Insecticidal phosphorus derivatives of 5-pyrimidinols

Phosphorus derivatives of 5-pyrimidinols which possess insecticidal properties and especially both systemic and foliar activity for plants against insect pests.

BACKGROUND OF THE INVENTION 
The present invention relates to new phosphorus derivatives of 
5-pyrimidinols which possess insecticidal properties and especially both 
systemic and foliar activity for plants against insect pests. The present 
invention is also directed to the preparation of said derivatives, active 
insecticidal compositions containing said derivatives and to the use of 
such compositions for the kill and control of said pests. 
SUMMARY OF THE INVENTION 
The present invention is directed to phosphorus derivatives of 
5-pyrimidinols which correspond to the formula 
##STR1## 
wherein A represents hydrogen, alkyl, alkoxy, perfluoroloweralkyl, 
cycloalkyl, alkyl(cycloalkyl), (cycloalkyl)alkyl, phenyl, alkylthioalkyl, 
alkoxyalkyl, dialkylaminoalkyl, alkylthio, alkylsulfinyl, alkylsulfonyl, 
phenylthio, phenylsulfinyl, phenylsulfonyl, (alkylthio)alkylthio, 
alkoxyalkylthio, dialkylaminoalkylthio, dialkylamino, morpholino, 
piperidino, N-methylpiperazino, pyrrolidino or 
((dimethylamino)methylene)amino (--N.dbd.CH--N(CH.sub.3).sub.2); 
D represents hydrogen or alkyl; 
X represents oxygen or sulfur; 
R.sup.1 represents alkyl; 
R.sup.2 represents alkyl, alkoxy or dialkylamino; and 
R.sup.3 represents hydrogen or alkyl. 
These above compounds have been found to have good pesticidal properties 
especially insecticidal, miticidal, acaricidal and nematicidal properties. 
The compounds also have systemic activity in plants and foliar activity on 
plants against attack by said pests. 
In the present specification and claims, the terms "alkyl", and "alkoxy" as 
employed in the terms "alkyl", "alkoxy" or as a part of the terms 
"alkyl(cycloalkyl)", "(cycloalkyl)alkyl", "alkylthio alkyl", 
"alkoxyalkyl", "dialkylaminoalkyl", "alkylthio", "alkylsulfinyl", 
"alkylsulfonyl", "(alkylthio)alkylthio", "alkoxyalkylthio", 
"dialkylaminoalkylthio" and "dialkylamino" designates straight or branched 
chain alkyl or alkoxy groups of 1 to 6 carbon atoms. 
In the present specification and claims, the term "cycloalkyl" as employed 
in the term "cycloalkyl" or as a part of the terms "alkyl(cycloalkyl)", 
"(cycloalkyl)alkyl" designates a cycloalkyl group of from 3 to 6 carbon 
atoms. 
The term "perfluoroloweralkyl" designates a perfluoroalkyl group of 1 to 3 
carbon atoms. 
The compounds of the present invention are largely somewhat viscous oils or 
solids which are rather readily soluble in many common organic solvents 
and of low solubility in water. 
The compounds of the present invention can be prepared by the reaction of a 
molar equivalent of an appropriate 5-pyrimidinyl phosphoramidothioate or 
phosphoramidate corresponding to the formula 
##STR2## 
with from about a 10 to about a 30 percent excess of an appropriate 
substituted dialkyl acetal corresponding to the formula 
##STR3## 
wherein A, D, X, R.sup.1, R.sup.2 and R.sup.3 are as hereinabove defined 
and R.sup.4 is alkyl. 
In carrying out this reaction, the dialkyl acetal reactant is added to a 
solution of the phosphoramidothioate (phosphoramidate) reactant in a 
solvent such as methylene chloride, diethyl ether, toluene or carbon 
tetrachloride. The mixture is stirred at room temperature for from about 
30 minutes to about 4 hours. The solvent is then removed by evaporation. 
The crude product which remains as a residue is taken up in a solvent such 
as ether (ethyl ether) and the ether solution washed with water and then a 
saturated sodium chloride solution. The ether solution is then dried and 
the ether is removed by evaporation leaving the desired product. 
The 5-pyrimidinyl phosphoramidothioate or phosphoramidate employed as a 
starting material and corresponding to the formula 
##STR4## 
wherein A, D, X and R.sup.1 are as hereinabove defined can be prepared by 
bubbling excess ammonia into a stirring mixture of a 5-pyrimidinyl 
phosphorochloridothioate or phosphorochloridate reactant in a solvent such 
as acetonitrile. The reaction is usually carried out at a temperature of 
from about minus (-) 10.degree. to about 80.degree. C. for a period of 
from about one to about 16 or more hours. After the completion of the 
reaction, the reaction mixture is filtered and the residue remaining is 
purified by high pressure liquid chromatography, if necessary. 
The 5-pyrimidinyl phosphorochloridothioate or phosphorochloridate employed 
as a starting material can be prepared by reacting substantially equimolar 
amounts of an appropriate 5-pyrimidinol reactant corresponding to the 
formula 
##STR5## 
wherein A and D are as hereinbefore defined, and an appropriate 
phosphorodichloridate or phosphorodichloridothioate corresponding to the 
formula 
##STR6## 
wherein R.sup.1 is as hereinbefore defined in the presence of a solvent 
and a hydrogen chloride absorber. 
In carrying out the reaction, the reactants are mixed in any suitable 
fashion and maintained together with agitation until the reaction is 
complete. It is convenient to first mix the pyrimidinol with the solvent 
and the HCl acceptor and then add the phosphorus reactant. The reaction is 
complete when all of the phosphorus reactant has been consumed. 
Representative solvents include, for example, acetonitrile, cyclohexane, 
benzene, toluene, xylene, acetone, methylene chloride, methylethyl ketone, 
diethylether, dioxane, tetrahydrofuran and the like. 
Representative hydrogen chloride absorbers (acid-binding agents) include, 
for example, alkali metal carbonates such as sodium and potassium 
carbonates and tertiary amines such as, for example, trimethylamine, 
triethylamine, pyridine and the like. 
At the completion of the reaction, the reaction mixture is filtered to 
remove any insolubles and the filtrate concentrated under reduced 
pressure. The residue is then taken up in ethyl ether, benzene, toluene, 
methylene chloride or chloroform and washed thoroughly with water and then 
with a saturated sodium chloride solution and dried. The solvent is 
removed by evaporation under reduced pressure leaving the desired product. 
While the above discussion is directed to the preparation and recovery of 
each of the intermediates, the present compounds can also be prepared in 
situ with no separation of the intermediates.

DESCRIPTION OF SOME PREFERRED EMBODIMENTS 
The following examples illustrate the present invention and the manner by 
which it can be practiced but, as such, should not be construed as 
limitations upon the overall scope of the same. 
EXAMPLE I 
N-((Dimethylamino)methylene) O-ethyl O-(2-(1-methylethyl)-5-pyrimidinyl) 
phosphoramidothioate 
##STR7## 
To a solution of 3.2 grams (g) (0.012 mole (m)) of O-ethyl 
O-(2-(1-methylethyl)-5-pyrimidinyl) phosphoramidothioate in 100 
milliliters (ml) of methylene chloride was added 1.77 g (0.015 m) of 
dimethylformamide dimethyl acetal. The mixture was stirred for one hour at 
room temperature and the solvent was then removed in a rotary evaporator. 
The oil which remained as a residue was dissolved in ethyl ether and the 
ether solution washed with water then with a saturated sodium chloride 
solution and then dried over anhydrous sodium sulfate. The ether was 
removed in a rotary evaporator leaving 2.7 g of the above-named product as 
an amber colored oil. The product had a refractive index of 
n(25/d)=1.5379. The IR and NMR spectra were in agreement with the desired 
structure. Upon analysis, the product was found to have carbon, hydrogen 
and nitrogen contents of 45.89, 6.83 and 17.34 percent, respectively, as 
compared with the theoretical contents of 45.55, 6.69 and 17.71 percent, 
respectively, as calculated for the above-named structure. 
EXAMPLE II 
N-((Dimethylamino)methylene) O-ethyl O-(2-cyclopropyl-5-pyrimidinyl) 
phosphoramidothioate 
##STR8## 
To a stirred mixture of 2.3 g (0.017 m) of 2-cyclopropyl-5-pyrimidinol, 3.0 
g of finely powdered potassium carbonate and 100 ml of acetonitrile was 
added 3.02 g (0.017 m) of O-ethyl phosphorodichloridothioate. The mixture 
was stirred at room temperature until no more of the phosphorus reactant 
could be detected by gas-liquid chromatography (glc). An excess of ammonia 
was then bubbled into the reaction mixture and stirring at room 
temperature was continued for about one hour. The mixture was filtered to 
remove the insoluble salts and the salts were washed with acetonitrile and 
the acetonitrile added to the filtrate. The filtrate was concentrated 
under reduced pressure to an amount of about 50 ml. To this solution, 2.1 
g (0.018 m) of dimethylformamide dimethyl acetal was added and the mixture 
was stirred at room temperature for 16 hours. The reaction mixture was 
concentrated in a rotary evaporator, the residual oil was taken up in 
ether, washed twice with 5% aqueous sodium hydroxide, once with a 
saturated sodium chloride solution and dried over anhydrous sodium 
sulfate. The solvent was removed in a rotary evaporator leaving 0.7 g of 
the desired product, as named above, as an amber colored oil. The product 
had a refractive index of n(25/d)=1.5553 and the IR and NMR spectra 
confirmed the structure. Upon analysis, the compound was found to have 
carbon, hydrogen and nitrogen contents of 45.87, 5.69 and 17.56 percent, 
respectively, as compared with the theoretical contents of 46.00, 5.79 and 
17.88 percent, respectively, as calculated for the above-named structure. 
EXAMPLE III 
N-((Dimethylamino)methylene) O-ethyl 
O-(2-(1,1-dimethylethyl)-5-pyrimidinyl) phosphoramidothioate 
##STR9## 
To a stirred mixture of 5.5 g (0.036 m) of 
2-(1,1-dimethylethyl)-5-pyrimidinol, 5.5 g of finely powdered potassium 
carbonate and 100 ml of acetonitrile was added 6.47 g (0.036 m) of O-ethyl 
phosphorodichloridothioate. The mixture was stirred at room temperature 
until no more of the phosphorus reactant could be detected by glc. A small 
excess of ammonia was then bubbled into the reaction mixture and stirring 
at room temperature was continued until all of the starting materials were 
converted to the amidothiophosphate. The salts were then removed by 
filtration and the filtrate concentrated under vacuum to .about.50 ml. To 
this solution was added 5.32 g of dimethylformamide dimethyl acetal and 
stirring at room temperature continued until no more starting material 
could be detected by glc. The mixture was concentrated under reduced 
pressure, and the residual oil taken up in ether. The ether solution was 
washed twice with 5% aqueous sodium hydroxide, once with a saturated 
sodium chloride solution and dried over anhydrous sodium sulfate. The 
solvent was removed in a rotary evaporator leaving 0.8 g of the 
above-indicated compound as an amber colored oil. The product had a 
refractive index of n(25/d)=1.5216 and the IR and NMR spectra confirmed 
the structure of the above-indicated compound. Upon analysis, the compound 
was found to have carbon, hydrogen and nitrogen contents of 47.46, 6.97, 
and 16.39, respectively, as compared with the theoretical contents of 
47.25, 7.01 and 16.95 percent, respectively, as calculated for the 
above-named compound. 
EXAMPLE IV 
O-Ethyl O-(2-(1-methylethyl)-5-pyrimidinyl)phosphoramidothioate 
##STR10## 
To a stirred mixture of 12.0 g (0.087 m) of 
2-(1-methylethyl)-5-pyrimidinol, 12.0 g of finely powdered potassium 
carbonate and 100 ml of acetonitrile was added 15.5 g (0.087 m) of O-ethyl 
phosphorodichloridothioate. The mixture was stirred at room temperature 
overnight. Excess ammonia was bubbled into the reaction mixture at 
0.degree. C. and the mixture was stirred overnight. The salts which formed 
were removed by filtration and the residual oil purified by high pressure 
liquid chromatography. The above-indicated compound was recovered as a 
pale amber oil in a yield of 13.4 g (60% of theoretical). The product had 
a refractive index of n(25/d)=1.5285 and the IR and NMR spectra confirmed 
the structure of the indicated compound. Upon analysis, the compound was 
found to have carbon, hydrogen and nitrogen contents of 41.64, 6.22 and 
16.89 percent, respectively, as compared with the theoretical contents of 
41.36, 6.17 and 16.08 percent respectively, as calculated for the 
above-named compound. 
By following the preparative procedures as outlined in the above methods of 
preparation and the above examples and employing the appropriate starting 
materials, the following compounds set forth in Table 1 are prepared. 
TABLE 1 
__________________________________________________________________________ 
##STR11## 
A D X R.sup.1 
R.sup.2 R.sup.3 
__________________________________________________________________________ 
H H S OCH.sub.3 
N(CH.sub.3).sub.2 
H 
H H O OC.sub.2 H.sub.5 
N(CH.sub.3).sub.2 
H 
CH.sub.3 CH.sub.3 
S OC.sub.2 H.sub.5 
N(CH.sub.3).sub.2 
CH.sub.3 
C.sub.6 H.sub.13 
C.sub.6 H.sub.13 
O OC.sub.6 H.sub.13 
N(C.sub.6 H.sub.13).sub.2 
H 
OCH.sub.3 C.sub.6 H.sub.13 
O OCH.sub.3 
OCH.sub.3 
CH.sub.3 
OC.sub.6 H.sub.13 
H O OC.sub.2 H.sub.5 
C.sub.3 H.sub.7 
H 
CF.sub.3 H S OC.sub.4 H.sub.9 
OC.sub.2 H.sub.5 
H 
C.sub.3 F.sub.7 
C.sub.3 H.sub.7 
S OC.sub.6 H.sub.13 
N(C.sub.2 H.sub.5).sub.2 
H 
##STR12## H S OC.sub.2 H.sub.5 
N(C.sub.3 H.sub.7).sub.2 
H 
##STR13## H S OC.sub.2 H.sub.5 
OCH.sub.3 
C.sub.6 H.sub.13 
.0. H S OC.sub.2 H.sub.5 
OC.sub.6 H.sub.13 
H 
CH.sub.2 SCH.sub.3 
H S OC.sub.2 H.sub.5 
N(C.sub.2 H.sub.5).sub.2 
H 
##STR14## H S OC.sub.5 H.sub.11 
CH.sub.3 
H 
##STR15## H O OC.sub.2 H.sub.5 
N(CH.sub.3).sub.2 
H 
C.sub.2 H.sub.4 OC.sub.6 H.sub.13 
CH.sub.3 
O OC.sub.3 H.sub.7 
OC.sub.2 H.sub.5 
CH.sub.3 
CH.sub.2N(CH.sub.3).sub.3 
CH.sub.3 
S OCH.sub.3 
OC.sub.2 H.sub.5 
C.sub.2 H.sub.5 
SCH.sub.3 C.sub.4 H.sub.9 
S OC.sub.2 H.sub.5 
OC.sub.2 H.sub.5 
H 
SOC.sub.4 H.sub.9 
H S OCH.sub.3 
OCH.sub.3 
CH.sub.3 
SO.sub.2 C.sub.2 H.sub.5 
H S OC.sub.2 H.sub.5 
OC.sub.2 H.sub.5 
H 
S.0. C.sub.2 H.sub.5 
S OC.sub.2 H.sub.5 
C.sub.4 H.sub.9 
C.sub.4 H.sub.9 
SO.0. C.sub.5 H.sub.11 
S OCH.sub.3 
OC.sub.4 H.sub.9 
H 
SO.sub.2 .0. 
H S OC.sub.3 H.sub.7 
N(C.sub.4 H.sub.9).sub.2 
H 
SCH.sub.2 SC.sub.4 H.sub.9 
H S OC.sub.2 H.sub.5 
N(CH.sub.3).sub.2 
CH.sub.3 
SC.sub.2 H.sub.4 OC.sub.6 H.sub.13 
H O OC.sub.2 H.sub.5 
N(CH.sub.3).sub.2 
CH.sub.3 
SC.sub.2 H.sub.4 N(CH.sub.3).sub.3 
H O OC.sub.2 H.sub.5 
CH.sub.3 
CH.sub.3 
N(C.sub.6 H.sub.13).sub.2 
H O OC.sub.2 H.sub.5 
CH.sub.3 
H 
NCHN(CH.sub.3).sub.2 
H S OC.sub.2 H.sub.5 
N(CH.sub.3).sub.2 
H 
3-Morpholino 
H S OCH.sub.3 
N(C.sub.2 H.sub.5).sub.2 
C.sub.2 H.sub.5 
3-Piperidino 
H S OC.sub.2 H.sub.5 
N(CH.sub.3).sub.2 
H 
4-Nmethyl H S OC.sub.3 H.sub.7 
CH.sub.3 
H 
piperazino 
3-Pyrrolidino 
H O OC.sub.2 H.sub.5 
N(C.sub.4 H.sub.9).sub.2 
H 
##STR16## CH.sub.3 
S OC.sub.2 H.sub.5 
N(CH.sub.3).sub.2 
H 
__________________________________________________________________________ 
The compounds of the present invention are very effective for the kill and 
control of insects found on the roots or aerial portions of growing 
plants. 
Representative of the various insects which are killed and controlled by 
the active compounds of the present invention include the mites (Acarina) 
in particular, the spider mites (Tetranychidae) such as the two-spotted 
spider mite (Tetranychus urticae), carmine spider mite (Tetranychus 
cinnabarinus) and the European red mite (Panonychus ulmi), blister mites, 
for example, the currant blister mite (Eriophyes ribis) and tarsonemids, 
for example, the broad mite (Hemitarsonemus latus), the cyclamen mite 
(Tarsonemus pallidus); leafhoppers and planthoppers, i.e., aster 
leafhopper (Macrosteles fascifrons), rice green leafhopper (Nephotettix 
virescens), zig-zag leafhopper (Recilia dorsalis), (Nephotettix apicalis), 
white-back planthopper (Sogattella furcifera), brown planthopper 
(Nilaparvata lugens), smaller brown planthopper (Laodelphax striatellus), 
grape leafhopper (Erythroneura sp) and potato leafhopper (Empoasca fabae); 
for insects such as aphids (Aphididae) such as the green peach aphid 
(Myzus persicae), the bean aphid (Aphis fabae), the black cherry aphid 
(Myzus ceraci), the pea aphid (Acythorsiphum pisum) and the potato aphid 
(Macrosiphum euphorbiae), the currant gall aphid (Cryptomyzus ribis), the 
mealy apple aphid (Sappaphis mali), the mealy plum aphid (Hyalopterus 
pruni), the cotton aphid (Aphis gossyppii); and other such insects 
including tobacco budworms (Heliothis virescens), Western spotted cucumber 
beetle (Diabrotica undecimpunctata undecipunctata), the rice water weevil 
(Lissorhoptrus orvsophilus), housefly (Musca domestica), beet armyworm 
(Spodoptora exigua), and codling moth (Laspeyresia pomonella); and borers 
such as rice stem borer (Chilo sp), the pink borer (Sesamia sp) and the 
paddy borer (Tryporyza sp). 
In the present specification and claims, the term "systemic" defines the 
translocation of the active compound employed in the present method 
through the plant. The active compound can be applied either to the 
above-ground or preferably to below-ground portions of the plant. 
The application of an insecticidally effective amount of an active compound 
of the present invention is critical to the method of the present 
invention. The active compound can sometimes be employed in unmodified 
form. Frequently, however, for easier application, the compound is 
modified by the employment with it of an adjuvant or inert carrier 
therefor. Therefore, the practical employment of the beneficial utilities 
of the present compound often requires that the compound be composited 
with one or more adjuvant substances which are chemically inert to the 
active compound, and the resulting compositions are comprehended within 
the present invention. 
The compositions can be formulated in various forms, such as emulsifiable 
concentrates, wettable powders, flowable suspension dusts, granules, 
microencapsulated granules, fine granules, oil sprays, aerosols, and the 
adjuvant employed can be any one or a plurality of materials including 
aromatic solvents, petroleum distillates, water, or other liquid carriers, 
propellant substances, surface-active dispersing agents, light absorbers, 
and finely divided carrier solids. In such compositions, the adjuvant 
cooperates with the active compound so as to obtain a composition to 
facilitate the method of the present invention, and to obtain an improved 
result. The use of either a surface-active dispersing agent or a finely 
divided carrier solid and the use of both a surface-active dispersing 
agent and a finely divided carrier solid, simultaneously, constitute 
preferred embodiments of the method of the present invention. Another 
preferred embodiment of the present invention is a composition comprising 
one or more of the presently claimed compounds, an organic liquid as a 
solvent and carrier therefor, and a propellant material. Numerous other 
embodiments will become available to those skilled in the art in view of 
the teachings set forth hereinbelow. 
The exact concentration of the active compound in a composition thereof 
with an adjuvant therefor can vary; it is only necessary that the active 
compounds be present in a sufficient amount so as to make possible the 
application of an insecticidally effective dosage. Generally, for 
practical applications, the active compounds can be broadly applied to the 
plants or to the soil around the roots of the plants or to water, such as 
in broadcast rice paddy applications in compositions containing from about 
0.00001 percent to about 98 percent by weight of the active compound. 
In preparation of dust compositions, the product can be compounded with any 
of the finely divided carrier solids such as prophyllite, diatomaceous 
earth, gypsum and the like. In such operations, the finely divided carrier 
is ground or mixed with the active compound, as active agent, or wetted 
with a solution of the active agent in a volatile organic solvent. 
Similarly, dust compositions containing the active product can be 
similarly compounded from various of the solid dispersing agents, such as 
fuller's earth, attapulgite and other clays. These dust compositions can 
be employed as treating compositions or can be employed as concentrates 
and subsequently diluted with additional solid dispersing agent or with 
pyrophyllite, diatomaceous earth, gypsum and the like to obtain the 
desired amount of active agent in a treating composition. Also, such dust 
compositions can be dispersed in water, with or without the aid of 
surfactant, to form spray mixtures. 
Further, the active compound or a dust concentrate composition containing 
said compound can be incorporated in intimate mixture with surface-active 
dispersing agents such as ionic and nonionic emulsifying agents to form 
spray concentrates. Such concentrates are readily dispersible in liquid 
carriers to form sprays containing the toxicant in any desired amount. The 
choice of dispersing agent and amount thereof employed are determined by 
the ability of the agent to facilitate the dispersion of the concentrate 
in the liquid carrier to produce the desired spray composition. 
In the preparation of liquid compositions, the active compound can be 
compounded with a suitable water-immiscible organic liquid and a 
surface-active dispersing agent to produce an emulsifiable liquid 
concentrate which can be further diluted with water and oil to form spray 
mixtures in the form of oil-in-water emulsions. In such compositions, the 
carrier comprises an aqueous emulsion, that is, a mixture of 
water-immiscible solvent, emulsifying agent and water. Preferred 
dispersing agents to be employed in these compositions are oil-soluble and 
include the nonionic emulsifiers such as the polyoxyethylene derivatives 
of sorbitan esters, complex ether alcohols and the like. However, 
oil-soluble ionic emulsifying agents such as mahogany soaps can also be 
used. Suitable organic liquids to be employed in the compositions include 
petroleum oils and distillates, toluene liquid halohydrocarbons and 
synthetic organic oils. The surface-active dispersing agents are usually 
employed in liquid compositions in the amount of from 0.1 to 20 percent by 
weight of the combined weight of the dispersing agent and active compound. 
When operating in accordance with the present invention, the active 
compound or a composition containing the active compound is applied to the 
plants or to their habitat in any convenient manner, for example, by means 
of hand dusters or sprayers. Application to the foliage of plants is 
conveniently carried out with power dusters, boom sprayers and fog 
sprayers. In such foliar applications, the employed compositions should 
not contain any appreciable amounts of any phytotoxic diluents. In large 
scale operations, dusts, or low-volume sprays can be applied from an 
airplane. 
In further embodiments, one of the compounds of the present invention or 
compositions containing the same, can be advantageously employed in 
combination with one or more additional pesticidal compounds. Such 
additional pesticidal compounds may be insecticides, nematocides, 
arthropodicides, herbicides, fungicides or bactericides that are 
compatible with the compounds of the present invention in the medium 
selected for application and not antagonistic to the activity of the 
present compounds. Accordingly, in such embodiments, the pesticidal 
compound is employed as a supplemental toxicant for the same or for a 
different pesticidal use, or as an additament. The compounds in 
combination can generally be present in the ratio of from about 1 to about 
99 parts of the compound of the present invention with from about 99 to 
about 1 part of the additional compound(s). 
Dosage amounts are generally from 15-1,000 grams (g) preferably from 40-600 
g of active compound and most preferably from 125-500 g of active compound 
per hectare. However, in special cases, it is possible to exceed or reduce 
the amount and this may sometimes be necessary. 
EXAMPLE V 
Aqueous dispersions were prepared by admixing one of the hereinafter set 
forth compounds, dissolved in a suitable inert solvent, with a 
predetermined quantity of water and a predetermined amount of a surfactant 
to give aqueous dispersions containing varying predetermined amounts of 
one of the compounds as the sole toxicant. Separate cotton plants were 
infested with .about.50-100 two-spotted spider mites and the plants 
injected at the base of the plants with one of the dispersions. In a like 
manner, .about.50-100 two-spotted spider mites were placed on control 
plants and the plants also injected at the base with a solution containing 
only water and surfactant. The plants were maintained under conditions 
conducive to the growth of the plants and the mites. After a period of 5 
days, the plants were examined to determine the percent kill and control 
by the active compound. It was found that at a dosage rate of 25 parts of 
the active compound per million parts of the ultimate dispersion (ppm) 
each of the compounds N-((dimethylamino)methylene) O-ethyl 
O-(2-(1-methylethyl)-5-pyrimidinyl) phosphoramidothioate, 
N-((dimethylamino)methylene) O-ethyl O-(2-cyclopropyl-5-pyrimidinyl) 
phosphoramidothioate and N-((dimethylamino)methylene) O-ethyl 
O-(2-(1,1-dimethylethyl)-5-pyrimidinyl) phosphoramidothioate gave 100 
percent kill and control of the two-spotted spider mites. 
EXAMPLE VI 
Aqueous dispersions were prepared by admixing one of the hereinafter set 
forth compounds with a predetermined quantity of water and a predetermined 
amount of a surfactant to give aqueous dispersions containing varying 
predetermined amounts of one of the compounds as the sole toxicant. 
Separate rice plants were dipped into each of the dispersions and permitted 
to dry. 
A plastic cylinder was placed around each of the plants and 10 adult aster 
leafhoppers were placed into the cylinder and the cylinder capped. In a 
like manner, 10 adult aster leafhoppers were placed on control plants 
which had been dipped in a solution containing only water and surfactant. 
The plants were maintained under conditions conducive to the growth of the 
plants and leafhoppers. After a period of three days, the cylinder and 
plants were examined to determine the concentration in parts of the active 
compound per million parts of the ultimate dispersion necessary to give 
100 percent kill and control of the aster leafhopper. It was found that at 
a dosage rate of 25 parts of the active compound per million parts of the 
ultimate dispersion (ppm) each of the compounds 
N-((dimethylamino)methylene) O-ethyl O-(2-(1-methylethyl)-5-pyrimidinyl) 
phosphoramidothioate, N-((dimethylamino)methylene) O-ethyl 
O-(2-cyclopropyl-5-pyrimidinyl) phosphoramidothioate 
N-((dimethylamino)methylene) O-ethyl 
O-(2-cyclopropyl-4-methyl-5-pyrimidinyl) phosphoroamidothioate and 
N-((dimethylamino)methylene) O-ethyl 
O-(2-(1,1-dimethylethyl)-5-pyrimidinyl) phosphoramidothioate gave 100 
percent kill and control of aster leafhoppers. 
EXAMPLE VII 
Aqueous dispersions were prepared by admixing one of the hereinafter set 
forth compounds with a predetermined quantity of water and a predetermined 
amount of a surfactant to give aqueous dispersions containing varying 
predetermined amounts of one of the compounds as the sole toxicant. 
Separate rice plants were treated by adding a predetermined amount of one 
of the test dispersions to the root of the plant to determine systemic 
activity. 
A plastic cylinder was placed around each of the plants and 10 adult aster 
leafhoppers were placed into the cylinder and the cylinder capped. In a 
like manner, 10 adult aster leafhoppers were placed on control plants 
which were treated at the root zone with a solution containing only water 
and surfactant. The plants were maintained under conditions conducive to 
the growth of the plants and leafhoppers. After a period of three days, 
the cylinder and plants were examined to determine the concentration in 
parts of the active compound per million parts of the ultimate dispersion 
necessary to give 100 percent kill and control of the aster leafhopper. It 
was found that at a dosage rate of 6.25 parts of the active compound per 
million parts of the ultimate dispersion (ppm) each of the compounds 
N-((dimethylamino)methylene) O-ethyl O-(2-(1-methylethyl)-5-pyrimidinyl) 
phosphoramidothioate, N-((dimethylamino)methylene) O-ethyl 
O-(2-cyclopropyl-5-pyrimidinyl) phosphoramidothioate, 
N-((dimethylamino)methylene) O-ethyl 
O-(2-cyclopropyl-4-methyl-5-pyrimidinyl) phosphoramidothioate and 
N-((dimethylamino)methylene) O-ethyl 
O-(2-(1,1-dimethylethyl)-5-pyrimidinyl) phosphoramidothioate gave 100 
percent kill and control of the aster leafhopper. 
EXAMPLE VIII 
In this operation, aqueous dispersions were prepared by admixing one of the 
hereinafter set forth compounds, dissolved in a suitable inert solvent, 
with a predetermined quantity of water and a predetermined amount of a 
surfactant to give aqueous dispersions of varying predetermined amounts of 
one of the compounds as the sole active toxicant. Separate 3 inch discs 
cut from cotton plant leaves were thoroughly wetted by briefly dipping 
into one of the dispersions and the wetted leaves were placed in an open 
petri dish and permitted to dry. After the leaves were dry, 5 live 2nd 
instar tobacco budworm larvae were placed in each petri dish. In identical 
operations, 5 like live tobacco budworm larvae were placed in control 
petri dishes, the leaf therein having been wetted with a solution 
containing only water and surfactant. The dishes were maintained at about 
80.degree. F. under moist conditions conducive for the growth of the 
tobacco budworm larvae for a period of about 2 days. At the end of the 
2-day period, the dishes were examined to determine the minimum 
concentration in parts of the active compound per million parts of the 
ultimate dispersion necessary to give at least a 100 percent kill and 
control of the tobacco budworm larvae. It was found that at a dosage rate 
of 600 parts of the active compound per million parts of the ultimate 
dispersion (ppm) each of the compounds N-((dimethylamino)methylene) 
O-ethyl O-(2-(1-methylethyl)-5-pyrimidinyl) phosphoramidothioate, 
N-((dimethylamino)methylene) O-ethyl O-(2-cyclopropyl-5-pyrimidinyl) 
phosphoramidothioate and N-((dimethylamino)methylene) O-ethyl 
O-(2-(1,1-dimethylethyl)-5-pyrimidinyl) phosphoramidothioate gave 100 
percent kill and control of tobacco budworm larvae. 
EXAMPLE IX 
Seventy-five grams of air-dried soil were placed in an 8-ounce container. 
To the soil was added sufficient volume of a 400 ppm dispersion, prepared 
by admixing a predetermined amount of N-((dimethylamino)methylene O-ethyl 
O-(2-cyclopropyl-5-pyrimidinyl) phosphoramidothioate, dissolved in a 
suitable inert solvent, with a predetermined amount of water and a 
predetermined amount of surfactant, to give various predetermined 
concentrations of the toxicant in the soil on a soil-chemical basis. The 
treated soil was air-dried and thoroughly mixed. To each treated 
container, and control containers treated with water and surfactant alone, 
was added 0.5 milliliters of an aqueous suspension of the eggs of the 
Western spotted cucumber beetle (WSCB) (70-80 eggs of 3-4 days old). 
Additional treated soil was used to cover the eggs and a corn seed was 
placed in the soil and covered with additional treated soil. The 
containers were thereafter maintained under conditions conducive to the 
growth of the seeds and the hatching of the eggs. Ten to twelve (10-12) 
days after treatment, the containers and the plants therein were examined 
and it was found that the above-indicated compound gave a 100 percent kill 
and control of the larvae from the hatched eggs at a dosage of 25 ppm in 
the soil. 
EXAMPLE X 
In this operation, aqueous dispersions were prepared by admixing one of the 
hereinafter set forth compounds, dissolved in a suitable inert solvent, 
with a predetermined quantity of water and a predetermined amount of a 
surfactant to give aqueous dispersions containing varying predetermined 
amounts of one of the compounds as the sole active toxicant. Separate 
cotton plant leaves were thoroughly wetted by briefly dipping into one of 
the dispersions and the wetted leaves placed in an open petri dish and 
permitted to dry. After the leaves were dry, 5 live beet armyworm larvae, 
approximately late 2nd instar were placed in each petri dish. In identical 
operations, 5 live late 2nd instar beet armyworm larvae were placed in 
control petri dishes, the leaf therein having been wetted with a solution 
containing only water and surfactant. The dishes were maintained under 
moist conditions conducive for the growth of the beet armyworm larvae for 
a period of about 5 days. At the end of the 5-day period, the dishes were 
examined to determine the concentration in parts of the active compound 
per million parts of the ultimate dispersion necessary to give at least a 
100 percent kill and control of the beet armyworm larvae. It was found 
that at a dosage rate of 600 parts of the active compound per million 
parts of the ultimate dispersion (ppm) each of the compounds 
N-((dimethylamino)methylene) O-ethyl O-(2-(1-methylethyl)-5-pyrimidinyl) 
phosphoramidothioate, N-((dimethylamino)methylene) O-ethyl 
O-(2-cyclopropyl-5-pyrimidinyl) phosphoramidothioate and 
N-((dimethylamino)methylene) O-ethyl 
O-(2-(1,1-dimethylethyl)-5-pyrimidinyl) phosphoramidothioate gave 100 
percent kill and control of beet armyworm larvae. 
EXAMPLE XI 
Aqueous dispersions were prepared by admixing one of the hereinafter set 
forth compounds, dissolved in a suitable inert solvent, with a 
predetermined quantity of water and a predetermined amount of surfactant 
to give aqueous dispersions containing varying predetermined amounts of 
one of the compounds as the sole toxicant. 
Small plastic pots were filled to 1/4 inch of the top with root-knot 
nematode infested soil. A predetermined amount of the test dispersion was 
poured onto the surface of the soil in each pot. In a like manner, a 
solution of only inert solvent, surfactant and water was poured onto the 
surface of the soil in each pot serving as a check. The pots were seeded 
to a host plant and mulch was added to fill the containers to the top. 
After 3 to 5 weeks of growth in the greenhouse, percent control was 
determined by comparing the infestation of the treated plants with the 
untreated checks. It was found that a dosage rate of 0.62 parts per 
million (ppm) of the active compound in the soil each of the compounds 
N-((dimethylamino)methylene O-ethyl O-(2-(1-methylethyl)-5-pyrimidinyl) 
phosphoramidothioate and N-((dimethylamino)methylene) O-ethyl 
O-(2-(1,1-dimethylethyl)-5-pyrimidinyl) phosphoramidothioate gave 100 
percent control of root-knot nematodes. 
The pyrimidinols employed as intermediates in the preparation of the 
present compounds are for the most part known compounds and all can be 
prepared according to methods described in the literature. 
The 2-alkyl-4-methyl-5-pyrimidinols can be prepared by reacting methyl 
methoxyacetate with sodium hydride in toluene and the product is then 
reacted with the requisite amidine to give 
2-alkyl-5-methoxy-6-methoxymethyl-4-pyrimidinol. This latter compound is 
chlorinated in the 4-position by reaction with phosphorus oxychlorides. 
The ring chlorine and the methoxy group in the methylmethoxy group are 
replaced with hydrogen on reduction with zinc in 1 normal NaOH and 
reaction with sodium ethyl mercaptide in dimethylformamide then yields the 
desired pyrimidinol. 
In a preferred method of preparation of 2-alkyl-5-pyrimidinols or 
2-alkylthio-5-pyrimidinols, phosgene is bubbled into dimethylformamide in 
methylene chloride medium forming a Vilsmeier reagent which is then 
allowed to react with methoxyacetaldehyde. The appropriate amidine is then 
added to the reaction mixture followed by sodium methoxide in methanol. 
The methylene chloride is distilled or flashed off and the mixture heated 
under reflux to form the desired 2-alkyl-5-methoxypyrimidine. The methoxy 
group is converted to the OH group using sodium ethyl mercaptide in 
dimethylformamide. 
In another preferred method of preparation of 5-pyrimidinols, 
N-(3-(dimethylamino)-2-(phenylmethoxy)-2-propenylidene)-N-methylmethanamin 
ium perchlorate (A. Holy and Z. Arnold, Collect. Czech. Chem. Commun. 38, 
1371-80 (1973)) is condensed with the requisite amidine, guanidine, 
isothiourea or isourea to give the corresponding 
2-substituted-5-(phenylmethoxy)pyrimidine. The phenylmethoxy group is 
converted to the OH group either by catalytic hydrogenation, or by 
hydrolysis with hydrochloric acid. 
The alkylsulfinyl-, phenylsulfinyl-, alkylsulfonyl- and 
phenylsulfonyl-5-pyrimidinols are prepared by the oxidation of the 
appropriate alkylthio- or phenylthio-5-pyrimidinol with hydrogen peroxide.