Note: Descriptions are shown in the official language in which they were submitted.
;;~.3..7~
Back round of the Invention
y
Among the many hdrbicidal compounds commercially avaii-
able the thiolcarbamates alone ox admixed with other herbicides,
such as the triazines, have reached a relatively high degree of
commercial success. These herbicides are immediately toxic to a
large number of weed pests at different concentrations varying
with the resistance of the weed pests. Some examples of these
compounds are described and claimed in the U.S. Patent Nos.
2,913,327, 3,037,853, 3,175,897, 3,135,720, 3,198,786 and
3,S82,314. It has been found in practice that the use of these
thiolcarbamates as herbicides on crops sometimes causes serious
injuries to the crop plant. When used in the recommended amounts
in the 80il to control many broadleaf weeds and grasses, serious
malformation and stunting of the crop plants result. This abnor-
mal growth in the crop plants results in loss of crop yield.
Previous attempts to overcome this problem involves the treatment
of the crop seed with certain antagonistic agents prior to planting,
see U.S. Patent No. 3,131,509. These antagonistic agents have
not been notably successful.
Description of the Invention
It has been discovered that plants can be protected
against injury by the thiolcarbamates alone or mixed with other
compounds and/or the tolerance of the plants can be substantially
increased to the active compounds of the above-noted U. S. Patents
4 865
by adding to the soil an an~idote compound corresponding to the
following ~ormula:
R_R_
R2
wherein R can be selected from the group consisting of haloalkyl;
haloalkenyl; alkyl; alkenyl; cycloalkyl; cycloalkylalkyl; halogen;
hydrogen; carboalkoxy; N-alkenylcarbamylalkyl; N-alkenylcarbamyl;
N-alkyl-N-alkynylcarbamyl; N-alkyl-N-alkynylcarbamylalkyl; N-
alkenylcarbamylalkoxyalkyl; N-alkyl~N-alkynylcarhamylalkoxyalkyl;
alkynoxy; haloalkoxy/,i thiocyanatoalkyl; alkenylaminoalkyl; alkyl-
carboalkyl; cyanoalkyl; cyanatoalkyl; alkenylaminos~lfonoalkyl;
alkylthioalkyl; haloalkylcarbonyloxyalkyl, alkyoxycarboalkyl;
haloalkenylcarbonyloxyalkyl; hydroxyhaloalkyloxyalkyl; hydroxy-
alkylcarboalkyoxyalkyl; hydroxyaikyl; alkoxysul~onoalkyl; furyl,
thienyl; alkyldithiolenyl; thienalkyl; phenyl and substituted
phenyl wherein said substituents can be selected from halogen,
alkyl, haloalkyl, alkoxy, carbamyl, nitro, carboxylic acids and
their salts, haloalkylcarbamyl; phenylalkyl; phenylhaloalkyl;
phenylalkenyl; substituted phenylalkenyl wherein said substituents
can be selected from halogen, alkyl, alkoxy; halophenoxy; phenyl-
alkoxy; phenylalkylcarboxyalkyl; phenylcycloalkyl; halophenyl-
alkenoxy; halothiophenylalkyl; halophenoxyalkyl; bicycloalkyl;
alkenyLcarbamylpyridinyl; alkynylcarbamylpyridinyl; dialkenyl-
carbamylbicycloalkenyl; alkynylcarbamylbicycloalkenyl; Rl and R2
can be the same or different and can be selected from the group
consisting of alkenyl; haloalkenyl; hydrogen; alkyl; haloalkyl;
alkynyl; cyanoalkyl; hydroxyalkyl; hydroxyhaloalkyl; haloalkyl-
carboxyalkyl; alkyIcarboxyalkyl; alkoxycarboxyalkyl; thioalkyl-
carboxyalkyl; alkoxycarboalkyl; alkylcarbamyloxyalkyl; amino;
formyl; haloalkyl-N-alkylamido; haloalkylamido; haloalkylamido-
alkyl; haloalkyl-N-alkylamidoalkyl; haloalkylamidoalkenyl; alkyl-
imino; cycloalkyl; alkylcycloalkyl; alkoxyalkyl; alkylsulfonyloxy-
- 5 -
~174865
alkyl; mercaptoalkyl; alkylaminoalkyl; alkoxycarboalkenyl; halo-
alkylcarbonyl; alkylcarbonyl; alkenylcarbamyloxyalkyl; cycloalkyl-
carbamyloxyalkyl; alkoxycarbonyl; haloalkoxycarbonyl; halophenyl-
carbamyloxyalkyl; cycloalkenyl; phenyl; substituted phenyl wherein
said substituents can be selected from alkyl, halogen, haloalkyl,
alkoxy, haloalkylamido, phthalamido, hydroxy, alkylcarbamyloxy,
alkenylcarbamyloxy, alkylamido, haloalkylamido, alkylcarboalkenyl;
phenylsulfonyl; phenylalkyl; substituted phenylalkyl wherein said
substituents can be selected from halogen, alkyl; dioxyalkylene,
halophenoxyalkylamidoalkyl; alkylthiodiazolyl; piperidylalkyl;
thiazolyl; alkylthiazolyl; benzothiazolyl; halobenzothiazolyl;
furylalkyl; pyridyl; alkylpyridyl; alkyloxazolyl; tetrahydrofuryl-
alkyl; 3-cyano, 4,5-polyalkylene-thienyl; O~-haloalkylacetamido-
phenylalkyl; ~-haloalkylacetamidonitrophenylalkyl; ~-haloalkyl-
acetamidohalophenylalkyl; cyanoalkenyl; Rl and R2 when taken to-
gether can form a structure consisting of piperidinyl; alkylpiperi-
dinyl; alkyltetrahydropyridyl; morpholyl; alkylmorpholyl; azo-
bicyclon~onyl; benzoalkylpyrrolidinyl; oxazolidyl; alkyloxazolidyl;
perhydroquinolyl; alkylaminoalkenyl; provided that when Rl is hy-
drogen R2 is other than hydrogen and halophenyl.
The compounds represented by the above formula can be
synthesized by mixing together an appropriate acid chloride with
an appropriate amine. A solvent such as benzene can be used if
desired. The reaction is preferably carried out at reduced
temperatures. After the reaction is complete, the end-product is
brought to room temperature and can be readily separated.
In order to illustrate the merits of the present inven-
tion, reference is made to the following examples:
.
`:
~174~36~i
Example 1
,CH2-CH-CH2
CHC12-C-N ~
CH2-CH=CH2
A solution was made by dissolving 3.7 g. (0.025 mole) of
dichloroacetyl chloride in 100 ml. of methylene dichloride which
was then cooled to about 5C. in an ice bath. Then, 4.9 g.
(0.05 mole) of diallyl amine was added dropwise while the tempera-
ture was maintained at below about 10C. The mixture was then
; stirred at room temperature for about 4 hours and washed twice
with water and dried over magnesium sulfate, filtered and stripped.
The yield was 4.0 g., n30 _ 1.4990.
Example 2
CHC12-C-N ~ 3 7
C3H7
A solution was made by dissolving 3.7 g. (0.025 mole) of
dichloroacetyl chloride in 100 ml. of methylene dichloride which
was then cooled to about 10C. in an ice bath. Then, 5.1 g.
(0.05 mole) of di-n-propylamine was added dropwise while the
temperature was maintained at below about 10C. The mixture was
then stirred at room temperature overnight and washed twice with
water and dried over magnesium sulfate, filtered and stripped.
The yield was 3.6 g., n30 _ 1.4778.
~74~3~5
}~ample 3
CHCl2-C-N ~ H3
~ H(CH3) C CH
A solution was made by dissolving 3.7 g. (0.025 mole)
of dichloroacetyl chloride in 80 ml. of methylene dichloride
which was then cooled to about 10C. in an ice bath. Then, 4.2 g.
(0.05 mole) of N-methyl, N-l-methyl-3-propynylamine in 20 ml. of
methylene dichloride was added dropwise while the temperature
was maintained about lO~C. The mixture was then stirred at
room temperature for about 4 hours and washed twice with water
and dried over magnesium sulfate, filtered and stripped. The
yield was 2.9 g., n30 _ 1.4980.
Example 4
CH2Cl -C -NH-CH2~
A solution was formed containing 100 ml. acetone, 5.05 g.
furfuryl amine (0.1 mole), then stirred with the addition of 7 ml.
triethylamine at 15C. Then, 5.7 g. of monochloro acetyl chloride
was added and stirred for 15 more minutes, wherein 500 ml. of
water was added. The reaction mass was filtered, washed with
dilute hydrochloric acid in additional water, and then dried to
constant weight.
1174~65
Example 5
CHC12-C-NH ~
A solution was formed consisting of 5.7 g. (0.05 mole)
of amino methyl thiazole in 100 ml. of benzene with 7 ml. of
triethylamine. This solution was stirred at 10-15C. and then
5.2 ml. (0.~ mole) of dichloro acetyl chloride was added dropwise.
The reaction was stirred at room temperature for 10 minutes.
; Then, 100 ml. water was added and the solution was then washed
with benzene solution, dried over magnesium sulate and then
filtered to remove the solvent.
Example 6
~ ~H
CHC12- -N ~ ~ Br
A solution was formed containing 200 ml. acetone and
17.5 g. (0.05 mole) of 2-amino-6-bromo benzothiazole and 7 ml. of
triethylamine. The solution was stirred 15C. with cooling. Then,
5.2 ml. ~0.05 mole) of dichloroacetyl chloride was added slowly.
This solution was stirred at room temperature for ten minutes.
The solid form was filtered off, which solid was washed with ether,
then cold water, and then filtered again and dried at 40-50C.
. , .
~ - j
4 ~6~S
Example 7
C-N~
C(CH3)zC- CH
3.4 g. of 3-methyl-3-butynyl amine was dissolved in 50 ml.
of methylene chloride, 4.5 g. of triethylzminewas added and 7.6 g.
of decanoyl chloridewas added dropwise with stirring and cooling
in a water bath. When the reactionwas complete the mixture
washed with water, dried and the solvent stripped off to give
7.1 g. of product.
Example 8
`~CH-8-N ~ 2 2
H2~ ~ CH2-CH-CH2
A solutionWaS formed containing 5.9 g. of diallyl amine
diæsolved in 15 ml. of methylene chloride and 6.5 g. of triethyl-
amine. Then, 6.3 g. of cyclopropane carbonyl chloride~as added
dropwlse with stirring and cooling in a water bath. When the
react~onwascomplete the mixture wes washed with water, dried and
the solvent stripped off to give 8.2 g. of product.
Example 9
~ ~CH2-CH=CH2
F CH2-CH=CH2
A solutionwas formed containing 4.5 g. of diallyl amine
dissolved in 15 ml. of methylene chl~ride and 5.0 g. of triethyl-
amine. Then, 7.1 g. of ortho-fluorobenzoyl chloridewas added
- 10 -
1~74865
dropwise with stirring and cooling in a water bath. When the
reac~ion was complete, the mixture was washed with water, dried
and the solvent stripped off to give 8.5 g. of product.
Example 10
Q
CHC12,,~_N~CH2 CH2-0-~-NH-CH3
"CH2-CH2-0-~ NH CH3
N,N-bis(2-hydroxyethyl) dichloroacetamide wss prepared
S ~ by reacting 26.3 g. of diethanolamine with 37 ~. of dichloroacetyl
chloride in the presence of 25.5 g. of triethylamine in 100 ml. of
acetone. Then, 6.5 g. of the N,N-bis(2-hydroxyethyl) dichloro-
acetamidewas dissolved in 50 ml. of acetone, then reacted with
4 g, of methyl isocyanate in the presence of dibutyl tin dilaurate
and triethylamine catalysts. The reaction productwas stripped
under vacuum to yield 8.4 g. of product.
Example 11
CH2=CH-CH2~ ~ R ,CH2-CH=CH2
,~N- -CH2-c-N
CH2=CH-CH2 ~CH2-CH=CH2
7.8 g. of diallyl amine was dissolved in 50 ml. of
methylene chloride, with 8.5 g. of triethylamine added dropwise.
Then, 5.6 g. of malonyl chloride was added dropwise with cooling
and stirring. When the reaction was complete, the mixture was
washed with water, dried over magnesium sulfate and stripped under
vacuum to yield 7.0 g. of product.
- 11 -
6 5 - -
Example 12
CH =CH-CH R R CH -CH=CH
2 2~ N-~-CH2-CH2-C-N ~ 2 2
CH2=CH-CH2~ ~ CH2-CH=CH2
7.9 g. of diallyl amine was dissolved in 50 ml. of
methylene chloride with 8.5 g. of triethylamine added dropwise.
Then, 6.2 g. of succinyl chloride was added dropwise with cooling
and stirring. When the reaction was complete, the mixture was
washed with water, dried over magnesium sulfate and stripped under
vacuum to yield 9.7 g. of product.
Example 13
~H3 ~ ~CH3
CH ~ C-CIH-N-~-CH2 CH2 ~ CH-C-= CH
CH3
6.7 g. of N~methyl-lqmethyl-3-propynylamine was dis-
solved in 50 ml. of methylene chloride with 8.5 g. of triethyl-
amine added dropwise. Then, 6.2 g. of succinyl chloride was
added dropwise with cooling and stirring. When the reaction was
complete, tbe mixture was washed with water, dried over magnesium
sulfate and stripped under vacuum to yield 7.0 g. of product.
Example 14
RC N ~CH2 CH CH2
e;~ ~CH2-CH=CH2
O=c-N(cH2-cH=cH2)2
7.9 g. of diallyl amine was dissolved in 50 ml. of
methylene chloride with 8.5 g. of triethylamine added dropwise.
Then, 8.1 g. of o-phthaloyl chloride was added dropwise with
- 12 -
1~74~365
cooling and stirring. When the reaction was complete, the m~xture
was washed with water, dried over magnesium sulfate and stripped
under vacuum to yield 10.9 g. of product.
Example 15
~ R ~H3
CH- -N-CH-C- CH
~ CH3
3.3 g. of N-methyl-l-methyl-3-propynylamine was dissolved
in 50 ml. of methylene chloride with 4.5 g. of triethylamine added
dropwise. Then, 9.2 g. of diphenyl acetyl chloride was added drop-
w~se with cooling and stirring. When the reaction was complete,
the mixture was washed with water, dried over magnesium sulfate
and stripped under vacuum to yield 9.9 g. of the product.
Example 16
~C- ~ H2 CH CH2
-CH=CH2
O-C-OH
4.9 g. of diallyl amine was dissolved in 50 ml. of
acetone with 7.4 g. of phthalic anhydride added portionwise with
stirring. The solvent was stripped off under vacuum to yield
13.0 g. of product.
- 13 - -
6 S
Example 17
C-NH-I_C---- CH
CH3
O=C~ONa
9.2 g. of N(l,l-dimethyl-3-propynyl)O-phthalamic acid
was dissolved in 50 ml. of methanol and 9.6 g. of sodium methoxide.
25% in methanol was added portionwise with stirring ~nd cooling.
The solvent was stripped or removed under vacuum to yield 9.0 g.
of product. The intermediate, N(l,l-dimethyl-3-propynyl)O-
phthalamate was prepared from 29.6 g. o~ phthalic anhydride and
16.6 g. of 3-amino-3-methylbutyne in 150 ml. of acetone. The
- intermediate was precipitated with petroleum ether as a white
solid and used without further purification.
Example 18
CHCl -~-N ~ 2H5
2 ~C2H5
A 500 cc. 4-necked flask was provided with stirrer,
thermometer and addition funnel. Then, 7.7 g. of diethylamine
(0.105 mole), 4.0 g. of sodium hydroxide solution and 100 ml.
o methylene chloride were charged to the flask and the mixture
~as cooled in a dry-ice-acetone bath. Then, 14.7 g. (0.10 mole)
of dichloroacetyl chloride was added portionwise. The mixture
was stirred for an additional hour and immersed in an ice bath.
It was then phase separated and the lower organic phase was washed
with two portions of 100 ml. of dilute hydrochloric acid~ two
100 ml. of sodium carbonate solutions, dried over magnesium sul-
fate and concentrated under vacuum to yield 16.8 g. of product.
- 14 -
~1'7~365
Example 19
C CH2-CH=CH2
CH3~C ~ C-CH2-0- -N
~CH2-CH=CH2
4.0 g. (0.025 mole) of N,N-diallylcarbamoyl chloride
was added to 50 ml. of methylene dichloride. Then, 1.8 g.
(0.025 mole) of 2-butyn-1-ol was added dropwise with 2.6 g. of
triethylamine in 10 ml. methylene chloride. The reaction pro-
duct was stirred at room temperature overnight, washed with water
twice and dried over magnesium sulfate to yield 4.0 g. of pro-
duct.
Example 20
~ ~CH2-CH-CH2
N -C-S-CH2-C-N~
CH2-CH=CH2
9.7 g~ (0.1 mole) of potassium thiocyanate was dis-
solved in 100 ml. of acetone. Then, 8.7 g. (0.05 mole) of
N,N-diallyl chloroacetamide were added at room temperature
~Jith 10 ml. of dimethyl formamide. The reaction product was
stirred overnight. The reaction product was partially stripped.
Water was added along with two portions of 100 ml. of ether. The
ether was separated, dried and stripped to yield 7.2 g.- of product.
- 15 -
i:~L7~365
Example 21
CHC12-~C_NH_C--f
--CH2
A solution of 50 ml. of benzene containing 7.4 g. (0.05
mole) of dichloro acetylchloride was formed. To this solution was
added 3.0 g. (0.05 mole) of cyclopropylamine and 5.2 g. of tri-
ethylamine in 2 ml. of benzene at a temperature of 5-10C. A
precipitate was formed and the mixture was stirred for two hours
at room temperature and one hour at 50-55C. The product was
worked-up as in previous examples to yield 5.7 g. of the product.
Example 22
CHC12-~-NH-CH ~ ~H
0' 2
To 4.7 g. (0.032 mole) of piperonylamine and 1.2 g. of
sodium hydroxide in 30 ml~ of methylene chloride and 12 ml. of
water was added 4.4 g. (0.03 mole) of dichloroacetyl chloride in
15 ml. of methylene chloride at -5 to 0C. The mixture was
stirred ten more minutes around 0C., then allo~ed to warm to
room temperature with stirring. The layers were separated and
the organic layer washed with dilute hydrochloric acid-, 10~/o
sodium carb~nate solution, water and dried to yie?d 5.9 g. of
product.
- 16 -
~ ~' i
1~'74~365
Example 23
~ ~H2-CH=CH2
~ CH=CH- -N
~ CH2-CH=CH2
Cl
In a solution of 75 ml. of benzene containing 5.7 g. of
meta-chlorocinnamyl chloride was formed. To this solution was ad-
ded 3.2 g. of diallyl amine and 3.3 g. of triethyl amine in 2 ml.
of benzene at a temperature of 5 to 10C. A precipitate was
; formed and the mLxture was stirred for two hours at room tempera-
ture and one hour at 55C. The product was washed and worked up
to yield 5.8 g. of product.
Example 24
CHCl2 ~ ~ CH3
CH3
A 500 cc. 4-necked flask was provided with a stirrer,
thermometer and addition unnel. Then, 11.9 g. 2,4-dimethyl-
piperidine, 4.0 g. of sodium hydroxide solution and 100 ml. of
methylene chloride were charged to the flask and the mixture
cooled in a dry-ice-acetone bath. Then, 14.7 g. (0.10 mole~ of
dichloroacetyl chloride were added in portions. The mixture was
stirred for one hour and ~mmersed in the ice bath, and then
separated with the lower organic phase washed with two portions
of 100 ml. of dilute hydrochloric acid and two portions of 100 ml.
of 5% sodium carbonate solution, dried over magnesium sulfate
and concentrated in a rotary evaporator under a water pump vacuum
to yield 19.3 g. of product.
- 17 -
365
.
Example 25
CHC12 ~
A 500 ml. 4-necked flask was provided with a stirrer,
thermometer and addition funnel. Then, 14.6 g. (0.105 mole) of
cis-trans-decahydroquinoline and 4.0 g. of sodium hydroxide so$u-
tion and 100 ml. of methylene chloride were added together. Then,
14.7 g. of dichloroacetyl chloride was added portionwise.
The reactio~ mixture was worked up by stirring for about an hour
and immersed in an ice bath and then phase separated with the
lower organic phase being washed with two portions of 100 ml.
dilute hydrochloric acid, two portions of 100 ml. of 5% sodium
carbonate, dried over magnesium sulfate and concentrated to yield
22.3 g. of product.
ExamPle 26
CHCl ~_N "CH2 CH2 CH2 NH 2
2 CH2-CH2-CH2-NH-~-CHC12
A 500 ml. 4-necked flask was provided with stirrer,
thenmometer and addition funnel. Then, 13.6 g. (0.104 mole) of
3,3'-iminobis-propylamine was added along with 12.0 g. of sodium
hydroxide solution and 150 ml. of methylene chloride. Thereafter,
the mixture was cooled in a dry ice-acetone bath and 44.4 g.
(0.300 mole) of dichloroacetyl chloride was added portionwise.
An oily product formed which was not soluble in methylene chloride
and was separated and washed with two portions of 100 ml. of
dilute hydrochloric acid and allowed to stand overnight. The next
morning the product was washed with two portions of 100 ml. of
5% sodium carbonate and the product was taken up in 100 ml. of
ethanol, dried over magnesium sulfate and concentrated to yield
- 18 -
~ 7~
21.0 g. of product.
ample 27
CHC12_~_N~ H2
C3H7 n
A S00 ml. 4-necked flask was provided with stirrer,
thermometer and addition funnel, Then, 7.5 g. of tetrahydrofur-
furyl-n-propylamine (0,0525 mole) and 2.0 g, sodium hydroxide
~ solution and 100 ml. of methylene c~loride were charged thereto.
Then, 7.4 g. (0.05 mole) of dichloroacetyl chloride were added
portionwise. The mixture was stirred for one additional hour in
an ice bath and then separated with the lower organic phase washed
with two portions of 100 ml, of dilute hydrochloric acid and two
portions of 100 ml, of 5% sodium carbonate solution, dried over
magnesium sulfate and concentrated to yield 12,7 g, of product.
ExamPle 28
cHcl2BrO
~ Example 27 was repeated in its entirety except that
8,9 g, of piperidine was used as the amine.
Example 29
CHcl2-~-N3
Example 28 was essentially repeated in its entirety
except 9,1 g. of morpholine was used as the amine,
- 19 -
Example 30
C NH-C-CHC12
CHC12- -NH-C ~
3.2 g. of benzaldehyde and 7.7 g. of dichloracetamide
were combined with 100 ml. of benzene and approximately 0.05 g.
of paratoluene sulfonic acid. The mixture was r~xed until
water ceased to come over. On cooling the product crystallized
from benzene yielding 7.0 g. of product.
Example 31
~ C-NH-C-C~CH
2.5 g. of 3-amino-3-methylbutyne was dissolved in 50 ml.
of acetone and 3.5 g. of triethylamine was added, followed by 6.0 g.
of adamantane-l-carbonyl chloride added dropwise with stirring and
cooling. The mixture was poured into water and the solid product
collected by filtration and dried under vacuum to give 6.5 g. of
product.
Example 32
ICH3
N - C-Ç-NH-C
CH3 ~ ~ C-NH-C-C - N
N~C- -MH- CH3
CH3
5.1 g. of 2-cyanoisopropylamine was dissolved in 50 ml.
of acetone with 6.5 g. of triethylamine added, followed by 5.3 g.
- 20 -
~ 7 ~
of benæene-1,3,5-tricarboxylic acid chloride added dropwise with
stirring and cooling. The mixture was poured into water and the
solid product collected by filtration and dried under vacuum to
give 7.6 g. of product.
Example 33
C-N(CH2-CH=CH2)2
S-N(CH2-CH=CH2)2
o
6.0 g. of diallylamine was dissolved in 50 ml. of
methylene chloride, 6.5 g. of triethylamine was added and 6.6 g.
of 3,6-endomethylene-1,2,3,6-tetrahydrophthaloyl chloride was
added dropwise with stirring and cooling. When the reaction was
complete the mixture was washed with water, dried over magnesium
sulfate and stripped under vacuum to yield 9.3 g. of product.
Example 34
CH -CH -3-N"'' 2 2
CH ~ CH2-CH=CH2
4.0 g. of diallylamine was dissolved in 50 ml. of
methylene chloride, 4.5 g. of triethylamine was added and 7.2 g.
of trans-2-phenylcyclopropane carbonyl chloride was added dropwise
with cooling and stirring. When the reaction was complete the
mixture was washed with water, dried over magnesium sulfate and
stripped under vacuum to yield 9.3 g. of product.
- 21 -
~7486~ - -
Example 35
CHC12-~-N
CH2
A solution was formed consisting of 4.0 g. (0.03 mole)
of 2-methyl indoline, 7.0 ml. triethylamine and 100 ml. of
methylene chloride. Then, 2.9 ml. of dichloroacetyl chloride was
added thereto over a period of about one minute with dry ice
' cooling, keeping the temperature under 0C. The solution was
allowed to warm to room temperature and stand for one hour and
then washed with water and then with dilute hydrochloric acid,
dried over magnesium sulfate and evaporated to give a soiid that
was washed with n-pentane to give 5.0 g. of product.
Example 36
CH C~ N ~ 3 7
2 ~, o
A 500 cc. 4-necked flask was provided with stirrer,
thermometer and addition funnel. Then, 8.9 g. of cyclooctyl n-
propylamine, 2.0 g. of sodium hydroxide solution and 100 ml. of
methylene chloride were charged to the flask and the mixture was
cooled in a dry ice-acetone bath. Then, 5.6 g. of chloroacetyl
chloride was added portionwise. The mixture was stirred for about
one additional hour, ~mmersed in the ice bath, then phase separated
and the lower organic phase was washed with two portions of 100 ml.
of dilute hydrochloric acid and two portions of 100 ml. 5% sodium
carbonate solution, dried over magnesium sulfate and concentrated
to yield 9.5 g. of product.
1~.74~
Example 37
CH2C~ N~C2H5
CH2~CH3
A 500 cc. 4-necked flask was provided with stirrer,
thermometer and addition funnel. Then, 7.8 g. (0.0525 mole)
of p-methylbenzyl ethylamine, 2.0 g. of sodium hydroxide solution
and 100 ml. of methylene chloride were charged to the flask. The
mixture was cooled in a dry ice-acetone bath. Then, 5.6 g. (0.05
mole) of chloroacetyl chloride was added portionwise. The mixture
was stirred for about one additional hour, immersed in the ice
bath, then phase separated with the lower organic phase being
washed with two portions of 100 ml. of dilute hydrochloric acid
and then two portions of 100 ml. of 5% sodium carbonate solution,
dried over magnesium sulfate and concentrated to yield 9.5 g. of
product.
ExamPle 38
CHC12-~-NH~
4.7 g. of amino pyridine were charged to a reaction
vessel along with 100 ml. of acetone and stirred at 10-15C. Then,
7.0 ml. of triethylamine were added dropwise. Thereafter, 5.25 ml.
o dichloroacetyl chloride in 10 ml: of acetone was added over a
period of five minutes and stirred at room temperature. The
solids were filtered off, washed with acetone to yield 10.0 g. of
product.
- 23 -
74~
Example 39
CHC12-C-NH~ ~H
8.1 g. (0.05 mole) of 4-aminophthalimide was dissolved
in 100 ml. of dimethylfuran, wherein 5.0 g. of dichloroacetyl
chloride was stirred in at 0-10C. over a period of 5 minutes.
Then, 7.0 ml. of triethylamine was added. The reaction mass was
5 , stirred for one-half hour at room temperature and then one liter
of water was added. The reaction was filtered with water and dried
to give 12.0 g. of product.
Example 40
-CH2-o-~ c3H7-i
CH2-CH2-0-C-NH-C3H7 -i
The compound of this example was prepared by reacting
5.4 g. of N,N-bis(2-hydroxyethyl) dichloroacetamide with 4.3 g.
of isopropyl isocyanate in 50 ml. of acetone in the presence of
dibutyltin dilaurate and triethylenediamine catalysts, to yield
8.2 g. of product.
- 24 -
~74~6S
Example 41 o
~0~ ~,CH2-CH2-0-C-N~
CH2Cl-C-N
\CH2 -CH2 - O-C~ -~
The compound of this example was prepared by xeacting
3.6 g. of N,N-bis(2-hydroxyethyl) chl~oroacetamide with 5.0 g. of
cyclohexyl isocyanate in the presence of 50 ml. of acetone and
dibutyltin dilaurate and triethylenediamine catalysts. The reac-
tion mass was heated to re~lux and stripped under vacuum to yield
6-9 g- of product.
Example 42
CHC12 C~o
3 H3
15 g. of acetone and 12.2 g. of ethanol amine were com-
bined in 150 ml. of benzene and refluxed until no additional water
came over. The resulting solution was examined and found to con-
tain 2,2-dimethyl-1,3-oxazolidine. A quarter of the benzene solu-
tion (0.05 mole) was reacted with 7.4 g. of dichloroacetyl chloride
and 5.5 g. of triethylamine, washed with water, dried and stripped
under vacuum to give a light tan solid. A portion was recrystal-
lized from ether giving a white product.
.
~ 15 Other compounds were prepared in an analogous manner
!~. starting with the appropriate starting materials as outlined above.
The following is a table of compounds representative of those em-
bodied by the present invention. Compound numbers have been
assigned ~o them and are used for identification throughout the
balance of the specification.
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- 81 -
1~74865
The co~positions of this invention were tested in the
following manner.
Test 1: Soil Incorporation
Small flats were filled with Felton loamy sand soil. The
herbicide and herbicide antidote were applied separately or in
combination to the soil as it is mi~ed in a five-gallon cement
mixer. The follow~ng stock solutions were made up of each compound
when the herbicide and antidote were applied separately. Stock
solutions of the herbicide were diluted with 100 ml. of water. For
the antidote, 700 mg. of technical material was diluted with 100 ml.
of acetone. One ml. of these stock solutions is equivalent to
7 mg. act~ve ingredient or one pound per acre when this treated
50il was placed into 8 x 12 x 3" flats. After the soil was
treated with the herbicide and the antidote at the desired rates,
the soil was transferred from the cement mixer back into 8 x 12 x 3"
flats where it was now ready for planting corn seed. A pint sample
of soil was then removed fro~ each flat and reta~*ed for covering
the seeds after planting. The æoil was leveled and rows one-half
~ncb deep ~ere made in each flat. Ehough seeds were planted to
obtain good stands in esch treatment. Seeds were then covered up
with the one pint of soil which had been removed just prior to
planting.
The flats were then placed on greenhouse benches where
~ temperatures were between 70-90F. The flats were watered by
! sprinkling as needed to assure good plant growth until rated. The
crop tolerance was rated after three to s~x weeks. The results of
these tests are set forth in Table II.
- 82 -
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,
Test 2: Corn Seed Treatment 1~74~6S
Small flats were filled with Felton loamy sand soil.
Soil incorporated herbicides were applied at this time. The soil
from each flat was placed into a five-gallon cement mixer where
the soil was mixed as the herbicides were applied as a stock solu-
tion in lOO ~l. of water. One ml. of stock solution was applied
to the soil in a volumetric pipet for each pound of herbicide de-
sired. One ml. of stock solution contains seven mg of herbicide
which equals one pound per acre when applied to soil in 8 x 12 x 311
flats. After the herbicide incorporation, the soil was placed back
into the flats.
Flats of herbicide-treated and untreated soil were then
ready to be planted. A pint sample of soil was then removed from
each flat and placed next to each flat for later use in covering
up the seeds. The soil was leveled and rows one-half inches deep
were made for planting seeds. Alternating rows of treated and un-
treated crop seeds were sown. In each test six or more seeds were
planted in eacb row. Rows were approximately l-l/2" apart in
the flat. Seed treatment was applied by placing 50 mg, of the
seed treatment compound with lO grams of seed in a suitable con-
tainer and shaking them until the seeds were uniformly covered
with the seed treatment. Seed treatment compounds were applied as
liquid slurries and powder or dust treatments. In some cases
acetone was used to dissolve powdered or solid compounds so they
could be more effectively applied to the seeds.
After flats were seeded they were covered with the one
pint of soil which had been removed just prior to planting. Flats
were placed on greenhouse benches where temperatures ranged from
- 95 -
1~L74~65 - -
70-90C. Flats were watered by sprinkling as needed to assure
good plant growth. Percent injury ratings were taken two to four
weeks after treatments were applied.
In each test, the herbicide is applied alone, in combina-
tion with the seed protectant and the seed protectant is applied
alone to check for phytotoxicity. The results of these tests are
tabulated in Table III.
- 96 -
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- 133 -
~i74865
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- 134 -
1~L7~865
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- 135 -
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- 136 -
4~365
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- 137 -
1~74~365
The antidote compounds of the present invention can be
used in any convenient form. Thus, the antidote compounds can be
made into emulsifiable liquids, emulsifiable concentrates, li~uid,
wettable powder, powders, granular or any other convenient form.
In its preferred form, the antidote compounds are admixed with
the thiolcarbamates and incorporated into the soil prior to or
after planting the seed. It is to be understood, however, that
the thiolcarbamate herbicide can be incorporated into the soil
and thereafter the antidote compound can be incorporated into the
10 ; soil. Moreover, the seed can be treated with the antidote com-
pound and planted into the soil which has been treated with herbi-
cides or untreated with the herbicide and subsequently treated
with the herbicide. The method of addition of the antidote
compound does not affect the herbicidal activity of the carba-
mate compounds.
The amount of antidote composition present can range
between about C.O~lto about 30 parts by weight per each part by
weight of thiolcarbamate herbicide. The exact amount of antidote
compound will usually be determined on economic ratios for the
most effective amount usable.
When used in the claims of this application, the phrase
"active herbicidal compound" is meant to include the active thiol-
carbamates alone or the thiolcarbamates admixed with other active
compounds such as the s-triazines and 2,~-D, or the active acet-
anilides and the like. Also, the active herbicidal compound is
different from the antidote compound.
~ - 138 -
1~7~65
It is clear that the classes of herbicidal agents
described and illustrated herein are characterized as effective
herbicides exhibiting such activity. The degree of this herbicidal
activity varies among specific compounds and among combinations of
specific compounds within the classes. Similarly, the degree of
activity to some extent varies among the species of plants to
which a specific herbicidal compound or combination may be applied.
Thus, selection of a specific herbicidal compound or combination
to control undesirable plant species readily may be made. Within
10 ~ the present invention the prevention of injury to a desired crop
species in the presence of a specific compound or combination may
be achieved. The beneficial plant species which can be protected
by this method is not intended to be limited by the specific crops
employed in the examples.
The herbicidal compounds employed in the method of this
invention are active herbicides of a general type. That is, the
members of the classes are herbicidally effective against a wide
range of plant species with no discrimination between desirable
and undesirable species. The method of controlling vegetation
comprises applying an herbicidally effective amount of the herein-
described herbicidal compounds to the area or plant locus where
control is desired.
An herbicide as used herein means a compound ~hich con-
trols or modifies the growth of vegetation or plants. Such con-
trolling or modifying effects include all deviations from natural
development; for example, killing, retardation, defoliation,
; desiccation, regulation, stunting, tillering, stimulation, dwarfing
and the like. By "plants" it is meant germinant seeds, emerging
seedlings, and established vegetation, including the roots and
above-ground portions.
- 139 -
~17~36S
The herbicides indicated in the tables are used at rates
which produce effective control of undesirable vegetation. The
rates are within the recommended amounts set forth by the supplier.
Therefore, the weed control in each instance is commercially
acceptable within the desired amount.
In the above description of the antidote compounds, the
following embodiments are intended for the various substituent
groups: alkyl includes, unless otherwise provided for, those
; members which contain from 1 to 20 carbon atoms, inclusive, in
both straight and branched chain configurations; alkenyl includes,
unless otherwise provided for, those members which contain at leas~
one olefinic double bond and contain from 2 to 20 carbon atoms,
inclusive, preferably from 2 to 12 carbon atoms, inclusive, in
both straight and branched chain configurations; and alkynyl
includes, unless otherwise provided for, those members which con-
tain at least one acetyLenic triple bond and contain from 2 to 20
carbon atoms, inclusive, preferably from 2 to 12 carbon atoms,
inclusive, in both straight and branched chain configurations.
- 140 -
