PROPIONIC ACID ESTERS

ESTERS DE L'ACIDE PROPIONIQUE

English Abstract

Abstract
The invention is concerned with propionic acid
esters of the formula
<IMG> I
wherein R1, R2, R3, R4, R5, m, n and p have the significance
given in the description, a process for their manufacture,
weed control compositions which contain these compounds as
the active substance, as well as the use of such compounds
or compositions for the control of weeds.

Claims

- 40 -
ES 6102/27
The embodiments of the invention in which an exclusive pro-
perty or privilege is claimed are defined as follows:
1. Compounds of the general formula
<IMG>
I
wherein R1 signifies chlorine, bromine,
iodine or trifluoromethyl,
R2 signifies hydrogen,chlorine,
bromine or iodine,
R3 signifies hydrogen or C1-4-
-alkyl,
R4 signifies hydrogen; C1-4-
alkyl; or phenyl, optionally
substituted with halogen,C1-4-
-alkyl and/or nitro,
whereby R3 and R4 together
with the carbon atom to which
they are attached can also
form a C5-8-cycloalkane ring
which, if desired, can be

- 41 - ES 6102/27
substituted with 1 to 3 C1-4-
-alkyl groups,
m, n and p signify the number
0 or 1
and R5 signifies one of the following
groups (a) - (f):
-NHCO-R6 (a)
-NHSO2-R7 (b)
<IMG> (c)
<IMG> (d)
<IMG> (e)
<IMG> (f)

- 42 - ES 6102/27
whereby in the above formulae of the
groups (a) - (f)
R6 signifies hydrogen; C1-6-
-alkyl; C1-4-haloalkyl; or
phenyl, optionally substituted
with halogen, C1-4-alkyl
and/or nitro,
R7 signifies C1-6-alkyl; or phenyl,
optionally substituted with
halogen, C1-4-alkyl and/or nitro,
R8 and R9 stand for hydrogen or
together signify a bond, tri-
methylene, tetramethylene, 2-
-butenylene or a fused benzene ring,
R10 signifies
C1-6-alkyl and R11 signifies
trifluoromethyl, C1 6-alkoxy,
C1-6-alkoxy-C1-4-alkyl, C2-7-
-alkanoyl, C2-7-alkoxycarbonyl
or C2-7-alkoxycarbonyl-C1-4-
-alkyl, or R10 and R11 together
with the carbon atom to which
they are attached form a cyclo-
pentane ring which, if desired,
can be substituted with 1 to 3
C1-4-alkyl groups and/or 1 C1-4-
-alkoxy group , whereby, where

- 43 -
ES 6102/27
R1O, R11 and the carbon
atom form an optionally
substituted cyclopentane ring,
R1 is chlorine, bromine or tri-
fluoromethyl,
R12 signifies hydrogen or C1-6-
-alkyl and R13 signifies C1-6-
-alkyl; or phenyl, optionally
substituted with halogen, C1-4-
-alkyl and/or nitro, or R12 and
R13 together with the carbon
atom to which they are attached
form a C5-7-cycloalkane ring,
and
R14 and R15 signify C1-6-alkyl or
phenyl,
and whereby, when R5 represents a group (a),
(b) or (c), m signifies the number 1, n
signifies the number 0 and p signifies the
number 0 or 1; when R5 represents a group
(d), m, n and p signify the number 0; when
R5 represents a group (e), m signifies the
number 0 and n and p signify the number 1;
and when R5 represents a group (f), m and
p signify the number 0 or 1 and n signifies
the number 1.

- 44 -
ES 6102/27
2. Compounds according to claim 1, wherein R1
signifies iodine or trifluoromethyl.
3. Compounds according to claim 1
wherein R2 signifies hydrogen or chlorine.
4. The D-isomers of the compounds according to any
one of claims 1 to 3.
5. Succinimidomethyl D-2-[p-(.alpha.,.alpha.,.alpha.-trifluoro-p-
-tolyloxy)phenoxy]-propionate.
6. Ethyl N-[D-2-[p-(.alpha.,.alpha.,.alpha.-trifluoro-p-tolyloxy)-
phenoxy]-propionoxy]-acetimidate.
7. n-Butyl N-[D-2-[p-(.alpha.,.alpha.,.alpha.-trifluoro-p-tolyloxy)-
phenoxy]-propionoxy]-acetimidate.
8. 2-Isopropylideneaminooxy-ethyl D-2-[p-(.alpha.,.alpha.,.alpha.-
-trifluoro-p-tolyloxy)phenoxy]-propionate.
9. Diethoxyphosphinylmethyl D-2-[p-(.alpha.,.alpha.,.alpha.-tri-
fluoro-p-tolyloxy)phenoxy]-propionate.
10. A compound according to claim 1, selected from:
Acetamidomethyl D-2-[p-(.alpha.,.alpha.,.alpha.-trifluoro-p-tolyloxy)-

- 45 - ES 6102/27
phenoxy]-propionate,
chloroacetamidomethyl D-2-[p-(.alpha.,.alpha.,.alpha.-trifluoro-p-
-tolyloxy)phenoxy]-propionate,
trichloroacetamidomethyl D-2-[p-(.alpha.,.alpha.,.alpha.-trifluoro-
p-tolyloxy)phenoxy]-propionate,
2-methanesulphonamido-ethyl D-2-[p-(.alpha.,.alpha.,.alpha.-tri-
fluoro-p-tolyloxy)phenoxy]-propionate,
phthalimidomethyl D-2-[p-(.alpha.,.alpha.,.alpha.-trifluoro-p-
-tolyloxy)phenoxy]-propionate,
2-diethoxyphosphinyl-ethyl D-2-[p-(.alpha.,.alpha.,.alpha.-trifluoro-
-p-tolyloxy)phenoxy]-propionate,
1-diethoxyphosphinyl-ethyl D-2-[p-(.alpha.,.alpha.,.alpha.-trifluoro-
-p-tolyloxy)phenoxy]-propionate,
1-diethoxyphosphinyl-n-butyl D-2-[p-(.alpha.,.alpha.,.alpha.-tri-
fluoro-p-tolyloxy)phenoxy]-propionate,
.alpha.-diethoxyphosphinyl-benzyl D-2-[p-(.alpha.,.alpha.,.alpha.-tri-
fluoro-p-tolyloxy)phenoxy]-propionate,
ethyl 3-[D-2-[p-(.alpha.,.alpha.,.alpha.-trifluoro-p-tolyloxy)-
phenoxy]-propionoxyimino]-butyrate,
D-2-[p-(.alpha.,.alpha.,.alpha.-trifluoro-p-tolyloxy)phenoxy]-
-propicnic acid 1,1,1-trifluoroacetone oxime ester,
ethyl N-[D-2-[p-(.alpha.,.alpha.,.alpha.-trifluoro-p-tolyloxy)-
phenoxy]-propionoxy]-n-butyrimidate,

- 46 - ES 6102/27
D-2-[p-(.alpha.,.alpha.,.alpha.-trifluoro-p-tolyloxy)phenoxy]-
-propionic acid methoxyacetone oxime ester,
D-2-[p-(.alpha.,.alpha.,.alpha.-trifluoro-p-tolyloxy)phenoxy]-
-propionic acid diacetone monoxime ester,
ethyl 2-[D-2-[p-(.alpha.,.alpha.,.alpha.-trifluoro-p-tolyloxy)-
phenoxy]-propionoxyimino ]-propionate,
ethyl 2-methyl-3-[D-2-[p-(.alpha.,.alpha.,.alpha.-trifluoro-p-
-tolyloxy)phenoxy]-propionoxyimino]-butyrate,
ethyl 4-[D-2-[p-(.alpha.,.alpha.,.alpha.-trifluoro-p-tolyloxy)-
phenoxy]-propionoxyimino]-n-valerate,
2-isopropylideneaminooxy-ethyl D-2-[p-(o-chloro-
-p-trifluoromethyl-phenoxy)phenoxy]-propionate,
D-2-[p-(.alpha.,.alpha.,.alpha.-trifluoro-p-tolyloxy)phenoxy]-
-propionic acid cyclopentanone oxime ester,
1-diethoxyphosphinyl-cyclohexyl D-2-[p-(.alpha.,.alpha.,.alpha.-
-trifluoro-p-tolyloxy)phenoxy]-propionate,
2-dimethoxyphosphinyl-2-propyl D-2-[p-(.alpha.,.alpha.,.alpha.-
-trifluoro-p-tolyloxy)phenoxy]-propionate and
3-diethoxyphosphinyl-propyl D-2-[p-(.alpha.,.alpha.,.alpha.-tri-
fluoro-p-tolyloxy)phenoxy]-propionate.
11. A compound according to claim 1, selected from:
2-Isopropylideneaminooxy-ethyl D-2-tp-(p-iodo-
phenoxy)phenoxy]-propionate,

ES 6102/27
- 47 -
2-methanesulpnonamido-ethyl D-2-[p-(p-iodophenoxy)-
phenoxy]-propionate,
succinimidomethyl D-2-[p-(p-iodophenoxy)phenoxy]-
-propionate.
diethoxyphosphinylmethyl D-2-[p-(p-iodophenoxy)-
phenoxy]-propionate,
2-diethoxyphosphinyl-ethyl D-2-[p-(p-iodophenoxy)-
phenoxy]-propionate,
2-isopropylideneaminooxy-ethyl D-2-[p-(o-chloro-p-
-iodophenoxy)phenoxy]-propionate,
2-methanesulphonamido-ethyl D-2-[p-(o-chloro-p-
-iodophenoxy)phenoxy]-propionate,
diethoxyphosphinylmethyl D-2-[p-(o-chloro-p-
-iodophenoxy)phenoxy]-propionate,
dibutoxyphosphinylmethyl D-2-[p-(.alpha.,.alpha.,.alpha.-trifluoro-
-p-tolyloxy)phenoxy]-propionate,
1-diphenoxyphosphinyl-ethyl D-2-[p-(.alpha.,.alpha.,.alpha.-trifluoro-
-p-tolyloxy)phenoxy]-propionate,
1-isopropylideneaminooxy-2-propyl D-2-[p-(.alpha.,.alpha.,.alpha.-
-trifluoro-p-tolyloxy)phenoxy]-propionate,
1-isopropylideneaminooxy-2-butyl D-2-[p-(.alpha.,.alpha.,.alpha.-
-trifluoro-p-tolyloxy)phenoxy]-propionate,
1-isopropylideneaminooxy-1-phenylethyl D-2-[p-(.alpha.,.alpha.,.alpha.-
-trifluoro-p-tolyloxy)phenoxy]-propionate,

- 48 - ES 6102/27
2-(2-butylideneaminooxy)-ethyl D-2-[p-(.alpha.,.alpha.,.alpha.-
-trifluoro-p-tolyloxy)phenoxy]-propionate,
2-(.alpha.-methylbenzylideneaminooxy)-ethyl D-2-[p-
-(.alpha.,.alpha.,.alpha.-trifluoro-p-tolyloxy)phenoxy]-propionate,
2-cyclohexylideneaminooxy-ethyl D-2-[p-(.alpha.,.alpha.,.alpha.-
-trifluoro-p-tolyloxy)phenoxy]-propionate and
3-diethoxyphosphinyl-propyl D-2-[p-(p-iodophenoxy)-
phenoxy]-propionate.
12. A process for the manufacture of compounds of the
general formula
<IMG> I
wherein R1 signifies chlorine, bromine,
iodine or trifluoromethyl,
R2 signifies hydrogen, chlorine,
bromine or iodine,
R3 signifies hydrogen or C1-4-
-alkyl,
R4 signifies hydrogen; C1-4-
-alkyl; or phenyl, optionally
substituted with halogen, C1-4-
-alkyl and/or nitro, whereby

- 49 -
R3 and R4 together with the
carbon atom to which they are
attached can also form a C5-8-
-cycloalkane ring which, if
desired, can be substituted with
1 to 3 C1-4-alkyl groups,
m, n and p signify the number
0 or 1
and R5 signifies one of the following
groups (a) - (f):
-NHCO-R6 (a)
-NHSO2-R7 (b)
<IMG> (c)
(d)
<IMG>
(e)
<IMG>

- 50 -
<IMG> (f)
whereby in the above formulae of the
groups (a) - (f)
R6 signifies hydrogen; C1-6-
-alkyl; C1-4-haloalkyl; or
phenyl, optionally substituted
with halogen, C1-4-alkyl and/or
nitro,
R7 signifies C1-6-alkyl; or phenyl,
optionally substituted with
halogen, C1-4-alkyl and/or nitro,
R8 and R9 stand for hydrogen or
together signify a bond, tri-
methylene, tetramethylene, 2-
-butenylene or a fused
benzene ring,
R10 signifies C1-6-alkyl and R11
signifies trifluoromethyl,
C1-6-alkoxy, C1-6-alkoxy-C1-4-
-alkyl, C2-7-alkanoyl or C2-7-
-alkoxycarbonyl or C2_7-
-alkoxycarbonyl-C1-4-alkyl,
or R10 and R11 together with
the carbon atom to which they
are attached form a cyclopentane

- 51 -
ring which, if desired, can be
substituted with l to 3 C1-4-
-alkyl groups and/or 1 C1-4-
-alkoxy group, whereby, where
R10, R11 and the carbon atom
form an optionally substituted
cyclopentane ring, R1 is
chlorine, bromine or trifluoro-
methyl,
R12 signifies hydrogen or
C1-6-alkyl and R13 signifies
C1-6-alkyl; or phenyl,
optionally substituted with
halogen, C1-4-alkyl and/or
nitro, or R12 adn R13
together with the carbon atom
to which they are attached
form a C5-7-cycloalkane ring,
and
R14 and R15 signify Cl-6-alkyl or
phenyl,
and whereby, when R5 represents a group (a),
(b) or (c), m signifies the number l, n
signifies the number O and p signifies the
number 0 or l; when R5 represents a group
(d), m, n and p signify the number 0; when
R5 represents a group (e), m signifies the

- 52 -
number O and n and p signify the number 1;
and when R5 represents a group (f), m and
p signify the number 0 or 1 and n signifies
the number 1,
which process comprises
(a) reacting an acid of the formula
<IMG> II
wherein R1 and R2 have the significance
given earlier in this claim,
or a reactive derivative thereof, with a compound of
the formula
<IMG> III
wherein R3, R4, R5, m, n and p
have the significance given earlier
in this claim and X signifies a
leaving group,
or

-53-
(b) reacting a phenol of the formula
<IMG>
IV
wherein R1 and R2 have the significance
given earlier in this claim,
or an alkali metal salt thereof, with a compound of the
formula
<IMG> V
wh rein R3, R4, R5, m, n and p
have the significance given
earlier in this claim and Y
signifies a leaving group.

- 54 -
13. A method for the control of weeds, which method
comprises treating the locus to be protected against weeds
and/or the weeds with an effective amount of one of the com-
pounds set forth in claim 1, 2 or 3.
14. A method for the control of weeds, which method
comprises treating the locus to be protected against weeds
and/or the weeds with an effective amount of one of the com-
pounds set forth in claim 5, 6 or 7.
15. A method for the control of weeds, which method
comprises treating the locus to be protected against weeds
and/or the weeds with an effective amount of one of the com-
pounds set forth in claim 8 or 9.
16. A method for the control of weeds, which method
comprises treating the locus to be protected against weeds
and/or the weeds with an effective amount of one of the com-
pounds set forth in claim 10 or 11.
17. Compounds according to claim 2, wherein R2 signifies
hydrogen or chlorine.
18. The D-isomers of the compounds according to
claim 17.

- 55 -
19. A method for the control of weeds, which method
comprises treating the locus to be protected against weeds
and/or the weeds with an effective amount of one of the com-
pounds set forth in claim 17 or 18.

Description

RAN 6102/27
The invention is concernedwith propionic acid
esters of the general formula
.
Rl_~0~0--CH--COO--(CH2~ (Cl: ) -RS
wherein Rl signifies chlorine, bromine~
iodine or trifluoromethyl,
R signiies hydrogen, chlorine,
bromine or iodine,
10R3 signifies hydrogen or Cl 4-
-alkyl,
R4 signifies hydrogen; Cl 4-
-alkyl; or phenyl, optionally
substituted with halogen,
Cl 4-alkyl and/or nitro,
whereby R3 and R4 together
with the carbon atom to which
Pa/19.10.81
.. ~; ~
. . . . . .. . .

they are attached can also
form a C5_8-cycloalkane ring
which, if desired, can be
substituted with 1 to 3 Cl 4-
-alkyl groups,
m, n and p signify the number
O or 1
and R5 signifies one of the following
groups (a~ - (f):
-NHCO-R (a)
-NHSO2-R (b)
~\ 8
~&yR
~N I (c)
d~C~\R
~ R10
-N=C ~ 11 (d)
/R12
-ON=C (e)
\R13
oRl 4
-P (f)
O \ OR15
' ;`
'
.: :.: -: .. .
'

whereby in the above formulae of the
groups (a) - (f)
R6 si~nifies hydrogen; Cl 6-
-alkyl; Cl 4-haloalkyl: or
phenyl, optionally substituted
with halogen, Cl 4-alkyl and/
or nitro,
R signifies Cl 6-alkyl~ or
phenyl, optionally substituted
with halogen, Cl 4-alkyl and/
or nitro,
R8 and R9 stand for hydrogen or
together signify a bond,
trimethylene, tetramethylene,
2 butenylene or a lused
benzene ring,
RlOsignifies Cl 6-alkyl and R
signifies trifluoromethyl,
Cl_6 alkoxy, Cl-6-alkoxy-
-Cl_4-alkyl, C2_7-alkanoyl,
C2 7-alkoxycarbonyl or C2 7-
-alkoxycarbonyl-Cl 4-alkyl,
or R and Rll together with
the carbon atom to which they
are attached form a cyclopentane
ring which, if desired, can be
. . . --~
,, .

-"~ 1156~3
-- 4 --
substituted with 1 to 3
Cl 4-alkyl sroups and/or 1
Cl_4-alkoxy group, whereby,
where R , R and the
carbon atom form an optionally
substituted cyclopentane ring,
Rl is chlorine, bromine or
trifluoromethyl,
R12 signifies hydrogen or Cl 6-
-alkyl and R13 signifies
Cl_6-alkyl; or phenyl,
optionally substituted with
halogen, Cl 4-alkyl and/or
nitro, or R12 and R13
together with the carbon atom
to which they axe attached
form a C5_7-cycloalkane ring,
and
Rl and R15 signify Cl 6-alkyl
or phenyl,
and whereby, when R5 represents a group (a),
(b) or (c), m signlfies the number 1, n
signifies the number 0 and p signifies the
number 0 or 1; when R5 repre ents a group
(d), m, n and p signif~ the number 0; when
R5 represents a group (e), m signifies the
. .

1 ~ 3
-- 5
number 0 and n and p signify the number
. l; and when R represents a group (f),
m and p signify the number 0 or 1 and n
signifies the number 1.
The compounds of formula I possess herbicidal
properties and are accordingly suitable as weed control
agents and as active substances of weed control
compositions. Accordingly, the invention also lncludes
weed co~trol compositions which contain at least one
compound of formula I as the active substance, a process
for the manufacture of these compounds as well as the use
of such compounds or compositions for th~ control of
weeds.
In formula I above the term "halogen" includes
fluorine, chlorine, bromine and iodine. The term
"Cl_4-alkyl" or "Cl_6-alkyl" means not only straight-
-chain but also branched-chain alkyl groups such as methyl,
ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert.butyl,
n-pentyl, isoamyl, neo-pentyl and n-hexyl. This is also
true for groups containing C1 4-alkyl groups or Cl_6-
-alkyl groups such as Cl_4- or Cl_6-alkoxy, C2_7-alkoxy-
carbonyl, Cl 4-haloalkyl, C2 7-alkoxycarbonyl-C1 4-alkyl,
Cl_6-alkoxy-Cl_4-alkyl and C2_7-alkanoyl. When two or
more substituents are present in a substituted phenyl

group, the substituents can be the same or different.
This is also true for the C5 8-cycloalkane ring
substituted with alkyl and the cyclopentane ring
substituted with alkyl and/or alkoxy. The term "haloalkyl"
includes alkyl substituted with one or more halogen atoms.
Since at least one asymmetric carbon atom is
present in the molecule, the compounds of formula I can
occur in optically active form. As a conse~uence of
the nitrogen-carbon double bond in the compounds of
~ormula I in which R5 signifies a group (d) or a group
~e) geometric isomerism also occurs in the case of those
compounds in which R and Rll or R12 and R13 have
different significances. Such geometric isomers are called
the syn- and anti-forms~ Inde~endently thereof, an
atropic isomerism is also present in certain cases.
Formula I is accordingly intended to include the racemates
as well as all of these possible isomeric forms.
Independently of one another R preferably
signifies iodine or trifluoromethyl and R2 preferably
signifies hydrogen or chlorine.
When R signifies Cl 4-alkyl, this is preferably
methyl.
: ~ '
.
~, .

1 156~3
R6 preferably signifies Cl 6-alkyl.
R7 preferably signifies optionally substituted
phenyl.
R8 and R9 both preferably signify hydrogen.
The D-forms of the compounds of formula I are
especially preferred.
Preferred compounds of formula I are:
Succinimidomethyl D-2-[p-(a,a,a-trifluoro-p-
-tolyloxy)phenoxy]-propionate,
ethyl N-/ D-2-[p-(a,a,a-trifluoro-p~tolyloxy)-
phenoxy]propionoxy_/-acetamidate,
n-butyl N- r D-2-[p-(a,a,a-trifluoro-p-tolyloxy)- :
phenoxy]propionoxy ~ -acetimidate,
2-isopropylideneaminooxy-ethyl ~-2-[p-(a,a,a-
-trifluoro-p-tolyloxy)phenoxy]-propionate and
diethoxyphosphinylmethyl D-2-[p-(a,a,a~trifluoro-p-
-tolyloxy)phenoxy]-propionate.
The process in accordance with the invention for
the manufacture of the compounds of formula I comprises
.
,, : ;, - : :
,

115~3
(a) reacting an acid of the formula
R1 ~ O ~ CH3
, R2
wherein Rl and R2 have the
significance given above,
or a reactive derivative thereof, with a compound of
the formula
X- (CH2)m -(I)n (C 2)p - III
R4
wherein R3, R4, R5, m, n and p
have the significance given
above and X signifies a leaving
group,
or
:
(b) xeacting a phenol of the formula
, " . . :

6~3
g
R1 ~ O ~ OH IV
wherein Rl and ~2 have the
significance given above,
or an alkali metal salt thereof, with a compound of
the formula
Y- CH- COO -(CH2)m - (C)n -(CH2)p R V
CH3 R
wherein R , R , R , m, n and p have
the significance given above and
Y signiries a leaving group.
Process variant (a) is an esterification which
can be carried out according to methods known per se;
for example, in accordance with the following variants
(a1), (a2) and (a3): .
~ , .. .

-- 10 --
Educt Rea~ent
(al) Free acid of formula II, Compound of formula
but especially a salt III in which X stands
thereof for example, for
chlorine, bromine,
iodine, mesyloxy or
tosylo~y
(a2) Halide, imidazolide or Compound of Eormula
anhydride of an acid of III in which X stands
formula II for hydroxy
(a3) Free acid of formula Compound of formula
II III in which X stands
for hydroxy (III
especially = oxime)
In process variant (al), the term "salt" signifies,
for example, an alkali metal salt (e.g. the sodium,
potassium or lithium salt), an alkaline earth metal sal~ `
(e.g. the magnesium, calcium or barium salt), a salt of an
organic base ~e.g. a mono-, di- or trialkylammonium salt
or a pyridinium salt) or the ammonium salt. The term
"leaving groupl' used in connection with X preferably
stands for chlorine, bromine, iodine, mesyloxy or tosyloxyO
The esterification of an acid of formula II or,
preferably, a salt thereof, with a compound of formula
III is preferably carried out in an inert solvent and at
a temperature of about -20C to 100C. A temperature
i . ,
: :: ~: , .::
.,~ .

11~6~3
range between 0C and 40C is especially preferred.
Inert organic solvents are preferably used as the solvent.
Preferred solvents are ethers (e.g. diethyl ether and
tetrahydrofuran), chlorinated hydrocarbons (e.g.
dichloromethane and chloroform~ and dimethylformamide.
When a free acid of formula II is used, the
reaction is conveniently carried out in -the presence o~
a base or an acid acceptor. For this purpose there can
be used all customarily usable inorganic and organic
acid-binding agents, preferably alkali metal and alkaline
earth metal carbonates and bicarbonates and tertiary amines
(e.g. triethylamine, dimethylaniline and pyridine).
The reaction according to process variant (a2)
is conveniently carried out in an inert solvent such
as an ether (e.g. diethyl ether~, a hydrocarbon (e.g.
- n-hexane)or a chlorinated hydrocarbon (e.g. dichloro
methane or chloroform) and at room temperature or an
elevated temperature (e.g. up to the reflux temperatuxe
of the reaction mixture). A temperature range between
0C and 40C is preferred and a temperature range between
10C and 20C is especially preferred.
When an acid halide of an acid of formula II is
used, the reaction is conveniently carried out in the
presence of an acid-binding agent. Inorganic bases (e~g.
.: .- . - , . . .
" , : ~ .
~: ,

8~3
- 12 -
alkali metal and alkaline earth metal carbonates and
bicarbonates) as well as organic bases (e.g. tertiary
amines, especially triethylamine or pyridine) have been
found to be suitable for this purpose. The acid h~lide
is preferably the acid chloride.
In process variant (a3), the reaction is
conveniently carried out in an inert organic solvent
such as an ether (e.g. tetrahydrofuran) or a chlorinated
hydrocarbon (e.g. dichloromethane or chloroform) and at a
temperature between 0C and 70C. A temperature range
between 10C and 30C is preerred. The reaction is
conveniently carried out in the presence of an acid
catalyst or a condensing agent such as, for example,
sulphuric acid, hydrochloric acid, p-toluenesulphonic
acid, dicyclohexylcarbodiimide or carbonyldiimidazole.
Process variant (a3) is especially suitable
where the compound of formula III is an oxime, i.e. R5
signifies a group (d), m, n and p signify the number 0
and X signifies a hydroxyl group. An acid of formula II
is preferably reacted with an oxime of formula III in
the presence of dicyclohexylcarbodiimide as the
condensing agent. The acid is conveniently dissolved in
an inert organic solven-t such as a chlorinated hydrocarbon
(e.g. dichloromethane, chloroformr carbon tetrachloride or
: .
, ~ ,' :: :
: . ,~ ,

- 13 -
;
trichloroethane), an ether (e.g. diethyl ether, diisopropyl
ether or dioxan) or an aromatic hydrocarbon (e.g. benzene,
toluene or xylene) and thereafter the oxime is suspended
in the solution. The dicyclohexylcarbodiimide is like~
wise dissolved in the same solvent and added to the
-reaction mixture. The reaction is preferably carried
out in a temperature range between 0C and the boiling
point of the reaction mixture, especially between room
temparature and 50C. The reaction is normally completed
after about 2 hours.
In process variant (b), the term "leaving group"
used in connection with Y signifies, for example, chlorine,
bromine, iodine, mesyloxy or tosyloxy. The reaction is
conveniently carried out in an inert organic solvent such
as a hydrocarbon (e.g. benzene or toluene~, an ether
(e.g. diethyl ether, dimethoxyethane or tetrahydrofuran)
or hexamethylphosphoric acid triamide. The reaction
temperature is not critical and the reaction is preferably
- carried out at a temperature between -20C and the reflux
temperature of the reaction mixture, especially at a
temperature between -10C and 30C.
~In each case the product obtained can be isolated
and purified according to methods known per se.
. .:
- . ~ ; i :
.
- . ~. , . J

I 1~6~3
- 14 -
Insofar as no planned synthesis for the isolation
of pure isomers is carried out, the product normally
occurs as a mixture of two or more isomers. The isomers
can be separated according to methods known per se. If
S desired, they can also be manufactured by synthesis
from corresponding optically active starting materials.
The starting materials of formulae II, III, IV
and V as well as reactive derivatives of the acids of
formula II and alkali metal salts of the phenols of
formula IV are either known or can be prepared in a
manner known per se.
The compounds of formula I possess herbicidal
properties and are especially suitable for the control
of weed grasses, especially of slender foxtail
(Alopecurus myosuroides) and types of millet such as,
for example, cock's foot ~Echinochloa crus-galli), great
foxtail millet (Setaria faberii) and hair-like millet
(Panicum capillare) in cereals, especially barley, oats
and wheat cultivations, as well as in rice, cotton, soya,
sugar beet and vegetable plantations. The compounds in
accordance with the invention are particularly suitable
~ for the control of weed grasses in cotton, soya, sugar
beet and vegetable plantations.
.
, . - :

- 15 -
In general, a concentration of 001-6 kg of active
substance of formula I per ha, preferably 0.6-2 kg of
active substance of formula I per ha, is sufficient
to produce the desired herbicidal effect.
The compounds o formula I are not only pre-
-emergence herbicides but also post-emergence herbicides.
The weed control compositions in accordance with
the invention contain an effective amount of at least one
compound of formula I, as defined above, as well as
formulation adjuvants. Tha compositions conveniently
contain at least one of the following formulation
adjuvants: solid carrier substances; solvents or
dispersion media ; tensides (wetting and emulsifying
agents); d~si~ ~n~ (without tenside action); and
stabilizers. When using these and other adjuvants the
compounds o formula I, namely the herbicidal active
substances, can be converted into the usual foxmulations
such as dusts, powders, granulates~ solutions, emulsions,
suspensions, emulsifiable concentrates, pastes and the
like.
The compounds of formula I are generally insoluble
in water and can be formulated according to the methods
which are usual for water-insoluble compounds using the
'' ` ':
. .:
. ~

6 3
- 16 -
respecti~e formulation adjuvant~ The manufacture of the
compositions can be carried out in a manner known per se;
for example, by mixing the respective active substance
with solid carrier substances, by dissolution or
suspension in suitable solvents or dispersion media, if
necessary using t~nsides as wetting or emulsifying agents
and/or d~ i~ ~, by diluting pre-prepared
emulsifiable concentrates with solvents or dispersion
media etc.
As solid carrier substances there essentially
come into consideration: natural mineral substances such
as chalk, dolomite, limestone, aluminas and silicic acid
and salts thereof (e.g. siliceous earth, kaolin, bentonite,
talc,attapulgite and montmorillonite); synthetic mineral
substances such as highly dispersible silicic acid,
aluminium oxide and silicates; organic substances such
as cellulose, starch, urea and synthetic resins; and
fertilizers such as phosphates and nitrates, whereby such
carrier substances can be present as powders oras granulates.
As solvents or dispersion media there essentially
come into consideration: aromatics such as benzene,
toluene, xylenes and alkylnaphthalenes; chlorinated
aromatics and chlorinated aliphatic hydrocarbons such as
chlorobenzenes, chloroethylenes and me~hylene chloride;
. .,
.
~'-.
'
.

1 1~6~63
- 17 -
aliphatic hydrocarbons such as cyclohexane and paraffins
(e.g. petroleum fractions); alcohols such as butanol and
glycol, as well as their ethers and esters; ketones such
as acetone, methyl ethyl ketone, methyl isobutyl ketone
and cyclohexanone; and s~y polar solvents or
dispersion ~e~ia such as dimethylformamide, N-methyl-
-pyrrolidone and dimethyl sulphoxide, whereby such
solvents preferably have flash points of at least 30C
and boiling points of at least 50C, and water. Among
the solvents or dispersion media there also come into
consideration so-called liquified gaseous extenders or
carrier substances, these being products which are gaseous
at room temperature and under normal pressure. Examples
of such products are especially aerosol propellant gases
such as halogenated hydrocarbons (e.g. dichlorodifluoro-
methane). If a weed control composition in accordance
with the invention is present in the form of a pressurized
pack, then a solvent is conveniently used in addition to
the propellant gas.
.
The tensides (wetting and emulsifying agents) can
be non--70nic compounds such as condensation products of
fatty acids, fatty alcohols or fatty-substituted phenols
with ethylene oxide; fatty acid esters and ethers of
sugars or polyvalent alcohols; the products which are
obtained from sugars or polyvalent alcohols by condensation
:. ~

-- 115~B63
- 18 -
with ethylene oxide; block polymers of ethylene oxide
and propylene oxide; or alkyldimethylaminè oxides.
The tensides can also be anionic compounds such
as soaps; fatty sulphate esters (e.g. dodecyl sodium
sulphate, octadecyl sodium sulphate and cetyl sodium
sulphate); alkyl sulphonates, aryl sulphonates and fatty-
-aromatic sulphonates, such as alkylbenzene sulphonates
(e.g. calcium dodecylbenzene sulphonate and butylnaphthalene
sulphonates; and more complex fatty sulphonates, for
example the amide condensation products of oleic acid and
N-methyltaurine and the sodium sulphonate of dioctyl
succinate.
Finally, the tensides can be cationic compounds such
as alkyldirnethylbenzylammonium chlorides, dialkyldimethyl-
ammonium chlorides, alkyltrimethylammonium chlorides andethoxylated quaternary ammonium chlorides~
As c~ siry ~(without tenside action) there
essentially come into consideration: lignin, sodium and
ammonium salts of lignin sulphonic acids, sodium salts of
maleic acid anhydride/diisobutylene copolymers, sodium and
: ^ ammonium salts of sulphonated polycondensation products of
naphthalene and formaldehyde, and sulphite lyes.
i; . , , . , ~ ~ ~ , : . .
:

- 19 -
As d~su~ ~, which are especially suitable as
thickening agents or anti-settling agents, there can be
used, for example, methylcellulose, carboxymethylcellulose,
hydro~yethylcellulose, polyvinyl alcohol, alginates,
caseinates and blood albumin.
Examples of suitable stabilizers are acid-binding
agents (e.g. epichlorohydrin, phenyl glycidyl ether and
soya epoxides~i antioxidants (e.g. gallic acid esters and
butylhydroxytolue~e); W-absorbers (e.g. substitute~
benzophenones, diphenylacrylonitrile acid esters and
cinnamic acid esters); and deactivators (e.g. salts of
ethylenediaminotetraacetic acid and polyglycols).
The weed control compositions in accordance with
the invention can contain, in addition to the compounds
of formula I, synergists and other active substances
(e.g. insecticides, acaricides, bactericides, other
herbicides, fungicides, plant growth regulators and
fertilizers). Such combination compositions are suitable
for intensifying the activity or for broadening the
spectrum of activity.
~ The weed control compositions in accordance with
the invention generally contain between 0.1 and 99 weight
percent~ preferably between 5 and 75 weight percent, of
' : ~

6~3
- 20 -
one or more compounds of formula I as the active
substance(s). They can be present, for example, in a form
which is suitable for storage and transport. In such
~ormulations ~e.g. emulsifiable concentrates) the active
substance concentration is normally in the higher range,
preferably between 10 and 75 weight percent, especially
between 25 and 50 weight percent. These formulations
can subsequently be diluted, for example, with the same
or different inert substances, to give active substance
concentrations which are suitable for practical use,
i.e. preferably about 0.1 to 10 weight percent, especially
about 1 to 5 weight percent. The active substance
concentrations can, however, also be smaller or greater.
Conveniently, in the weed control compositions in
accordance with the invention the solid carrier substances
are present in a concentration range between 1 and 99.9~,
the solvents or dispersion ~e~ia are present in a
concentration range between 1 and 99.9%, the tensides are
present in a concentration range between l and 20~, the
~ rs~ are present in a concentration range between
1 and 20%, the d~ s~ ~sas thickening or anti-settling
agents are present in a concentration range between 0.1
and 5% and the stabilizers are present in a concentration
range between 0.1 and 5%, these percentages referring to
the total weight of the composition.
,,
~. ':' . ...

- 21 -
As mentioned above, the manufacture of the weed
control compositions in accordance with the invention can
be carried out in a manner known per se.
For the manufacture of pulverous preparations
the active substance, i.e. at least one compound of
formula I, can be mixed with solid carrier substance
(e.g. by grinding together); or the solid carrier
substance can be impregnated with a solution or suspension
of the active substance and then the solvent or dispersion
medium can be removed by evaporation, heatihg or suc]cing-
-off under reduced pressure. By adding tensides or
d~ s~ such pulverous preparations can be made
readily wettable with water, so that they can be converted
` into aqueous suspensions which are suitable, for example,
- 15 as spray compositions.
The compounds of formula X can also be mixed with
a tenside and a solid carrier substance to form a wettable
powder which is dispersible in water, or they can be mixed
with a solid pre-granulated carrier substance to form a
product in the form of a granulate.
~ If desired, the compounds of formula I can be
dissolved in a water-immiscible solvent such as, for exampIe,
a high-boiling hydrocarbon, which conveniently contains
; .
~.

6 3
- 22 -
a dissolved emulsifying agent, so that the solution
becomes self-emulsifying upon addition to water.
Alternatively, the active substance can be mixed with an
emulsifying agent and the mixture can then be diluted
with water to the desired concentration. Moreover,
the active substance can be dissolved in a solvent and
thereafter the solution can be mixed with an emulsifying
agent. Such a mixture can likewise be diluted with water
to the desired concentration. In this manner there are
obtained emulsifiable concentrates or ready-for-use
emulsions.
The use of the weed control compositions in
accordance with the invention can be carried out according
to usual application methods such as sprinkling, spraying,
dusting, pouring or scattering. The metho* in accordance
with the invention for the control or weeds comprises
treating the locus to be protected against weeds and/or
the weeds with a compound in accordance with the invention
or with a weed control composition in accordance with
the invention.
.: :
.
.
.` : :
:
: ~ .

6 3
- 23 -
The following Examples illustrate the present
invention:
I. Manufacture of the active substances of formula I:
~E~
0.47 g of pyridine is added dropwise to a solution,
cooled at 5C, of 1.72 g of D-2-[p-(a,a,a-trifluoro-p-
-tolyloxy)phenoxy]-propionyl chloride and 0.58 g of 2-iso-
propylidineaminooxy-ethanol in 40 ml of benzene. The
mixture is stirred at room temperature for 1 hour and
subsequently evaporated to dryness under reduced pressure.
Thereafter, the residue is dissolved in diethyl ether/n-
hexane (l:l) and the solution is extracted with water and
dilute sodium bicarbonate solution, dried over a drying
agent and finally evaporated to dryness.
The liquid residue is purified by chromatography
on silica gel with acetone/n-hexane (1:7). There is
obtained 2-isopropylideneaminooxy-ethyl D-2-[p-(a,~,a-
-trifluoro-p-tolyloxy)phenoxy]-propionate; nD = 1.5088;
[a]D = +13.9 (c = l.0~ in CHCl3).
In an analogous manner,
from D-2-[p-(a,a,a-trifluoro~p-tolyloxy)phenoxy]-propionyl
chloride and N-hydroxymethyl-acetamide there is obtained
'': ' .

- 24 -
acetamidomethyl D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy~
-propionate; m.p. 103-105C; [a]D = 13.5 (c -- l 1%
in CHC13)i
from D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenox~-propionyl
chloride and N-hydroxymethyl-chloroacetamide there is
obtained chloroacetamidomethyl D-2-~p-(a,a,a-trifluoro-p-
-tolyloxy)phenox~-propionate; m.p. 98-99C; [a]22
19.8 (c = 0.7% in CHCl3);
from D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-propionyl
chloride and N-hydroxymethyl-trichloroacetamide there is
obtained trichloroacetamidomethyl D-2-[p-(a,a,a-trifluoro-
-p-tolyloxy)phenoxy]-propionate; n20 = 1.5320; [a]D =
+14.8 (c = 0.6% in CHCl3);
from D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-propionyl
chloride and 2-methanesulphonamido-ethanol there is obtained
2-methanesulphonamido-ethyl D-2-[p-(a,a,a-trifluoro-p-tolyl-
oxy)phenoxy]-propionate; m.p. 65-68C; [a]D = +24.6
(c = 1.1% in CHCl3);
from D-2-[p-(a, a, a-trifluoro-p-tolyloxy)phenoxy]-propionyl
chloride and N-hydroxymethyl-succinimide there is obtained
succinimidomethyl D-2- EP- ( a, a,a-trifluoro-p-tolyloxy)-
phenoxy]-propionate; m.p. 74-76C; [a] D = +13.5
(c = 1-3% i~ CHC13);
~', ' '` '' '. ~' ~ .
.
. .
.
.,: ,.
,~ : ..

- 25 -
from D-2-[p-(a,a,a~trifluoro-p-tolyloxy)phenoxy]-propionyl
chloride and N-hydroxymethyl-phthalimide there is obtained
phthalimidomethyl D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phen-
oxy]-propionate; m.p. 99-100C; [a]D = ~4 9 (c = 0.7%
in CHC13)i
from D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-propionyl
chloride and diethoxyphosphinylmethanol there is obtained
diethoxyphosphinylmethyl D-2-[p-(,a,a-trifluoro-p-tolyl-
oxy)phenoxy]-propionate; nD = 1.5008; E a]D = +27.5
(c = l.0~ in CHCl3);
from D-2-~p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-propionyl
chloride and 2-diethoxyphosphinyl-ethanol there is obtained
2-diethoxyphosphinyl-ethyl D-2-[p-(a,a,a-trifluoro-p-
tolyloxy)phenoxy]-propionate; nD = 1.5001; La]D2 =~20.7
(c = 0.7% in CHCl3);
- from D-2-~p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-propionyl
chloride and l-diethoxyphosphinyl-ethanol there is obtained
l-diethoxyphosphinyl-ethyl D-2-[p-(a,a,a-trifluoro-p-
tolyloxy)phenoxy]-propionate; nD = 1.4963; [a]D
20 +20.3 (c = 1.3%in CHCl3);
from D-2-[p-(a,a,-trifluoro-p-tolyloxy)phenoxy]-propionyl
chloride and l-diethoxyphosphinyl-n-butanol there is
obtained l-diethoxyphosphinyl-n-butyl D-2-[p-(~, a, a-
,
-; :

1 ~ 3
- 26 -
-trifluoro-p-tolylo~y)phenoxy]-propionate; nD = 1.4945;
[a]D2 = +23.0 (c = 1.4% in CHC13);
from D-2-[p-(,a,a-trifluoro-p-tolyloxy)phenoxy]-propionyl
chloride and a-diethoxyphosphinyl-benzyl alcohol there is
obtained a-diethoxyphosphinyl-benzyl D-2-[p-(a,a,a-trifluoro-
-p-tolyloxy)phenoxy]-propionate; n20 = 1.5228; [a]D
+25.5 (c = 0.7% in CHC13);
from D-2-[p-(p-iodophenoxy)phenoxy]-propionyl chloride and
2-isopropylideneaminooxy-ethanol there is obtained 2-
~isopropylideneaminooxy-ethyl D-2-[p-(p-iodophenoxy)phenoxy]-
-propionate; [a]D = +12.6 (c = 1.2% in CHC13);
from D-2-[p--(p-iodophenoxy)phenoxy]-propionyl chloride and
2-methanesulphonamido-ethanol there is obtained 2-methane-
sulphonamido-ethyl D-2-[p-(p-iodophenoxy)phenoxy]-propionate;
mOpu 84-87Ct ~a]22 = +23.2 (c = 1.0% in CHC13);
,
..,, , , ~. . .. .
. . . ~

- 27 -
from D-2-[p-(p-iodopheno~y)phenoxy]-propionyl chloride
and N-hydroxymethyl-succinimide there is obtained
succinimidomethyl D-2-[p-(p-iodophenoxy)phenoxy]-propionate;
[a]D = +11.5 (c = 0.8% in CHC13);
from D-2-[p-(p-iodophenoxy)phenoxy]-propionyl chloride
and diethoxyphosphinylmethanol there is obtained diethoxy-
phosphinylmethyl D-2-[p-(p-iodophenoxy)phenoxy]-propionate;
[a]D = +23.7 (c = 1.7% in CHC13);
from D-2-[p-(p-iodophenoxy)phenoxy]-propionyl chloride
and 2-diethoxyphosphinyl-ethanol thexe is obtained 2-
-diethoxyphosphinyl-ethyl D-2-[p-(p-iodophenoxy)phenoxy]-
propionate; [a]D = +19.7% (c = 1.3% in CHC13);
from D-2-[p-(o-chloro-p-iodophenoxy)phenoxy]-propionyl
chloride and 2-isopropylideneaminooxy-ethanol there is
obtained 2-isopropylideneaminooxy-ethyl D-2-[p-(o-chloro
p-iodophenoxyjphenoxy]-propionate; [a]D = +11.7 (c =
0.9% in CHC13);
from D-2-[p-(o-chloro-p-iodophenoxy)phenoxy]-propionyl
chloride and 2-methanesulphonamido-ethanol there is obtained
2-methanesulphonamido-ethyl D-2-[p-(o-chloro-p-iodo-
phenoxy)phenoxy]-propionate; [~]20 = ~19.4 (c = 008% in
C~C13);
;~

15~3
- 28 -
from D-2-[p-(o-chloro-p-iodophenoxy)phenoxy]-propionyl
chloride and diethoxyphosphinylmethanol there is obtained
diethoxyphosphinylmethyl D-2-[p-(o-chloro p-iodophenoxy)-
phenoxy]-propionate; ~a]D = +19.7 (c = 1.6% in CHC13);
from D-2-[p (a,a,a-trifluoro-p-tolyloxy)phenoxy]-propionyl
chloride and ~ibutoxyphosphinylmethanol there is obtained
di~utoxyphosphinylmethyl D-2-[p-(a,a,a-trifluoro-p-tolyloxy)-
phenoxy]-propionate; nD = 1.4932; [a]D = ~23.2 (c =
0.60~ in CHC13);
from D-2-[p-(a, a,a-trifluoro-p-tolyloxy)phenoxy]-propionyl
chloride and l-diphenoxyphosphinyl-ethanol there is
obtained l-diphenoxyphosphinyl-ethyl D- 2-[p-( a,a,a~tri-
fluoro-p-tolyloxy)phenoxy]-propionate; nD ~ 1.5449;
[a]D = +7 3 ~c = 1.1% in CHC13);
lS from D-2-[p-(a,a, a-trifluoro-p-tolyloxy)phenoxy]-propionyl
chloride and l-isopropylideneaminooxy-2-propanol ~here is
o~,tai.ned 1-isopropylideneaminooxy-2-propyl D 2 ~p-~a,a,a-

- 29 -
-trifluoro-p-tolyloxy)phenoxy]-propionate; nD
1.5026; [a]D = +19.0 (c.= 1.1% in CHC13);
from D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-propionyï
chloride and l-isopropylideneaminooxy-2-butanol there is
obtained 1-isopropylideneaminooxy-2-butyl 3-2-~p-(a,a,a-
-trifluoro-p-tolyloxy)phenoxy]-propionate; nD = 1.5023,
[a]D = +20.7 (c = 1.0% in CHC13);
from D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-propionyl
chloride and 2-isopropylideneaminooxy-1-phenyl-ethanol
there is obtained 2-isopropylideneaminooxy-1-phenylethyl
D-2-[p-(a, ar a-trifluoro-p-tolyloxy)phenoxy]-propionate;
[a]D2 = +19.8 tc = 0.9% in CHC13);
from D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phe~oxy]-propionyl
chloride and 2-(2-butylideneaminooxy)-ethanol there is
obtained 2-(2-butylideneaminooxy)-ethyl D-2-[p-(a,a,a-
-trifluoro-p-tolyloxy)phenoxy]-propionate; nD = 1.5072;
[a]D = +13.7 (c = 1.1% in CHC13);
from D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-propionyl
chloxide and 2-(a-methylbenzylideneaminooxy)-ethanol
~o there is obtained 2-(a-methylbenzylideneaminooxy)-ethyl
D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-propionate,
nl~ - 1.5456; [a]D = +7.6 (c = 1.0% in CHC13);
: ,~

-~ tl~63
- 30 -
from D-2-[p-(a,a,a-tri~luoro-p-tolyloxy)phenoxy]-propionyl
chloride and 2-cyclohexylideneaminooxy-ethanol there is
obtained 2-cyclohexylideneaminooxy-ethyl D-2-[p-~a,a,~
-trifluoro-p-tolyloxy)phenoxy]-propionate; nD = 1.5201;
[]20 = +11.7 (c = 1.1% in CHC13).
Exam~le_2
3.0 g of D-2-[p-(a,a,a-trifluoro-p-tolyloxy)-
phenoxy]-propionic acid are suspended in 10 ml of
dichloromethane and 1.3 g of ethyl ~k~oxime are
added at room temperature. A solution of 1.9 g of
dicyclohexylcarbodiimide in 10 ml of dichloromethane is
added dropwise to the suspension during 10 minutes,
the temperature of the mixture thereby rlsing to40C ~.e
mixture is stirred at room temperature for a ~urther 2
hours and subsequently filtered. The filtrate is
evaporated to dryness under reduced pressure. There is
obtained ethyl 3-/ D-2-[p-(a,a,a-trifluoro-p-tolyloxy)
phenoxy]-propionoxyimino ~-butyrate; ~a]20 = ~39.8 (c =
1.0~ in CEC13)u
In an analogous manner,
- from D-2~[p-( a~ a,a-trifluoro-p-tolyloxy)phenoxy]-propionic
acid and l,l,l-trifluoroacetone oxime there is obtained
. .: :, - .
~: .

-- 31 --
D-2- [p- ( a, a, a-trifluoro-p-tolyloxy)phenoxy]-propionic
acid l,l,l-trifluoroacetone oxime ester; [a]20 = +39.50
(c = 1.0% in CHC13);
from D-2- [p- ( a, a, a-trifluoro-p-tolyloxy)phenoxy]-propiorl~c
acid and l-hydroxyimino-diethyl ether there is obtained
ethyl N-/ D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-
-propionoxy_7-acetimidate; nD = 1.5087; [a]D = +53
(c = 0.9~ in CHC13);
from D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-
propionic acid and n-butyl (l-hydroxyimincethyl) ether
there is obtained n-butyl N- r D-2-[p-(a,a,-trifluoro-p-
-tolyloxy)phenoxy]-propionoxy /-acetimidate; n20 = 1.5036;
[a]D2 = +49.87 (c = 1.2~ in CHC13);
.,
from ~-2-[p-(ala,a-trifluoro-p-tolyloxy)phenoxy]-propionic
acid and ethyl (l-hydroxyimino-n-butyl) ether there is
obtained ethyl N-~ D-2-Lp-(a,a,a-trifluoro~p-tolyloxy)-
phenoxy]-propionoxy ~ -n-butyrimidatei n20 = 1.5058;
[a]D = +52.58 (c = 1.0~ in CHC13)j
from D-2-[p-(a,a,a~trifluoro-p-tolyloxy)phenoxy]-propionic
acid and methoxyacetone oxime there is obtained D-2-[p-
-(a,a,a-trifluoro-p-tolyloxy)phenoxy]--propionic acid
methoxyacetone oxime ester; [a]20 = ~48.77 (c - 1.9
in CHC13);
'
.,, ~
:
,:

6 3
- 32 -
from D-2-[p-(a,a,a-trifluoro-p--tolyloxy)phenoxy]-
-propionic acid and diacetone monoxime there is obtained
D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-propionic acid
diacetone monoxime ester; [a]D = +30.7 (c = 1.0% in
CHC13)i
from D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy~-proplonic
acid and ethyl pyruvate oxime there is obtained ethyl
2- r D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-propionoxy-
imino /-propionate; [a]D = +45.01 (c = 2.0% in CHC13);
from D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy-propioniC
acid and ethyl a-methyl-acetoacetate oxime there is obtained
ethyl 2-methyl-3-/ D-2-[p-(a,a,a~trifluoro-p-tolyloxy)-
phenoxy]-propionoxyimino_/-butyrate; [a]20 - +41.07
(c = 0.9% in CHC13);
from D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-propionic
acid and ethyl levulinate oxime there is obtained ethyl
4-/ D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-propionoxy-
imino /-n-valerate; ~]D = +37 4 (c = 1~2% in CHC13);
from D-2-[p-(o-chloro-p-trifluoromethyl--phenoxy)phenoxy]-
-propionic acid and 2-isopropylideneaminooxy-ethanol there
is obtained 2-isopropylideneamlnooxy-ethyl D-2-[p (o-
-chloro-p-trifluoromethyl~phenoxy)phenoxy] propionate;
[a]20 = +12.3 (c = 0.69% in CHC13);
.

1 15~6~3
from D-2-[p-(~,a,a-tri~luoro-p-tolyloxy)phenoxy]-propionic
acid and cyclopentanone oxime there is obtained D-2-
-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-propionic acid
cyclopentanone oxime ester; [a]D = ~40.8 (c = 1.0%
in CHC13).
Example 3
A solution of 1.79 g of D-2-~p-(a,a,a-trifluoro-
-p-tolyloxy)phenoxy]-propionic acid, 1.30 g of l-diethoxy-
phosphinyl-cyclohexanol and 0.06 g o 4-dimethylamino-
-pyridine in 20 ml of dichloromethane is treated at room
temperature with 1.13 g of dicyclohexylcarbodiimide and
the mixture is stirred for 24 hours. The mixture is then
evaporated to dryness under reduced pressure, the residue
is dissolved in diethyl ether/n-hexane (1:1) and the
insoluble part of the residue is filtered off under
suction. Subsequently, the filtrate is washed twice with
30 ml of 5~ acetic acid each time and three times with
30 ml of water each time, dried over a drying agent and
evaporated to dryness. The liquid residue is puxified
20 by chxomatography on silica gel with dichloromethane/ ..
diethyl ether (1:1). There is obtained l-diethoxy~
phosphinyl-cyclohexyl D-2-[p-( a, a, a-trifluoro-p-tol~yloxy)
phenoxy]-propionate; n20 = 1.5073.
'' ' ' ~ ' .

B~3
- 34 -
In an analogous manner,
from D-2-[p-( a, a, a-trifluoro-p-tolyloxy)phenoxy]-
-propionic acid and 2-dimethoxyphosphinyl-2-propanol
there is obtained 2-dimetho.~phosphinyl-2-propyl D-2-
5 - [p- ~a, a, a-trifluoro-p-tolyloxy)phenoxy]-propionate;
nD = 1.5019; [alD = +7.6 (c = 1.2~ in CHC13).
Example 4
A mixture of 1.89 g of D-2-[p-(a,a,a-trifluoro-
-p-tolyloxy)phenoxy]-propionic acid, 1.43 g of 3-
-diethoxyphosphinylpropyl bromide, 0.40 g of potassium
carbonate and 50 ml of absolute acetone is heated at
reflux for 15 hours~ Thereafter, the mixture is
evaporated to dryness under reduced pressure and the
residue is dissolved in diethyl ether. The solution is
lS washed twice with 25 ml of water each time and extracted
twice wit~ 25 ml of sodium bicarbonate solution each time,
dried over a drying agent and evaporated to dryness.
The liquid residue is purified by chroma~ography on
silica gel with dichloromethane. There is obtained 3-
-diethoxyphosphinyl-propyl D-2-[p-ta,a,a-trifluoro-p
~tolyloxy)phenoxy]-propionate; nD = 1.4986; [a]D
+20.52 (c = 0.9~ in CHC13)o
.

- 35 -
In an analogous manner,
from D-2-[p-(p-iodophenoxy)phenoxy]-propionic acid and
3-diethoxyphosphinylpropyl bromide there is obtained
3-diethoxyphosphinyl-propyl D-2-[p-(p-iodophenoxy)phenoxy]-
-propionate; [a]D = +20.4 (c = 1.2% in CHC13).
II. Formulation Examples:
Example 5
For the manufacture of an emulsifiable concentrate
the following ingredients are mixed with one another:
10 Compound of formula I 500 g
Mixture of condensation products of an
alkylphenol and ethylene oxide and
- calcium dodecylbenzenesulphonate100 g
Epoxidated soya oil with an oxirane
15 oxygen content of about 6~ 25 g
Butylated hydroxytoluene 10 g
: The mixture is made up to 1 litre with xylene.
The thus-obtained concentrate emulsifies
spontaneously in water. The resulting emulsion is
suitable as a ready-for-use spray liquor.
- ,
. . .,:
~: ~
:
:,

6 ~ 3
- 36 -
Example 6
For the manufacture of an emulsifiable
concentrate the following ingredients are mixed with one
another:
5 Compound of formula I 250 g/l
N-Methyl-2-pyrrolidone 300 g/l
Emulsifier A ) 100 g/l
Emulsifier B ) 25 g/l
Solvent mixture of alkylbenzenes to lO00 ml
~Emulsifier A: Emulsifier consisting of 60
parts of a block polymerisate of ethylene oxide and
proplyene oxide, 20 parts of the calcium salt of a
branched-chain dodecylbenzenesulphonic acid and ?0 parts of
a solvent mixture of isobutanol and C10~alkylbenzenes.
2)Emulsifier B: Mixture of 70 parts of the
calcium salt of a branched-chain dodecylbenzenesulphonic
acid and 30 parts of a solvent mixture of isobutanol and
C10-alkylbenzenes .
The thus-obtained concentrate emulsifies
spontaneously in water. The resulting emulsion is
suitable as a ready-for-use spray liquor.
..

- 37 -
III. Blological Results:
Exam~le 7
The formulation of Example 6 is sprayed on the
test weeds (Lolium multiflorum or Bromus inermis) in
fixed dilutions with water containing 0.5 volume percent
of Nonoxynol (condensation product of nonylphenol and
ethylene oxide~. The spraying is carried out by means
of a logarithmic spray apparatus which enables the
concentration of the active substance to be halved
automatically after fi~Yed ~ intervals. The ispray
volume amounts to SOO l/ha. 33 days after the spraying
the weeds are investigated for the effect which has
occurred, i.e. there is determined the dosage at which a
satisfactory control of the weeds is achieved. The
results are compiled in Table I hereinafter.
~;
'' : " " ~, ' ' ' :

1 1 ~ 3
- 38 -
Table I
..
Dosage (g of active substance/
~ ~a) _
Active substance ofLolium Bromus
formula I multiflorum inermis _
Ethyl N-/~ -2-[p-(a,a,a-
-trifluoro-p-tolyloxy)-
phenoxy]-propionoxy /-n-
-butyrimidate 165 165
n-Butyl N-/ D-2-[p-(a,a,a-
-trifluoro-p-tolyloxy)- .
phenoxy]-propionoxy_/-
-acetimidate 125 220
_ . . _.~
Example 8
The active substance is tested in the formulation
of Example 6. Shortly before the beginning of the test,
it is diluted to the desired concentration with water
containing 0.5 volume percent of Nonoxynol as the wetting
agent.
The test weeds (Oryza sativa) in -the 2 leaf stage
are sprayed in a greenhouse with the thus-formulated
active substance. Subsequently, a 16 hours day is
,~ .
- ~........... . . ..
. ~ :
- ,~
.

1 ~ 3
- 39 -
simulated by means o~ mercury lamps. Three weeks arter
the spraying the weeds are investigated for the effect
which has occurred, i.e. the percentage necrosis is
determined, with a 100% necrosis corresponding to a
complete destruction of the weeds. The results are
compiled in the Table II hereinafter.
Table II
Acti~e substance of Dosage % Necrosis
formùla I q/ha (Oryza sativa)
D-2-[p-(a,a,a-Trifluoro-
-p-tolyloxy)phenoxy~-
propionic acid methoxy-
acetone oxime ester 150 90
.; . : : . ~