Substituted 2-(carbamoyl)oxyimino-3-iminobutyramides and 2-(carbamoyl)oxyimino-3-iminobutyrates of the formula ##STR1## where Q is --OR.sub.4 or --NR.sub.5 R.sub.6, and A, R, R.sub.2, R.sub.3, R.sub.4, R.sub.5, and R.sub.6 are as hereinafter defined are useful as aphicides. The compounds are made by reacting an amine with a substituted 2-hydroxyiminoacetoacetamide (or 2-hydroxyiminopropionylacetamide) or an alkyl 2-hydroxyiminoacetoacetate (or 2-hydroxyiminopropionylacetate), then carbamylating the resulting substituted 2-hydroxyimino-3-iminobutyramide (or 2-hydroxyimino-3-iminovaleramide) or 2-hydroxyimino-3-iminobutyrate (or 2-hydroxyimino-3-iminovalerate).

BACKGROUND OF THE INVENTION 
Buchanan, U.S. Pat. No. 3,530,220, issued Sept. 22, 1970, discloses a class 
of alkyl 1-carbamoyl-N-(substituted carbamoyloxy)thioformimidates such as 
methyl 1-(dimethylcarbamoyl)-N-(methylcarbamoyloxy)thioformimidate 
(oxamyl) which can be represented by the formula 
##STR2## 
The compounds are useful as nematocides, acaricides and insecticides. 
Fuchs and Loux, U.S. Pat. No. 3,694,431, issued Sept. 26, 1972, discloses a 
method of making the compounds of U.S. Pat. No. 3,530,220 which involves 
nitrosating an acetoacetamide to produce a 2-hydroxyiminoacetoacetamide, 
e.g. 
##STR3## 
then chlorinating, reacting with a mercaptan, and carbamylating. The 
2-hydroxyiminoacetoacetamides are also starting materials for making the 
substituted 2-hydroxyimino-3-iminobutyramides of the present invention. 
Buchanan U.S. Pat. No. 3,557,190, issued Jan. 19, 1971, discloses a method 
of making the compounds of U.S. Pat. No. 3,530,220 which involves reacting 
a 2-hydroxyimino ester with two moles of an amine in the presence of water 
or an alcohol to give the corresponding amide. The amide is then reacted 
further to give the desired compounds, e.g., 
##STR4## 
This amination procedure also is useful for the conversion of the 
3-imino-2-hydroxyiminoacetoacetates and propionylacetates of this 
invention to the corresponding 2-hydroxyimino-3-iminobutyramides and 
2-hydroxyimino-3-iminovaleramides. 
Beilstein, Organische Chemie, Vol. III, Fourth Edition, page 745, discloses 
.alpha.,.beta.-dioximino-butyric acid ethyl ester (A), 
.alpha.,.beta.-dioximino-butyric acid amide (B), ethyl 
.alpha.-oximino-acetoacetate phenylhydrazone (C), ethyl 
.alpha.-acetoximino-acetoacetate (D), and ethyl 
.alpha.-acetoximino-acetoacetate phenylhydrazone (E), compounds which can 
be represented by the formulae: 
##STR5## 
No utility is disclosed for compounds (A)-(E) in the Beilstein reference. 
SUMMARY OF THE INVENTION 
This invention is a class of novel aphicidal substituted 
2-(carbamoyl)oxyimino-3-iminobutyramides and alkyl 
2-(carbamoyl)oxyimino-3-iminobutyrates of the formula: 
##STR6## 
wherein: 
A is hydrogen or methyl; 
R is C.sub.1 -C.sub.18 alkyl; C.sub.3 -C.sub.4 alkenyl; C.sub.5 -C.sub.7 
cycloalkyl optionally substituted with methoxy or with 1 or 2 methyl 
groups; C.sub.6 -C.sub.8 cycloalkylalkyl; C.sub.1 -C.sub.3 alkoxy; 
alkoxyalkyl with a total of 3-6 carbon atoms; benzyl; phenethyl; 
(CH.sub.3).sub.2 N--; (CH.sub.3)C.sub.2 H.sub.5 N--; (C.sub.2 
H.sub.5).sub.2 N--; 1-(4-methylpiperazinyl); N-morpholino; 
##STR7## 
wherein: R.sub.1 is hydrogen, methyl, methoxy, (CH.sub.3).sub.2 N--, 
CH.sub.3 S--, or fluorine; 
R.sub.2 is hydrogen, methyl, or ethyl; 
R.sub.3 is methyl, ethyl, or allyl; 
Q is --OR.sub.4 or --NR.sub.5 R.sub.6 wherein: 
R.sub.4 is C.sub.1 -C.sub.2 alkyl; 
R.sub.5 is methoxy, C.sub.1 -C.sub.4 alkyl or allyl; 
R.sub.6 is hydrogen, methyl, or ethyl; and 
R.sub.5 and R.sub.6 can be taken together to form a ring and are 
##STR8## 
or --(CH.sub.2).sub.n -- where n is 4-6, with the provisos that 
(i) the total carbon content of Q, R.sub.2, and R.sub.3 is not greater than 
8C; 
(ii) when R is 
##STR9## 
R.sub.2 is hydrogen and R.sub.3 is CH.sub.3 ; and 
(iii) when R is 
##STR10## 
R.sub.2 and R.sub.3 are both methyl. 
This invention includes a method of protecting plants from aphids by 
application of a compound of Formula I and formulations for agricultural 
use consisting essentially of an inert diluent and/or a surfactant and 
means for controlling aphids selected from compounds of Formula I. 
The invention also includes a novel process, described hereinbelow, for 
producing the compounds of Formula I. 
For each of the compounds of Formula I, there are theoretically four 
geometric isomers.

DESCRIPTION OF THE INVENTION 
Preferred for economic reasons are those compounds of Formula I wherein: 
A is hydrogen; 
R is C.sub.5 -C.sub.7 cycloalkyl, methylcyclohexyl, allyl, methoxy, 
(CH.sub.3).sub.2 N--, N-morpholino, 
##STR11## 
R.sub.2 is hydrogen, methyl, or ethyl; 
R.sub.3 is methyl; and 
Q is --NR.sub.5 R.sub.6 where 
R.sub.5 is methyl or ethyl and 
R.sub.6 is hydrogen, methyl, or ethyl. 
More preferred because of higher aphicidal activity are those compounds of 
Formula I wherein 
A is hydrogen; 
R is methoxy or (CH.sub.3).sub.2 N--; 
R.sub.2 is hydrogen, methyl, or ethyl; 
R.sub.3 is methyl; and 
Q is --NR.sub.5 R.sub.6 wherein 
R.sub.5 is methyl or ethyl and 
R.sub.6 is hydrogen, methyl, or ethyl. 
Most preferred for highest aphicidal activity are the following compounds 
of Formula I: 
N,N-dimethyl-2,3-bis[(dimethylcarbamyl)oxyimino]butyramide 
N,N-dimethyl-2-[(methylcarbamyl)oxyimino]-3-(2-methylcyclohexylimino)butyra 
mide 
N,N-dimethyl-2-[(dimethylcarbamyl)oxyimino]-3-dimethylhydrazonobutyramide 
N,N-dimethyl-2-[(methylcarbamyl)oxyimino]-3-(N-morpholine)iminobutyramide 
N,N-dimethyl-2-[(dimethylcarbamyl)oxyimino]-3-(N-morpholine)iminobutyramide 
N,N-dimethyl-3-methoxyimino-2-[(methylcarbamyl)oxyimino]butyramide 
N,N-dimethyl-2-](dimethylcarbamoyl)oxyimino]-3-methoxyiminobutyramide 
Compound Synthesis 
The compounds of Formula I can be prepared by the following steps: 
[R.sub.7 is --OH, C.sub.1 -C.sub.18 alkyl, C.sub.3 -C.sub.4 alkenyl, 
C.sub.5 -C.sub.7 cycloalkyl optionally substituted with methoxy or with 1 
or 2 methyl groups; C.sub.6 -C.sub.8 cycloalkylalkyl; C.sub.1 -C.sub.3 
alkoxy; alkoxyalkyl with a total of 3-6 carbon atoms; benzyl; phenethyl; 
(CH.sub.3).sub.2 N--; (CH.sub.3)C.sub.2 H.sub.5 N--; (C.sub.2 
H.sub.5).sub.2 N--; 1-(4-methylpiperazinyl); N-morpholino; or 
##STR12## 
or 
##STR13## 
wherein R.sub.1 is hydrogen, methyl, methoxy, (CH.sub.3).sub.2 N--, 
CH.sub.3 S--, or fluorine] 
1.a. Reacting an amine of the formula R.sub.7 NH.sub.2 with a 
2-hydroxyiminoacetoacetamide or 2-hydroxyiminoacetoacetate of the formula: 
##STR14## 
wherein A and Q are as defined for Formula I with the added proviso 
(i) if Q is --NR.sub.5 R.sub.6, A is hydrogen to produce a substituted 
2-hydroxyimino-3-iminobutyramide or 2-hydroxyimino-3-iminobutyrate of the 
formula: 
##STR15## 
1.b. An alternative route for the synthesis of 
2-hydroxyimino-3-iminobutyramides of Formula II (where A is hydrogen and Q 
is --NR.sub.5 R.sub.6) and a preferred route for the synthesis of 
2-hydroxyimino-3-iminovaleramides of Formula II (where A is methyl and Q 
is --NR.sub.5 R.sub.6) is carried out by aminating the esters obtained in 
Step 1.a., following the Buchanan amination procedure, U.S. Pat. No. 
3,557,190, referred to previously. 
2. Carbamylating the compound of Formula II by reacting it with one mole of 
a carbamylating agent selected from 
a. an isocyanate of the formula R.sub.3 NCO and 
b. a base and a dialkylcarbamoyl chloride of the formula 
##STR16## 
wherein R.sub.2 in 
##STR17## 
is methyl or ethyl, provided that when R.sub.7 is --OH, R.sub.3 in R.sub.3 
NCO is methyl, R.sub.2 and R.sub.3 in 
##STR18## 
are both methyl, and two moles of the carbamylating agent are reacted. 
The processes can be represented schematically as follows: 
##STR19## 
The starting 2-hydroxyiminoacetoacetamides of Formula III (A=hydrogen and 
Q=--NR.sub.5 R.sub.6) can be prepared by the process described in Fuchs 
and Loux, U.S. Pat. No. 3,694,431, issued Sept. 26, 1972. The process 
involves reacting diketene with an amine (NHR.sub.5 R.sub.6) to produce a 
substituted acetoacetamide, then nitrosating the acetoacetamide by 
reaction with a source of nitrous acid, e.g., sodium nitrite and HCl. 
The starting alkyl 2-hydroxyiminoacetoacetates or alkyl 
2-hydroxyiminopropionylacetates of Formula III (Q=--OR.sub.4) can be made 
as described by Rodinov et al. [J. Gen. Chem., USSR 18, 917 (1948)]. An 
aqueous solution of sodium nitrite is slowly added to an acetic acid 
solution of the acetoacetate or propionylacetate at low temperature. 
Modifications of this synthesis are described in German Patent No. 
1,137,434 and Belgian Patent No. 610,194. 
In Step 1.a., the amine can be used directly as a free base or it may be 
used as a salt in which the free base is released for reaction by using an 
alkali metal carbonate or a tertiary amine such as pyridine for this 
purpose. Typical amines used for this step are methylamine, ethylamine, 
sec-butylamine, octylamine, methoxyamine hydrochloride, ethoxyamine 
hydrochloride, hydroxylamine hydrochloride (a special case where the 
product, a 2,3-dioxime derivative is used to make products where R is 
##STR20## 
p-anisidine, aniline, N-aminomorpholine, and 1,1-dimethylhydrazine. When 
the amine is an aniline or a high-boiling amine, provision is often made 
for removal of by-product water. Details of these variations will be shown 
with specific examples which follow. The Step 1 reaction can be carried 
out under the following general conditions: time, 1 to 72 hours, 
preferably 2 to 18 hours; temperature, 5.degree. to 140.degree. C., 
preferably 20.degree. to 85.degree. C.; pressure, 1/2 to 10 atmospheres, 
preferably 1 atmosphere; medium, inert organic solvent such as ethanol, 
methanol, benzene, toluene, or water, in some cases, where the 
intermediate is water soluble. 
For Step 1.b., both the starting 2-hydroxyiminoacetamides and 
2-hydroxyiminopropionylvaleramides of Formula II (A=hydrogen and methyl, 
respectively, and Q=--NR.sub.5 R.sub.6) can be made by aminating the 
corresponding acetoacetates and propionylacetates obtained in Step 1. of 
Formula III (Q=--OR.sub.4) essentially as described in Buchanan U.S. Pat. 
No. 3,557,190, issued Jan. 19, 1971. The process involves reacting a 
substituted 2-hydroxyiminoacetate ester with an amine in the presence of 
water and/or lower alcohol (C.sub.1 -C.sub.3). Two moles of a primary or 
secondary amine are necessary because one mole forms a salt with the 
hydroxyimino function while another mole participates directly in the 
reaction. A tertiary amine such as triethylamine can be substituted for 
these amines with about the same results. In a few instances, no solvent 
other than excess amine is used. A catalytic amount of sodium methylate 
can be used to accelerate this reaction. 
The products can be isolated in a conventional manner by filtration or 
evaporation of the solvent. It is desirable to isolate these products or 
at least to remove any excess amine prior to performing the carbamylation 
step (Step 2). 
In Step 2.a., the reaction is often catalyzed with a tertiary amine such as 
triethylamine, pyridine, or triethylenediamine and/or a tin catalyst such 
as dibutyl-tin dilaurate. The ratio of reactants is generally 
stoichiometric, although a slight excess of the isocyanate is sometimes 
desirable. The following general conditions can be used: time, one-half to 
72 hours, preferably 1 to 4 hours; temperature, 5.degree. to 140.degree. 
C., preferably 20.degree. to 110.degree. C.; pressure, one-half to 10 
atmospheres, preferably 1 atmosphere; reaction medium, inert organic 
solvent such as acetone, acetonitrile, methyl ethyl ketone, 
dimethylformamide, or methylene chloride. After the reaction, removal of 
the solvent gives a residual product which often is of satisfactory 
quality for its application. If the product is a solid, it can be purified 
by recrystallization from a suitable solvent. Several of the residues are 
oils which are very slow to crystallize, particularly in the ester series, 
so that other conventional purification procedures must be used. 
In the Step 2.b. and 3.b. reactions, a sodium salt is first formed by 
portionwise addition of sodium methoxide or of a mineral oil dispersion of 
sodium hydride to a solution of the intermediate in an inert organic 
solvent such as tetrahydrofuran, dioxane, benzene, or toluene. The 
temperature is maintained in the range of about 5.degree. to 60.degree. 
C., preferably 15.degree. to 35.degree. C., until, in the case of the 
hydride, evolution of hydrogen ceases. Other salts, such as the 
trimethylamine and triethylamine salts, also work satisfactorily. Reaction 
of the carbamoyl chloride with the salt can be carried out under the 
following general conditions: time, one-half to 72 hrs., preferably 1-4 
hrs., temperature, 5.degree.-140.degree. C., preferably 
20.degree.-65.degree. C.; pressure, 1/2-10 atmospheres, preferably 1 
atmosphere. After separation from the reaction medium, the product is 
obtained usually in sufficiently pure condition to be used as an aphicide; 
however, the usual purification procedures can be used if desired. 
The procedures for synthesis of the compounds of this invention are further 
illustrated in the following examples wherein parts and percentages are by 
weight unless otherwise noted. 
EXAMPLE 1 
To a stirred mixture of 336 parts of 
N,N-dimethyl-2-hydroxyiminoacetoacetamide (a compound of Formula III), 
1500 parts ethanol and 203 parts of methoxyamine hydrochloride were added 
dropwise 210 parts of pyridine over one-half hour while maintaining the 
reaction mixture at 10.degree. C. by external cooling. The mixture was 
allowed to warm slowly to 25.degree. C. and maintained at this temperature 
for 18 hours. Finally, it was stirred and refluxed for one-half hour. The 
solvent was removed under reduced pressure (15 mm.) at 40.degree. C. bath 
temperature. Approximately 2000 parts of ice water were added, which 
caused the residue to solidify. The solid was filtered, washed twice with 
ice water, filtered, and dried. There was obtained 340 parts of 
N,N-dimethyl-2-hydroxyimino-3-methoxyiminobutyramide (a compound of 
Formula II), m.p. 144-147, which is of satisfactory quality for use as an 
intermediate. The product was, however, recrystallized from ethyl acetate, 
whereupon it melted at 146.degree.-148.degree.. 
This procedure can be repeated by substituting comparable molar amounts of 
the indicated compound of Formula III in Table I below and the amine 
(either used as free amine or released through use of pyridine or sodium 
carbonate) to produce the indicated compound of Formula II. A 
slight-to-moderate excess of amine is desirable for best yields (one to 
two moles amine per mole of compound of Formula III). External heating is 
not always required, especially when the reaction is exothermic. 
TABLE I 
__________________________________________________________________________ 
##STR21## 
##STR22## 
##STR23## 
Compound of Compound of Compound 
Melting 
Formula III Formula II Formula I Point 
A Q Amine R.sub.7, R of Form. I 
Isocyanate 
R.sub.2 
R.sub.3 (.degree. 
__________________________________________________________________________ 
C.) 
H N(CH.sub.3).sub.2 
CH.sub.3 ONH.sub.2HCl 
CH.sub.3 O C.sub.2 H.sub.5 NCO 
H C.sub.2 H.sub.5 
87-89 
H N(CH.sub.3).sub.2 
CH.sub.3 ONH.sub.2HCl 
CH.sub.3 O CH.sub.2CHCH.sub.2 NCO 
H CH.sub.2CHCH.sub.2 
66-68 
CH.sub.3 
N(CH.sub.3).sub.2 
CH.sub.3 ONH.sub.2HCl 
CH.sub.3 O CH.sub.3 NCO 
H CH.sub.3 
H N(CH.sub.3).sub.2 
C.sub.2 H.sub.5 ONH.sub.2HCl 
C.sub.2 H.sub.5 O 
CH.sub.3 NCO 
H CH.sub.3 139.5- 
140.5 
H N(CH.sub.3).sub.2 
C.sub.2 H.sub.5 ONH.sub.2HCl 
C.sub.2 H.sub.5 O 
C.sub.2 H.sub.5 NCO 
H C.sub.2 H.sub.5 
H N(CH.sub.3).sub.2 
C.sub.2 H.sub.5 ONH.sub.2HCl 
C.sub.3 H.sub.7 O 
CH.sub.3 NCO 
H CH.sub.3 
CH.sub.3 
NHCH.sub.3 CH.sub.3 ONH.sub.2HCl 
CH.sub.3 O CH.sub.3 NCO 
H CH.sub.3 169-173 
H NHCH.sub.3 CH.sub.3 ONH.sub.2HCl 
CH.sub.3 O CH.sub.3 NCO 
H CH.sub.3 169-173 
H NHCH.sub.3 CH.sub.3 ONH.sub.2HCl 
CH.sub.3 O C.sub.2 H.sub.5 NCO 
H C.sub.2 H.sub.5 
H OC.sub.2 H.sub.5 
CH.sub.3 ONH.sub.2HCl 
CH.sub.3 O CH.sub.3 NCO 
H CH.sub.3 
H OC.sub.2 H.sub.5 
C.sub.2 H.sub.5 ONH.sub.2HCl 
C.sub.2 H.sub.5 O 
CH.sub.2CHCH.sub.2 NCO 
H CH.sub. 2CHCH.sub.2 
H OCH.sub.3 CH.sub.3 ONH.sub.2HCl 
CH.sub.3 O C.sub.2 H.sub.5 NCO 
H C.sub.2 H.sub.5 
H OCH.sub.3 CH.sub.3 ONH.sub.2HCl 
CH.sub.3 O CH.sub.3 NCO 
H CH.sub.3 
H NHC.sub.2 H.sub.5 
CH.sub.3 ONH.sub.2HCl 
CH.sub.3 O CH.sub.3 NCO 
H CH.sub.3 
CH.sub.3 
NHC.sub.2 H.sub.5 
CH.sub.3 ONH.sub.2HCl 
CH.sub.3 O C.sub.2 H.sub.5 NCO 
H C.sub.2 H.sub.5 
H NHC.sub.3 H.sub.7 
C.sub.2 H.sub.5 ONH.sub.2HCl 
C.sub.2 H.sub.5 O 
CH.sub.3 NCO 
H CH.sub.3 
H NHC.sub.4 H.sub.9 
CH.sub.3 ONH.sub.2HCl 
CH.sub.3 O CH.sub.3 NCO 
H CH.sub.3 125-128 
H NHC.sub.4 H.sub.9 
CH.sub.3 ONH.sub.2HCl 
CH.sub.3 O C.sub.2 H.sub.5 NCO 
H C.sub.2 H.sub.5 
138-140 
H NHCH(CH.sub.3).sub.2 
CH.sub.3 ONH.sub.2HCl 
CH.sub.3 O CH.sub.3 NCO 
H CH.sub.3 
H N(C.sub.2 H.sub.5).sub. 2 
CH.sub.3 ONH.sub.2HCl 
CH.sub.3 O CH.sub.3 NCO 
H CH.sub.3 118-120 
##STR24## CH.sub.3 ONH.sub.2HCl 
CH.sub.3 O CH.sub.3 NCO 
H CH.sub.3 
CH.sub.3 
OC.sub.2 H.sub.5 
CH.sub.3 NH.sub.2 
CH.sub.3 CH.sub.3 NCO 
H CH.sub.3 
H 
##STR25## CH.sub.3 ONH.sub.2HCl 
CH.sub.3 O CH.sub.3 NCO 
H CH.sub.3 137-140 
H 
##STR26## CH.sub.3 ONH.sub.2HCl 
CH.sub.3 O CH.sub.3 NCO 
H CH.sub.3 
H 
##STR27## CH.sub.3 ONH.sub.2HCl 
CH.sub.3 O CH.sub.3 NCO 
H CH.sub.3 99-103 
H 
##STR28## CH.sub.3 ONH.sub.2HCl 
CH.sub.3 O C.sub.2 H.sub.5 NCO 
H C.sub.2 H.sub.5 
97.5-101 
H 
##STR29## CH.sub.3 NH.sub.2 
CH.sub.3 CH.sub.3 NCO 
H CH.sub.3 
H 
##STR30## (CH.sub.3).sub.2 CHONH.sub.3HCl 
(CH.sub.3).sub.2 CHO 
CH.sub.3 NCO 
H CH.sub.3 
H 
##STR31## C.sub.4 H.sub.9 NH.sub.2 
C.sub.4 H.sub.9 
C.sub.2 H.sub.5 NCO 
H C.sub.2 H.sub.5 
H N(CH.sub.3).sub.2 
(CH.sub.3).sub.2 NNH.sub.2 
(CH.sub.3).sub.2 N 
CH.sub.3 NCO 
H CH.sub.3 146-148 
H N(CH.sub.3).sub.2 
##STR32## 
##STR33## CH.sub.3 NCO 
H CH.sub.3 141-142.5 
H N(CH.sub.3).sub.2 
##STR34## 
##STR35## C.sub.2 H.sub.5 NCO 
H C.sub.2 H.sub.5 
128-130 
CH.sub.3 
N(CH.sub.3).sub.2 
(CH.sub.3).sub.2 NNH.sub.2 
(CH.sub.3).sub.2 N 
CH.sub.3 NCO 
H CH.sub.3 
H N(CH.sub.3).sub.2 
##STR36## 
##STR37## CH.sub.3 NCO 
H CH.sub.3 128-129 (dec) 
H N(CH.sub.3).sub.2 
CH.sub.2CHCH.sub.2 NH.sub.2 
CH.sub.2CHCH.sub.2 
CH.sub.3 NCO 
H CH.sub.3 
H N(CH.sub.2).sub.2 
##STR38## 
##STR39## CH.sub.3 NCO 
H CH.sub.3 
H N(CH.sub.3).sub.2 
##STR40## 
##STR41## CH.sub.3 NCO 
H CH.sub.3 
H N(CH.sub.3).sub.2 
##STR42## 
##STR43## CH.sub.3 NCO 
H CH.sub.3 
H N(CH.sub.3).sub. 2 
CH.sub.3 NH.sub.2 
CH.sub.3 CH.sub.3 NCO 
H CH.sub.3 135-137 
H N(CH.sub.3).sub.2 
CH.sub.3 NH.sub.2 
CH.sub.3 C.sub.2 H.sub.5 NCO 
H C.sub.2 H.sub.5 
H N(CH.sub.3).sub.2 
C.sub.2 H.sub.5 NH.sub.2 
C.sub.2 H.sub.5 
CH.sub.3 NCO 
H CH.sub.3 135-138 
H N(CH.sub.3).sub.2 
C.sub.3 H.sub.7 NH.sub.2 
C.sub.3 H.sub.7 
CH.sub.3 NCO 
H CH.sub.3 130-132 
H N(CH.sub.3).sub.2 
(CH.sub.3).sub.2 CHNH.sub.2 
(CH.sub.3).sub.2 CH 
CH.sub.3 NCO 
H CH.sub.3 158-159 
H N(CH.sub.3).sub.2 
##STR44## 
##STR45## CH.sub.3 NCO 
H CH.sub.3 139-141 
H N(CH.sub.3).sub.2 
C.sub.6 H.sub.13 NH.sub.2 
C.sub.6 H.sub.13 
CH.sub.3 NCO 
H CH.sub.3 91-93 
H N(CH.sub.3).sub.2 
C.sub.8 H.sub.17 NH.sub.2 
C.sub.8 H.sub.17 
CH.sub.3 NCO 
H CH.sub.3 91-93 
CH.sub.3 
N(CH.sub.3).sub.2 
C.sub. 8 H.sub.17 NH.sub.2 
CH.sub.3 CH.sub.3 NCO 
H CH.sub.3 
H N(CH.sub.3).sub.2 
C.sub.18 H.sub.37 NH.sub.2 
C.sub.18 H.sub.37 
CH.sub.3 NCO 
H CH.sub.3 
H N(CH.sub.3).sub.2 
C.sub.4 H.sub.9 OCH.sub.2 CH.sub.2 NH.sub.2 
C.sub.4 H.sub.9 OCH.sub.2 CH.sub.2 
CH.sub.3 NCO 
H CH.sub.3 
H N(CH.sub.3).sub.2 
CH.sub.3 OCH.sub.2 CH.sub.2 CH.sub.2 NH.sub.2 
CH.sub.3 OCH.sub.2 CH.sub.2 CH.sub.2 
CH.sub.3 NCO 
H CH.sub.3 Vis. liq 
IR: 
3.0(NH); 
5.78 (CO) 
H NHCH.sub.3 
##STR46## 
##STR47## CH.sub.3 NCO 
H CH.sub.3 
H NHC.sub.2 H.sub.5 
##STR48## 
##STR49## CH.sub.3 NCO 
H CH.sub.3 
CH.sub.3 
OC.sub.2 H.sub.5 
CH.sub.3 ONH.sub.2HCl 
CH.sub.3 O CH.sub.3 NCO 
H CH.sub.3 159-164 
__________________________________________________________________________ 
table i.a. 
__________________________________________________________________________ 
compound of Compound of Compound of Melting 
Formula III Formula II Formula I Point 
A Q Amine R.sub.7 
Isocyanate R.sub.2 
R R.sub.3 
(.degree. 
__________________________________________________________________________ 
C.) 
H N(CH.sub.3).sub.2 
NH.sub.2 OHHCl 
HO CH.sub.3 NCO (2 molar equivalents) 
H 
##STR50## 
CH.sub.3 
169,5- 170.5 
H OCH.sub.3 NH.sub.2 OHHCl 
HO CH.sub.3 NCO (2 molar equivalents) 
H 
##STR51## 
CH.sub.3 
H OC.sub.2 H.sub.5 
NH.sub.2 OHHCl 
HO CH.sub.3 NCO (2 molar equvalents) 
H 
##STR52## 
CH.sub.3 
H NHCH.sub.2 CH(CH.sub.3).sub.2 
NH.sub.2 OHHCl 
HO CH.sub.3 NCO (2 molar equivalents) 
H 
##STR53## 
CH.sub.3 
__________________________________________________________________________ 
example 2 
a mixture of 142 parts of N,N-dimethyl-2-hydroxyiminoacetoacetamide (a 
compound of Formula III), 1200 parts of toluene, 123 parts of p-anisidine 
and 1 part of p-toluenesulfonic acid was refluxed overnight in a flask 
fitted with a Dean-Stark distilling trap and water condenser. Eighteen 
parts of water were removed in this manner. On cooling, a heavy slurry of 
solid product precipitated. This was filtered and washed with butyl 
chloride thereby providing a product which melted at 
201.5.degree.-203.degree. C. Recrystallization from acetonitrile gave 151 
parts of N,N-dimethyl-2-hydroxyimino-3-(4-methoxyphenylimino)butyramide (a 
compound of Formula II) as a yellow solid, m.p. 204.degree.-205.5.degree. 
C. 
In a similar manner to Example 2, the following "Compounds of Formula II" 
in Table II, following, can be made by substituting essentially 
stoichiometric ratios of the indicated "Compound of Formula III" and 
"Amine". In some instances, the toluenesulfonic acid catalyst used in the 
above example is unnecessary. In others, benzene is a satisfactory 
solvent. 
TABLE II 
__________________________________________________________________________ 
Compound of Compound of Compound of 
Melting 
Formula III Formula II Formula I Point 
A Q Amine R.sub.7, R of Form. I 
Isocyanate 
R.sub.2 
R.sub.3 (.degree. C.) 
__________________________________________________________________________ 
H N(CH.sub.3).sub.2 
##STR54## 
##STR55## 
CH.sub.3 NCO 
H CH.sub.3 
155-157.5 
H NHC.sub.2 H.sub.5 
##STR56## 
##STR57## 
CH.sub.3 NCO 
H CH.sub.3 
H N(CH.sub.3).sub.2 
##STR58## 
##STR59## 
CH.sub.3 NCO 
H CH.sub.3 
121-124.5 
H N(CH.sub.3).sub.2 
##STR60## 
##STR61## 
CH.sub.3 NCO 
H CH.sub.3 
125-130 
H N(CH.sub.3).sub.2 
##STR62## 
##STR63## 
C.sub.2 H.sub.5 NCO 
H C.sub.2 H.sub.5 
CH.sub.3 
N(CH.sub.3).sub.2 
##STR64## 
##STR65## 
CH.sub.3 NCO 
H CH.sub.3 
H N(CH.sub.3).sub.2 
##STR66## 
##STR67## 
CH.sub.3 NCO 
H CH.sub.3 
160.5-162 
H N(CH.sub.3).sub.2 
##STR68## 
##STR69## 
CH.sub.3 NCO 
H CH.sub.3 
162-164 
H N(CH.sub.3).sub.2 
##STR70## 
##STR71## 
C.sub.2 H.sub.5 NCO 
H C.sub.2 H.sub.5 
H N(CH.sub.3).sub.2 
##STR72## 
##STR73## 
CH.sub.3 NCO 
H CH.sub.3 
175-177 
H NHCH.sub.3 
##STR74## 
##STR75## 
CH.sub.3 NCO 
H CH.sub.3 
H N(CH.sub.3).sub.2 
##STR76## 
##STR77## 
CH.sub.3 NCO 
H CH.sub.3 
169-170 
H N(CH.sub.3).sub.2 
##STR78## 
##STR79## 
CH.sub.3 NCO 
H CH.sub.3 
176-177.5 
H N(CH.sub.3 2 
##STR80## 
##STR81## 
C.sub.2 H.sub.5 NCO 
H CH.sub.3 
H N(CH.sub.3).sub.2 
##STR82## 
##STR83## 
CH.sub.3 NCO 
H CH.sub.3 
170-172 
CH.sub.3 
N(C.sub.2 H.sub.5).sub.2 
##STR84## 
##STR85## 
CH.sub.3 NCO 
H CH.sub.3 
170-172 
CH.sub.3 
N(C.sub.2 H.sub.5).sub.2 
##STR86## 
##STR87## 
CH.sub.3 NCO 
H CH.sub.3 
Compound of Compound of Compound of Melting 
Formula III Formula II Formula I Point 
A Q Amine R.sub.7 Isocyanate 
R.sub.2 
R.sub.3 (.degree. 
__________________________________________________________________________ 
C.) 
CH.sub.3 
N(C.sub.2 H.sub.5).sub.2 
##STR88## 
##STR89## 
CH.sub.2CHCH.sub.2 NCO 
H CH.sub.2CHCH.sub.2 
H N(CH.sub.3).sub.2 
##STR90## 
##STR91## 
CH.sub.3 NCO 
H CH.sub.3 156-157 
CH.sub.3 
##STR92## 
##STR93## 
##STR94## 
CH.sub.3 NCO 
H CH.sub.3 
##STR95## 
(C.sub.2 H.sub.5).sub.2 NNH.sub.2 
(C.sub.2 H.sub.5).sub.2 N 
CH.sub.3 NCO 
H CH.sub.3 
H NHCH.sub.2 CHCH.sub.2 
##STR96## 
##STR97## 
CH.sub.3 NCO 
H CH.sub.3 
H N(CH.sub.3).sub.2 
##STR98## 
##STR99## 
CH.sub.3 NCO 
H CH.sub.3 -H 
N(CH.sub.3 
).sub.2 
##STR100## 
CH.sub.3 
NCO H CH.sub.3 
H N(CH.sub.3).sub.2 
##STR102## 
##STR103## 
CH.sub.3 NCO 
H CH.sub.3 
Compound of Compound of Compound of 
Melting 
Formula III Formula II Formula I Point 
A Q Amine R.sub.7 R of Form. I 
Isocyanate 
R.sub.2 
R.sub.3 (.degree. C.) 
__________________________________________________________________________ 
H NHCH.sub.3 
##STR104## 
##STR105## 
CH.sub.3 NCO 
H CH.sub.3 
H N(CH.sub.3).sub.2 
##STR106## 
##STR107## 
CH.sub.3 NCO 
H CH.sub.3 
H N(CH.sub.3).sub.2 
##STR108## 
##STR109## 
C.sub.2 H.sub.2 NCO 
H CH.sub.3 
H OCH.sub.3 
##STR110## 
##STR111## 
CH.sub.3 NCO 
H CH.sub.3 
CH.sub.3 
N(CH.sub.3).sub.2 
##STR112## 
##STR113## 
CH.sub.3 NCO 
H CH.sub.3 
H N(CH.sub.3).sub.2 
##STR114## 
##STR115## 
CH.sub.3 NCO 
H CH.sub.3 
##STR116## 
##STR117## 
##STR118## 
CH.sub.3 NCO 
H CH.sub.3 
H N(CH.sub.2).sub.2 
##STR119## 
##STR120## 
CH.sub.3 NCO 
H CH.sub.3 
161-162 
H N(CH.sub.3).sub.2 
##STR121## 
##STR122## 
CH.sub.3 NCO 
H CH.sub.3 
143-145 
__________________________________________________________________________ 
example 3 
a mixture of 7.6 parts ethyl 2-hydroxyimino-3-methoxyiminovalerate was 
mixed with 7 parts 40% aqueous methylamine solution at 25.degree. C. and 
stirred till homogeneous (5 minutes). The mixture was allowed to stand 18 
hours and then evaporated under reduced pressure (15 mm) at 50.degree. C. 
water-bath temperature to dryness. Recrystallization of the residue from 
acetonitrile gave 4.3 parts of 
N-methyl-2-hydroxyimino-3-methoxyiminovaleramide, m.p. 
168.degree.-170.degree. C. 
The compounds tabulated in Table III can be prepared according to the 
procedure of Example 3 by substituting comparable stoichiometric amounts 
of the indicated "Compound of Formula II (Q=OR.sub.4)" and "Amine" to 
produce the "Compound of Formula II (Q=NR.sub.5 R.sub.6)". Some variations 
in solvent systems, reaction times, and use of catalyst can be made as 
discussed previously. 
3 TABLE III 
Compound of Formula II (QOR.sub.4) Compound od Formula II (QNR.sub.5 
R6) Compound of Formula I A R.sub.4 R.sub.7 Amine R.sub.5 R.sub.6 
Isocyanate R.sub.2 R R.sub.3 
H CH.sub.3 CH.sub.3 O CH.sub.3 NH.sub.2 CH.sub.3 H CH.sub.3 NCO H 
CH.sub.3 O CH.sub.3 H C.sub.2 H.sub.5 C.sub.3 H.sub.7 O CH.sub.3 
NH.sub.2 CH.sub.3 H C.sub.2 H.sub.5 NCO H C.sub.3 H.sub.7 O C.sub.2 
H.sub.5 H C.sub.2 H.sub.5 (CH.sub.3).sub.2 N CH.sub.3 NH.sub.2 CH.sub.3 
H CH.sub.2CHCH.sub.2 NCO H (CH.sub.3).sub.2 N CH.sub.2CHCH.sub.2 H 
C.sub.2 H.sub.5 CH.sub.3 (CH.sub.3).sub.2 NH CH.sub.3 CH.sub.3 CH.sub.3 
NCO H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 C.sub.8 H.sub.17 C.sub.4 
H.sub.9 N(CH.sub.3)H C.sub.4 H.sub.9 CH.sub.3 CH.sub.3 NCO H C.sub.8 
H.sub.17CH.sub.3 CH.sub.3 C.sub.2 
H.sub.5 
##STR123## 
CH.sub.2CHCH.sub.2 NH.sub.2 CH.sub.2CHCH.sub.2 H CH.sub.3 NCO H 
##STR124## 
CH.sub.3 H CH.sub.3 HO 
##STR125## 
CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 NCO(2 molarequivalents) H 
##STR126## 
CH.sub.3 
EXAMPLE 4 
A mixture of 34 parts of 
N,N-dimethyl-2-hydroxyimino-3-methoxyiminobutyramide, 350 parts of 
methylene chloride, 13 parts of methyl isocyanate and one-tenth part 
triethylenediamine was stirred at 25.degree. C. for 3 hours and then 
refluxed for 1 hour. The solvent was removed by stripping under reduced 
pressure (15 mm.) at 50.degree. bath temperature, thereby affording the 
solid crude product. Recrystallization from a benzene-acetonitrile mixture 
gave 32 parts of 
N,N-dimethyl-3-methoxyimino-2-[(methylcarbamoyl)oximino]butyramide, m.p. 
172.degree.-173.degree. C. 
The procedure of Example 4 can be repeated substituting comparable 
stoichiometric amounts of the indicated "Compound of Formula II" and 
"Isocyanate" to produce the "Compound of Formula I". Some variations in 
solvent systems, reaction times, and catalyst can be made as discussed 
previously (see Tables I, II, and III). 
EXAMPLE 5 
To a stirred mixture of 75 parts of 
N,N-dimethyl-2-hydroxyimino-3-methoxyiminobutyramide and 1500 parts of 
tetrahydrofuran was added portionwise over a fifteen-minute period 19 
parts of 50% sodium hydride, mineral oil dispersion. The temperature was 
maintained in the range of 20.degree. C. to 30.degree. C. After about 
one-half hour, evolution of hydrogen gas ceased, and rapid addition of 55 
parts diethylcarbamoyl chloride was begun. The temperature spontaneously 
rose to 33.degree. C., and rapid thinning-out of the oxime salt slurry 
occurred. The mixture was refluxed and stirred for three hours. The 
inorganic solids were then removed by filtration and the product recovered 
by removal of the solvent under reduced pressure. The residue was twice 
triturated with hexane and the liquid decanted to remove the mineral oil. 
After drying, there was obtained 90 parts of 
N,N-dimethyl-2-[(diethylcarbamoyl)oxyimino]-3-methoxyiminobutyramide, m.p. 
59.degree.-61.degree.. 
The compounds tabulated in Table IV, following, can be prepared according 
to the procedure of Example 5 using the indicated "Compound of Formula II" 
and "Carbamoyl Chloride" to produce the corresponding "Compound of Formula 
I". 
TABLE IV 
__________________________________________________________________________ 
Compound of Melting 
Compound of Formula II Carbamoyl Formula I Point 
A Q R.sub.7, R of Form. I 
Chloride R.sub.2 
R.sub.3 (.degree. C.) 
__________________________________________________________________________ 
H N(CH.sub.3).sub.2 
CH.sub.3 O 
##STR127## C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
59-61 
##STR128## 
##STR129## 
##STR130## CH.sub.3 
CH.sub.3 
H 
##STR131## CH.sub.3 O 
##STR132## CH.sub.3 
CH.sub.3 b.p. 193 at 0.5 mm. 
H 
##STR133## CH.sub.3 O 
##STR134## CH.sub.3 
CH.sub.3 87-89 
H N(CH.sub.3).sub.2 
##STR135## 
##STR136## CH.sub.3 
CH.sub.3 108-110 
CH.sub.3 
NHCH.sub.3 
##STR137## 
##STR138## CH.sub.3 
CH.sub.3 
H N(CH.sub.3).sub.2 
##STR139## 
##STR140## CH.sub.3 
CH.sub.3 122-124 
H OC.sub.2 H.sub.5 
##STR141## 
##STR142## CH.sub.3 
CH.sub.3 
H N(CH.sub.3).sub.2 
##STR143## 
##STR144## CH.sub.3 
CH.sub.3 107-109 
H N(CH.sub.3).sub.2 
##STR145## 
##STR146## CH.sub.3 
CH.sub.3 
H N(CH.sub.3).sub.2 
##STR147## 
##STR148## CH.sub.3 
CH.sub.3 138-141.5 
H N(CH.sub.3).sub.2 
(CH.sub.3).sub.2 N 
##STR149## CH.sub.3 
CH.sub.3 Liq. IR:3.0(NH); 
5.8(CO) 
H N(CH.sub.3).sub.2 
##STR150## 
##STR151## CH.sub.3 
CH.sub.3 142-144 (dec) 
H OC.sub.2 H.sub.5 
CH.sub.3 O 
##STR152## CH.sub.3 
CH.sub.3 Liq. IR:3.1(NH); 
5.78(CO, carbamate); 
5.82(CO,ester) 
H OC.sub.2 H.sub.5 
CH.sub.3 O 
##STR153## C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
CH.sub.3 
OCH.sub.3 (CH.sub.3).sub.2 N 
##STR154## CH.sub.3 
CH.sub.3 
H N(CH.sub.3).sub.2 
CH.sub.3 
##STR155## CH.sub.3 
CH.sub.3 
CH.sub.3 
##STR156## t-C.sub.4 H.sub.9 
##STR157## C.sub.2 H.sub.5 
CH.sub.3 
H 
##STR158## CH.sub.3 O 
##STR159## CH.sub.3 
CH.sub.3 
H 
##STR160## CH.sub.3 O 
##STR161## CH.sub.3 
CH.sub.3 
H 
##STR162## C.sub.3 H.sub.7 O 
##STR163## CH.sub.3 
CH.sub.3 
CH.sub.3 
##STR164## C.sub.2 H.sub.5 O 
##STR165## C.sub.2 H.sub.5 
CH.sub.2CHCH.sub.2 
H NHC.sub.2 H.sub.5 
(CH.sub.3).sub.2 N 
##STR166## CH.sub.3 
CH.sub.2CHCH.sub.2 
H NHOCH.sub.3 
##STR167## 
##STR168## CH.sub.3 
CH.sub.3 
H N(CH.sub.3).sub.2 
##STR169## 
##STR170## CH.sub.3 
CH.sub.3 
H N(CH.sub.3).sub.2 
##STR171## 
##STR172## CH.sub.3 
CH.sub.3 
H N(CH.sub.3).sub.2 
CH.sub.3 CH.sub.2 CH.sub.2 
##STR173## CH.sub.3 
CH.sub.3 N.sub.D.sup.25 = 
1.4842 
H N(CH.sub.3).sub.2 
CH.sub.3 (CH.sub.2).sub.5 
##STR174## CH.sub.3 
CH.sub.3 N.sub.D.sup.25 = 
1.4842 
H N(CH.sub.3).sub.2 
CH.sub.3 CH.sub.2 
##STR175## CH.sub.3 
CH.sub.3 N.sub.D.sup.25 = 
1.4842 
H N(CH.sub.3).sub.2 
CH.sub.3 
##STR176## CH.sub.3 
CH.sub.3 130-132.degree. 
H N(CH.sub.3).sub.2 
CH.sub.3 O 
##STR177## CH.sub.3 
CH.sub.3 102-103.5.degree. 
__________________________________________________________________________ 
table iv.a. 
__________________________________________________________________________ 
compound of Formula II 
Carbamoyl 
Compound of Formula I 
Melting Point 
A Q R.sub.7 
Chloride 
R.sub.2 
R R.sub.3 
(.degree. C.) 
__________________________________________________________________________ 
H 
N(CH.sub.3 9.sub.2 
HO 
##STR178## 
CH.sub.3 
##STR179## 
CH.sub.3l 117-120 
(2 molar 
equivalents) 
H 
OCH.sub.3 
HO 
##STR180## 
CH.sub.3 
##STR181## 
CH.sub.3 
(2 molar 
equivalents( 
__________________________________________________________________________ 
Formulation and Use 
Useful formulations of the compounds of Formula I for control of aphids can 
be prepared in conventional ways. They include dusts, granules, pellets, 
solutions, suspensions, emulsions, wettable powders, emulsifiable 
concentrates and the like. Many of these may be applied directly. 
Sprayable formulations can be extended in suitable media and used at spray 
volumes of from a few pints to several hundred gallons per acre. High 
strength compositions are primarily used as intermediates for further 
formulation. The formulations can be described broadly as consisting 
essentially of about 1% to 99% by weight of active ingredient(s) and at 
least one of (a) about 0.1% to 20% surfactant(s) and (b) about 5% to 99% 
solid or liquid diluent(s). (The expression "consisting essentially of" is 
used to indicate that in addition to the essential ingredients, i.e. those 
specifically recited, the formulations can contain other ingredients 
provided they do not destroy the aphicidal usefulness of the 
formulations.) More specifically, the formulations contain these 
ingredients in the following approximate proportions: 
______________________________________ 
Percent by Weight 
Active 
Ingredient 
Diluent(s) 
Surfactant(s) 
______________________________________ 
Wettable Powders 
20-90 0-74 1-10 
Oil Suspensions, 
5-50 40-95 0-15 
tions (including 
emulsifiable con- 
centrates) 
Aqueous Suspensions 
10-50 40-84 1-20 
Dusts 1-25 70-99 0-5 
Granules and Pellets 
1-95 5-99 0-15 
High Strength 
90-99 0-10 0-2 
Compositions 
______________________________________ 
Lower or higher levels of active ingredient can, of course, be present 
depending on the intended use and the physical properties of the compound. 
Higher ratios of surfactant to active ingredient are sometimes desirable, 
and are achieved by incorporation into the formulation or by tank mixing. 
Typical solid diluents are described in Watkins, et al., "Handbook of 
Insecticide Dust Diluents and Carriers", 2nd Edn., Dorland Books, 
Caldwell, N.J. The more absorptive diluents are preferred for wettable 
powders and the denser ones for dusts. Typical liquid diluents and 
solvents are described in Marsden, "Solvents Guide", 2nd Edn., 
Interscience, New York, 1950. Solubility under 0.1% is preferred for 
suspension concentrates; solution concentrates are preferably stable 
against phase separation at 0.degree. C. "McCutcheon's Detergents and 
Emulsifiers Annual", Allured Publ. Corp., Ridgewood, New Jersey, as well 
as Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical 
Publ. Co., Inc., New York, 1964, list surfactants and recommended uses. 
All formulations can contain minor amounts of additives to reduce foam, 
caking, corrosion, microbiological growth, etc. Preferably, ingredients 
should be approved by the U.S. Environmental Protection Agency for the use 
intended. 
The methods of making such compositions are well known. Solutions are 
prepared by simply mixing the ingredients. Fine solid compositions are 
made by blending and, usually, grinding as in a hammer or fluid energy 
mill. Suspensions are prepared by wet milling (see, for example, Littler, 
U.S. Pat. No. 3,060,084). Granules and pellets may be made by spraying the 
active material upon preformed granular carriers or by agglomeration 
techniques. See J. E. Browning, "Agglomeration", Chemical Engineering, 
Dec. 4, 1967, pp. 147ff. and "Perry's Chemical Engineer's Handbook", 4th 
Edn., McGraw-Hill, N.Y., 1963, pp. 8-59ff. 
For further information regarding the art of formulation, see for example: 
J. B. Buchanan, U.S. Pat. No. 3,576,834, Apr. 27, 1971, Col. 5, Line 36 
through Col. 7, Line 70 and Ex. 1-4, 17, 106, 123-140. 
R. R. Schaffer, U.S. Pat. No. 3,560,616, Feb. 2, 1971, Col. 3, Line 48 
through Col. 7, Line 26 and Ex. 3-9, 11-18. 
E. Somers, "Formulation", Chapter 6 in Torgeson, "Funcigides", Vol. I, 
Academic Press, New York, 1967. 
EXAMPLE 6 
______________________________________ 
Wettable Powder Percent 
______________________________________ 
Compound of Formula I where A = H, 
Q = N(CH.sub.3).sub.2, R = 0CH.sub.3, R.sub.2 = H, 
and R.sub.3 = CH.sub.3 40 
Dioctyl sodium sulfosuccinate 
1.5 
Sodium ligninsulfonate 3 
Low-viscosity methyl celloluse 
1.5 
Attapulgite 54 
______________________________________ 
The ingredients are thoroughly blended, passed through an air mill to 
produce an average particle size under 15 microns, reblended, and sifted 
through a U.S.S. No. 50 sieve (0.3 mm. opening) before packaging. 
All compounds of Formula I may be formulated in the same manner. 
EXAMPLE 7 
______________________________________ 
Water-soluble Powder Percent 
______________________________________ 
Compound of Formula I where A = H, 
Q = N(CH.sub.3).sub.2, R = OCH.sub.3, R.sub.2 and R.sub.3 = 
CH.sub.3 95 
Dioctyl sodium sulfosuccinate 
0.5 
Sodium ligninsulfonate 1.0 
Synthetic fine silica 3.5 
______________________________________ 
The ingredients are blended and coarsely ground in a hammer mill so that 
only a few percent of the active exceeds 250 microns (U.S.S. No. 60 sieve) 
in size. When added to water with stirring, the coarse powder initially 
disperses and then the active ingredient dissolves so that no further 
stirring is needed during application. 
EXAMPLE 8 
______________________________________ 
Liquid Concentrate Percent 
______________________________________ 
Compound of Formula I where A = H, 
Q = N(CH.sub.3).sub.2, R = OCH.sub.3, R.sub.2 = CH.sub.3, 
and R.sub.3 = CH.sub.3 31 
24/76 Wt. ratio methanol/water solvent 
68.5 
85% H.sub.3 PO.sub.4 0.5 
______________________________________ 
The compound of Formula I and the H.sub.3 PO.sub.4 are added to the solvent 
system. The mixture is agitated until a solution is obtained. The solution 
is clarified by filtration, if necessary. 
EXAMPLE 9 
______________________________________ 
Granules Percent 
Compound of Formula I where A = H, 
Q = N(CH.sub.3).sub.2, R = N(CH.sub.3).sub.2, 
R.sub.2 = H, and R.sub.3 = CH.sub.3 
5 
Celatom MP78 (diatomaceous earth) granules 
95 
______________________________________ 
The compound of Formula I is dissolved in enough methanol to thoroughly wet 
the granules when blended with them. Enough compound of Formula I is 
dissolved in the methanol. This solution is added to the granules, and the 
mixture is agitated to uniformly wet the granules. The methanol solvent is 
removed by evaporation. 
EXAMPLE 10 
______________________________________ 
Dust Percent 
______________________________________ 
Compound of Formula I where A = H, 
Q = N(CH.sub.3).sub.2, R = N(CH.sub.3).sub.2, 
R.sub.2 = CH.sub.3, and R.sub.3 = CH.sub.3 
10 
Attapulgite 10 
Talc 80 
______________________________________ 
The active ingredient is blended with attapulgite and then passed through a 
hammer mill to produce particles substantially all below 200 microns. The 
ground concentrate is then blended with powdered talc until homogeneous. 
The compounds of this invention are useful for control of aphids which 
attack plants. When applied to aphids or to the locus of aphid 
infestation, these pests are killed or driven from the plants. The 
preferred compounds of this invention are particularly useful in 
protecting plants from aphids. The compounds are highly systemic and are 
translocated upwards from both soil and foliar applications. They have a 
very low order of phytotoxicity and exhibit good safety margins whether 
applied to foilage or to soil. While they degrade in the biosphere in a 
reasonable period of time, they are not so short lived as to lose 
effectiveness immediately upon application. Consequently, cost for control 
of aphids is not excessive. The preferred compounds are water soluble and 
can be inexpensively formulated in aqueous systems. Once a spray solution 
is prepared, no agitation is required to maintain a uniform concentration. 
After treatment the aphids drop from the plant leaving clean leaf tissue. 
This is important on green leafy vegetables where the leaves are consumed 
as food for humans. Some insecticides kill so rapidly that the aphids do 
not have time to withdraw their beak and, therefore, remain attached to 
the leaf. These dead aphids are not easily washed or removed from the 
leaves and lower the quality and desirability of the produce as food. 
When applied as a foliar spray the compounds readily penetrate the leaves 
of plants and move freely within the tissue. Once within the plant they 
cannot be washed off by rain. The spray does not need to be uniformly 
distributed over the surface to be effective, nor does it need to contact 
the aphids per se. When applied to soil, the compounds are absorbed 
through the roots of the plants and are translocated upward to the leaf 
tissue on which the aphids are feeding. The soil acts as a reservoir 
making the compounds available to the plants over a prolonged period of 
time. The quantity applied to the soil can be calculated to supply the 
plants with sufficient material to last through the cool part of the 
season during which aphids are most destructive. Greater quantities will 
need to be applied where the aphid season is longer or where overlapping 
species prolong the season. Soil applications minimize harm to naturally 
occurring parasites and predators and fit well into an integrated pest 
control program. The term "applying to the plant" includes application to 
the plant foliage or through the soil. 
The quantities of the compounds needed to control aphids depend on many 
factors such as intensity of the infestation, time of year, species of 
aphid, species of plant, type of application, frequency and amount of 
rainfall, temperature and others. As low as 1 ppm in a foliar spray 
applied to run-off or 200 grams per hectare applied in the row can give 
control of mild infestations under conditions favorable to the compound. 
Larger amounts, up to about 10,000 ppm in a foliar spray or 25 kilograms 
per hectare, are required as the conditions conducive to the compound 
become adverse. Preferred under practical conditions are concentrations of 
from 20-1000 ppm and soil rates of 0.5-12.5 kg/ha. Most preferred are 
concentrations of 40-250 ppm and soil rates of 1.2-2.5 kg/ha. 
Aphids controlled by the compounds of this invention include but are not 
limited to the black bean aphid, Aphis fabae; the green peach aphid, Myzus 
persicae; the apple aphid, Aphis pomi; the potato aphid, Macrosiphum 
euphorbiae; the green bug, Toxoptera graminum; the corn root aphid, 
Anuraphis maidiradicis, cabbage aphid, Brevicoryne brassicae; and green 
citrus aphid, Aphis spiraecola. 
The compounds of this invention can be mixed with other agricultural 
chemicals for application to either foliage or soil. Such mixtures broaden 
the scope of the pests controlled, save costs of multiple applications, 
and can result in unusual beneficial effects. Soil applications with low 
rates of oxamyl provide for improved aphid control along with control of 
nematodes, thrips and other early season insects. Foliar applications in 
combination with benomyl provide good control of such fungi as apple scab 
and powdery mildew along with good aphid control on apples. Many other 
mixtures provide useful results. 
Aphicidal activity of compounds of formula I is shown by the results of the 
following tests: 
Test 1-Control of Black Bean Aphids via Foliar Spray 
The test units used to demonstrate aphicidal effectiveness through foliar 
application consisted of two excised nasturtium leaves contained in a 
2-ounce narrow mouthed bottle. The bottle contained water for the plant 
tissue, and cotton was packed around the stems in the neck of the bottle 
to prevent the spray solution from contacting the water. The two leaves 
supported approximately 80 aphids in various stages of growth. The test 
units were sprayed to run off with various concentrations of the compounds 
made up in aqueous solution containing 1:3000 parts of sodium lauryl 
sulfate surfactant. Results were observed 1 day after application and are 
set forth below. 
______________________________________ 
Spray Concentra- 
% Con- 
Compound tions (%) trol 
______________________________________ 
N,N-dimethyl-3-methoxy- 
.002 100 
imino-2-[(dimethylcar- 
.001 98 
bamoyl)oxyimino]butyramide 
.0005 100 
.00025 100 
.0001 96 
N,N-dimethyl-3-methoxy- 
.001 100 
imino-2-[(methylcar- 
.0005 100 
bamoyl)oxyimino]butyramide 
.00025 97 
.0001 76 
N,N-dimethyl-2-[(ethyl- 
.005 100 
carbamoyl)oxyimino]-3-methoxy- 
.002 98 
iminobutyramide .001 95 
.0005 88 
N,N-dimethyl-2-[(methylcar- 
.001 100 
bamoyl)oxyimino]-3-dimethyl- 
.0005 99 
hydrazonobutyramide 
.00025 96 
.0001 54 
N,N-dimethyl-3-(4-methoxy- 
.01 100 
phenylimino)-2-[(methylcar- 
.005 96 
bamoyl)oxyimino]butyramide 
.002 64 
N,N-dimethyl-3-dimethylhydra- 
.005 100 
zono-2-[(dimethylcarbamoyl)oxyi- 
.001 100 
mino]butyramide .0005 100 
.00025 99 
.0001 92 
None -- 0 
______________________________________ 
Test 2-Systemic Control of Black Bean Aphids 
The systemic nature of the compounds was demonstrated by preparing test 
units as described in Test 1, but substituting solutions of the compounds 
at the indicated concentrations for the water in which the excised 
nasturtium leaves were placed. Results were observed one day later and are 
recorded below. 
______________________________________ 
Solution Con- 
% Con- 
Compound centrations (%) 
trol 
______________________________________ 
N,N-dimethyl-3-methoxy- 
.01 99 
imino-2-[(dimethylcar- 
.005 98 
bamoyl)oxyimino]- .002 0 
butyramide 
N,N-dimethyl-3-methoxy- 
.005 100 
imino-2-[(methylcar- 
.002 99 
bamoyl)oxyimino]butyramide 
.0005 99 
.00025 99 
.0001 79 
N,N-dimethyl-2-[(ethyl- 
.01 99 
carbamoyl)oxyimino]-3- 
.005 99 
methoxyiminobutyramide 
.001 94 
.0005 80 
N,N-dimethyl-2-[(methylcar- 
.001 100 
bamoyl)oxyimino]-3-dimethyl- 
.0005 99 
hydrazonobutyramide 
.00025 96 
.0001 54 
N,N-dimethyl-3-(4-methoxy- 
.01 100 
phenylimino)-2-[(methylcar- 
.005 96 
bamoyl)oxyimino]butyramide 
.002 64 
N,N-dimethyl-3-dimethylhydra- 
.005 100 
zono-2-[(dimethylcarbamoyl)oxy- 
.001 100 
imino]butyramide .0005 97 
.00025 99 
.0001 95 
None -- 0 
______________________________________ 
Test 3-Leaf Penetration by 
N,N-dimethyl-3-methoxyimino-2-[(dimethylcarbamoyl)oxyimino]butyramide 
A stock solution of 
N,N-dimethyl-3-methoxyimino-2-[(dimethylcarbamoyl)oxyimino]butyramide was 
prepared by dissolving 20 mg. of the compound in 10 ml. of acetone, adding 
1 ml. of a 1% methocel suspension and diluting to 50 ml. with water 
containing 6 drops of sodium lauryl sulfate surfactant per 500 ml. 
Subsequent dilutions were made with the water-surfactant mixture. Three 
drops of each of the test dispersions indicated below were spread over the 
top side of each nasturtium leaf. Aphids were left undisturbed on the 
lower surface. Data set forth below indicates control of black bean aphids 
one day after treatment. 
______________________________________ 
Concentra- % Con- 
Compound tions(%) trol 
______________________________________ 
N,N-dimethyl-3-methoxy- 
.04 100 
imino-2-[(dimethylcar- 
.02 98 
bamoyl)oxyimino]- 
.01 98 
butyramide 
None -- 0 
______________________________________ 
These results indicate effective penetration of the leaf surface by the 
compound and translocation within the leaf sufficient to control aphids 
feeding on the lower surface. 
Test 4-Control of Apple Aphids with Foliar Sprays of 
N,N-dimethyl-3-methoxyimino-2-[(dimethylcarbamoyl)oxyimino]butyramide 
Small branches of apple trees each infested with approximately 300 apple 
aphids were placed in small vases of water and the foliage sprayed to 
run-off with aqueous solutions of 
N,N-dimethyl-3-methoxyimino-2-[(dimethylcarbamoyl)oxyimino]butyramide at 
various concentrations. The control branch was sprayed with water alone. 
Results were observed 1 day later and are recorded below. 
______________________________________ 
Spray Concentra- 
% Con- 
Compound tions (%) trol 
______________________________________ 
N,N-dimethyl-3-methoxy- 
.001 100 
imino-2-[(dimethylcar- 
.0005 79 
bamoyl)oxyimino]- 
.0001 42 
butyramide 
None -- 8 
______________________________________ 
Test 5-Control of Black Bean Aphids via Soil Applications of 
N,N-dimethyl-3-methoxyimino-2-[(dimethylcarbamoyl)oxyimino]butyramide 
Nasturtium seeds were planted in pots 7.5 cm in diameter containing soil 
which had been treated at rates of 1 and 5 kg/ha in the row. Ten days 
later the young plants were artificially infested with black bean aphids. 
The percent control of aphids on the test plants were observed and 
recorded one week later. The same soil was again planted to nasturtiums 
one month after the initial treatment. Ten days later these plants were 
infested with aphids as before and results read 1 week later. Observations 
are recorded below. 
______________________________________ 
% Kill 
of Aphids 
Time After 
Amount Applied to 
Treatment 
Soil (Kg/ha)in 
17 48 
Compound the row Days Days 
______________________________________ 
N,N-dimethyl-3-methoxy- 
imino-2-[(dimethyl- 
1 100 100 
carbamoyl)oxyimino]- 
butyramide 5 100 100 
None -- 0 0 
______________________________________ 
The results of this experiment demonstrate both the excellent upward 
translocation and good residual properties possessed by the compound. 
Test 6-Control of Three Species of Aphid with Soil Applications of 
N,N-Dimethyl-3-methoxyimino-2-[(dimethylcarbamoyl)oxyimino]butyramide 
Nasturtium, cabbage and Chinese cabbage plants approximately 8-10 cm in 
height were infested with black bean aphids, cabbage aphids and green 
peach aphids, respectively. One week after infestation the soil was 
treated with a solution of 
N,N-dimethyl-3-methoxyimino-2-[(dimethylcarbamoyl)oxyimino]butyramide at 1 
and 5 kg/ha rates. Seven days later all treated plants were completely 
free of aphids while all of the control plants were badly damaged by 
continuously increased aphid feeding. 
Test 7-Control of Black Bean Aphid with Seed Treatments of 
N,N-Dimethyl-3-methoxyimino-2-[(dimethylcarbamoyl)oxyimino]butyramide 
Ten grams of nasturtium seed were treated with 0.05 g of 
N,N-dimethyl-3-methoxyimino-2-[(dimethylcarbamoyl)oxyimino]butyramide 
dissolved in 5 ml of water. An additional ten grams of seed were treated 
with the same compound at one-fifth that rate. The treated seed was 
allowed to dry and then planted. Two weeks after sowing the growing plants 
were infested with black bean aphids. Results were read two weeks later at 
which time the plants were again infested. Results were read again two 
weeks later and are recorded below. 
______________________________________ 
Amount Applied 
Chronology % 
Based on of Test Control 
Treatment Weight of Seed 
Days of Aphids 
______________________________________ 
N,N-Dimethyl-3- 
.5% 0 Planted 
methoxyimino-2- 13 Infested 
[(dimethylcarbam- 
oyl)oxyimino]- 28 Rated 100% 
butyramide 
28 Infested 
41 Rated 100% 
.1% 0 Planted 
13 Infested 
28 Rated 100% 
28 Infested 
41 Rated 30% 
______________________________________ 
Test 8-Effects of 
N,N-Dimethyl-3-methoxyimino-2-[(dimethylcarbamoyl)oxyimino]butyramide on 
Convergent Lady Beetles 
Lady beetles were sampled in groups of 25 beetles per cage and then sprayed 
with a 0.1% aqueous solution of 
N,N-dimethyl-3-methoxyimino-2-[(dimethylcarbamoyl)oxyimino]butyramide. 
Observations made 48 hours after spraying indicated that no beetles were 
killed by this treatment. 
In an ancillary experiment nasturtium plants growing in soil treated with 
10 kg/ha of 
N,N-dimethyl-3-methoxyimino-2-[(dimethylcarbamoyl)oxyimino]butyramide were 
caged with 50 convergent lady beetles. No beetle mortality resulted from 
their contact with treated plants. 
Test 9-Control of Green Apple Aphid with 
N,N-Dimethyl-3-methoxyimino-2-[(dimethylcarbamoyl)oxyimino]butyramide in a 
Delaware Orchard 
Semi-dwarf Red Delicious apple trees in an orchard located at Newark, 
Delaware, infested with green apple aphids to the extent of approximately 
500 aphids/terminal were sprayed with solutions of 
N,N-dimethyl-3-methoxyimino-2-[(dimethylcarbamoyl)oxyimino]butyramide at 
concentrations of 40, 160 and 320 ppm. Each treatment was run in 
triplicate and results evaluated four days after spraying. Data for two 
similar tests carried out about six weeks apart are set forth below. 
______________________________________ 
Spray % Control 
Concentration 
Early Late 
Treatment (ppm) Test Test 
______________________________________ 
N,N-Dimethyl-3-methoxy- 
40 70 80 
imino-2-[(dimethylcarbam- 
oyl)oxyimino]butyramide 
160 87 89 
320 97 98 
Untreated Check 
0 0 0 
______________________________________ 
Test 10-Control of Green Citrus Aphid with 
N,N-Dimethyl-3-methoxyimino-2-[(dimethylcarbamoyl)oxyimino]butyramide in a 
Florida Citrus Grove 
Valencia orange trees located in a grove in Bradenton, Florida, were 
selected for this test. The trees were in a stage of rapid growth and were 
heavily infested with green citrus aphids. Solutions of 
N,N-dimethyl-3-methoxyimino-2-[(dimethylcarbamoyl)oxyimino]butyramide at 
concentrations of 40, 160 and 320 ppm were applied with a single-nozzle 
orchard gun. Each treatment was applied in four replicates and results 
were recorded three days later. Data are expressed for each replicate in 
terms of the number of 25 leaves selected at random that were found to be 
infested. The totals for all four replicates of each treatment 
consequently represent % infestation. 
______________________________________ 
Spray 
Concentration 
% 
Treatment (ppm) Infested Leaves 
______________________________________ 
N,N-Dimethyl-3-methoxy- 
40 42 
imino-2-[(dimethylcarbam- 
oyl)oxyimino]butyramide 
160 10 
320 7 
Untreated Check 
0 97 
______________________________________ 
Test 11-Effectiveness of Compounds for Aphid Control at the 1% Spray Level 
Nasturtium leaflets containing black bean aphids in all stages of growth 
were selected for testing. These were impaled singly in an upside-down 
position on a turntable which was rotated beneath a nozzle. Solutions 
containing 1% of the test compounds in acetone were applied to the 
leaflets as a spray. After treatment, leaflets were stored for 
approximately 20 hrs with their stems in water. Aphicidal results, 
expressed as % control, were then made and are recorded for the compounds 
tested. 
__________________________________________________________________________ 
A R R.sub.2 
R.sub.3 Q % Control 
__________________________________________________________________________ 
H OCH.sub.3 H CH.sub.3 
##STR182## 
100 
H OCH.sub.3 H CH.sub.3 
N(C.sub.2 H.sub.5).sub.2 
100 
H OCH.sub.3 H CH.sub.3 
##STR183## 
100 
##STR184## H CH.sub.3 
N(CH.sub.3).sub.2 
100 
H 
##STR185## CH.sub.3 
CH.sub.3 
N(CH.sub.3).sub.2 
100 
H 
##STR186## H CH.sub.3 
N(CH.sub.3).sub.2 
100 
H 
##STR187## H CH.sub.3 
N(CH.sub.3).sub.2 
100 
H 
##STR188## H CH.sub.3 
N(CH.sub.3).sub.2 
95 
H OCH.sub.3 H CH.sub.3 
OC.sub.2 H.sub.5 
100 
CH.sub.3 
OCH.sub.3 H CH.sub.3 
OC.sub.2 H.sub.5 
95 
H 
##STR189## CH.sub.3 
CH.sub.3 
N(CH.sub.3).sub.2 
100 
H 
##STR190## CH.sub.3 
CH.sub.3 
N(CH.sub.3).sub.2 
100 
H 
##STR191## H CH.sub.3 
N(CH.sub.3).sub.2 
100 
H (CH.sub.2).sub.3OCH.sub.3 
H CH.sub.3 
N(CH.sub.3).sub.2 
95 
CH.sub.3 
OCH.sub.3 H CH.sub.3 
N(CH.sub.3).sub.2 
100 
H OCH.sub.3 CH.sub.3 
CH.sub.3 
##STR192## 
100 
H OCH.sub.3 H CH.sub.3 
##STR193## 
100 
H OCH.sub.3 H C.sub.2 H.sub.5 
##STR194## 
100 
H OCH.sub.3 H CH.sub.3 
N(CH.sub.3).sub.2 
100 
H OCH.sub.3 H C.sub.2 H.sub.5 
N(CH.sub.3).sub.2 
100 
H OCH.sub.3 C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
N(CH.sub.3).sub.2 
100 
H OCH.sub.3 H CH.sub.2 CHCH.sub.2 
N(CH.sub.3).sub.2 
100 
H N(CH.sub.3).sub.2 
H CH.sub.3 
N(CH.sub.3).sub.2 
100 
H N(CH.sub.3).sub.2 
CH.sub.3 
CH.sub.3 
N(CH.sub.3).sub.2 
100 
H 
##STR195## H CH.sub.3 
N(CH.sub.3).sub.2 
100 
H 
##STR196## H CH.sub.3 
N(CH.sub.3).sub.2 
95 
H 
##STR197## H CH.sub.3 
N(CH.sub.3).sub.2 
100 
H 
##STR198## H CH.sub.3 
N(CH.sub.3).sub.2 
100 
H 
##STR199## H CH.sub.3 
N(CH.sub.3).sub.2 
100 
H 
##STR200## H CH.sub.3 
N(CH.sub.3).sub.2 
100 
H 
##STR201## H CH.sub.3 
N(CH.sub.3).sub.2 
100 
H 
##STR202## H CH.sub.3 
N(CH.sub.3).sub.2 
95 
H 
##STR203## H CH.sub.3 
N(CH.sub.3).sub.2 
100 
H 
##STR204## H CH.sub.3 
N(CH.sub.3).sub.2 
100 
H 
##STR205## H CH.sub.3 
N(CH.sub.3).sub.2 
95 
H 
##STR206## H CH.sub.3 
OC.sub.2 H.sub.5 
100 
C.sub.2 H.sub.5 
OCH.sub.3 H CH.sub.3 
OC.sub.2 H.sub.5 
100 
H CH.sub.3 H CH.sub.3 
N(CH.sub.3).sub.2 
100 
H CH.sub.2 CH.sub.2 CH.sub.3 
H CH.sub.3 
N(CH.sub.3).sub.2 
100 
H CH.sub.2 CH.sub.3 
H CH.sub.3 
N(CH.sub.3).sub.2 
100 
H CH(CH.sub.3).sub.2 
H CH.sub.3 
N(CH.sub.3).sub.2 
100 
H 
##STR207## H CH.sub.3 
N(CH.sub.3).sub.2 
100 
H 
n-C.sub. 8 H.sub.17 
H CH.sub.3 
N(CH.sub.3).sub.2 
100 
H 
n-C.sub. 6 H.sub.13 
H CH.sub.3 
N(CH.sub.3).sub.2 
100 
H 
##STR208## CH.sub.3 
CH.sub.3 
N(CH.sub.3).sub.2 
100 
H CH.sub.3 CH.sub.3 
CH.sub.3 
N(CH.sub.3).sub.2 
H 
##STR209## H CH.sub.3 
N(CH.sub.3).sub.2 
100 
H 
##STR210## H CH.sub.3 
N(CH.sub.3).sub.2 
100 
H (CH.sub.2).sub.9 CH.sub.3 
H CH.sub.3 
N(CH.sub.3).sub.2 
100 
H (CH.sub.2).sub.17 CH.sub.3 
H CH.sub.3 
N(CH.sub.3).sub.2 
100 
H (CH.sub.2).sub.17 CH.sub.3 
CH.sub.3 
CH.sub.3 
N(CH.sub.3).sub.2 
100 
__________________________________________________________________________ 
pg,62