ 
1 6-F O S CH OC.sub.2 H.sub.5 
OC.sub.2 H.sub.5 
pale yellow 
1.5798 
liquid 
2 H O O CH SPrn* 
OC.sub.2 H.sub.5 
pale yellow 
1.5790 
liquid 
3 6-F O O CH SPrn OC.sub.2 H.sub.5 
pale yellow 
1.5769 
liquid 
4 6-Br 
O O CH SPr n 
OC.sub.2 H.sub.5 
pale yellow 
1.6093 
liquid 
5 6-Cl 
O S N OC.sub.2 H.sub.5 
OC.sub.2 H.sub.5 
pale yellow 
1.5909 
liquid 
6 6-F O S N OC.sub.2 H.sub.5 
OC.sub.2 H.sub.5 
pale yellow 
1.5629 
liquid 
7 H O O N SPrn OC.sub.2 H.sub.5 
pale yellow 
1.5542 
liquid 
8 6-F O O N SPrn OC.sub.2 H.sub.5 
pale yellow 
1.5779 
liquid 
9 6-Cl 
O O N SPrn OC.sub.2 H.sub.5 
pale yellow 
1.5729 
liquid 
10 6-CF.sub.3 
O O N SPrn OC.sub.2 H.sub.5 
pale yellow 
1.5506 
liquid 
11 7-Br 
O O N SPrn OC.sub.2 H.sub.5 
pale yellow 
1.6000 
liquid 
12 6-Cl 
NCH.sub.3 
O N SPrn OC.sub.2 H.sub.5 
pale yellow 
1.6048 
liquid 
13 6-Cl 
S O N SPrn OC.sub.2 H.sub.5 
pale yellow 
1.6298 
liquid 
14 6-F O S N SPrn OC.sub.2 H.sub.5 
pale yellow 
1.6008 
liquid 
15 6-Cl 
O S N SPrn OC.sub.2 H.sub.5 
pale yellow 
1.6222 
liquid 
16 6-Cl 
O O N SPrn OCH.sub.3 
pale yellow 
liquid 
17 H O S N SPrn OC.sub.2 H.sub.5 
pale yellow 
1.6168 
liquid 
18 7-Br 
O O N SPrn OCH.sub.3 
pale yellow 
liquid 
19 7-Br 
S O N SPrn OC.sub.2 H.sub.5 
pale yellow 
1.6349 
liquid 
20 7-Br 
S S N SPrn OC.sub.2 H.sub.5 
pale yellow 
1.6675 
liquid 
21 6-Cl 
NCH.sub.3 
S N SPrn OC.sub.2 H.sub.5 
pale yellow 
Viscous 
liquid 
liquid 
__________________________________________________________________________ 
*"SPrn" herein represents Snpropyl group. 
TABLE 2 
______________________________________ 
Syntheses of the compounds of the formula (Ib): 
##STR20## (Ib) 
Com- 
pound Appear- 
No. X Y Z A R R.sup.1 
ance N.sub.D.sup.20 
______________________________________ 
22 6-Cl O O N SPrn OC.sub.2 H.sub.5 
pale 1.5963 
yellow 
liquid 
23 7-Br O O N SPrn OC.sub.2 H.sub.5 
pale 1.5765 
yellow 
liquid 
24 6-Cl O S N SPrn OC.sub. 2 H.sub.5 
pale 1.6302 
yellow 
liquid 
______________________________________ 
TABLE 3 
______________________________________ 
Syntheses of the compounds of the formula (Ic): 
##STR21## (Ic) 
Com- 
pound Appear- 
No. X Y Z A R R.sup.1 
ance N.sub.D.sup.20 
______________________________________ 
25 H O O N SPrn OC.sub.2 H.sub.5 
pale 1.5936 
yellow 
liquid 
26 7-Br O O N SPrn OC.sub.2 H.sub.5 
pale 1.6042 
yellow 
liquid 
27 6-CF.sub.3 
O O N SPrn OC.sub.2 H.sub.5 
pale 1.5519 
yellow 
liquid 
28 6-F O O N Sprn OC.sub.2 H.sub.5 
pale 1.5753 
yellow 
liquid 
29 6-Cl O O N SPrn OC.sub.2 H.sub.5 
pale 1.5968 
yellow 
liquid 
30 6-Cl O S N SPrn OC.sub.2 H.sub.5 
pale 1.6178 
yellow 
liquid 
______________________________________ 
SYNTHESIS EXAMPLE 5 
O-ethyl S-n-propyl 
O-[2-chloro-4-(7-bromoquinoxalyl-2-oxy)phenyl]thiophosphate 
##STR22## 
In 50 ml of chloroform are dissolved 
2-chloro-4-(7-bromoquinoxalyl-2-oxy)phenol (1.0 g), O-ethyl S-n-propyl 
thiophosphoryl chloride (0.86 g) and triethylamine (0.43 g), and the 
resulting solution is heated under reflux for 20 hours. 
The reaction liquid is washed with 5% NaOH aqueous solution then with 
water, dried and concentrated to give yellow, oily residue. The resulting 
oily residue is subjected to purification by means of column 
chromatography to yield 0.57 g of compound No. 33 of the present invention 
as a pale yellow liquid. N.sub.D.sup.20 =1.6062 
In the same manner as the above example, the compounds listed in Table 4 
were synthesized. 
TABLE 4 
______________________________________ 
Syntheses of the compounds of the formula (Id): 
##STR23## (Id) 
Compound 
No. X B Z R R.sup.1 
N.sub.D.sup.20 
______________________________________ 
32 H 2-Br O SPrn OC.sub.2 H.sub.5 
1.5891 
33 7-Br 2-Cl O SPrn OC.sub.2 H.sub.5 
1.6062 
34 7-Br 3-Cl O SPrn OC.sub.2 H.sub.5 
1.5969 
35 6-CF.sub.3 
2-CH.sub.3 
O SPrn OC.sub.2 H.sub.5 
1.5564 
36 H 2-Br S SPrn OC.sub.2 H.sub.5 
1.6242 
______________________________________ 
SYNTHESIS EXAMPLE 6 
O-ethyl S-n-propyl 
O-[2-chloro-5-(6-chloroquinoxalyl-2-oxy)phenyl]thiophosphate 
##STR24## 
A mixture of 2,6-dichloroquinoxaline (6.0 g), 4-chlororesorcinol (12.6 g), 
anhydrous potassium carbonate (8.4 g) and dimethyl formamide (30 g) is 
reacted with stirring at 110.degree. C. for 4 hours. After completion of 
the reaction, dimethyl formamide in the reaction mixture is distilled off 
under reduced pressure and the resulting residue is added with water to 
precipitate crystals. 
The crystals thus obtained are filtered, washed with water and dried. The 
resulting crude product is subjected to purification by means of column 
chromatography to obtain 1.3 g of white crystals of 
4-chloro-3-(6-chloroquinoxalyl-2-oxy)phenol in the first eluate (m.p. 
195.degree.-199.degree. C.), and as the second eluate 1.0 g of white 
crystals of 2-chloro-5-(6-chloroquinoxalyl-2-oxy)phenol. (m.p. 
172.degree.-176.degree. C.). 
In 50 ml of chloroform are added 
2-chloro-5-(6-chloroquinoxalyl-2-oxy)phenol (0.90 g), O-ethyl S-n-propyl 
thiophosphoryl chloride (0.89 g) and triethylamine (0.45 g), and the 
resulting solution is heat under reflux for 24 hrs. 
The reaction liquid is subjected to post-treatment as in Synthesis Example 
5 to obtain 0.73 g of pure compound No. 37 as a pale yellow liquid. 
N.sub.D.sup.20 =1.5982 
In the manner similar to that of Synthesis Example 6, the compounds listed 
in Table 5 were synthesized. 
TABLE 5 
______________________________________ 
Syntheses of the compounds of the formula (Ie): 
##STR25## (Ie) 
Compound 
No. X B Z R R.sup.1 
N.sub.D.sup.20 
______________________________________ 
38 6-Cl 4-Cl O SPrn OC.sub.2 H.sub.5 
1.6025 
39 6-Cl 6-CH.sub.3 
O SPrn OC.sub.2 H.sub.5 
1.5851 
______________________________________ 
In the same manner as any of Synthesis Examples 1 to 6, the compounds 
listed in Tables 6 and 7 may be synthesized. 
TABLE 6 
__________________________________________________________________________ 
Syntheses of the compounds of the formula (If): 
##STR26## (If) 
Compound 
No. X Y Z A B R R.sup.1 
__________________________________________________________________________ 
40 H O O CH H SPrn OCH.sub.3 
41 H O O CH H SBun** OC.sub.2 H.sub.5 
42 H O O CH H SBusec*** 
OC.sub.2 H.sub.5 
43 H O O CH 2-Br 
SPrn OC.sub.2 H.sub.5 
44 H O O CH 2-Cl 
SPrn OC.sub.2 H.sub.5 
45 6-F O O CH H SPrn OCH.sub.3 
46 6-F O O CH H SBun OC.sub.2 H.sub.5 
47 6-F O O CH H SBusec OC.sub.2 H.sub.5 
48 6-F O O CH 2-Br 
SPrn OC.sub.2 H.sub.5 
49 6-F O O CH 2-Cl 
SPrn OC.sub.2 H.sub.5 
50 6-Br 
O O CH H SBusec OC.sub.2 H.sub.5 
51 H O O N H SPrn OCH.sub.3 
52 H O O N H SBun OC.sub.2 H.sub.5 
53 H O O N H SBusec OC.sub.2 H.sub.5 
54 H O O N 2-Br 
SPrn OCH.sub.3 
55 H O O N 2-Br 
SBun OC.sub.2 H.sub.5 
56 H O O N 2-Br 
SBusec OC.sub.2 H.sub.5 
57 H O O N 2-Cl 
SPrn OC.sub.2 H.sub.5 
58 H O O N 3-Cl 
SPrn OC.sub.2 H.sub.5 
59 H NH O N H SPrn OC.sub.2 H.sub.5 
60 H NC.sub.2 H.sub.5 
O N H SPrn OC.sub.2 H.sub.5 
61 H SO O N H SPrn OC.sub.2 H.sub. 5 
62 H SO.sub.2 
O N H SPrn OC.sub.2 H.sub.5 
63 6-Cl 
O O N H SPrn OCH.sub.3 
64 6-Cl 
O O N H SPrn OPrn**** 
65 6-Cl 
O O N H SBun OC.sub.2 H.sub.5 
66 6-Cl 
O O N H SBusec OC.sub.2 H.sub.5 
67 6-Cl 
O O N 2-Br 
SPrn OC.sub.2 H.sub.5 
68 6-Cl 
O O N 2-Br 
SBusec OC.sub.2 H.sub.5 
69 6-Cl 
O O N 2-Cl 
SPrn OC.sub.2 H.sub.5 
70 6-Cl 
O O N 2-Cl 
SBusec OC.sub.2 H.sub.5 
71 6-Cl 
O O N 3-Cl 
SPrn OC.sub.2 H.sub.5 
72 6-Cl 
O O N 2-CH.sub.3 
SPrn OC.sub.2 H.sub.5 
73 6-Cl 
O O N 3-CH.sub.3 
SPrn OC.sub.2 H.sub.5 
74 6-Cl 
NH O N H SPrn OC.sub.2 H.sub.5 
75 6-Cl 
NC.sub.2 H.sub.5 
O N H SPrn OC.sub.2 H.sub.5 
76 6-Cl 
SO O N H SPrn OC.sub.2 H.sub.5 
77 6-Cl 
SO.sub.2 
O N H SPrn OC.sub.2 H.sub.5 
78 6-F O O N H SPrn OCH.sub.3 
79 6-F O O N H SPrn OPrn 
80 6-F O O N H SBun OC.sub.2 H.sub.5 
81 6-F O O N H SBusec OC.sub.2 H.sub.5 
82 6-F O O N 2-Cl 
SPrn OC.sub.2 H.sub.5 
83 6-F O O N 3-Cl 
SPrn OC.sub.2 H.sub.5 
84 6-F NCH.sub.3 
O N H SPrn OC.sub.2 H.sub.5 
85 6-F S O N H SPrn OC.sub.2 H.sub.5 
86 6-CF.sub.3 
O O N H SPrn OCH.sub.3 
87 6-CF.sub.3 
O O N H SBun OC.sub.2 H.sub.5 
88 6-CF.sub.3 
O O N H SBusec OC.sub.2 H.sub.5 
89 6-CF.sub.3 
O O N 2-Br 
SPrn OC.sub.2 H.sub.5 
90 6-CF.sub.3 
O O N 2-Cl 
SPrn OC.sub.2 H.sub.5 
91 6-CF.sub.3 
O O N 3-Cl 
SPrn OC.sub.2 H.sub.5 
92 6-CF.sub.3 
NH O N H SPrn OC.sub.2 H.sub.5 
93 6-CF.sub.3 
NCH.sub.3 
O N H SPrn OC.sub.2 H.sub.5 
94 6-CF.sub.3 
NC.sub.2 H.sub.5 
O N H SPrn OC.sub.2 H.sub.5 
95 6-CF.sub.3 
S O N H SPrn OC.sub.2 H.sub.5 
96 6-CF.sub.3 
SO.sub.2 
O N H SPrn OC.sub.2 H.sub.5 
97 7-Br 
O O N H SPrn OCH.sub.3 
98 7-Br 
O O N H SBusec OC.sub.2 H.sub.5 
99 7-Br 
O O N 2-Br 
SPrn OC.sub.2 H.sub.5 
100 6-Cl 
O S N 2-Cl 
SPrn OC.sub.2 H.sub.5 
101 6-Cl 
O S N 3-Cl 
SPrn OC.sub.2 H.sub.5 
__________________________________________________________________________ 
TABLE 7 
__________________________________________________________________________ 
Syntheses of the compounds of the formula (Ig): 
##STR27## (Ig) 
Compound 
No. X Y Z A B R R.sup.1 
__________________________________________________________________________ 
102 H O O N H SPrn OC.sub.2 H.sub.5 
103 H O O N H SBusec*** 
OC.sub.2 H.sub.5 
104 H O O N 2-Cl 
SPrn OC.sub.2 H.sub.5 
105 H O O N 4-Cl 
SPrn OC.sub.2 H.sub.5 
106 H O O N 6-CH.sub.3 
SPrn OC.sub. 2 H.sub.5 
107 6-F O O N H SPrn OC.sub.2 H.sub.5 
108 6-F O O N 2-Cl 
SPrn OC.sub.2 H.sub.5 
109 6-F O O N 4-Cl 
SPrn OC.sub.2 H.sub.5 
110 6-F O O N 6-CH.sub.3 
SPrn OC.sub.2 H.sub.5 
111 6-Cl 
S O N H SPrn OC.sub.2 H.sub.5 
112 6-Cl 
O O N H SPrn OPrn**** 
113 6-Cl 
O O N H SBun** OC.sub.2 H.sub.5 
114 6-Cl 
O O N H SBusec OC.sub.2 H.sub.5 
115 6-Cl 
O O N 4-Cl 
SBun OC.sub.2 H.sub.5 
116 6-Cl 
O O N 4-Cl 
SBusec OC.sub.2 H.sub.5 
117 6-Cl 
NCH.sub.3 
O N H SPrn OC.sub.2 H.sub.5 
118 7-Br 
O O N H SBusec OC.sub.2 H.sub.5 
119 7-Br 
O O N 2-Cl 
SPrn OC.sub.2 H.sub.5 
120 7-Br 
O O N 4-Cl 
SPrn OC.sub.2 H.sub.5 
121 7-Br 
S O N H SPrn OC.sub.2 H.sub.5 
122 6-CF.sub.3 
O O N H SPrn OC.sub.2 H.sub.5 
123 6-CF.sub.3 
O O N 2-Cl 
SPrn OC.sub.2 H.sub.5 
124 6-CF.sub.3 
O O N 4-Cl 
SPrn OC.sub.2 H.sub.5 
125 6-CF.sub.3 
O O N 6-CH.sub.3 
SPrn OC.sub.2 H.sub.5 
126 6-CF.sub.3 
NCH.sub.3 
O N H SPrn OC.sub.2 H.sub.5 
127 6-Cl 
O S N 2-Cl 
SPrn OC.sub.2 H.sub.5 
128 6-Cl 
O S N 4-Cl 
SPrn OC.sub.2 H.sub.5 
129 6-Cl 
O S N 6-CH.sub.3 
SPrn OC.sub.2 H.sub.5 
130 6-Cl 
O S N 6-C.sub.2 H.sub.5 
SPrn OC.sub.2 H.sub.5 
__________________________________________________________________________ 
**"SBun" represents S nbutyl group. 
***"SBusec" represents S sec. butyl group. 
****"OPrn" represents O npropyl group. 
In the following are indicated formulation examples in which the compounds 
of the present invention are used for insecticides. In these examples, all 
the parts mean parts by weight, if not otherwise specified. 
Formulation Example 1: Emulsifiable concentrates 
an active substance (a compound according to the present invention)--5 
parts 
xylol--80 parts 
Sorpol 2680 (trade name, supplied by Toho Chemicals Co., Ltd., Japan)--15 
parts 
The above components are uniformly mixed to give an emulsifiable 
concentrate. The concentrate thus obtained is diluted with water either 50 
times to spray the resulting emulsion in an amount of 25 to 50 ml/m.sup.2 
or 1000-2000 times to spray in an amount of 100 to 150 l/m.sup.2. 
Formulation Example 2: Oil solutions 
an active substance (a compound according to the present invention)--0.1 
part 
piperonyl butoxide--0.9 part 
white kerosene--99.0 parts 
The above components are uniformly mixed to give an oily solution. The oily 
solution thus obtained is applied onto a drain or puddle in an amount of 
25 to 50 ml/m.sup.2. 
Formulation Example 3: Wettable powders 
an active substance (a compound according to the present invention)--10 
parts 
Siegreit (trade name, supplied by Siegreit Mining Industries Co., 
Ltd.,)--75 parts 
Carplex (trade name, supplied by Shionogi Seiyaku K.K., Japan)--10 parts 
Sorpol 8048 (trade name, supplied by Toho Chemicals, Co., Ltd., Japan)--3 
parts 
Runox 1000 (trade name, supplied by Toho Chemicals, Co., Ltd., Japan)--2 
parts 
The above components are uniformly mixed and ground to give an wettable 
powder. In application, the resulting wettable powder is diluted 100 to 
2000 times with water and sprayed in an amount of 50 to 500 l/10a. 
Formulation Example 4: Dusts 
an active substance (a compound according to the present invention)--0.4 
part 
piperonyl butoxide--1.6 parts 
talcum--98 parts 
The above components are uniformly mixed to give a dust. The resulting dust 
is sprayed in an amount of about 15 g/m.sup.2 or 3-4 kg/10a. 
Formulation Example 5: Granules 
an active substance (a compound according to the present invention)--5 
parts 
bentonite--95 parts 
The above components are uniformly mixed and ground. After addition of a 
small amount of water with sufficient stirring, the resulting mixture is 
granulated by means of an extruder granulator and dried to give granules. 
The granules thus obtained are directly sprayed in an amount of 3-12 
kg/10a. 
Excellent insecticidal actions of the compounds according to the present 
invention are explained below in comparison with that of the commercial 
product under generic name of "prothiophos", which contains active 
substance of the formula: 
##STR28## 
TEST EXAMPLE 1 
Insecticidal action on house fly (Musca domestica) adult 
One ml of acetone solution containing 100 ppm of the compound to be tested 
was added dropwise to a laboratory dish 9 cm in diameter so that the 
solution is evenly spread over the dish. After completely evaporating the 
acetone at room temperature, ten house fly adults were placed in the dish 
and then the dish was covered with a plastic cap provided with some pores. 
The dish containing the adults is placed in a thermostatic chamber kept at 
25.degree. C. An evaluation was made after 24 hours by counting the adults 
killed and calculating the mortality of adults in accordance with the 
following equation: 
##EQU1## 
The results thereof are listed in Table 8. 
Incidentally, each test was repeated twice. 
TABLE 8 
______________________________________ 
Test compound Mortality (%) 
______________________________________ 
Control 100 
(prothiophos) 
Compound No. 2 100 
Compound No. 3 100 
Compound No. 4 100 
Compound No. 5 80 
Compound No. 6 80 
Compound No. 7 100 
Compound No. 8 100 
Compound No. 9 100 
Compound No. 10 100 
Compound No. 11 100 
Compound No. 12 100 
Compound No. 13 100 
Compound No. 14 100 
Compound No. 15 100 
Compound No. 17 100 
Compound No. 19 100 
Compound No. 20 100 
Compound No. 21 100 
Compound No. 22 100 
Compound No. 23 100 
Compound No. 24 100 
Compound No. 25 100 
Compound No. 26 100 
Compound No. 27 100 
Compound No. 28 100 
Compound No. 29 100 
Compound No. 30 100 
Compound No. 32 100 
Compound No. 33 100 
Compound No. 34 100 
Compound No. 35 100 
Compound No. 36 100 
Compound No. 37 100 
Compound No. 38 100 
Compound No. 39 100 
______________________________________ 
TEST EXAMPLE 2 
Insecticidal action on green peach aphid (Myzus persicae) 
Two ml of an aqueous emulsion containing 100 ppm of a compound according to 
the present invention was sprayed onto a laboratory dish of 3 cm in 
diameter charged with a leaf of cabbage infested with green peach aphids 
aphid. After spraying, the dish was fitted with a cap and stored in a 
thermostatic chamber kept at 25.degree. C. 
The mortality of the green peach aphids aphid in the dish was determined in 
the same manner as in Test Example 1 after 48 hours. The results are shown 
in Table 9. 
TABLE 9 
______________________________________ 
Test compound Mortality (%) 
______________________________________ 
Control 100 
(prothiophos) 
Compound No. 19 100 
Compound No. 25 100 
Compound No. 26 100 
Compound No. 27 100 
Compound No. 28 100 
Compound No. 29 100 
Compound No. 33 100 
Compound No. 34 100 
Compound No. 35 100 
Compound No. 37 100 
Compound No. 38 100 
Compound No. 39 100 
______________________________________ 
TEST EXAMPLE 3 
Contact insecticidal action on tobacco cutworm (Spodoptera litura) larvae 
A leaf of cabbage was immersed in an aqueous emulsion containing 100 ppm of 
a compound according to the present invention for about 10 seconds, and 
then air-dried. The leaf thus treated was placed in a laboratory dish, 
into which 10 second inster tobacco cutworm larvae were released. The dish 
was fitted with a cap provided with some pores and then placed in a 
thermostatic chamber kept at 25.degree. C. The mortality of the tobacco 
cutworm after 48 hours was determined in the same manner as in Test 
Example 1. The results thereof are shown in Table 10. 
TABLE 10 
______________________________________ 
Test compound Mortality (%) 
______________________________________ 
Control 100 
(prothiophos) 
Compound No. 2 100 
Compound No. 3 100 
Compound No. 4 100 
Compound No. 7 100 
Compound No. 8 100 
Compound No. 9 100 
Compound No. 10 100 
Compound No. 11 100 
Compound No. 12 100 
Compound No. 13 100 
Compound No. 14 100 
Compound No. 15 100 
Compound No. 17 100 
Compound No. 21 100 
Compound No. 22 100 
Compound No. 23 100 
Compound No. 24 100 
Compound No. 25 100 
Compound No. 28 100 
Compound No. 29 100 
Compound No. 30 100 
Compound No. 32 100 
Compound No. 33 100 
Compound No. 34 100 
Compound No. 36 100 
Compound No. 37 100 
Compound No. 38 100 
______________________________________ 
TEST EXAMPLE 4 
Insecticidal action on 28-spotted lady beetle 
(Epilachna vigintioctopunctata) 
A piece of potato was immersed in an aqueous emulsion containing 100 ppm of 
a compound according to the present invention and then air-dried. The 
potato thus treated was placed in a laboratory dish, into which 10 second 
inster 28-spotted lady beetle larvae were released. The resulting dish was 
fitted with a cap provided with pores and then placed in a thermostatic 
chamber kept at 25.degree. C. The number of the larvae killed was checked 
after 48 hours and the mortality thereof was determined in the same manner 
as Test Example 1. 
Incidentally, the above test was repeated twice. 
The test results are shown in Table 11. 
TABLE 11 
______________________________________ 
Test compound Mortality (%) 
______________________________________ 
Control 0 
(prothiophos) 
Compound No. 2 100 
Compound No. 3 100 
Compound No. 4 100 
Compound No. 7 100 
Compound No. 8 100 
Compound No. 9 100 
Compound No. 10 100 
Compound No. 11 100 
Compound No. 12 100 
Compound No. 13 100 
Compound No. 17 100 
Compound No. 19 100 
Compound No. 22 100 
Compound No. 23 100 
Compound No. 24 100 
Compound No. 25 100 
Compound No. 26 100 
Compound No. 27 100 
Compound No. 28 100 
Compound No. 29 100 
Compound No. 30 100 
Compound No. 32 100 
Compound No. 33 100 
Compound No. 34 100 
Compound No. 35 100 
Compound No. 36 80 
Compound No. 37 100 
Compound No. 38 100 
Compound No. 39 100 
______________________________________ 
TEST EXAMPLE 5 
Acaricidal action on Kanzawa spider mite (Tetranychus Kanzawai) 
A leaf of kidney bean was cut into a round piece of 1.5 cm in diameter by a 
leaf punch, and then placed on moistened filter paper put on a styrol cup 
of 7 cm in diameter. Each piece of the leaf was infested with 10 Kanzawa 
spider mite nympha. Half a day after the infestation, 2 ml of an aqueous 
emulsion containing 100 ppm of the active compound of the present 
invention was applied with a spreader to each styrol cup by means of a 
rotary sprinkler. The number of the nymphs killed was checked after 48 
hours and the mortality of the nymphs was determined. The results are 
shown in Table 12. 
TABLE 12 
______________________________________ 
Test compound Mortality (%) 
______________________________________ 
Control 100 
(prothiophos) 
Compound No. 2 100 
Compound No. 3 100 
Compound No. 4 95 
Compound No. 7 100 
Compound No. 8 100 
Compound No. 9 100 
Compound No. 11 100 
Compound No. 13 95 
Compound No. 17 95 
Compound No. 19 100 
Compound No. 22 100 
Compound No. 23 100 
Compound No. 24 100 
Compound No. 25 100 
Compound No. 26 100 
Compound No. 27 100 
Compound No. 28 100 
Compound No. 29 100 
Compound No. 32 100 
Compound No. 33 100 
Compound No. 34 100 
Compound No. 35 100 
Compound No. 36 100 
Compound No. 37 100 
Compound No. 38 100 
Compound No. 39 100 
______________________________________ 
TEST EXAMPLE 6 
Nematocidal action on root-knot nematodes (Meloidogyne sp.) 
Soil contaminated with root-knot nematodes was placed in a styrol cup of 8 
cm in diameter. A liquid containing 100 ppm of an active substance was 
prepared by diluting an emulsifiable concentrate according to the present 
invention with water and adding a spreader thereto. The soil contaminated 
with nematodes and placed in the cup as described above was drenched with 
50 ml of the resulting mixture. After 48 hours, a tomato seedling as an 
indicator is transplanted into the soil thus treated. 30 days after the 
transplantation, the roots of the tomato were washed with water and the 
root-knot parasitism was checked by observation. The results are shown in 
Table 13. 
Rating of root-knot parasitism 
0 . . . no root-knot is observed at all. 
1 . . . a few root-knots are observed. 
2 . . . a medium number of root-knot is observed. 
3 . . . many root-knots are observed. 
4 . . . considerably many root-knots are observed. 
TABLE 13 
______________________________________ 
Root-knot 
Test compound parasitism rating 
______________________________________ 
Control 0 
(prothiophos) 
Compound No. 2 0 
Compound No. 3 0 
______________________________________ 
Root-knot 
Test compound parasitism index 
______________________________________ 
Compound No. 4 0 
Compound No. 7 0 
Compound No. 8 0 
Compound No. 9 0 
Compound No. 10 0 
Compound No. 11 1 
Compound No. 12 0 
Compound No. 13 1 
Compound No. 14 1 
Compound No. 15 1 
Compound No. 22 0 
Compound No. 23 1 
Compound No. 30 1 
Compound No. 32 0 
Compound No. 33 0 
Compound No. 34 0 
Compound No. 35 0 
Compound No. 36 0 
Compound No. 37 0 
Compound No. 38 0 
Compound No. 39 0 
______________________________________