HALOACETAMIDES INSATURES ET LEUR EMPLOI A TITRE D'HERBICIDES ET DE REGULATEURS DE LA CROISSANCE VEGETALE

UNSATURATED HALOACETAMIDES AND THEIR USE AS HERBICIDES AND AS PLANT-GROWTH REGULATORS

Abrégé anglais

Abstract of the Disclosure
The present invention relates to new N,N-disubstituted
monohaloacetamides with an unsaturated branched-chain
N-substituent, to a process for preparing safe and to
their use in compositions for pre-and post-emergent con-
trol of weeds and for post-emergent plant growth regulation.

Revendications

CLAIMS
1. New N-alken-(1)-yl-(1)-monohaloacetamides of
formula I
<IMG> (I)
wherein
R1 represents chlorine or bromine,
R2 represents an alkyl radical or cycloalkyl radical
having in each case at most 6 carbon atoms,
R3 and R4 each represent hydrogen or an alkyl radical
having 1-6 carbon atoms, or
R3 and R4 together also represent a polymethylene-ring
bridge member, and the conditions applies that the
sum of the carbon atoms in the radicals R2, R3 and
R4 is 1 to 8, and
R5 represents an alkyl radical or alkoxyalkyl radical
having in all at most 6 carbon atoms, or an
alkenyl radical having 2-4 carbon atoms.
2. N-Alken-(1)-yl-(1)-haloacetamides according to
Claim 1, characterised in that in formula I
R2 represents an alkyl radical having 1 to 4 carbon atoms,
- 31 -

R3 and R4 each independently represent hydrogen
or an alkyl radical having 1 to 3 carbon atoms,
and the sum of the carbon atoms in the radicals
R2 to R4 is 2 to 8, and
R5 represents a C1-C5-alkyl radical, a C2-C6-
alkoxyalkyl radical or a C3-C4-alkenyl radical.
3. N-Alken-(1)-yl-(1)-haloacetamides according to Claims
1 and 2, characterised in that in formula I R1 represents
chlorine, R2 represents an alkyl radical having 1 to 4
carbon atoms, R3 and R4 each represent hydrogen or an
alkyl radical having 1 to 3 carbon atoms, and the sum of
the carbon atoms in the radicals R2 to R4 is 2 to 8, and
R5 represents an alkoxyalkyl radical having in all 2 to 6
carbon atoms.
4. The compound of the formula
<IMG>
- 32 -

5. The compound of the formula
<IMG>
6. The compound of the formula
<IMG>
7. The compound of the formula
<IMG>
8. Process for the production of new N-alken-(1)-yl-(1)-
monohaloacetamides of formula I of Claim 1, characterised
- 33 -

in that a ketone of formula II
<IMG> (II),
wherein R2, R3 and R4 have the meanings given under
formula I, is converted with an amine of formula III
R5-NH2 (III),
wherein R5 has the meanings given under formula I,
into a Schiff base of the formula IV
<IMG> (IV),
and this is reacted with a haloacetic acid halide of
formula V
R1 - CH2 - CO - Hal (V),
wherein R1 has the meanings given under formula I, and
Hal stands for chlorine or bromine, in the presence of
an acid-binding agent.
- 34 -

9. A method of combating or inhibiting the growth of weeds which
comprises applying to the weed or to a habitat thereof, an effective amount
of a compound as defined in claim 1, either before or after emergence of the
weed.

Description

105~2~9
The present invention relates to new N-alken-(l)-
yl~ monohaloacetamides, to processes for producing
them, and to the use of these compounds as herbicidal
active substances and as active substances regulating
plant growth; this invention also relates to herbicidal
compositions containing these new active substances
as active constituents.
The new alken-(l)-yl-(l)-monohaloacetamides
correspond to formula I
- '
1 2 7 ~ (I)
R~ R4
wherein
Rl represents chlorine or bromine,
R2 represents an alkyl radical or cycloalkyl radical
having in each case at most 6 carbon atoms,
. 15 R3 and R4 each represent hydrogen or an alkyl radical
having 1-6 carbon atoms, or
R3 and R4 together also represent a polymethylene-ring
bridge member, with the condition applying that the
sum of the carbon atoms in the radicals R2, R3
and R4 is 1 to 8, and
2 -
:'
. - . ~ .
. . , . ~ . . .
., , ,, ,, . . : , . . .
,

-`' 105~S9
R5 represents an alkyl radical or alkoxyalkyl radical
having in all at most 6 carbon atoms, or an
alkenyl radical having 2-4 carbon atoms.
A number of N-mono- or di-substituted haloacetamides
have been suggested as herbicides, with application both
before and after germination of the plants (see US-
Patent No. 2~864,683, US-Patent No. 3,586,496 and
German 'Offenlegungsschrift' No. 2,155,494). The object
of the present inven~ion is the development of herbicidal
haloacetamides which have a wide range of action against
weeds, even against very resistant species of weeds, but
which do not damage useful plants. Compared with the
known herbicidal haloacetamides, the N-disubstituted `
unsaturated monohaloacetamides according to the invention
surprisingly possess substantially better herbicidal
properties, and are further characterised by plant-growth-
regulating properties. Thus the new haloacetamides have
an inhibiting action on the growth in height of various
mono- and dicotyledons without any evidence being shown
of a reduction of crop yield in the case of, for example,
cereals and leguminosae. Furthermore, so~.e of the halo-
acetamides according to the invention can be effective
vis-à-vis certain herbicides such as phenyiureas, chloro-
~.
;
.
.

105~59
acetanilides, etc., in useful crops, such as soya bean
and maize, as antagonists (English linguistic usage:
safening agent or "antidote"), i~e. they affect
various cultivated plants in such a manner that in the
case of these plants the simultaneous application of
a herbicide that would otherwise damage them becomes
possible without, however, the herbicidal action on the
weed flora being lost. In this respect, some active
substances of formula I exhibit a behaviour similar to
the dichloroacetamides of the recently published
USP 3,867,444 (Stauffer). The main form of application
of the active substances according to the invention is
their application as herbicides; they are applied either
s before or after germination of the plants, that is, either
to the field not yet sown or already sown (pre-emergence3, or to
the field after germination of the seed (post-emergence). When
applied after germination, the new active substances may
also be employed as growth inhibitors for grasses,
, cereals and leguminosae. Some also have a fungicidal action.
For use in cereal and leguminose crops, particularly
suitable active substances of formula I are those wherein
Rl represents chlorine or bromine,
R2 represents an alkyl radical having 1 to 4 carbon atoms,
~ ~ .
~ ~ .
~. . -, .
. .
`',.,.,.. .: . ~.' . , ' `' . ''
":
: . : . . ,
:: ' . ,: , ' . :

~ 5~
R3 and R4 each independently represent hydrogen or an
alkyl radical having 1 to 3 carbon atoms, with
the condition that the sum of the carbon atoms
in the radicals R2 to R4 is 2 to 8, and
- 5 R5 represents a Cl-C5-alkyl radical~ a C2-C6-alkoxy-
alkyl radical or a C3-C4-alkenyl radical.
Compounds of formula I to be more especially emphasised
on account of their outstanding herbicidal action are
those wherein Rl represents chlorine, R2 represents a
Cl-C4-alkyl radicalj R3 and R4 each represent hydrogen
or a Cl-C3-alkyl radical, with the sum of the carbon atoms
in the radicals R2 to R4 being 2 to 8~ and R5 represents
an alkoxyalkyl radical having in all 2 to 6 carbon atoms.
The new N-alken-(l)-yl-(l)-haloacetamides of formula I
are obtained by a process in which a ketone of formula II
O
R2 - C - CH - R3 (II)
R4
' is converted with an amine of formula III
5 2 (III)
into a Schiff base of formula IV
,
:
. . _ 5 _ _ _ . _ . _ . _ _ _ _ . _ .
'. ' . ' ' ' . .
'
' , ' . ~ ~ . ' '
', ' ' ' ' ' ~ .,~ ' ' ', '

5i3~59
R2 ~ R3
R5 - N = C - CH (~V),
and this is reacted with a haloacetic acid halide of
formula V
Rl - CH2 - CO - Hal (V)
in the presence of an acid-binding agent.
In the above formulae II to V, thé symbols Rl, R2,
R3, R4 and R5 have the meanings given under formula I;
Hal in formula V stands for chlorine or bromine.
The following ketones can be used as starting
materials of formula II:
acetone, methyl ethyl ke~one, methyl-n-propyl ketone, methyl-
isopropyl ketone, ethyl-n-propyl ketone, ethylisopropyl
ketonej~Z methyl-tert.butyl ketone, methyl-n-butyl ketone,
methyl-sec.butyl ketone, methyl-isobutyl ketone,
Zl 15 diisopropyl ketone, di-n-propyl ketone, pinacolone, ethyl-
isobutyl ketone, 4,4-dimethyl-2-pentanone, 2-heptanone,
di-n-butyl ketone, ethyl-n-pentyl ketone, ethyl-isopentyl
, ketone, sec.pentyl-isopropyl ketone, methyl-hexyl ketone,
,~ - 6 -
.
Z
'' ' ' ' . .: , :

` 1053;~S~
ethyl-vinyl ketone, n-butyl-n-propyl ketone, ethyl-hexyl
ketone, methyl-n-heptyl ketone, methyl-vinyl ketone,
methyl-cyclopropyl ketone, 5-methyl-5-hexen-2-one,
n-propyl-isopropyl ketone, 3-methyl-2-heptanone, isopropyl-
n-pentyl ketone, diisobutyl ketone, n-propyl-isopentyl
ketone, n-propyl-n-pentyl ketone, diisobutyl ketone,
methyl-cyclohexyl ketone, ethyl-n-heptyl ketone,
n-propyl-n-hexyl ketone and methyl-n-octyl ketone.
The following can be used as amines of formula III:
methylamine, ethylamine, n-propylamine, isopropylamine,
2-methoxyethylamine, sec.butylamine, isobutyla~ine,
n-butylamine, tert.butylamine, 2-ethoxyethylamine, l-methyl-
2-methoxy-ethylamine, 1-methyl-2-ethoxy-ethylamine,
isobutylamine, 2-isopropoxy-ethylamine and n-hexylamine.
The reaction of a ketone of formula II with an amine
'-~ of formula III is performed in the presence of solvents
and/or diluents that are inert to the reactants, and
preferably in the presence of such ones which form with
water azeotropic mixtures. Suitable for the purpose are:
benzene, toluene, xylene, chlorobenzene, Tetralin and
dialkyl ether, as well as ketones of formula II which
are then used in excess in the reaction. --
-- 7 --
. .
;:

1~ 59
It can be advisable in some cases to add to the
reaction mixture additives promoting the splitting-off
of water. In the case of low-boiling amines, these
are preferably passed through the boiling solution of
the ketone in one of the aforementioned solvents until
; the pre-calculated amount of water has been separated.
In the case of sterically hindered ketones and amines,
it can be advantageous to continuously dry the solvent
through a molecular sieve.
The Schiff base of formula IV can often be reacted
; without further purification, and without being isolated,
directly with the haloacetic acid halide of formula V~ This
I reaction step is performed in the presence of acid-binding
J agents, e.g. a tertiary amine such as trialkylamine,
y 15 pyridine or another pyridine base, etc., or the formed
hydrohalic acid is removed by heating of the reaction
mixture in the presence of dialkylamides such as dimethyl-
.~ .
formamide. Suitable solvents or diluting agents are those
mentioned in the foregoing.
The reaction temperatures can vary within a wide
range. They are generally between 20 and 150C.
As a consequence of the described production method,
- 8 -
.~.
, . :: . : ~''' ' ' - : ' , ':: ' ' , ' ': . ''' . . ' , :
.:

~0 ~ 59
it can occur with the use of asymmetric ketones as
starting materials that the position of the occurring
double bond cannOt be clearly determined, i.e. tha~
mixtures can be formed which contain another substance
in addition to the desired compound.
- The radicals R3 and R4 are mutually interchangea~le.
In differentiating between R3 and R4, the Table does not
therefore relate to speci~ic cis-trans isomers.
The following Example illustrates the production
of an active substance of formula I according to the
invention. The temperature value are given in degrees
Centigrade.
., ~
xample
37.5 g of 2-methoxyethylamine, 50 g o~ methylisopropyl
ketone and 2 g of ammonium sulphate in about 200 ml of
benzene are boiled in a reflux apparatus with water
separator until no further water separates off. There
is thus obtained a crude benzene solution of the Schiff - -
base (pure base b.p.: 65-70/12 Torr~, which can be
directly further used. This solution is added dropwise
at 5 to 10 to a solution of 51 ~ of chloroacetyl
chloride in 25~ ml of anhydrous toluene. Stirring is
- g _
. ~ .
' "', ' " .', . ' '' ' ' ' ' ' ' '. . '.', .' ,', ' ' ' ', ' ,, . ~':"' " . . ' '.' .. .' " '~ . '. ' ' . ', . "' " "'' ' ' '.
. " ''- . ':: ,' ,~ " ' ' ''"', ' '.'~.': ' "- '. ' '' ' ' . . ' : . ' ,. . ' . '.' ,. .','". ''' . ' ' ', ,'',''.,, '' :' ' ' ' ," :. : '
i "''' ,. ,' ' ,'' '' ' . , '.' ' ' ' '. , ' '. ' .' ,' . .. ~ . ..
', '' " ' - , : ' , ' : ." . , ' ,
. . ' ' ; , ., ~ '' . '.. ' ,. ' : ','' ' :. ' '

~ 5~
maintained for about 30 minutes before an addition is
made of 63 ml of triethylamine at 10 to 20 to the
reaction solution. The whole is allowed to stand
overnight and is subsequently stirred with about
500 ml of water; the organic layer is separated,
concentrated by evaporation and the residue is distilled
twice in vacuo.
The resulting N-(l-isopropyl-vinyl)-N-2'-methoxyethyl-
chloroacetamide has the boiling point 89 to 92C/
0.005 Torr (51 g).
.
,
- 10 -
i
: .- . . :. . , , . . . . . - . .
.. . . . . , . - ............. .
., .: -

10~ 5~
In the manner described in the preceding Example there are pro-
duced, wi~h th~ use o~ corresponding ketones, amines ana haloacetic acid
halides, the ~ollowing compounds:
Table I
Compounds with R1 = Cl (chlorine)
~ompound R3 R4 b.p. C/Torr, D
l C3H7(i) H H CH2-CH2-OCH3 89-92/0,005
2 C3H7(n) H C2H5 CH2-CH2-OCH3 97-98 /0,005
3 C3H7(i) CH3 CH3 CH2-CH2-OCH3 96-103 /0,3
4 C2H5 H CH3 2 2 3 97-98 /0,08
CH3 H CH3 CH2-CH2-OCH3 90-92/0,1 :-
6 CH3 CH3C2H5 2 2 3 87 /0,13
7 C3H7(i) H CH3 CH2-CH2-OCH3 98 /O,Oô
. 8 CH3 CH3 CH3 2 2 2 5 95 /0,02 ..
9 CH3 H C3H7(i) CH2-CH2-OCH3 95 /0,2
CH3 H C2H5 CH2-CH2-OCH3 98 /0,35
11 CH3 H C3H7(n) CH2-CH2-OCH3 94/0,07
l 12 CH3 H C4Hg(t) CH2-CH2-OCH3 86 /o,o6
i 13 C4H9(i) H C3H7(i) CH2-CH2-OCH3 93 /0,003
14 C4Hg(t) H H CH2-CH2-OCH3 104 /0,4
C2H5 H CH3 C4Hg(sec) 1]0/0,15
16 CH3 H H C~Hg(i) 75 /0,1
17 C2H5 H C3H7(i) CH2-CH2-OCH3 97 /0,2
18 CH3 H C4H9(n) C4H9(i) 105/0,2
~ 19 CH3 H C4H9(n) C~2-CH2-OCH3 98 /0,07
i 20 C3H7(i) H H -CH2-CH-CH2 78-80/0,1
21 C3H7(n) H ~C2H5 CH3 91-99 /0,22 :
22 C2H5 H CH3 -CH(CH3)-CH2-OCH 93 /0,15
23 C2H5 H ~ H C4H9(n) 96 /0,3 :~
24 ~ l ~ CH2-CH2-OCH3 121-126 /0,08
3 9 H 2 5 CH(CH3)-CH -OCH 91-101 /o,o8
- 11-
.
.~ .

-` lQS;~
~ompound R2 R R4 R5 Physical data
No. _ 3 _ _ _ _ _ b.p. C/Torr; D
26 C3H7(n) H C2H5 C2H5 93 /0,15
27 C2H5 H CH3 C4H9( n ) 95 0 ,15
28 3 7 H C2H5 CH2-CH=CH2 110 /0, 5
29 CH3 H C3H7(i) 3 7 90 /0,07
CH3 H CH3 2 2 2 5 108 /o ,2
31 C2H5 H CH3 2 2 2 5 106-112 /0,2
32 CH3 H C3H7(i) c4H9(n) 95 /0,08
33 CH3 H 3 7( ) 2 2 C2H5 110/0,]5
34 CI~Hg(i) H 3 7 2 2 2 5 116-120 /0,4
CX3 H 3 7 2 2 2 5 127-130 /1
36 C2H5 H CH3 C3H7(nJ 95-100 /0,3
37 C2H5 H CH3 C3H7(i) 107 /0,3
38 C3H7(i) CH3 CH3 C4H9(n) nD3 = 1,4850
39 C3H7(i) H H C4H9(n) 88-96 /0,033
4 C2H5 H CH3 C4Hg( n ) 95 /0,15
`41 C2H5 H CH3 CH3 80-85 /0,2
42 3 7 H H (CH ) -O-CH 95-98 /0,02
43 C3H7(i) H H (CH2)3-OC3H7(i~ 114-116 /0,1
44 C3H7(i) H H 2 3 2 5 99-102 /0,1
C2H5 H CH3 (CH2)3-OC3H7(i) 115 /0,04
46 C3H7(i) H H (CH2)3-OC3H7(i) 86-89 /0,1
47 C2~I5 H CH3 C4H9(n) 93 /0,013
48 CH3 H C6H13(n) C4H9(n) nD = 1,4742
49 CH3 H C4H9(i) C4H9(n) 112-115 /0~027
C3H7(n) H C6H13(n) C4H9(n) 141-145 /o,o6
51 CH3 H C3H7(i) CH3 85/o,oO
52 3 7 CH3 CH3 2 2 2 5 112 /0,05
53 C2H5 H CH3 2 3 2 5 108-113 /0,05
54 C2H5 H CH3 CH -CH -OC H (i` 95-99 /0,03
- 12 -
... .
,
. .

105;~
Compound R2 ~ R3 R4 _Physical data
No . ~ b . p . C/Torr nD
._ _ j . .
3 ~ H 2 5 H2 CH2 OC3H7 i) 98-103ClO~l
56C3H7 ~n )j H CH3 CH2-CH2-OC3H7 (i) 103-108~ /0,08
573 7 ( ) CH3 CH2-CH2-OC3H7 (i) 95-100 /0 ,08
58 C3 7 (i) H H CH (CH3) -CH2-OCH3 79 80~ /0 ,02
59 CH3 H C5H'l~n) C4H9 (n) _ 122 /0 ,05
60 C3 7 ( ) H4 9 ( ) C4Hg (n) 127 /0 ,04
61 3 7( ) H4 9( ) C4H9(n) 1 127-131/0,08
62 C2H5 HC2H5 CH (CH3 ) -CH2 -OCH3~ 104 - 10 8 /0, lS
63 CH3 H3 7 ( ) C4Hg (sec) 104-108 /0, 2
64 C2H5 H 3 C2H5 70 /0 ,1
CH3 H C3H7 (l) C2H5 90-95 /0 ,08
66 3H7( ) CH3 CH3 CH2-CH2-OC~H7(i) 112-115/0,08
67 C3 7( ) CH3 CH3 (CH2)3-OC2H5 1 121/0,15
68 3 7( ) H C5Hll(n) CH2-CH2-C3H7(i) 136/0906
69 3 7 ( ) H C2H5 CH2-CH2-C2HS ~ 130 /0 ,1
. ~ CH3 H C2H5 CH (C~3) -~H2 -0CX3 83- 86 /0 ~04
71 3 7 ( ) CH3 CH3 C2H4-C2H4-CH I 148-150 /0 ,1
72 C6H13 (n H CH3 CH2-CH2-OCH3 134-38 /0,3
73 C6 13 (n~ H CH3 CH2 CH2 C2HS 132 /0 ,02
74 ~} H H C4Hg (n) 120 /0 ,03
C2H5 H H CH (CH3) -C4Hg (i) 92 /0 ,075
76 C2H5 H CH3 CH ~CH3) -C4H9 (i) 99-109 /0, 2
77 C3 7~ ) H 4 9( ) CH(CH3)-C4Hg(i) 115/0,1
78 CH3 H 6 13( ) ( 3) C4Hg(i) n~ = 1,4760
79 3 7( ) H H CH(CH3)-C4H9(i) nD ~ 1,484? .
CH3 H CSHll(n) CH(CH3)-C4H9(i) n~3= 1,4756
81 3 7 ( ) H 4 9 (i) CH (CH3) ~C4Hg (i) nD
82 ~>~ H _13 _ ~ H(CH3)-C4H9(i ) nD3= 1,4873
.
. , .
''_. . .~: .
- - . .. .
~ ; . , ~ , .:
~ ' `''; ' . .~, '

1q[~5~
.
Compound R2 R3 _ __~ ~ Physical data
No . b . p . C/Torr nD
_ _., _~_
~ .
83 ~ ~~ H CH3 H2 CH2 OCH3 1650/1,2
84 2H5 H C2H5 CH3 93~/0 05
H3 H C4H9(i) ~H(CH3)-C4H9( ) n~3= 1 4773
86 3H7(n) H C6H13(n) CH(CH3)C4H9~i) Oi1
87 H3 H 4 9 t) CH2-CH2-0C2H5 1070/0,4
88 CH3 H 3 7( ) CH3 930/0 35
89 3 7( ) H C2H5 CH2-CH2-OCH3 110-1150/0 1
g CH3 H C2H5 CH3 54010,015
91 3 7( ) H CH3 -CH-CH-C2H5 104-1100/0 12
CH3CH3
92 C2H5 H C4H9(n) CH3 920/0,1
93 C6H13 H C2H5 CH3 1280/0 5
94 3 7( ) H CH3 3 7( ) 980/0 2
CH3 H C2H5 3H7(i) 700/0,1
96 C4H9(i) H ~H3 CH3 CH3 900/0,15
97 CH3 H CH3 CH2-CH2-C~-CH3 nD5 1 4825
98 -CH CHH3 CH3 CH3 CH n20 1 4820
99 C2H5 H CH3 CH2CH2CH-CH3 nD2 1 4826
/ H3
100 CH3 CH3 3 CH2CH2CH-CH3 nD : 1 4804
101 CH3 H CH2CH-CH3 CH2CH2CH-CH3 nD: 1,4782
CH3
102 (~> H H CH2CH2CH-CH 3 n20 1 5027
5~31
103 CH3 H -(C~2)4C~3 CH2CH2CH-CH3 nDO: 1,47S2
1 104 ~ H ¦H ~-(CH2) CH31 CH2C~2C 3 nD: 1,4762
. . . . .
'', ~,:
'',, :, ` - ; ~ , . - . . ~ , .' . , . -. :. . - . . . , ., .: ., : . :
~: : . ,, - . .

S;~S9
, .,, _ , ,
. ~Compound R2 R31 R4 R5 Phys cal data
, ., _ _ . . ._
&H
105 C3H7-n H ~H2)sCH3 CH2CH2CH-CH3 nD : 1,4739
106 C3H7-n H -(CH2)~CH3 CH CH ~ CH3 nD~: 1,4771
107 3 7 n H-CH2CH-CH3 CH2CH2CH-~3 nD 1,4776
108 CH3 H C4Hg(i) CH3
: 109 CH3 H C4H9(i) C2H5
110 CH3 H C4Hg(i) 3 7(n)
111 CH3 H 4 g( ) 3 7( )
112 CH3 H 4 g(i) CH~CH2 0 CH3
113 ~H3 H C4Hg(i) C4Hg(i)
114 CH3 H C4Hg(l) C4Hg (sec)
115 CH3 HC4H9(i) CH2-CH2-C2H5
116 CH3 HC4Hg(i) -CH-CH2-0CH3
. CH3
117 C2H5 HC4H9(i) CH3
118 C2H5 HC4Hg(i) C2H5
119 C2H5 H4~9(i) 3H7(n)
120 C2H5 H4 g(i) 3 7(i) :
121 C2H5 HC4H9(i) CH2-CH2-OCH3
122 C2H5 HC4Hg(i) C4Hg(n)
123 C2H5 HC4Hg(i) C4H9(i) : :
124 C2H5 HC4Hg(i) C4Hg (sec)
125 C2H5 HC4H9(i) CH2-CH2-C2H5
126 C2H5 H4 9( ) -CH-CH2-OCH3
., _ ~ 3 ___ _
.¦ . .
., .
..
, . - lS -
.
~ .
~: : .- - - ., . . - . . - . .
. ~ . . ., .. ~ ,. ~ . . . :, . - . .
.:, , " ~ ",~ , , " ,: ,
. . ... .. ...
,

Table II
Compounds with Rl = Br (bromine) 1053~59
. .. . ., ~
Compound R2 3 ~ R4 R5 Physical data
__ ~,, ,
127 CH3 3 CH3 CH2-CH2-OCH3 118/0,3
12 83 7 ( ) 3 CH32 2 OCH 3116 /0, 03
129C2H5 H HCgHg (n) 88 /0 ,035
130C2H5 H CH3C4H9(n) nD = 1,4970
131 C3H7 ~i) H HC4H7 (n) n23= 1,4993
132 CH3 H C4H (i)C4H9~n) g8-105/0,02
133 CH3 H 3 7 ( ) 2 CH2 OC2H5100-105 /0, 4
134 C3H7 (i) H CH3 C3H7 (i) 86 /0, 2
135 C2H5 H CH3 CH3 85 /0 ,1
136 C3H7 (i) H H (CH2) 3 OCH3103 -107 fo ,02
137 G2H5 H CH3 ( 2)3 OC3H7(i110/0,01
138 CH3 CH3 CH3 CH2-CH2-OC2Hs97o /o ,07
13~ 3 7 (n) CH3 CH3 C4H9 (n) oil
140 3 7 ( ) H C6Hl3n) C4H9 (n) 138 /0 ,07
141 C2H5 H ~H3 (CH2)3 C2H5108-111 /0 ,03
142 CH3 H ~,3H7 (i) CH3 90 /0 ,12
143 C3H7 (n) H ~4Hg (i) C4Hg (n) n21= 1,4891
144 C3 7 ( ) H ~4H9 (n) C4Hg (n) Oel
C2H5 H :-13 CU~CH3) -G4H9 ~i Oel
. . .
- 16 -
.
. , . -; . . - ,
- :: , . . . ~ . :, . : : .
. .
: . ,.,: ~ -
.

- -
lOS~
Inhibition of the ~rowth of ~rasses
(Application after germination of the plants (post-emergence))
Seeds of the grass species Lolium perenne, Poa
pratensis, Festuca ovina and Dactylis glomerata were
sown in plastics dishes containing a soil/peat/sand
. mixture. After 3 and 4 weeks, the emerged grasses were~ .
cut back to 4 cm above the soil, and 2 days after the
second cutting, they were sprayed with an aqueous spray
liquor of the active substance. The amount of active :
- 10 substance was 5 k~ of active substance per hectare.
14 days after application, the growth of the grasses
was evaluated according to the following linear scale
of values:
1 = severe inhibition, no growth from the
time of application;
9 = no inhibition, growth as in the case of
the control specimen.
- 17 -
. . ~ . . , , ~. ................................. .
~ ~ - , . . . ~ ; . .. . . - . .

- 1~35~;~S~
In this test, the compounds of formula I, and in
particular the following
N-[l-isopropyl-propen~ yl-(l)]-
N-2'-methoxyethyl-chloroacetamide,
N-ll-methyl-propen-(l)-yl(l)~-
N-2'-methoxyethyl-chloroacetamide,
N-ll-ethyl-buten-(l)-yl(l)]-
N-2'-methoxyethyl-chloroacetamide~
N-(l-isopropyl-vinyl)-N-2'-methoxy-
ethyl-chloroacetamideg
N-ll-isopropyl-2-methyl-propen-
(l)-yl-(l)]-N-2'-methoxyethyl-
chloroacetamide, and
N-[l-n-propyl-propen-(l)-yl-(l)]-
N-2'-methoxyethyl-chloroacetamide,
have an excellent growth-inhibiting action on the species
of grasses used.
- 18 -
.
.,, -. . . - - . -, ;- . . .. - .. ~ ~ . :
- .. , ~ .. . ., ., -. . . ~ . , . ~ . .. .
: , ,. . : . - - . . - ~ . - : . - . :
, - .. , ... ~ ... . . . .. . ,
.,- , . ~ ,. . . ... ~ . .
, . . . ,... - .. . , . - ~

ll~S;~;~S9
Herbicidal action with application of the active substances
before ~ermination (pre-emer~ence~ of the plants.
Immediately after sowing of the test plants, the
surface of the soil is treated with an aqueous suspension
of the active substances, obtained from 25% wettable
powders. The amoun~ applied is chosen to correspond to
16 kg and 4 kg respectively of active substance per
hectare. The seed trays are kept in a greenhouse at
. 22-25C with 50-70% relative humidity.
- 10 The followin~ are used as test plants:
Avena sativa Sinapis alba
Setaria italica Stellaria media
The test is evaluated 20 days after application of
; the active substances. Evaluation is made on the basis
of a scalP of 9 values as follows:
1 = plants dead,
2-4 = intermediate stages of damage (over 50%
irreversible damage),
5-8 = intermediate stages of damage (below 50%
reversible damage),
9 plants undamaged (control).
Also in this test the active substances according
to the invention produce outstanding results, particularly
the Compounds Nos~ (Table) 1, 3, 8 and 22.
,
.,
.. . .
- . , . '' .
.

-`~105;~;~S9
Herbicidal action in the case of application of the
active substances after ~ermination (post-emer~ence2 of
the plants.
The test plants are trea~ed in the 2-4-leaf stage
with aqueous suspensions of active substances, obtained
from 25% emulsion concentrates. The amount applied
corresponds to 4 kg of active substance per hectare.
The following are used as test plants:
Avena sativa Sinapis alba
Setaria italica Stellaria media
Lolium perenne Gossypium hirsutum
Solanum lycopersianum Phaseolus vulgares
After the treatment, the plants are kept for ~4 days
in a greenhouse under normal conditions.
15Evaluation is made according to a scale of 9 values:
1 = plants dead,
' 2-4 intermediate stages of damage (over 50%
irreversible damage),
' 5-8 = lntermediate stages of damage (under 50%
20reversible damage),
9 - plants undamaged.
. ' .
, . . , . ~ , . . .. .. . .
. . . - - .. , - , . . . . ' - . ~ ~ .. .
, ,, , .. . , ... ... ~ . . . .- . . . .
. . . - , . ... .. ~ . . ::
, ,
.: : , : .............. : , ~ ', .. .. .

lOS3;~S~
In these tests, the compounds of fonmula I,
particularly N-[l-isopropyl-2-methyl-propen-(1)-yl-
(l)]-N-2'-methoxyethyl-chloroacetamide, have a very
good action against weeds but do no damage at all to
: 5 cultivated plants. An equally good action is obtained
with Compounds Nos. 1 and 33 of the Table.
The active substances according to the invention
are with regard to their action clearly superior to the
constitutionally related commercial product N,N-diallyl-
. 10 chloroacetamide ("Randox").
.
~ tv~a o/~ f~a r~
~.
.
- 21 -

0 ~ ~ 5~
The compositions according to the invention are
produced in a manner known per se by the intimate mixing
and/or grinding of active substances of the general
formula I with suitable carriers, optionally with the
addition of dispersing agents or solvents which are
inert to the active substances. The active substances
can be obtained and used in the following forms:
solid preparations: dusts, scattering agents, granulates,
coated granulates, impregnated granulates
and homogeneous granulates;
water-dispersible active-substance concentrates:
wettable powders, pastes and emulsions;
li~uid preparations: .
solutions.
The solid preparations (dusts, scattering agents and
granulates3 are produced by the mixing of the active
: substances with solid carriers. Suitable carriers are,
e.g., kaolin, talcum, bole, loess, chalk, limestone,
ground limestone, attapulgite, dolomite, diatomaceous earth,
precipitated silicic acid, alkaline-earth silicates,
sodium and potassium aluminium silicates (feldspar and
mica), calcium and magnesium sulphates, magnesium oxide,
ground synthetic materials, fertilisers such as ammonium
- 22 -
.
,; - - . , , . , , , -
: . : .
: .. . . .

~ ~ 5 ~ ~9
sulphate, ammonium phosphate, ammonium nitrate, urea,
ground vegetable products such as bran, bark dust,
sawdust, ground nutshells, cellulose powder, residues
of plant extractions, active charcoal, etc., alone or
in admixture with each other.
The particle size of the carriers is for dusts
advantageously up to approx. 0.1 mm; for scattering
agents approx. 0.075 to 0.2 mm; and for granulates 0.2 mm
or coarser.
The concentration of active substance in the solid
preparations is 0.5 to 80%.
It is possible to add to these mixtures also additives
stabilising the active substance, and/or nonionic, anion-
active and cation-active substances which improve, e.g.,
the adhesiveness of the active substances on plants and
parts of plants (adhesives and agglutinants), and/or
ensure better wettability (wetting agents) as well as
dispersibility (dispersing agents). Suitable adhesives
are, for example, olein/lime mixture, cellulose derivatives
(methyl cellulose, carboxymethyl cellulose)~ hydroxy-
ethylene glycol ethers of monoalkyl and dialkyl phenols
having 5 to 15 ethylene oxide radicals per molecule and
23 -
~ .
. - ~ , .
. ..... . ~, -
.

l~S3~5!~
8 to 9 carbon atoms in the alkyl radical, lignin-
sulphonic acid, the alkali metal salts and alkaline-
earth metal salts thereof, polyethylene glycol ethers
1~ CQ~bo ~aJ~e5 ~
A (earbo~axc3), fatty alcohol polyglycol ethers having
5 to 20 ethylene oxide radicals per molecule and 8 to
18 carbon atoms in the fatty alcohol moiety, condensation
products of ethylene oxide, propylene oxide, polyvinyl-
pyrrolidones, polyvinyl alcohols, condensation products
of urea and formaldehyde, as well as latex products.
Water-dispersible concentrates of active substances,
i.e. wettable powders, pastes and emulsion concentrates,
are agents which can be diluted with water to obtain any
desired concentration. They consist of active substance,
carrier, optionally additives stabilising the active
substance, surface-active substances, and anti-foaming
agents and, optionally, solvents. The concen~ration of
active substance in these preparations is 5 - 80%.
The wettable powders and pastes are obtained by the
mixing and grinding of the active substances with
dispersing agents and pulverulent carriers, in suitable
I devices, until homogeneity is obtained. Suitable carriers
i are, e.g., those previously mentioned in the case of
solid preparations. It is advantageous in some cases to
- 24 -
~ r~O(~e ~rk ~:
:~; . .
'
,~ , . : ' . .. ~ ' ' ' '

5~
use mixtures of different carriers. As dispersing agents
it is possible to use, e.g.: condensation products of
sulphonated naphthalene and sulphonated naphthalene
derivatives with formaldehyde, condensation products
of naphthalene or of naphthalenesulphonic acids with
phenol and formaldehyde, as well as alkali metal salts,
ammonium salts and alkaline-earth metal salts of
ligninsulphonic acid, also alkylarylsulphonates, alkali
metal salts and alkaline-earth metal salts of dibutyL
naphthalenesulphonic acid, fatty alcohol sulphates such
as salts of sulphated hexadecanoLs, heptadecanols,
octadecanols, and salts of sulphated fatty alcohol
glycol ethers, the sodium salt of oleyl methyl tauride,
ditertiary acetylene glycols, dialkyl dilauryl ammonium
chloride, and fatty acid alkali-metal and alkaline-earth
metal salts.
Suitable anti-foaming agents are, e.g., silicones.
The active substances are so mixed, ground, sieved
and strained with the above-mentioned additives that the
solid constituent in the case of wettable powders has a
1 particle size not exceeding 0.02 to 0.04 mm, and in the
case of pastes not exceeding 0.03 mm. For the preparation
of emulsion csncentrates and pastes, dispersing agents
- 25 -
,,, ~ .
, . . .
,~,, . ~ : . , ~
' :. ' ' ~ ' ' :
, ~

are used such as those mentioned in the preceding
paragraphs, organic solvents and water. Suitable solvents
are, e.g., alcohols, benzene, xylenes, toluene,
dimethylsulphoxide~ N,N-dialkylated amides, N-oxides
of amines, especially trialkylamines, and mineral oil
fractions boiling in the range of 120 to 350C. The
solvents must be practically odourless, nonphytotoxic,
inert to the active substances and not readily
combustible.
Furthermore, the agents according to the invention
can be used in the form of solutions. For this purpose,
the active substance, or several active substances, of
the general formula I is dissolved in suitable organic
solvents, solvent mixtures, water, or mixtures of organic
solvents with water. As organic solvents, it is possible
to use aliphatic and aromatic hydrocarbons, their
chlorinated derivatives, alkylnaphthalenes, mineral
oils on their own or in admixture with each other. The
; ~olutions should contain the active substances in a
concentration of 1 to 20%.
These solutions can be applied either by means of a
propellent gas (as spray), or by means of special
sprayers (as aerosol).
- - 26 -
, . . . . .
..
.
. . .

~ lQ ~
Other biocidal active substances or agents can be
mixed with the described compositions of the invention.
For the broadening of their sphere of action, the new
compositions can contain, in addition to the stated
compounds of the general formula I, for example other
herbicides, as well as fungicides, bactericides,
fungistatics, bacteriostatics or nema~ocides. The
compositions of the invention may also contain fertilisers,
trace elements, etc..
Preparations of the new active substances of the
general formula I are described in the following. Parts
are given as parts by weight.
,
., ~
'
. :
~, .
,~ .

~ ~ S ~ 5
Wettable powders
The following constituents are used to prepare
a) a 40%, b) and c) a 25%, and d) a lQ% wettable powder:
a~ 40 parts of active substance,
parts of sodi~m lignin sulphonate,
1 part of sodium dibutyl-naphthalene sulphonate,
54 parts of silicic acid;
b~ 25 parts of active substance,
4.5 parts of calcium lignin sulphonate,
1.9 parts of Champagne chalk/hydroxyethyl
cellulose mixture (1
1.5 parts of sodium dibutyl naphthalene sulphonate,
19.5 parts of silicic acid,
19~5 parts of Champagne chalk,
lS 28.1 parts of kaolin;
c) 25 parts of active substance,
2.5 parts of isooctylphenoxy-polyoxyethylene-
ethanol,
1.7 parts of Champagne chalk/hydroxyethyl
20cellulose mixture (1:1), - -
, 8.3 parts of sodium aluminium silicate,
16.5 parts of kieselguhr,
46 parts of kaolin;
- 28 -
. . ~

`;~s~
d) 10 parts of active substance,
3 parts of a mixture of the sodium salts of
saturated fatty alcohol sulphates,
parts of naphthalenesulphonic acid/
formaldehyde condensate,
82 parts of kaolin.
The active substances are intimately mixed with the
additives in suitable mixers, and the mixture is then
ground on the appropriate mills and rollers. There are
obtained wettable powders that can be diluted with
water to give suspensions of any desired concentration.
'
~ . .
~ .
- 29
,
: ,. . . .

1~ 5
Emulsifiable concentrates:
,
The following substances are used to produce a) a
10% and b) a 25% emulsifiable concentrate:
a) 10 parts of active substance,
3.4 parts of epoxidised vegetable oil,
3.4 parts of a combination emulsifier consisting
of fatty alcohol polyglycol ether and alkyl- -
arylsulphonate calcium salt,
40 parts of dimethylformamide,
43.2 parts of xylene;
b) 25 parts of active substance,
2.5 parts of epoxidised vegetable oil,
10 parts of an alkylarylsulphonate/fatty alcohol- :
polyglycol ether mixture,
5 parts of dimethylformamide,
57.5 parts of xylene. ..
It is possible to obtain from these concentrates,
by dilution with water, emulsions of any desired
concentration.
- 30 -
.. .. .. - .. ., . .. . - . . ;
... .. - . . . . . . . . ~ .
., : . ...... .
. '' - ' - : . ' ' . ~' ' . . '::