Note: Descriptions are shown in the official language in which they were submitted.
-
2818
The present invention relates to novel phenoxyphenyl-
sulphinyl- and phenoxyphenylsulphonyl-alkanecarboxylic acid
derivatives which possess a herbicidal and plant growth-regulating
action, processes for their production, and plant growth-regulating
compositions which contain these derivatives as active ingredients,
and the use of the novel compounds, or of comp,ositions containing
them, as herbicides and/or for regulating plant growth.
The novel phenoxyphenylsulphinyl- and phenoxyphenyl-
sulphonyl-alkanecarboxylic acid derivatives have the formula I
Haln S(O)p-Q-A
E ~ D C ~ Hal (I)
wherein
A represents the cyano group or the radical -COB,
B represents a radical -O-N=CRlR2, -OR3, -SR4 or -NR5R6,
C represents hydrogen, halogen, cyano, nitro, Cl-C4 allcyl or Cl-C4alkoxy,
D represents hydrogen, halogen, cyano, nitro or trifluoromethyl,
E represents hydrogen, halogen, cyano, nitro, C1-C4 alkyl, C1-C4alkoxy,
methylsulphonyl or dimethylsulphamoyl,
Hal represents halogen,
n is O, 1 or 2,
p is 1 or 2,
Q represents an unbranched or branched C1-C4alkylene bridge, both of
Rl and R2 represent Cl-C4alkyl or one of them represents hydrogen,
R3 represents hydrogen or the cation of a base 1 M n wherein
8i8
~I representsthe cation of an alkali metal or alkaline
earth metal or an iron, copper, zinc, manganese or
nickel cation, or an ammonio radical
R - N - R
a /\ d
Rb Rc
n is an integer 1, 2 or 3 which corresponds to the
valency of the cation, and Ra, Rb, Rc and Rd, each
independently of the other, represent hydrogen,
benzyl or a Cl-C4alkyl radical which can be
substituted by -OH, -NH2 or Cl-C4alkoxy,
R3 and R4 represent a Cl-C18alkyl radical which is
unsubstituted or substituted by halogen, nitro,
cyano, Cl-C8alkoxy, C2-C8alkoxyalkoxy, C3-C6alkenyi-
oxy, Cl-C8alkylthio, C2-C8alkanoyl, C2-C8acyloxy,
C2-C8alkoxycarbonyl, carbamoyl; bis~Cl-C4alkyl)
amino, tris(Cl-C4alkyl)ammonio, C3-C8cycloalkyl,
C3-C8cycloalkenyl, and also by a benzyl or phenoxy
radical;
-a C3-C18alkenyl radical which is unsubstituted or
mono- to tetra-substituted by halogen or mono-
substituted by phenyl or methoxycarbonyl;
-a C3-C8alkynyl radical;
-a C3-C12cycloalkyl radical which can be substituted
by halogen or Cl-C4alkyl;
-a C3-C8cycloalkcnyl radical;
-a phenyl radical which is unsubstituted or mono- or
~lC2`t318
polysubstitutcd by halogen, Cl-C4alkyl, Cl~C4alkoxy,
Cl-C4alkylthio, NO2, CF3, COOH, CN, O11, SO31-1, N1-12 or
-NH(Cl-C4alkyl) or -N(Cl-C4alkyl)2;
R5 and R6 represent hydrogen or unsubstituted or
substituted (cyclo)aliphatic radicals, preferably
Cl-C4alkyl, aromatic, C2-C8alkoxyalkyl or Cl-C4alkoxy
radicals.
The alkyl and alkenyl radicals in the above formula can
be branched or unbranched and contain the indicated number
of carbon atoms.
The symbols R5 and R6 can be hydrogen or aliphatic,
cycloaliphatic or aromatic radicals. However, hydrogen and
lower alkyl radicals of l to 4 carbon atoms are preferred.
The active compounds of the formula (I) of the
present invention possess advantageous growth-regulating effects
(growth inhibition). In particular, they inhibit the growth
of dicotyledonous plants. Exemplary of the useful application
of the compounds of the present invention are:
-the reduction of the vegetative growth in soya and
similar leguminosae, resulting in an increase in the
yield of these plants;
-the inhibition of the undesirable growth of suckers in
~ -3-
Z8i8
- 4
tobacco plants, the leading shoots of which have been
cut, thus promoting the formation of larger and finer
leaves;
-the inhibition of the growth of growth of grass and
dicotyledonous plants, such as fruit trees, ornamental
trees, bushes and hedgerows, ~ith the object of saving
cutting work.
The compounds of the present invention have a low
toxicity to warm-blooded animals and their application
causes no problems. The rate of application is between
0.1 and 5 kg per hectare.
The novel compounds of the formula I are obtained by
methods which are in themselves known, for example in
accordance with the following reaction scheme:
.
81
-- 5 --
,
Hal aprotic solvent
Ual + HO ~ ~3, ;~ U~C
S Q A aprotic solvent ~ -~ .
H ~ \ - base j ` VI
n C
VII Haln ~
D ~ C
II
. oxidation
~Hal ~ .
n
~S(O)p-Q-A
D al C
In the above formulae, A, C, D, E, Q, n and p are as
defined in formula I and Hal represents a halogen atom,
preferably a chlorine or bromine atom.
A start is made for example from an unsubstituted or
substituted halobenzene of the formula III, which is
condensed with an optionally further substituted methyl-
thiophenol of the formula IV in the presence of an acid
acceptor in an aprotic solvent at elevated temperature to
give the phenoxymethylthio compound of the formula V.
This latter compound can then be further reacted at
elevated temperature with an a-haloalkanecarboxylic acid
... . ... .. .. . .. . _ . . . . . . . _ _ . . . .
8 1~3
-- 6 --
derivative of the formula VI to give the phenoxyphenyl-
thioalkanecarboxylic acid of the formula II. The pro-
duction of such phenoxyphenylthioalkanecarboxylic acid
derivatives is also described, inter alia, in German
Offenlegungsschrift 2,223,894.
A further route for obtaining these phenoxyphenylthio-
alkanecarboxylic acid derivatives of the formula II also
starts from the optionally substituted halobenzenes of
the formula III, which are condensed for example with a
hydroxyphenylthioalkanecarboxylic acid of the formula VII
which can be further substituted in the ring, in the
presence of an acid acceptor, for example an inorganic
base, and in an aprotic solvent at elevated temperature.
The process of the present invention for the production
of the novel phenoxyphenylsulphinyl- and phenoxyphenyl-
sulphonylalkanecarboxylic acid derivatives comprises
treating a phenoxyphenylthioalkanecarboxylic acid
derivative of the formula II (see reaction scheme),
wherein A, C, D, E, Q, Hal and n are as defined in
formula I, with an oxidising agent until the sulphide
bridge has become oxidised to the sulphinyl (-SO-) or
sulphonyl (-SO2-) bridge.
.
Suitable oxidising agents for this reaction are for
example hydrogen peroxide, oxygen, or also air which is
bubbled through the reaction mixture. The phenoxyphenyl-
thioalkanecarboxylic acid derivative can furthermore be
added to dilute sodium hydroxide solution and then
chlorine is slowly bubbled into the reaction mixture.
-" llC~Z818
The compounds of the formula I can also be obtained by
reducing a correspondingly substituted diphenyl ether
sulphochloride with sodium sulphite to sulphinic acid
and reacting this latter, or a salt thereof, with a
radical Hal-Q-A, wherein A, Q and Hal are as defined in
formula I.
The following Examples illustrate the manufacture of
the active compounds of the formula I. Further active
compounds obtained in corresponding manner are listed
in Table 1. Phenoxyphenylthioalkanecarboxylic acids
of the formula II obtained as intermediates are listed
in Table 2.
"`` 11C~2818
~ .
-- 8 --
Example 1
a-[4-(2'-Chloro-4'-trifluoromethylphenoxy)-phenyl-
sulphonyl]propionic acid methyl ester
Cl
C~3 ~ ~ CH3
215 g of 3,4-dichlorobenzotrifluoride and 148 g of 4-
methylmercaptophenol are stirred with 64 g of 88%
potassium hydroxide in 600 ml of dimethyl sulphoxide for
10 hours at 150C. For working up, the reaction mixture
is poured into ice-water and extracted with methylene
chloride. The methylene chloride solution is concentrated
and the residue is distilled, affording 240 g of 2-chloro-
4-trifluoromethyl_4'_methylmercapto-diphenyl ether.
Boiling point: 130-131C/0.4 mm Hg.
In a distillation apparatus, 32 g of this compound are
heated with 20 g of methyl a-bromopropionate for 3 hours
to 185C. The subsequent distillation yields 24.5 g of
a-[4-(2'-chloro-4'-trifluoromethylphenoxy)-phenylthio]-
propionic acid methyl ester which boils at 161-164C/
0.3 torr. 16.7 g of this ester are refluxed in 100 ml of
glacial acetic acid with excess 30% hydrogen peroxide for
25 hours. For working up, the reaction mixture is poured
lnto ice-water and extracted with methylene chloride. The
methylene chloride solution is concentrated and the
residue distilled, affording 11.5 g of a-[4-(2'-chloro-
4'-trifluoromethylphenoxy)-phenylsulphonyl] propionic
acid methyl ester which boils at 190C/0.023 torr.
g
Example 2
3-(2',4'-Dichlorophenoxy)-6-iodo-phenylsulphinylacetic
acid methyl ester
o
Cl S-CH2-C0-CH3
C ~ 0 ~ I
a) 12 g of 4-chloro-2-methylmercapto-nitrobenzene are
heated to 160C in 50 ml of dimethyl sulphoxide with
10 g of 2,4-dichlorophenol and 2.5 g of sodium hydroxide.
After two hours, the batch is poured onto ice and extracted
with ethyl acetate. The organic solu~ion is concentrated
and the residue ecrystallised from toluene/hexane,
affording 16 g of 2,4-dichloro-3'-methylmercapto-4'-
nitrodiphenyl ether with a melting point of 120-122C.
The catalytic reduction in dioxane with Raney nickel
affords 2,4-dichloro-3'-methylmercapto_4'_amino_diphenyl
ether in virtually quantitative yield. Melting point:
40-42C.
b) 65 g of this compound are mixed with 300 ml of water
and 144 ml of conc. sulphuric acid and the mixture is
cooled to 0C. By reaction with a 5% sodium nitrite
solution at 0 to 5C a diazonium salt solution is
prepared, to which a solution of 39.5 g of potassium
iodide in 370 ml of water is added dropwise at 0C after
1 hour. A tacky precipitate forms, which is dissolved
after 2 hours by addition of methylene chloride. The
organic phase is separated and concentrated. The residue
is extracted repeatedly with warm hexane and the combined
hexane extracts are concentrated and cooled. Crystal-
lisation yields 67 g of 2,4-dichloro-3'-methylmercapto-
4-iodo-diphenyl ether.
818
- 10 -
c) 10 of 2,4-dichloro-3'-methylmercapto-4'-iodo-diphenyl
ether are refluxed for 10 hours with 20 ml of methyl
bromopropionate and purification is effected by chromato-
graphy on-a column of silica gel with cyclohexane as
eluant. The solvent is evaporated off, yielding 7 g of
3-(2',4'-dichlorophenoxy)-6-iodo-phenylthioacetic acid
methyl ester with a refractive index n24: 1.6528.
c) 5.4 g of the compound obtained in c) in 100 ml of
methylene chloride are slowly treated with 2.5 g of 85%
3-chloroperbenzoic acid. After 2 hours the batch is
extracted with dilute sodium hydroxide solution. The
organic phase is dried over sodium sulphate and concentra-
ted. Recrystallisation of the residue from toluene/hexane
affords 3.5 g of the title compound with a melting point
of 120-122C.
Example 3
CH3
Cl S02-CH-C0-OCH3
CL_ ~ O ~ Cl
-[3-(2',4'-Dichlorophenoxy)-6-chlorophenylsulphonyl]
propionic acid methyl ester
a) To a solution of 400 g of di-(2'~4'-dichlorophenoxy)-
nitrobenzene, 64 g of 85% potassium hydroxide and 100 ml
of dioxane are added 45 g of methyl mercaptan at 50-70C.
After 1 hour the solvent is stripped off in vacuo and the
residue is taken up in toluene. The solution freed from
2,4-dichlorophenol by washing with dilute sodium
hydroxide solution is added dropwise to a boiling mixture
of 500 g of iron powder, 500 g bf ethanol and 50 ml of
conc. hydrochloric acid. After refluxing for 15 hours,
11(~2~18
.
11 -
the batch is made alkaline with 30% sodium hydroxide
solution, iron sludge is removed by suction filtration
-and the filter cake is washed with toluene. The organic
phase of the filtrate is concentrated and distilled,
affording 192.5 g pf 4_(2',4'-dichlorophenoxy-2-methyl-
mercaptoaniline with a boiling point of 170C/0.1.
b) 180 g of the compound of Example 3 a) are dissolved
in 1.5 litres of glacial acetic acid and 153 ml of
hydrochloric acid are added to the solution. A diazo
solution is prepared by the dropwise addition of a
solution of 41.5 g of sodium nitrite in 100 ml of water
at 5C. After destroying excess nitrite with sulphamic
acid, the diazo solution is added dropwise at 75-90C
to 2 litres of 18% hydrochloric acid and 118 g of
copper (I) chloride. After 1 hour the batch is extracted
with toluene and the organic phase is concentrated.
Distillation of the residue yields 172 g of 3-(2',4'-
dichlorophenoxy)-6-chloromethylmercaptobenzene with a
boiling point of 158C/O.OS.
c) 140 g of the compound of Example 3 b) are refluxed
for 16 hours with 105 ml of methyl 2_bromopropionate and
a crystal of potassium iodide. The subsequent distillation
yields 150 g of a-[3-(2',4'-dichlorophenoxy)-phenol-6-
chlorophenolthio] propionic acid methyl ester with a
boiling point of 186C/0.09.
d) Treatment of 7 g of the above compound with 8.2 g of
3-chloroperoxy-benzoic acid in methylene chloride in
accordance with Example 2 e) yields 6 g of the title
compound in the form of an oil with a refractive index
n24: 1.5890.
llCZ818;
12
Example 4
~3
Cl ___r~O-CH-CO-OCH3
CF3 ~ ~ Cl
~-[3_(2'-Chloro-4'-trifluoromethylphenoxy)-6-
chloro hen lsul hinvl] ~ro~ionic acid methyl ester
P Y P
a) With efficient stirring, ~41 g of 2_chloro-5-methoxy-
aniline are added to 310 ml of water and 385 ml of conc.
hydrochloric acid, followed by the addition of 750 g of
ice. The mixture is cooled to -10C and a solution of
111 g of sodium nitrite in 150 ml of water are added all
at once, whereupon the temperature rises to 10C. After
30 minutes excess nitrite is destroyed with sulphamic
acid and the solution is clarified by filtration. This
diazo solution is added dropwise at 55-60C to a
solution of 300 ml of water, 800 ml of toluene, 225 g of
potassium methylxanthogenate, 85 g of sodium bicarbonate
and 75 ml of 30% sodium hydroxide solution. When the very
vigorous evolution of gas has ceased the organic phase is
separated, washed with water, dried over sodium sulphate
and added dropwise to 100 ml of triethylamine at 70C.
After refluxing for 2 hours, cooling, and adding 200 ml
of 30% sodium hydroxide solution, the organic phase is
separated and distilled, affording 160 g of 4-chloro-3-
methylmercaptoanisole with a boiling point of 138-145C/
11.
152.2 g of this compound are saponified to 110 g of 4-
chloro-3-methyl-mercaptophenol by a procedure analogous
to that described in J. Am. Chem. Soc. 79, 720. Boiling
point: 117-121C/0.03.
11&2818
b) 50 g of 4-chloro-3-methylmercaptophenol, 62 g of 3,4-
dichlorobenzotrifluoride and 12 g of sodium hydroxide are
stirred in 150 ml of dimethyl sulphoxide for 6 hours at
142C. The reaction mixture is then poured onto ice and
extracted with toluene. Distillation of the organic phase
yields 81 g of 3-(2'-chloro-4-trifluoromethylphenoxy)-
6-chlorothioanisole with a boiling point of 158C/0.4.
20 g of this compound are stirred with 30 ml of methyl
2-bromopropionate for 20 hours at 190C, followed by
distillation in a bulb tube.
Yield:21 g of ~-[3-(2'-chloro-4'-trifluoromethylphenoxy)-
6-chlorophenylthio] propionic acid methyl ester. Boiling
point: 200C/0.13.
c) 10 of this compound are reacted in 200 ml of methylene
chloride with 3-chloroperbenzoic acid as in Example 2 e).
Working up yields 9.5 g of a viscous oil with a re-
fractive index nD3: 1.3295.
Haln
~0 ~S (o ) p - Q -A
11~2~18 -
.
- 14 _
Table 1
¦1 ¦ 4 ~ C~ l S2 ¦-CH;CC53 nD 1. 5330
2 2 ~N2 4 'OE3 _ SO -CH;COOCH3
3 2 ~N02 4 ~CF3 _ S02 -CH;COOCH3 m.p. 73-75
4 2 ~Cl 4 ~ CF3 - S2 -Cl~;COOCH3 b. p. 190 /0 ,02
2 ~ Cl 4 ~ CF 3 _ SO~ -CH-COOH b p. > 200 /0, 0
6 2 ~ N2 4 ~ Cl _ SO -CH;COOC2H5 nD 1. 6092
7 2 ~N2 4 ~Cl _ 52 -CH;COOC2H5 m.p. 131-133
8 2 ~No24 ~Cl _ S2 -CH-COOCH3 m.p. 89-91
- 15 .-
No . 3 ~ -~ ¦ S (O) p ¦ -Q-A ¦ constant
l ~ CU3 I ~
9 ¦2'CI 4' 1 ~ lso2 ~-CH-COOCU3 j nD 1.5723 ¦
021 Cl 4 ' N2 - S02 -CH-COOC2H5 oil
2 ~ C1 4 ' Cl ~ S2 -CH2 -COOC2H5 21
1221 Cl 4 ~N2 - S2 . -CH;COOC{3 nD 1,5978
132 ' Cl 4 ' CF 3 6 Cl S02 ~ CH -COOCH3
142 ' Cl 4 ~N2 - S2 H2
152 ' C1 4 INO2 - SO2 -CH;COOH .
16 2 ~CN 4 ~Cl ~ S2 -CH;COOCH3
17 2 'CN 4 'Cl . _ S2 -CH;COOisoC4H
18 2 ' CN 4 ' CF3 - S2 -CH -COOCH3 .
1~ 2 ' Cl 41 CH3 - S2 -CH;COOCH3 ,.
2 ~Cl 4 ~ Cl - S2 -CH--COOH
:
Z~l~
16
¦ ND ~ ¦ 4 ~ s (Ol p ~ -Q-A ¦ Physlcal
.' ~ _ _
21 2'C1 4'C15'C 1 ~ S02 -CH;COOCH3
22 2'Br ~ S2 -CH;COOCH3
23 2~C1 4'Cl 2 Cl S02 -C -COOCH3
24 3~Cl S'Cl ~ S2 -CH-COOCH3
25 2'C1 4'C~ 2CH3 ~2 -CH-COOCH .
26 4'N02 ~ ~2 C, 3 m.p. 132-134
27 4~N02 ~ S2 -CH-COOCH3 m.p. 126-128
. 28 4'N02 ~ S2 -C2H4COOCH3 m.p. 149-151
29 2'N025'Cl 2 CH3 S02 ~ 3 m.p. 91
30 2~No25'Cl 2 CH3 SO , 3 oil
31 3'S02CH3 4 N12 S02 , 3 resin
32 2'C1 4'C1 ¦ 2 CH3 S02 -CH-COOCH3 nD 1.5410
11&2818
. No. - ~ - 3 2 l5(0)P -q-A rhy .L
_5'` 6~ 5 6 _ _ ¦ CH
332'C1 4'N022 CH3 S02 C, 3 m.p. 110-114
342'Cl 4'N02 _ SO CH3 o L
352'C1 4'N02 _ SO -CH-COOCH3 nD 1.6015
362'~2 4'Cl _ SO -CH-COOC2H5 m.p. 85-86
37 4'N02 2 CH3 SO C,H3 nD3 1.5862
382'C1 4'CF3 _ SO ~ 3 nD 1,5535
392'C1 4'CF32 CH3 SO -CH-COOCH3 oil
40 4'CF3 _ SO -CH-COOCH3 nD 1.5455
412~C1 4'Cl _ SO -CH-COOCH3 n23 1.5925
42 4'N02 _ SO -CH2COOCH3 nD 1.6218
432 N02 3 2 Cl SO -CH2COOCH2C] i
442~C1 4~N02 - S2 CH3
452'C1 4'N02 _ S02 -CH-COOH
462~C1 4~N02 ~ S2 -CH-COSCH2
' .
11¢2818
8 -
_ 3 2- -- ~ .
No. 4. ~ _ ~ S(O)P -~-A Physical
_ 5'~ 6~ 5 6 . ~ . constant .
. CH3
47 2'C1 4'N02 - S2 -C~H3
48 2'C1 4'N02 - S2 -CH-COO
-
ll~Z818
Hal
S(O) p-Q-A
~ ~ Hal
Table 2
'2' ~ 2
No, ~ ~6 S ()n -Q-A Phoystanl
5' 6 4 5 (C)
~_ j CH
1 2 ' Cl 4 ' CF3 6 Cl 52 -CH COOCH3 23
2 2 ' Cl 4 ' CF3 6 Cl S02 -cH-coocH3 nD1. 5359
3 2 ' Cl 4 ' CF ¦ 6 Cl S02 -CH-COOH
4 2 'Cl 4 'N02 6 Cl S02 -CH-COOCH3 .
2 'Cl 4 'NO ¦6 Cl S02 -CH-COOCH3
6 2 ' Cl 4 ' CF ¦ 6 Cl S02 -CH-COOCH3 24
7 2 ' Cl 4 ' Cl - S2 ~ -CH-COOCH3 nD 1. 5890
8 2 ~ Cl 4 ~ Cl ~ S2 -CH-COOH .
9 2 ' Cl 4 ' Cl ~ So2 -CH-COOCH3 .
2 ' Cl 4 ' Cl 6 Cl S02 -CH2COOCH3
Z818
20 -
No. 4 ~ ~ . 5 () -Q-A Physical ;
n constant
5'~ 6~ 5 6 . (C)_ _ ,
_ _ ...... _
11 2 ' Cl 4 ' Cl 6 Cl S02 -CH~COOH
12 2 'Cl 4'Cl 6 Cl S02 -CH2COO~ Na~9 .
13 2 ' Ci 4 ' Cl 6 Cl 52 ' 3 nD 1. 5 855
14 2'C1 4'CF ¦ 6 N02 S02 -C~-COOCH3 nD 1.5243
L5 2 'N02 4 'CF3 6 Cl S02 ~ 3 23
16 2 'Cl 4 'CF3 _ SO -CH-COOCH3 nD 1.5500
17 2'C1 4'Cl 6 Cl SO -CH2COOCH3 nD2 1.6042
18 2 'Cl 4 'CF3 6 Cl SO -CH2COOCH3 oil
19 2 'Cl 4 'Cl 6I SO -C~H3COOCH3 m. p 120-122'
2 'Cl 4 'CF3 6 Cl SO -CH-COOCH3 nD 1. 3295
21 2 'Cl 4 'CF3 6 N02 S02 -CH-COOC2H4CN
22 2 ~Cl 4 'CF3 6 N02 S2 ` -CH-COOC2H40CH3
24 2 'Cl 4 'CF3 6 N02 S2 -CH-COONH2 ¦
2 'Cl 4 'CF3 6 N02 S02 -CH-COON(C2H5)2 .
llg~Z818
21 -
~.
No . 4 ~l -o~5 6 S () D -Q-A ¦ Phys cal
_ . ~ ~ _ .
26 2 'N02 4 'CF3 6 Cl S0 CH2-COCH3 nD 1.5520
27 2 'N02 4 'CF3 6 Cl S0 CH2COOC2 4
28 2 'N02 4 'CF3 6 Cl S0 CH2C00C2H4N(c2H5)2
29 2 'N02 4 'CF3 6 Cl S0 CH2COONH2
30 2 'N02 4 'CF3 6 Cl S0 CH2COONHC2H40 3
31 2 'Cl 4 'CF3 6 Cl S02 CH-COOCU2-CH-CH2
32 2 'Cl 4 'CF3 6 Cl S02 CH-COSCH2-CH-CH2
33 2 'Cl 4 'CF3 6 Cl S02 CH-COOCH2~)
34 2 'Cl 4 'CF3 6 Cl S02 CH-COOC2H4Cl ¦
I~L L I I s02 ICH-COOH I ~
~ 11~2~18
- 22 -
n
D H~
n C
Table 3 (Intermediates of the formula II)
_ Q - A ~ Phys cal
. ~
1 4 ~Cl _ -C~HH500H m,p. 110 (known)
2 4~Cl _ -CH-Coo~ NH3 m.p. 118 ~known)
CH3 ~-CH2
3 2 ~C1 4 I CF3 _ -CH-COOCH3 b. p . - 161-3 /0 . 3 torr
4 2 N02 C 3 _ -CH-COOC2H5 b. p. 197-205/0 05
5 2 ~ Cl 4 ~ CF3 _ -CH-COOCH3 b . p . 161-164 /0 03
6 2 ~No24 ~ CF I _ -CH-COOCH3 b. p. 195-204 lO 5
7 2 ~N024 ~Cl _ C 3 b p > 200 /0 1
8 2IN024lCl _ -CH-COOCH3 b p ~ 200/0 1
9 2 ~ CN4 ~ Cl _ -CH-COOCH3
ll~Z818
- 23 - .
. - - 3~ 2~ 3 2 _ .
No;4, ~ 0 ~ S -Q-A Physical
5' 6' 5 6 co(OsC)nt
- - CH3
10 2~C1 4'Cl _ -C ;COOCH3
11 2 'Cl 4'Cl 5 Cl -CH-COOCH3
. l C,H3
12 2~C1 4'NO _ -CH-COOCH3
134'N0 _ -CH-COOC2H5b.p. 210-220/
CH 0,1 torr
144~NO _ -CH-COOCH3 b.p. 160 /0,03 ~-
154~NO _ C2H4COOCH3m.p. 57-5g
164'N0 _ -CH2-COOCH3 nD 1.6240
174~NO 2 CH3 -CH2-COOCH3m.p. 48-50
- 184~NO 2 CH3 -CH2-COOCH3 nD3 1. 6040
194~NO 2 CH3 C2H4-COOCH3 m.p. 61-62
202'No2 5'C _ -CH-COOC2H5 b.p. 190~0,001 *
The boiling points marked * were determined during the
bulb tube distillation.
11~2818
_ 24 -
No .b '~,j ~ 9 -Q-A Physical .
-constant
5'~ 6' 5 6 (C)
_ ~ l . ,
. . CH3 .
21 2'N25'Cl 2 CH3 -CH-COOCH3 b.p. 220/
0,01 torr *
C,H3
22 2'C14'N02 _ -CH-COOC2H5b.p. 220 /
0,01 torr *
C,H3
23 2'C14'N02 2 CH3 -CH-COOCH3 b.p. 180/
CH3 0,01 torr
24 2'C14'CF3 2 CH3 -CH-COOCH3 b.p. 148/
0,14 torr-~
C2H 5
2'C1 4' Cl _ -CH-COOC2H5 b.p. 195/ *
.0,02 torr
. C2H5
26 2'C1 4' CF3 _ -CH-COOC2H5 b.p. 165/
0,04 torr
27 4'N02 _ -CH2-CN m.p. 86-87
28 4lNo2 2 CH3 -CH2-CN m.p. 80-82
29 4'C1 2'N02 _ -CH2-CN m.p. 76-78
.._. .
~lG2818
Hal
S -Q-A
E~D ~ C
- Table 4 (Intermediates of the formula II)
.
No . 3 ' 2 '2 S Physical
~ A (~C) .
__
1 2'C1 4 'Cl 6 CN CH2-COOCH3m24P- 95
2 2'Cl. 4 'Cl 6 I CH2-COOCH3nD 1.6528
3 2' Cl 4 'Cl 6 Cl C2H4 3 n22 1. 6059
4 2 'Cl 4 'Cl 6 Cl CH-COOCH3 nDl 1.6026
2 'Cl 4 'Cl 6 Cl CH2-COOCH3 b p 230 /0 01
6 2 ' C l 4 ' C 1 _ C2H4COOCH 3 nD 1.5972
7 2 'Cl 4 'Cl 6 I CH-COOC2H5 nD 1.6185
8 2 'Cl 4 'CF3 _ CH-COOCH3 b p 140 /0 08
9 2 'Cl 4 'CF3 _ C2H4COOC2Hc torr *
2'N02 4'CF3 6 Cl CH2COOCH3 b.p. ~35/0,5
~l~Z811
26 -
No . 3 ' 2 ' 2 S
4, ~ Physical
. 5 ' 6 ' O~ 6 -Q-A constant
_ _ C~ ~
11 2 'NO2 4 ' CF 3 6 Cl CH;COOCH3 m.p. 235/0,45
12 2' Cl 4 ' CF3 6 Cl CH-COOCH3 torr *
13 2'C1 4'CF3 6 OCH3 CU-COOCH3 m p 195/0 04
14 2'C1 4'Cl 6 Cl C,2H5 m.p. 185/0,02
2 'Cl 4'Cl _ CH;COOC2H5 m.p. 165/o,ool
16 2'CN 4'CF3 6 Cl CH;COOCH3 m.p. 195/0,001
17 2~C1 4'CF3 6 OCH3 CH-COOC2H5 m.p. 190/0,001
18 2'C1 4'CF3 6 Cl ClH22500CH3 m.p. 190 /0,005
¦ 2'N 2 ~'CF I _ ¦CH-COOCH3 ¦ m.p. 85/0,04
~1~2811~
No. 3'2' 2 S
5~ 6' O ~ 6 _Q_~ Pch(nOYc)ant
_ ~, __ .
4'CF3 _ C 3 nD3 1.5401
21 2'C1 4'CF3 6 N02 CH-COOCH3 b.p 190-195/
0,04 torr
22 4'Cl _ 2 4 3 nD3 1.5972
23 2'N02 4'CF3 6 N02 CH-COOCH3 b p 165/0 001
24 2'C1 4'CF3 ~ Cl O~-CUOC~l15 b.p. 155/0,001
The phenoxyphenylsulphinyl- and phenoxyphenylsulphonyl-
alkanecarboxylic acid derivatives of the formula I are
stable compounds which are soluble in conventional or-
ganic solvents, such as alcohols, ethers, ketones,
dimethyl formamide, dimethyl sulphoxide etc.
The invention also relates to herbicidal and plant
growth-regulating compositions which contain a novel
active compound of the formula I, and to methods of
controlling weeds by pre- and post-emergent application
and of inhibiting the growth of mono- and dicotyledonous
plants, especially grasses, cereals, soya and tobacco
shoots
28 -
The compositions of the present invention can be in the
conventional formulations.
The compositions of the present invention are obtained in
known manner by homogeneously mixing and grinding active
substances of the general forrnula I with suitable
carriers, with or without the addition of dispersants or
solvents which are inert to the active substances. The
active substances can be processed to the following
formulations:
solid forrnulations:
dusts, tracking powders, granules (coated granules,
impregnated granules and homogeneous granules);
active substance concentrates which are dispersible in
water:
wettable powders, pastes, emulsions;
liquid formulations: solutions.
Solid formulations (dusts, tracking powders, granulates),
are prepared by mixing the active compounds with solid
carriers. Suitable carriers are, for example:
kaolin, talcum, bolus, loess,
chalk, limestone, ground limestone, attaclay, dolomite,
diatomaceous earth, precipitated silica, alkaline earth
silicates, sodium and potassium aluminium silicates
(feldspar and mica), calcium and magnesium sulphates,
magnesium oxide, ground synthetic materials, fertilisers,
for example ammonium sulphate, ammonium phosphate,
ammonium nitrate, urea, ground vegetable products, such
as corn meal, bark dust, sawdust, nutshell meal,
cellulose powder residues of plant extractions, activated
charcoal etc. These substances can either be used singly
or in admixture with one another.
The content of active substance in the above described
compositions is between 0.1 and 95%, prererably between
1 and 80%. Formulations can be diluted to concentrations
81 8
- 29 -
as low as 0.001%. The rates of application are ordinarily
0.1 to 10 kg, preferably 0.25 to 5 kg, of active substance
per hectare. The active compounds of the formula I can be
formulated for example as follows: (parts are by weight):
Dusts: The following substances are used to prepare
a) 5% and b) a 2% dust:
a) 5 parts of a- [4-(2'-chloro-4'-trifluoromethyl-
phenoxy)-phenylsulphonyl] propionic acid
methyl ester],
- 95 parts of talc;
b) 2 parts of active substance
1 part of highly dispersed silicic acid
97 parts of talc.
The active substances are mixed with the carriers and ground.
Granulate: The following substances are used to prepare
a 5% granulate:
parts of the above active substance
0.25 part of epichlorohydrin
0.25 part of cetyl po-lyglycol ether
3.25 parts of polyethylene glycol
91 parts of kaolin (particle size 0.3-0.8 mm).
The active substance is mixed with epichlorohydrin and the
mixture is dissolved in 6 parts of acetone. Then poly-
ethylene glycol and cetyl polyglycol ether are added. The
resulting solution is sprayed on kaolin and subsequently
evaporated in vacuo.
Wettable Powders
The following constituents are used for prepare
a) a 50%, b) a 25% and c) a 10% wettable powder:
a) 50 parts of -[4-(2'-chloro-4'-trifluoro-
methylphenoxy)-phenylsulphonyl] propionic
acid methyl ester,
~1~2818
- 30
parts of sodium dibutylnaphthylsulphonate,
3 parts of naphthalenesulphonic acid/phenolsuL-
phonic acid/formaldehyde condensate (3:2:1),
parts of kaolin,
22 parts of Champagne chalk;
b) 25 parts of the above active substance,
parts of sodium oleylmethyltauride,
2.5 parts of naphthalenesulphonic acid/formaldehyde
condensate,
0.5 part of carboxymethyl cellulose,
parts of neutral potassium aluminium silicate,
62 parts of kaolini
c) 10 parts of the above 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 indicated active substance is applied to the
corresponding carriers (kaolin and chalk) and then these
are mixed and ground, to yield wettabIe powders of excellent
wettability and suspension power. By diluting these wettable
powders with water it is possible to obtain suspensions of
the desired concentration of active substance. Such
suspensions are used for controlling weeds and grass-like
weeds in crops of cultivated plants by the preemergent
method and for treating areas of grass.
Paste
The following substances are used to manufacture a
45/0 paste:
.45 parts of _[4-(2'-chloro-4'-trifluoro-
methylphenoxy)-phenylsulphonyl] propionic
acid methyl ester],
.
;Z818
~ 31 -
parts of sodium aluminium silicate,
14 parts of cetyl polyglycol ether with 8 moles
of the ethylene oxide,
1 part of oleyl polyglycol ether with 5 moles
of the ethylene oxide,
2 parts of spindle oil,
parts of polyethylene glycol,
23 parts of water.
The active substance is homogeneously mixed with the
adjuvants in appropriate devices and ground, yielding a
paste from which, by dilution with water, it is possible
to obtain suspensions of the desired concentration of
active substance. The suspensions are suitable for treating
areas of grass.
Emulsifiable Concentrate
The following ingredients are mixed to manufacture a
25% emulsifiable concentrate:
parts of a- [4-(2'~chloro-4'-trifluoro-
methylphen~ y)-phenylsulphonyl] propionic
acid methyl ester],
parts of a mixture of nonylphenolpolyoxy-
ethoxy-ethylene and calcium dodecylenesul-
phonate,
parts of 3,5,5-trimethyl-2-cyclohexan-1-one,
parts of dimethyl formamide.
This concentrate can be diluted with water to give emulsions
in the desired concentrations.
Instead of using the respective active substance indicated
in the foregoing formulation examples, it is also possible
to use another of the compounds comprised by the formula I.
ll~Z818
- 32
The active substances contained in the compositions
of the present invention influence the plant growth in
different ways. Thus they inhib:it, delay or-prevent
primarily the growth and germination. Their action is
consequently both a pre- and post-emergent herbicidal and
growth-inhibiting action.
Compositions of the present invention, which contain
as active component at least one compound of the formula I,
are particularly suitable for inhibiting and controlling
the growth of monocotyledonous and dicotyledonous plants,
such as grasses, shrubs, trees, crops of cereals and legum-
inous plants, sugar cane, tobacco plants, soya, onion and
potato tubers, ornamentals, fruit trees and vines.
The primary effect attained by the compounds of the
formula I consists in the desired reduction of the plant
size, in particular of the growth in height. In general, a
certain change in the form of the plant is allied to this
reduction in size. As a direct consequence of the reduction
of the growth in height the plant is strengthened: leaves
and stems are better developed. By shortening the distances
between internodes in monocotyledonous plants the breaking
strength is increased. In this way it is possible to prevent
to a great extent harvest losses caused by thunderstorms,
prolonged rainfall etc., which usually result in a lodging
of crops of cereals and leguminous plants, and thereby to
facilitate harvesting. As side-effect, the reduced growth in
height of useful plants results in a saving of fertilisers.
This also applied equally to ornamental plants and ornamental
grass plots, turf for sporting activities, grass-covered
open spaces etc.
11~28~8
- 33 -
One of the greatest problems posed by pure grass
cultivations, however, is the actual cutting of the grass
itself, whether in open spaces of urban areas, industrial
sites, playing fields, along main roads, on airport runways,
on railway embankments or the bmbankments of water bodies.
In all these cases it is necessary to cut the turf or grass
periodically. This operation is not only time-consuming,
complicated and expensive in respect of labour and machinery,
but involves the personnel concerned and traffic users in
considerable hazard.
For this reason there is an urgent need in areas
with extensive traffic networks to maintain and tend the
grassy covering for strengthening road shoulders and
embankments on traffic routes on the one hand, and on the
other to keep it at a reasonable height by simple means
during the entire vegetation period. This need is fulfilled
in a very advantageous manner by applying the compounds of
the formula I.
In analogous fashion, the labour expended on cutting
can be reduced by treating trees, shrubs and hedges,
principally in urban and industrial areas, with the compounds
of the present invention of the formula I.
The use of the active compounds of this invention
of the formula I can also advantageously influence the
growth of shoots and/or the fertility of fruit trees and
vines.
Ornamental plants of pronounced growth in length can
be reared as compact potted plants by treating them with the
active compounds of this invention.
The active compounds of the formula I are also useful
for inhibiting the growth of undesired suckers, for example
in tobacco and ornamental plants, thereby avoiding the labour-
., :
2818
34 -
consuming detaching of these suckers by hand. They are also
useful for inhibiting the formation of shoots in stored
tubers, for example those of ornamental plants, onions and
potatoes, and finally for increasing the yield of cultivated
plants with marked vegetative growth, such as soya and sugar
cane, by accelerating the transition from the vegetative
to the generative growth phase by applying the active
compounds of the invention.
Preferably the active compounds of the formula I are
used to inhibit the growth of grasses, cereal crops, tobacco
plants, soya and ornamental plants.
The rates of application very and depend on the time
of application. In general they are between 0.1 and 5 kg of
active substance per hectare for preemergence application
and up to 4 kg per hectare for treating existing crops.
In addition, many of the active compounds of the
formula I are also suitable for influencing plant growth
in other ways, especially for facilitating fruit and
leaf abscission by the formation of separation tissues
at the fruit and leaf stems. This results in a substantial
reduction in the plucking force and consequently
facilitates harvesting greatly. A thinning of blossom
and fruit on fruit trees also occurs.
11~2818
The facilitation of fruit abscission in the mechanical
and manual harvesting of olives and citrus fruit has become
of great economic importance. Leaf abscission and defoliation
is important in the harvesting of cotton.
The active substances of the present invention develop
their action both via the parts of plants above the soil
(contact action), especially the leaves, and via the soil,
as preemergent herbicide (inhibition of germination).
The action of the compounds of the formula I as
strong growth inhibitors is evident from the fact that
most of the species of plants treated in the post-emergent
state exhibit stationary growth after a test period of
three weeks, whilst the treated parts of the plants assume
a dark green colouration. The leaves, however, do not drop.
In some plant species this growth inhibition occurs even
at a rate of application of 0.5 kg/ha and below. As not all
plant species are equally strongly inhibited in their growth,
a selective use is possible by choosing a specific low rate
of application.
Z818
- 3~ -
The active substances of the invention are also of
interest for combination with a number of herbicides of the
phenylurea and triazine series for use in cereal crops,
maize, sugar cane, and in fruit culture and viticulture.
In areas where there is a high risk of erosion, the
active substances of the invention can be used as growth
inhibitors in a very wide variety of crops. The weed cover
is not eliminated, but only so strongly inhibited that it
no longer competes with the cultivated plants.
In addition, the active substances of the formula I
are distinguished by a very pronounced preemergent
herbicidal action and are thus also strong germination
inhibitors.
The following test methods were employed to establish
the usefulness of the compounds of the formula I as
herbicides (pre- and postemergent).
Preemer~ent herbicidal action (~ermination inhibition)
In a greenhouse, immediately after sowing the test plants
in seed dishes the surface of the soil is treated with an
aqueous suspension of the active substances obtained from
a 25% wettable powder. Four different concentration series
were used, corresponding to 4, 2, 1 and 0.5 kg of active
substance per hectare respectively. The seed dishes are
kept in the greenhouse at 22-25C and 50 to 70% relative
humidity. The test is evaluated 3 weeks later according to
the following rating:
1 = plants have not germinated or are totally
withered
2-8 = intermediate stages of damage
9 c plants ~mdamaged (as untreated control).
~GZ818
- 37 -
Post-emer~ent herbicidal action (Contact herbicide)
A large number (at least 7) of weeds and cultivated plants,
both mono~ and dicotyledonous, were sprayed after emergence
in the 4- to 6-leaf stage with an aqueous active substance
emulsion in rates to 0.5, 1, 2 and 4 kg of active substance
per hectare and kept at 24-26C and 45-60% relative humidity.
The test was evaluated, as in the preemergent test, 5 and 15
days after treatment in accordance with the same rating.
The tested compounds of the present invention had a strong
contact herbicidal action on some plants and in many others
effected stationary growth as a symptom of the growth-
inhibiting properties.
Growth inhibition in ~rasses
Seeds of the grasses Lolium perenne, Poa pratensis, Festuca
ovina, and Dactylis glomerata were sown in plastic dishes
filled with an earth/turf/sand mixture (6:3:1). The emergent
grasses were cut back weekly to a height of 4 cm above the
soil and 1 day after the last cut were sprayed with aqueous
spray mixtures of an active substance of the formula I. The
amount of active substance corresponded to a rate of appli-
cation of 5 kg of active substance per hectare. The growth
of the grasses was evaluated 10 and 21 days after appli-
cation.
Growth inhibition in cereals
Spring wheat (Triticum aestivum), summer barley (Hordeum vul-
gare) and rye (Secale) was sown in sterilised soil in plastic
beakers and reared in a greenhouse. The cereal shoots were
treated 5 days after sowing with a spray broth of the active
substance. The leaf application corresponded to 6 kg of
active substance per hectare. Evaluation is made 21 days
later. The active substances of the invention effect a
marked growth inhibition both qf grasses and cereal crops.
