PROPIONIC ACID ESTERS

ESTERS D'ACIDE PROPIONIQUE

English Abstract

-a-
Abstract
The invention is concerned with propionic acid
esters of the formula
<IMG> I
wherein A signifies one of the following
groups (a) or (b)
<IMG> <IMG>
(a) (b)
R signifies hydrogen, halogen, C1-4-
alkyl, trifluoromethyl, C1-4-alkoxy
or C1-4-alkylthio,
X signifies oxygen, sulphur or -NR5-,
Y signifies the methine group, i.e.
the group -CH=, or a nitrogen atom,
R1 signifies hydrogen or C1-4-alkyl and
R2 signifies hydrogen, C1-4-alkyl,
C1-4-haloalkyl or optionally mono-
substituted or multiply substituted
phenyl, the optionally present sub-
stituents being halogen atoms, C1-4-

-b-
alkyl groups, C1-4-alkoxy groups
and nitro groups, or R1 and R2
together with the carbon atom to
which they are attached signify
an optionally substituted C5-8-
cycloalkane ring, the optionally
present substituents being one to
three C1-4-alkyl groups,
R3 and R4 each independently signify
C1-6-alkyl or phenyl,
R5 signifies hydrogen or C1-4-alkyl,
m, n and p each independently signify
the number 0 or 1, the sum thereof
being at least 1,
and q signifies the number 1 or 2,
a process for their manufacture, weed control
compositions which contain these compounds as the
active substance as well as the use of such com-
pounds or compositions for the control of weeds.

Claims

- 26 -
CLAIMS:
1 Compounds of the general formula
<IMG> I
wherein A signifies one of the following
groups (a) or (b)
<IMG> <IMG>
(a) (b)
R signifies hydrogen, halogen, C1-4-
alkyl, trifluoromethyl, C1-4-alkoxy
or C1-4-alkylthio,
X signifies oxygen, sulphur or -NR5-,
Y signifies the methine group or a nitro-
gen atom,
R1 signifies hydrogen or C1-4-alkyl and
R2 signifies hydrogen, C1-4-alkyl, C1-4-
haloalkyl or optionally monosubstituted
or multiply substituted phenyl, the
optionally present substituents being
halogen atoms, C1-4-alkyl groups, C1-4-
alkoxy groups and nitro groups, or R1
and R2 together with the carbon atom to
which they are attached signify an

- 27 -
optionally substituted C5-8-cyclo -
alkane ring, the optionally present
substituents being one to three C1-4-
alkyl groups,
R3 and R4 each independently signify
C1-6-alkyl or phenyl,
R5 signifies hydrogen or C1-4-alkyl,
m, n and p each independently signify
the number 0 or 1, the sum thereof
being at least 1,
and q signifies the number 1 or 2.
2. Compounds according to claim 1, wherein R sig-
nifies chlorine.
3. Compounds according to claim 1 wherein R1
signifies hydrogen, methyl or ethyl.
4. Compounds according to any one of claims 1 to 3,
wherein R2 signifies hydrogen, methyl or ethyl.
5. Compounds according to any one of claims 1 to 3,
wherein R3 and R4 each independently signify C1-6-alkyl.
6. Compounds according to any one of clalms 1 to 3
wherein q signifies 1.
7. Compounds according to any one of claims 1 to 3
in the D-form.
8. Diethyl [D-2-[p-(6-chloro-2-quinoxalyloxy)phenoxy]-
propionyloxy]methylphosphonate.
9. Diethyl [D-2-[p-(6-chloro-2-quinolyloxy)pheroxy]-
propionyloxy]methylphosphonate.
10. A compound according to claim 1, selected from:

- 28 -
Diethyl [D-2-[p-(6-fluoro-2-quinoxalyloxy)phenoxy]-
propionyloxy]methylphosphonate,
diethyl 2-[D-2-[p-(6,7-dichloro-2-quinoxalyloxy)-
phenoxy]-propionyloxy]-ethylphosphonate,
diethyl [D-2-[p-(6,7-dichloro-2-quinoxalyloxy)-
phenoxy]-propionyloxy]methylphosphonate,
diethyl 2-[D-2 [p-(5,6-dichloro-2-quinoxalyloxy)-
phenoxy]-propionyloxy]-ethylphosphonate,
diethyl DL-1-[D-2-[p-(6-chloro-2-quinoxalyloxy)-
phenoxy]-propionyloxy]-ethylphosphonate,
diethyl 2-[D-2-[p-(p-chloro-2-quinoxalyloxy)phenoxy]-
propionyloxy]-ethylphosphonate,
dibutyl[D-2-[p-(6-chloro-2-quinoxalyloxy)phenoxy]-
propionyloxy]methylphosphonate,
diethyl DL-1-[D-2-[p-(6-chloro-2-quinolyloxy)-
phenoxy]-propionyloxy]-ethylphosphonate,
diethyl 2-[D-2-[p-(6-chloro-2-quinolyloxy)phenoxy]-
propionyloxy]-ethylphosphonate,
diethyl 3-[D-2-[p-(6-chloro-2-quinolyloxy)phenoxy]-
propionyloxy]-propylphosphonate,
diethyl[D-2-[p-(2-benzthiazolyloxy)phenoxy]-
propionyloxy]methylphosphonate,
diethyl[D-2-[p-(5-chloro-2-benzthiazolyloxy)-
phenoxy]-propionyloxy]methylphosphonate and
diethyl[D-2-[p-(4,6-dichloro-2-benzthiazolyloxy)-
phenoxy]-propionyloxy]methylphosphonate.
11. A compound according to claim 1 as a weed control
agent.
12. A weed control composition which contains an effective
amount of at least one compound of the general formula

- 29 -
<IMG> I
wherein A signifies one of the following
groups (a) or (b)
<IMG>
(a) (b)
R signifies hydrogen, halogen, C1-4-
alkyl, trifluoromethyl, C1-4-alkoxy
or C1-4-alkylthio,
X signifies oxygen, sulphur or -NR5-,
Y signifies the methine group or a
nitrogen atom,
R1 signifies hydrogen or C1-4-alkyl and
R2 signifies hydrogen, C1-4-alkyl,
C1-4-haloalkyl or optionally mono-
substituted or multiply substituted
phenyl, the optionally present sub-
stituents being halogen atoms, C1-4-
alkyl groups, C1-4-alkoxy groups and
nitro groups, or R1 and R2 together
with the carbon atom to which they
are attached signify an optionally
substituted C5-8-cycloalkane ring,
the optionally present substituents
being one to three C1-4-alkyl groups,

- 30 -
R3 and R4 each independently signify
C1-6-alkyl or phenyl,
R5 signifies hydrogen or C1-4-alkyl,
m, n and p each independently sig-
nify the number 0 or 1, the sum
thereof being at least 1,
and q signifies the number 1 or 2,
as well as formulation adjuvants.
13. A weed control composition according to claim 12
which contains an effective amount of diethyl [D-2-[p-
(6-chloro-2-quinoxalyloxy)phenoxy]-propionyloxy] methyl-
phosphonate or diethyl [D-2-[p-(6-chloro-2-quinolyloxy)-
phenoxy]-propionyloxy] methylphosphonate as well as form-
ulation adjuvants.
14. A process for the manufacture of compounds of
the general formula
<IMG> I
wherein A signifies one of the following
groups (a) or (b)
<IMG> <IMG>
(a) (b)

- 31 -
R signifies hydrogen, halogen, C1-4-
alkyl, trifluoromethyl, C1-4-alkoxy
or C1-4-alkylthio,
X signifies oxygen, sulphur or -NR5-,
Y signifies the methine group or a nitrogen
atom,
R1 signifies hydrogen or C1-4-alkyl and R2
signifies hydrogen, C1-4-alkyl, C1-4-
haloalkyl or optionally monosubstituted
or multiply substituted phenyl, the
optionally present substituents being
halogen atoms, C1-4-alkyl groups, C1-4-
alkoxy groups and nitro groups, or
R1 and R2 together with the carbon atom
to which they are attached signify an
optionally substituted C5-8-cycloalkane
ring, the optionally present substituents
being one to three C1-4-alkyl groups,
R3 and R4 each independently signify C1-6-
alkyl or phenyl,
R5 signifies hydrogen or C1-4-alkyl,
m, n and p each independently signify the
number 0 or 1, the sum thereof being at
least 1,
and q signifies the number 1 or 2,
which process comprises
a) reacting an acid of the general formula
<IMG> II
wherein A has the significance given above,
or a reactive derivative thereof, with an alcohol of the
general formula

- 32 -
<IMG> III
wherein R1, R2, R3, R4, m, n and p have
the significances given above
and Z' signifies hydroxy or a leaving
group,
b) reacting a phenol of the general formula
<IMG> IV
wherein A has the significance given above,
or an alkali metal salt thereof, with a compound of the
general formula
<IMG> V
wherein R1, R2, R3, R4, m, n and p have
the significances given above
and Z2 signifies a leaving group,
or
c) reacting a halide of the general formula
A-Hal VI

- 33 -
wherein A has the significance given above
and Hal signifies halogen,
with a phenol of the general formula
<IMG> VII
wherein R1, R2, R3, R4, m, n and p have
the significances given above,
or an alkali metal salt thereof.
15. A method for the control of weeds, which method com-
prises 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 claims 1 to 3.
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 a composition as set forth in claim 12 or 13.
17. Compounds according to claim 1 wherein R signifies
chlorine and R1 signifies hydrogen, methyl or ethyl.
18. Compounds according to claim 17 wherein R2
signifies hydrogen, methyl or ethyl.
19. Compounds according to claim 18 wherein R3 and
R4 each independently signify C1-6-alkyl.
20. Compounds according to any one of claims 17, 18
or 19 wherein q signifies 1.
21. Compounds according to any one of claims 17, 18
or 19 in the D-form.

- 34 -
22. 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 compounds set forth in claims 17, 18 or 19.
23. The compositions according to claims 12 or 13
wherein the formulation adjuvants are selected from
solid carrier substances; solvents or dispersion media;
tensides including wetting and emulsifying agents;
dispersing agents and stabilizers.

Description

57~
RaN 6102/40
The invention is concerned with propionic acid
esters of the seneral formula
Rl 0 3
~ /OR
A-O--/ O ,o-o-cH-coo-(cH2~ )n (C~2)P \oR4
CH3 R
~; wherein A signifies one of the following
groups (a) or (b)
~ i/ \~ (R)
(a) (b)
R signlfies hydrogen, halogen, Cl_4-
alkyl, trifluoromethyl, Cl 4~alkoxy
or Cl_4-alkylthio,
X signi~ies oxygen, sulphur or -NR -,
Y signifies the methine group, i.e.
the group -CH=, or a nitrogen atom,
Rl s gnifies hydrogen or Cl 4 alkyl and
R signifies hydrogen, Cl_4-alkyl,
Cl_4-haloalkyl or optionally mono-
substituted or multiply substltuted
phenyl, the optionally present sub-
stit~en~ being halogen atoms, Cl 4-
Pa/30.1.84

~J~ ~7
-- 2 --
al~yl sroups, Cl_4-alkoxy groups
and nitro groups, cr Rl and R2
together wlth ~he carbon atom to
which ~hey are at~ached signify
an o~tionally substituted C5_8-
cycloalkane ring, the optionally
present substituents being one to
three Cl_4-alkyl groups,
R and R each independently signify
Cl 6-alkyl or phenyl,
R signifies hydrogen or Cl 4~alkyl,
m, n and p each independently signify
the number 0 or 1, the sum thereof
being at least 1,
and q signifies the number 1 or 2.
The compounds of ormula I possess herbicidal prop-
exties and are ~uita~l~ as actlve substances of weed con-
trol compositions. Accordingly, the invention also in-
cludes weed control compositions which contain compounds
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 the control of weeds.
In formula I above the term "halogen" embraces
fluorine, chlorine, bromine and iodine and the term "Cl_4-
haloalkyl" embraces Cl 4-alkyl substituted with one or more
halogen atoms. The term "Cl 4-alkyl'l or "Cl 6-alkyl" means
not only straight-chain but also branched-chain alkyl
groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl,
isobut~l, tert.butyl, n-pentyl, isoamyl, neo-pentyl and
n-hexyl. This also applies to the alkyl portion of the
alkoxy, alkylthio and haloalkyl groups. In the case of
multiple substitution the substituents can be the same or
different. Where q signifies 2, the symbols R can likewise
be the same or different.
The pre~ence of at leas. one asymmetric carbon atom

57~
- 3 -
in the com2ounds of formula I means that ~he compounds can
occur in isomeric forms which stand in enantiomeric or
diastereomeric relationship ~o one ano~her. The same
applies ~o the compounds of formula I in which~ in addition,
R3 and R4 have different significances. The separated
isomeric forms have optical activity. Accordingly, formula
I is intended to embrace the racemates as well as all of
the possible isomeric forms.
In the compounds of formula I a ha:Logen atom which
may be present is preferably chlorine. Cyclohexane is the
preferred C5 ~-cycloalkane group (CRlR2)O
Independently of one another R preferably signifies
hydrogen or halogen, especially chlorine; Rl and R2 each
preferably slgnify hydrogen, methyl or ethyl; R3 and R4
each preferably signify Cl_4-alkyl; and q pre~erably signi-
fies 1.
Furthermore, the D-forms of the compounds o~ formula I
are preferred.
Especially preferred compounds of formula I are:
Diethyl / D-2-[p-(6-chloro-2-quinoxalyloXy)phenoxy]-
propionyloxy /methylphosphonate and
diethyl r D-~-~p-(6-chloro-2-quinolyloxy)phenoxy]-
propionyloxy 7methylphosphonate.
The process in accordance with the invention for the
manufacture of the compounds of formula I comprises
a) reacting an acid of the general formula

~2~&57~
- 4 -
A-O--\ O /--O-C~-COOH II
C'~3
wherein A has the significance given above,
or a reactive derivative thereof, with an alcohol of the
.10 general formula
Rl O / OR
lSgl-~CH2)m~~l2n 2 P \oR4 III
h in Rl R2 R3, R4, m, n and p have the
significances given above
20and zl signifies hydroxy or a leavlng group,
b) reacting a phenol of the general formula
A-O- / O ~.-OH IV
30wherein A has the significance given above,
or preferably an alkali metaL salt thereof, with a compound
of the general formula
R / OR
z2_cH-COO-(CH2)m~(l)n (C~2)P \ 4 V
.: 3

57~
- 5 -
wherein R-, ~2, R3, R4, m, n and p have the
significances given above
and z2 signifies a leaving group (e.g~
chlorine, bromine, iodi.ne, mesylo~y
or tosyloxy),
or
c~ reactlng a halide of he general formula
A-Hal VI
wherein A has the significance given above
and Hal signifies halogen, especially
chlorine,
with a phenol of the general formula
Rl 0 3
.~ OR
HO--\ O /~-O-CH-COO~(CH2)m~(C)n (C~2)P \ 4 VII
CH3 R
h in Rl R2 R3 R4~ m, n and p have the
significances given above,
or preferably an alkali metal salt thereof.
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 alj, a2) and a3):
Educt ~2~
,
al) Free acid of ~ormula II Compound of formula III
35or a sal~ thereof in which Z signifies a
leaving group such as
chlorine, bromine, iodine,
mesyloxy or tosyloxy

~2~ 7~
.
- 6 -
a2) Halide, imldazolide or an~ Compound of formula
hydride of an acid of III i~ which zl signifies
formula II hydroxy
a3) Free acid of formula II Compour.d of formula III
in which 2 signifies
hydrox~.
In process variant al) the term "salt" signlfies, for
example, an alkali metal salt (e.g. the sodium, potassium
or lithium salt), an alkaline ~axth metal salt (e.g. the
maynesium, 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 'lleav:Lng
group" used in connection ~ith æl preferably stands for
chlorine, bromine or iodine.
The esterification of an acid of formula II or,
pre~erably, a salt thereof with a compound of formula III
ls pref2rably carried out in an inert diluent and at a
temperatuxe of about -10C to 100C. ~ temperature range
between 20C and 70C is especially preferred. Inert
organic solvents are preferably used as the diluent. Pre-
ferred solvents are aliphatic ketones (e.g. ace~one andethyl methyl ketone) and dipolar aprotic solvents (e.g.
dimethylformamide, dimethyl sulphoxide, N-methylpyrrolidone,
sulpholane and hexamethylphosphoric acid triamide).
When the free acid of formula II is used, the reaction
is conveniently carried out in the presence of 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 diluent such as an

571
- 7 -
ether (e.g. diethyl ether), a hydrocar~on ~e.g. n-hexane,
henzene or tolue~e) or a chlorinatPd hydxocarbon ~e.g.
dichloromethane, chloro~orm or carbon te~:rachlorlde) and at
room temperature or an eleva~ed temperature (e.g. up to the
reflux temperature of the reaction mixtuxe~.
When an acid halide o the acid of formuLa II is used,
the reaction is conveniently carried out in the presence of
an acid-binding a~ent at about -10C to 30C. 5uitab1e acid-
binding agentC are inorganic bases (e.g. alkali m tal and
al~aline earth metal carbonates and bicarbonates), but
especially organic bases (e.g. tertiary amines, especially
triethylamine or pyridine)~ The acid halide is preferably
the acid chloride. When t~e anhydride of thQ acid of formula
II is used, the reaction i5 conveniently carried out in
the presence of an acid-binding agent, especially an organic
base such as a tertlary amine (e.g. triethylamine, dimethyi-
aniline or pyridine) at a temperature between 0C and 40C,
especially at room temperature, or in the absence of an
acid-binding agent at an elevated temperature.
In process variant a3), the reaction is conveniently
carried out in an inert organic diluent such as an ali-
phatic or cyclic ether (e.g. diethyl ether, diisopropylether, 1,2-dimethoxyethane, tetrahydrofuran or dioxan), a
chlorinated hydrocarbon (e.g. dichloromethane, chloroform,
car~on tetrachloride or trichloroethane) or an aromatic
hydrocarbon (e.g. benzene, toluene or a xylene) and at a
temperature between 0C and the reflux temperature of the
reaction mixture. The reaction is conveniently carried
out in the presence of an acid catalyst or a condensing
agent such as sulphuric acid, hydrochloric acid, p-toluene-
sulphonic acid, dicyclohexylcarbodiimide or carbonyldi-
imidazole. Carbonyldiimida201e is preferably used 25the condensing agent a~d in this case the reaction is
preferably carried out in the presence of an ether as the
diluent. Thus, for example, the acid of for~ula II is

5~
- 8 -
dissolved or suspended in an iner~ organic diluent,
especially an alicyclic or cyclic ether, and the solution
or suspension is added to a solution or suspension of
c~rbonyldiimidazole in the same diluent. After the
resulting evolution o~ carbon dioxide has finished ~he
mlxture is treated with a solution of ~he alcohol o formula
III which has previously been treated wi~h a catalytic
amou~t of ~odium or sodium hydride until the hydrogen
evolution has finished. The reaction is preferably carried
out in a temperature range between room temperature and
about 50C and is normally completed within about 2 hours4
The reaction according to process variant b~ is con-
veniently carried out in an inert organic qolvent, espec-
ially a dipolar aprotic solvent such as dimethylormamide,
dimethyl sulphoxide, N-me~hylpyrrolidone, qulpholane or
hexamethylphosphoric a~id trlamide. The reaction temp-
erature is not critlcal; it preferably lies between 20C
and lS0C, especially between 40C and 80C. The phenol
of formula IV is preferably reacted in the form of an
alkali metal salt, especially the sodium salt. This
can be carried out by reacting the phenoL with the compound
of formula V in the presencs of a base such as sodium or
potassium hydroxide or ~odium or potassium carbonate. In
a further embodiment or this process variant the phenol is
reac~ed with the compound of formula V in the presence of
an acid-binding agent such as calcium hydroxide, triethyl~
amine or pyridine in a manner known per se.
Process variant c) can be carried out conveniently
by convarting the phe~ol of formula VII into an alkali metal
salt, ~or example using sodium hydride or potassium hydro-
xide with azeotropic removal of water, and subsequently re-
acting thesaltwith the halide of formula VI. The last-
mentioned reaction step is conveniently carried out in a
dipolar aprotic solvent (e.g. dimethylformamide, dimethyl
sulphoxide, N-methylpyrrolidone, sulpholane or hexamethyl-
phosphoric acid triamide) or in pyridine at a temperature

~2~57~
be~ween 50C and 200C, pre~erably between 80C and 150C.
In a further embodiment o~ this process varian~ the halide
is reacted with the phenol itselC in ~he presence of an
5 organic acid-binding agent such as triethylamir.e ox pyri-
dine in a manner known per se.
In each case the product obtained can ~e isolated and
purified according to methods known per se.
Insofar as no planned synthesis for the isolation of
pure isomers is carried out, the product normally results
as a mixture o two or more isomers. The isomers can be
separated according to methods known per se. If desired,
they can also be manufactured by synthesis from correspond-
ing optically active starting materials.
The startlng materials of ormulae II, III, IV and VI
as well as reactive derivatives o~ the acids of 0rmul3 II
and the alkali metal salts of the phenols of formula IV are
either known or can be produced in a ~anner known per se.
The compounds of formula V used as starting materials
in process variant b) are novel; they can be produced, for
example, in accordance with ~he following Reaction Scheme:

57~L
-- 10 --
Z~-C~ COOH
S
C~3
VIII
so~l2
R _ oR3
Z2_lH. COCl + ~o-(CX2)m (C)n ( 2 P \ oR4
IX (Acid-binding agent) III'
R O / OR
Z~-C -COO-(I ~2)m (l)~ 2 P \oR4
In the above Reaction Scheme Rl, R2, R3, R4, m, n~ p
and Z have the signlficances given above. The reaction
conditions are familiar to the person skilled Ln the art.
The phenols of formula VII and their alkali metal
salts used as starting materials in process variant c) are
also novel; they can be produced, fox example, as illu-
strated in the following Reaction Scheme:

~.2~57~
o ~ o
o o~v ~
=~ o
'0~ 0. ~ ' ~
~, ~/
O O ~ er
o,
o=~
. ,_~
. ,,~
~-1 _ ' U .
Q ~ O
u~ O Q ~ ~
\ / ~o --
O ~ ~ 0=~
~ Q~ Y
_ _I _ O O
C~ ~ .~ / . ,. _
~ U E~ ~ ,
o
~ O
V _ O ~
a ,~ ~ , u
o~ + ~
Ci ~ O ~0 ~ ~ I I / T ~ ~ y--
:~ ~ O = ~ I f-`) I , ~ ~ O
U~ / x
_ C) I / \
S ~0
o ~ 0
. O I T ~ ~ ) H
\./ g ,., ~ 3r)
0 i

?.~57~
- 12 -
In Ihe above Reaction Scheme Rl, R2, R , R4, m, n, p
and z2 have the significances given above and R6 signi~ies
methyl or benzyl. The reaction conditions are familiar to
the person skilled in the art; for the final step ~J
(R6 = CH3) _ VII (ether cleavage) reference is made
especially to J. Org. Chem. 44, 1247-1251 (1979).
The compounds of formula I possess herbicidal prop-
ertles and are especially suitable for the control ofweeds, especially of slender fox~ail (Alopecurus myosuroides)
and types of millet such as, for example, coc~ls foot
(Echinochloa crus-galli), great oxtail millet (Setaria
faberii) and hair-like millet (Panicum capillare) in
cereals, especially barley, oats and wheat plantations, as
well as ln rice, cotton, soya, sugar beet and vegetable
plantations. The compounds in accordance with the ln-
vention are particularly suitable for the control of weeds
in cotton, soya and sugar beet plantations.
In general t a concentration of 10-100 g o~ active
substance of formula I/ha, preferably 20-50 g of active
substance of formula I/ha, is sufficient to produce the
desired her~icidal effect.
The compounds of formula I are not only pre-emergence
herbicides but also post-emergence herbicides.
The weed controL composition in accordance with the
invention contains an efective amount of at least one
compound of formula I, as defined above, as well as form-
ulation adjuvants. The composition conveniently contains
at least one of the fGllowing formulation adjuvants:
solid carrier substances; solvents or dispersion medla;
tensides (wetting and emulsifying agents); dispersing agents
(without tenside action); and stabilizers. With the use
of these and other adjuvants the compounds of formula I,
namely the herbicidal active substances, can be converted

57~L
- 13 -
into the usual formulations such as dusts, pcwders, gran-
ulates, solutions, emulsions, suspensions, emulsifiable
concentrates, pastes and ~he li~e.
The compounds of formula I are generally insoluble
in water and can be formulated according to ~.he methods
which are usual for water-insoluble compounds using the
respective formulation adjuvants. The manufacture of the
composltions can be carried out in a manner known per se;
for example, by mixing the xespective active substance
with solid carrier substances, by dissolution or suspension
in quitable solvents or dispersion media, lf necessary using
tensides as wetting or emulsifying agents and/or dispersing
agents, by diluting pre-prepared emulsifiable concentrates
with solvents or dispersion media etc.
As solid carrier substances there essentially come
into consideration: natural mlneral substances such as
chalk, dolomite, limestone, aluminas and silicic acid and
salts thereof (e.g. siliceous earth, kaolin, bentonite,
talc, attapulgite and montmorillonite); synthetic mi~eral
substances such as highly dispersible silicic acid, alumin-
ium oxide and silicates; organic substances such as cel-
lulose, starch, urea and synthetic resins; and fertilizerssuch as phosphates and nitrates, whereby such carrier sub-
stances can be present, for example, as powders or as gran-
ulates.
As solvents or di~persion media there essentially
come into consideration: aromatics such as benze~e,
toluene, xylenes and alkylnaphthalenes~ chloxinated aro-
matics and ch1Orinated aliphatic hydrocarbons such as chloro-
benzenesl chloroethylenes and methylene chloride; aliphatic
hydrocarbons such as cyclohexane and paraffins (e.g. pet-
roleum fractions); alcohols such as butanol and glycol,
as well as their ethers and esters; ketones such as ace-
tone, methyl e~hyl ketone, methyl isobutyl ketone and cyclo-

~J~ 57
- 14 -
hexanone; and strongly polar solvents or d~ spersion medla
such a~ dimethylformamide, N-methylpyrrolidone and dimethyl
sulphoxide, such solvents preferably having flash points of
s at least 30C and boiling points o~ at least 50C, and
water. Among the solvents or dispersion media there also
come into consideration so-called liquifiad gaseous extend-
ers or carrier substances, these being products w~ich are
gaseous at room temperature and under normal pressure.
Examples of such products are especially aerosol propellan.s
such as halogenated hydrocarbons (e.g. dichlorodifluoro-
methane). If the weed control com~osition 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.
The tensides (wetting and emulsifying agents) can be
non-ionic compounds such as condensation products o~ fatty
ac~ds, fatty alcohols or fatty~substituted phenols with
ethylene oxide; fatty acid esters and ethers o~ sugars or
polyvalent alcohols; the products which are obtained from
sugars or polyvalent alcohols by condensation with ethylene
oxide; block polymers of ethylene oxide and propylene
oxide; or alkyldimethylamlne 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 alXylbenzene sulphonates (e.g. calcium
dodecylbenzene sulphonate) and butylnaphthalene sulphonates;
and more ccmplex fatty sulphonates, for example the amide
condensation Products of oleic acid and N~methyltaurine and
the sadium sulphonate of dioctyl succinate.
Finally, the tensides can be cationic compounds such
as alkyldimethylbenzylammonium chlorides, dialkyldimethyl-
ammonium chlorides, alXyltrimethylammonium chlorides and
ethoxylated ~uaternary ammoniu~ chlorides.

~.?,'Y,~57~
- 15 -
As dispersing agents (wi~hout tenside action) thers
essentially come into consi deration: lignin, sodium and
ammonium salts of lignin sulphonic acids, sodium salts o
maleic anhydride-diisobutylene copolymers, sodium and
ammonium salts of sulphonated polycondensation products of
naphthalene and formaldehyde, and sulphite lyes.
As dispersing agents, which are especially suitable
as thickening or anti-settling agents, there can be used,
for example, methylcellulose, carboxyme~ylcellulose,
hydroxyethylcellulose, polyvinyl alcohol, alginates,
caseinates and blood albumin.
lS Ex~nples of suitable stabilizers are acid-binding
agents (e.g. epichlorohydrin, phenyl glycidyl ether and
soya epoxides); antioxidants (e.g. gallic acid esters and
butylhydroxytoluene); UV-absorbers (e.g. substituted benzo-
phenones, diphenylacrylonitrile acid esters and cinnamlc
acid esters); and deactivators ~e.g. salts of ethylenedi-
aminotetraacetic acid and polyglycols).
The weed control compositions in accordance with the
in~ention can contain, in addition ~o the compounds or
formula I, synergists and other active substances ~e.g. in-
secticides, 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 0.001 and 95 weight
percent, pre~erably between 5 and 75 weight percent, of one
or more compounds of formula I as the active substance(s).
They can be present, for example, in a form which is suitable
.or storage and transport. In such formulations (e.g.
emulsifiable concentrates) the active substance concen-
tration is normally in the higher range, preferably between
lO and 75 weight percent, especially between 25 and 50

7~
- 16 -
weight percent. These formulations can then be diluted,
for example with the same or dif~erent inert substances, to
give activ~ substance concentrations which are suitable for
practical use, i.e. preferably about 0.1 to 10 weight per-
cent, especially about 1 to 5 weight percent~ The active
substance concentrations can~ however, also be smaller or
greater.
As mentioned above, the manufacture of the weed con-
trol compositions in accordance with th~ in~ention can be
carried out in a manner known ~er 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 grlnd-
ing together) or the solid carrier substance can be im-
pregnated with a solution or suspensio~ o~ the active sub-
stance and then the solvent or dispersion medium can be
removed by evaporation, heating or sucking-off under reduced
pressure. By adding tensides or dispersing agents such
pulverous preparations can be made readily wettable with
water, so that they can be converted into aqueous suspen-
sions which are suitable, or example, as spray compositions.
The compound of formula I can also be mixed with a
tenside and a solid carrier substance to form a wettable
powder which is d~spersible in water or it can be mixed
with a so~id pre-granulated carrier substance to form a
product in the form of a granulate.
When desired, the compound of formula I can be dis-
solved in a water-immiscible solvent ~uch as, for example,
a high-boiling hydrocarbon, which conveniently contains
dissolved emulsifying agent, so that the solution becomes
self-emulsifying upon addition to water. Alternatively,
the active subs~ance can be mixed with an emulsifying agent
and the mixture can then be diluted with water to the
desired concen~ration. Moreover, the active substance can

- 17 ~
be dissolved in a solvent and thereafter the solution can
be mixed with an em~lsifying agent~ Such a mixture can
like~ise be diluted wi~h water to the desired concentration~
In this manner there are obtained emulsiiab1e concentrates
or ready-for-use emulsions.
The use of the weed con~rol compositions in accordance
with the invention can be carried out according ~o usual
application methods such as sprinkling, spra~ing, dusting,
watering or scattering. The method in accordance with tha
invention for the control of weeds comprises treating
the locus to be protected against weeds and/or the weeds
with a compound in accordance with the invention or a weed
control composition in accordance with the invention.

~2~ 57~
The following Exa~ples illustrate the invention in
more detail:
I Manufacture of the active substances of ~ormula I:
Exam~le 1
A solution of 2.37 g ~ pyridine in 10 ml of dichloro-
methane is added dropwise while stirring to a solutior.,
cooled to 0C, of 10.53 g Qf D-2-[p-(6-chloro 2-quinoxalyl-
oxy)phenoxy]-propionyl chloride and 4.88 g of dieth~l
hydrox~methylphosphonate in 50 ml o~ dichloromethane. The
mixture is stirred at room temperature for l hour and sub-
sequently evaporated to dryness under reduced pressure.
Therea~ter ~he residue ls dlssolved in ethyl acetate and
~he solution i9 extracted with water and dilute sodium
bicarbonate solution, dried over a drying agent and
evaporated to dryness.
The residue is purified by chromatography on silica
gel with dichloromethane/diethyl ether (7:1). There is
obtained diethyl ~ D-2-~p-(6-chloro-2-quinoxalyloxy)phenoxy]-
propionyloxy 7methylphosphonate; [a]D ~ 34.67 (c = 0.93%
i~ CXC13).
In an analogous mannar,
from D-2-~p-(6-fluoro-2 quinoxalyloxy)phenoxy]-propionyl
chloride and diethyl hydroxymethylphosphonate there is
obtained diethyl / D-2-[p~(6-fluoro-2-quinoxalyloxy)phenoxy]-
propionyloxy 7methylphosphonate, ~a]20 + 28.08 (c = 1.14%
i~ C~C13);
from D-2-[p-(6~7-dichloro-2-quinoxalyloxy)phenoxy~-
propionyl chloride and diethyl 2-hydroxyethylphosphonate
there is obtained diethyl 2-r D-2-[p-(6,7 dichloro-2-
; quinoxalyloxy)phenoxy]-propionyloxy 7-ethylphosphonate,
E~] ~ ~ 32.08 (c = 0.95% in CHC13);

5~
-- 19 --
from D-2-[p-(6,7-dichloro-2-quinoxalyloxy)phenoxyj-pro-
pionyl chloride and diethyl hydroxyme~hylphosphonate there
is obtained diethyl / D-2- [p- ~6, 7~dichloro-2-qulnoxalyloxy) -
phenoxy]-propionylo~xy_7methylphosphonate, ~]20 ~ 35.67
(c - 1.00~ in CHC13);
rom D-2-[p-(i,6-dichloro-2-quinoxalyloxy)phenoxy]-propion-
yl chloride and diethyl 2~hydroxyethylphosphona~e th~re is
obtained diethyl 2-/ D-2-Lp-(5,6-dlchloro--2-quincxalyloxy)-
phenoxy]-propionyloxy /-e~hylphosphonate, [a]20 + 27.69
( c = 1 ~ 07% in CHC13 );
from D-2-[p-(6-chloro-2-quinoxalyloxy)phenoxy~-propionyl
chloride and diethyl DL-l-hydroxy~thylphosphonats there is
obtained diethyl DL-l-~ D-2-[p-(6-chloro-2-quinoxalylcxy)-
phenoxy]-propionyloxy 7-ethylphosphonate, [a]20 + 26.80
(c = 1.10% in CHC13);
from D-2-[p-t6-chloro-2-~uinoxalyloxy)phenoxy]-propionyl
chloride and diethyl 2-hydroxyethylphosphonate there is
obtained diethyl 2- r D-2-[p-(6-chloro-2-quinoxalyloxy)-
phenoxy]-propionyloxy 7-ethylphosphonate, []D0 +27.92
(c = 1.04~ in CHC13);
from D-2-[p-(6-chloro-2-quinoxalyloxy)phenoxy]-propionyl
chloride and dibutyl hydroxymethylphosphonate there is
obtained dibutyl / D-2-[p-(6-chloro-2-quinoxalyloxy)phenoxy]-
propionyloxy /methylphosphonate, [a]20 + 33.11 (c = 1.06
in CHC13~i
,;""s~

-
.L~)57
20 -
from D 2-[p~(6-chloro~2-quinolyloxy)phenoxy]-prooionyl
chloride and diethyl hydroxymetnylphosphonate there is
obtained diethyl / D-2-[p-( 6-chloro-2-qu:inolylo~y) phenoxy3 -
propionyloxy 7methylphosphonate, [~]20 ~34.24 ~c = 1.03~ in
C~C13);
from D-2-~p-(6-chloro-2-quinolyloxy)phenoxy]-propionyl
chloride and diethyl DL-l-hydroxyethylphosphonate there is
10 obtained diethyl DL-l-/ D-2- [p- (6-chloro 2-quinolyloxy)-
phenoxy]-propionyloxy 7-ethylphosphonate, ~a]20 ~30,550
(c = 1.02% in CHC13); and
from D-2~[p-(6-chloro-2-quinolyloxy~phenoxy]-propionyl
chloride and diethyl 2-hydro~yethylphosphonate there is
obtain~ldiethyl 2-/ D-2-~p-(6-chloro-2-qulnolyloxy)-
phenoxy]-pro~lonyloxy 7-ethylphosphonate, ~a~20 ~ 27.39
(c = 1.02% ln C~Cl3).
Example 2_
A solution of 10.29 g of D-2-[p-(6-chloro-2-quinolyl-
oxy)phenoxy]-propionic acid in 50 ml of absolute dimethyl-
formamide is added dropwise at room temperature to a sus-
pension of 1.37 g of a 55~ sodium hydride dispersion in150 ml of absolute dimethylformamide and the mixture is
stirred at 50C for 30 minutes. A solution of 8.16 g of
diethyl 3-bromopropylphosphonate in 10 ml of absolute di-
methylformamide is subsequently added thereto and the
mixture is stirred at room temperature for 3 hours. The
mixture is then adjusted to pH 5-6 with 2N hydrochloxic
acid. The sol~ent is then distilled of at 50C under
reduced pressure a~d the residue is treated with 200 ml
of ethyl acetate and extracted three times with 100 ml of
water each time. The organic phase is dried over anhydrous
sodium sulphate and evaporated to dry~ess under reduced
pressureO The residue is purified by chromatography on
silica gel with dichloromethane/ethyl acetate (3:1).

- 21 ~ 5~
There is obtained diethyl 3~/ D-2-[p-~6~chlors~2-quinolyl
oxy)phenoxy]-propionyloxy 7-propylphosphonate, [~120 1 29.08
tc = 0.83% in C~C13).
s
Example 3
a) 24.42 g of L~2-~p toluenesulphonyloxy)-propionic acid
are heated to boiling for 4 hours with 59.5 g of thio~yl
chloride and the mixture is subsequently evaporated to
dryness under reduced pressure. The residue is dissolved
in 150 ml of dichloromethane and treated at room temperature
with 16.82 g of die~hyl hydroxymethylphosphonate. The
mixture is then cooled to 0-5C while s~irring and treated
dropwise during 15 minutes with a solution of 8.70 g o~
pyridine in 25 ml o~ dichloromethane. The mixture is
subsequently stirred at room temperature for 3 hours and
the solvent is distilled of~ under rPduced pressure. The
residue is dissolved in ethyl acetate, the solution is
washed wlth water and the organic phase is dried o~er
anhydrous sodium sulphate and evaporated. The resulting
residue is purified by chromatography on silica gel with
diethyl ether and subsequently distilled in a bulb-tube.
Th~re is ob~ained diethyl ~L-2-~p-toluenesulphonyloxy)-
propionyloxy]methylphosphonate, b.p. abou~ 210C/0.05 mm~g,[a~20 -30.32 (c = l.lO~ in C~C13).
b) 2.72 g of p-~6-chloro-2-quinoxalyloxy)-phenol are
added to a suspension of 0.43 g of a 55~ sodium hydride
dispersion in 25 ml of dimethylformamide and the mixture
is stirred at room temperature for 2 hours. A solution of
3,94 g of diethyl [~-2-(p-toluenesulphonyloxy) propionyloxy~
methylphosphonate in 15 ml of dimethylformamide is added
dropwise during lO minutes and the mixture is stirred at
room temperature for 3 hours and subsequently evaporated
under reduced pressure. The residue is then dissolved in
ethy} acetate, the solution is washed with water and the
organic phase is dried over anhydrous sodium sulphate and
evaporated under reduced pressure. The resulting residue

- 22 -
is purified by chromatography on silica gel with die~hyl
ether,
There is obtained diethyl / D-2-[p-~6-chloro-2-quin-
oxalyloxy)phenoxy]-propionyloxy 7methylphosphonate, [a]20
~33.21 (c = 1.06~ in CHC13).
a) 46 g of D-2 (p-benzyloxyphenoxy)-propionic acid are
stirred at 90C for 2 hours with 110 ml Qf thionyl chloride~
The mixture is subsequently evaporated to dryness under
reduced pressure, the residue is dissolved in 190 ml of
di~hloromethane and the solution is treated at room temp-
erature with 29.4 g of diethyl hydroxymethylphosphonate~
The mlxture is cooled to 5-10C while stirring and treated
dropwise during 20 minutes with a.soLution of 14.22 g o~
pyridine in 20 ml of dichloromethane. The mlxture is then
stirred at room temperature ~or a further 30 minutes,
washed in sequence with 2N hydrochloric acid, 2N sodium
hydroxide solution and water, dried over anhydrous sodium
sulphate and evaporated to dryness. The residue is
purified by chromatography on silica gel with ethyl acetate/
n-hexane (3:1).
There is obtained diethyl ~D-2-(p~benzyloxyphenoxy)-
propionyloxy]methylphosphonate, [a]20 1 36.04 (c = 1.07
in CHC13), ~ = 1.5304.
b) 10 g of diethyl [D-2-(p-benzyloxyphenoxy) propionyl-
oxy]methylphosphonate are dissolved in 150 ml of methanol
and 1 g of pall~dium/active carbon (10% Pd) is added to
the solution. The mixture is hydrogenated at normal
pressure and room temperature for 20 hours, the catalyst
is subsequently filtered off and the filtrate is evaporated
to dryness under reduce pressure. The residue is purified
. by chromatography on silica gel with ethyl acetate/~-
hexane (2~

57~L
- 23 -
There is obtained diethyl ~D~2 (p-hydroxypheno~y)-
propionyloxy]methylphosphonate, [a]20 ~39.40o (c = 1.00%
in CXCl3), nD = 1.5033.
c~ A solution of 2 g of diethyl [D-2-(p-hydroxyphenoxy)-
propionyloxy~methylphosphonate in 25 ml of dimethyl sul-
phoxide is treated wi~h 0.14 g of sodium hydride and the
mixture is stirred at room temperature ror 30 minutes.
A solution of l.Ol g o 2-chlorobenzthiaæole in lO ml of
dimethyl sulphoxide is subsequently added dropwise thereto
during 5 minutes and the mixture is stirred at 95C for
12 hours. The mixture ~s then poured on to lO0 ml of ice-
water and extracted with ethyl acetate. The organic phase
is washed with water~ dried over anhydrous sodium sulphate
and evaporated under reduced pressure. The residue is
puriied by chromatography on silica gel with ethyl acetate~
n-hexane (2:l).
There is obtained diethyl r D-2-[p-(2-benzthiazolyl-
oxy)phenoxy]-propionyloxy 7methylphosphonate, [a]20 +9~06
(c = 0.89~ in CHCl3).
In an analogous manner,
from diethyl ~D-2-(p-hydroxyphenoxy)-propionyloxy]methyl-
phosphonate and 2,5-dichlorobenzthiazole there is obtained
diethyl / D-2-[p-~5-chloro-2-benzthiazolyloxy)phenoxy]-
propio~yloxy_7methylphosphonate, [a]D ~18.00 (c = l.06
in CHCl3); and
from diethyl [D-2-(p-hydroxyphenoxy)-propionyloxy]methyl-
phosphonate and 2,4,6-trichlorobenzthiazole there is ob-
tained diethyl / D-2 ~p-(4~6-dichloro-2-benzthiazolylo~y)-
phenoxy]-propionyloxy /methylphosphonate, [a]D 119.47
(c - 0.76~ in CHCl3).

~?71~7
- 2~ -
II. Formulation Exam~les:
Exam~le 5
For the manufacture of an emulsifia~le concentrate
the ingredients listed hereinafter are mixed with one
another:
10 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 ad1000 ml
Emulsifier consisting of 60 parts of an ethylene
oxide-propylene oxide block polymerizate, 20 parts of
calcium dodecylbenzene sulphonate and 20 parts of a
mixture of isobutanol and C10-alkylbenzenes.
Emulsifier consisting of 70 parts of calcium dodecyl-
benzenesulphona~e and 30 parts of a mixture of isobutanol
and C10-alkylbenzenes.
The thus obtained concentrate emulsifies spontan-
eously in water. The resulting emulsion is suitable 25 a
ready-for-use spray liquor.
Exam~e 6
For the manufacture of a suspension concentrate the
ingredients listed hereinafter are mixed with one another
and rinely ground in a bead mill:
Welght E~ent
Compound of formula I 25
Ethylene glycol 8.0
: Formaldehyde (30%) 1.0

5~
- 25
Silicic acid, highly dispersible C.5
Silicon anti-foam agent 0.5
Nonylphenol-(10)-etho.Yylate 2.0
5 Sodium polyphsnol~ormaldehyde sulphonate 4.0
Xanthan gum 0.3
Distilled water ad 100.0
The thus-obtained suspension concentrate disperses
spontaneously in watex and gives a ready-for-use spray
liquor.
1~