Note: Descriptions are shown in the official language in which they were submitted.
~21~ ~
O.Z. 0050/41~99
Herbiçide~ which contain c~clohexenone derivat.ive~
as herbicidal active inqredients and naPh~halene
derivative~ as.antidote~
Th~ pre~ent invention relate~ to herbicide3 which
contain cyclohexenone deriva~ives a~ herbicidal active
ingredient~ and naphthalen~ derivatives as antidote~, and
methods for selectively con~rolling unde~irable plant
growth with these herbicides.
Th~ herbicidal active ingredient~ rom the group
consisting of the cyclohexenone derivative3 are compounds
of the formula II
~ Xn (~I)
where
~1 iS cl-~6-a~
A is a C4~al~ylene or C4-alkenylene chain/ where the~e
chain~ may carry from one to three Cl~C3-alkyl groups
and/or halogen atoms;
: ~ is hydrogen, nitro, cyano, halogen, Cl-C4-al~yl, Cl-C4-
alko2y, Cl C4-alkylthio~ Cl-C4-haloalkyl, Cl-C4-haloalkoxy,
: 20 carboxyl, Cl-C4-alko~ycarbonyl, benzyloxycarbonyl and/or
~ phenyl, where the aromatic radicals may carry from one to
: three o~ the following sub~tituents: nitro, cyano, halo-gen, Cl~C4-alkyl, Cl-C4-alkoxy, Cl-C4-alXylthio, Cl-C4-
haloalkyl,C1-C4-haloalkoxy,carboxyl,C1-C4-alkoxycarbonyl
and/or b~n~yloxycarbonyl;
n is from 1 to 3, or is from 1 to 5 when X is hydrogen or halogen;
R2 ~ Cl-C4-alkoxy-Cl-C6-alkyl or Cl-C4-alkylthio-Cl-C6-
alkyl,
C3-C7-cyclo~lkyl or C~-C7-cycloalkenyl, where these group~
may carry from one to three o~ th~ following ~ubstitu-
ents: C1-C4-alkyl, C1-C4-alkoxy, Cl-C4-alkylthio/ Cl-C4-
haloalkyl, hydro~yl and/or halogen,
:~ a 5 membered 3aturated heterocyclic structure which
contain~ one or tw~ oxygan and/or 3ulfur atom~ a~ hetero
2 ~
- 2 - O.Z. 0~50/41599
atoms and which may car~y from one to three of the
followinggroup~s Cl-C4-alkyl, Cl-C4-alkoxy, Cl-C4-alkylthio
and/or Cl-C4-haloalkyl,
a 6~membered or 7-membered haterocyclic structure con-
taining one or two oxygen and/or sulfur atom~ and one or
two double bonds, where this ring may carry from one to
three of the following substituent~: hydroxyl, halogen,
Cl-C4-alkyl, Cl-C4-alkoxy, C1-C4-alkylthio and/or Cl-C4-
haloalkyl,
a 5-membered heteroaromatic structure containing one or
two nitrogen atoms and one oxygen atom or one ~ulfur
atom, where this ring may carry from one to three of the
following substituent~: halogen, cya~o, C1-C4-alkyl,
Cl-C4-alkoxy, Cl-C~,-alkylthio, (::l-C4-haloalkyl, C2-C6-
alkenyl, C2-C6-alkenyloxy, C2 C6-haloalkenyl and/or Cl-C4-
alkoxy-Cl-C4,-alkyl,
phenyl or pyridyl, where the~e group~ may carry from one
to three of the following ~ub~tituent~: halogen, nitro,
cyano, Cl~C4-alkyl, C1-C4-alkoxy, Cl-C4-alkylthio, Cl-C4-
haloalkyl,C3-C6-alkenyloxy,C3-C8-alkynyloxy,Cl-C4-alkoxy-
Cl-C4-alkyl, C1 C4-alkylthio-C1-C4 al~yl and/or -NRl3Rl4,
whera
R13 1~ hydrogen, C1-C4-alkyl, C3-CB alkenyl or C3-C6-alkynyl
and
Rl4 i~ hydrogen, Cl-C4-alkyl, C3-C6-alkenyl, C3-C6-alkynyl,
C1-C~-acyl or ben~oyl, where the aromatic ring may carry
from ona to thxee o~ the following ~ub~titu~nts: nitro,
cyano, halogen, Cl-C4~alky}~ Cl-C4-alko~y, Cl-C4-alkylthio
and/or Cl~C4-haloalkyl,
and their agriçulturally useful ~alts and ester~ of
Cl-C1O-ca.rboxylic acid3 and inorganic acid~.
The cyclohexonones IX are e~idently acidic, ie.
they can form slmple reaction pxoduct~, such as sal.t~ of
alkali metal or alkaline earth metal compounds or enol
: 35 e~ter3.
The compounds of the formula II can occur in a
plura.lity of tau~omeric form~, and the claim rela~e~ to
~ ~ .
:
2 ~ ~ 2 ~
- 3 O.Z. 0050/41599
all of the~e.
The cyclohexenones of the formula II can be
prepared in a conventional manner from known derivative~
of th~ formula III (EP-A-80 301~ EP-A-125 0~4, EP-A-142
741, US-A-4 249 937, EP-A-137 174 and EP~A-177 913) and
the corresponding hydro~ylamines of the formula IV
(Houben-Weyl, 10/1, page 1181 et ~eq.) (EP-A-169 521).
0~ NOA~ ~ ~f n
III ~V ~I
The reaction i~ advantageou~ly carried out i~ the
~ heterogeneous phase in a solvent at an adequate tempera-
: 10 ture balow about 8noc, in the pre~ence of a base, and the
hydroxylamine IV i8 u3ed in the form of it~ ammlonium
sal~.
~xample~ o suitable base~ are carboIlates,
bicarbonate~, acetate~ 9 alcoholate~ or oxid2~ o alkali
metal~ or of alkaline earth metal~, in parti~ular ~odium
hydroxide, potassiu~ hydroxide~ magnesium o~ide and
caIcium oxide. Organic basss, such a~ pyridine or
tertiary amin*s, can al~o be uxed. The ba~e i~ added,
for example, in an amount of from ~.5 to 2 mol equiva-
lent~, based on the ammonium compound.
Examples o~ ~uitable ~olvent~ are dimethyl
~ulfoxide, alcohol~t ~uch a~ methanol, e~hanol and
isopropanol, aromatic hydrocarbons, ~uch a~ henzene and
toluene, chlorohydrocarbon~, such a~ chloroform and
dichloxoethane, allphatic hydrocarbon~, ~uch as hexane
and cyclohexane, ester~, ~uch as ethyl acetate, and
ether~, such a~ diethyl ether, dioxane and ~etrahydro-
furan. The reaction i praferably carrisd out i.n ~ethan-
ol, using sodi~n blcarbonato as ~he ba~e.
The r~ac~ion is comple~e a~ter a few hour~. The
desirsd compound can be isolated, for examp~e, by
,
:i :
.
.. . . .
~ . .
: '
- 4 - O.Z. 0050/41599
evaporating down the mixture, partitioning the re idue
betwesn methylene chloride and water and distilling off
the solvent under reduced pressure.
~owever, the free hydroxylamine base, for example
in the form of an aqueous solution, can also be used
directly for this reaction; a single-pha~e or two-pha~e
reaction mixture is obtained, depending on the solvent
used for the compound III.
Suitable solvents for thi~ variant are, for
example, alcohols, such as methanol, ethanol, isopropanol
and cyclohexanol, aliphatic and aromatic hydrocarbons and
chlorohydrocarbon , ~uch as hexane, cyclohexane, meth-
ylene chloride, toluene and dichloroethane r e~ter~, such
as ethyl acetate, nitriles, such a~ acetonitrile, and
cyclic ether~, such a3 dioxane and tetrahydrofuran.
Alkali metal salt~ of the compound~ II can be
obtained by treating 3-hydroxy compounds with sodium
hydroxide~ pota99ium hydroxide or a sodium or potassium
- alcoholate in aqueous solution or in an organic ~olvent,
~uch as methanol, ethanol, a~etone or toluene.
Other metal alts, such a~ mangana3e, copper,
2inc, iron. calcium, magnesium and barium salt~, can bo
prepared from the ~odium ~alt~ in a con~entional manner,
as can ammonium and phosphonium salt~ using ammonia or
ammonium, pho~phonium, sulfonium or sulfoxonium
hydroxides.
The compounds of type III can be prepared, for
example, from the corresponding cyclohexane-1,3-dione of
the ormula V
OH
R2~ V
y
whare Y i~ hydrogen or methoxycarbonyl, by known method~
(Tetrahedron Latt. (1975), 2491).
It i~ also po3~ible to prepsre ~he compound~ of
the formula III via the enol e~t~r intenmaditlte~ VI,
.
:` ' ~ - ' ' ' ' .:"' ' '
- , : - -
~21~
- 5 - O. Z . 0050/41599
which are obtained in the reaction of compounds of the
formula V with acyl chloride~ VII in the pre~ence oP a
base and subsequently undergo a rearrangement reaction
with certain imidazole and pyridine derivati~res (Japane~e
Preliminary Publication Application79/063 052).
OH O O ~R ~ Oh
., R 2~ ~ R I J~C l --`~ R 2~ 0 - Dl R 2{~(/
Y O Y O O
V Vlr Vl ~
- ~rhe compounds o:f the formula V are obtained via
a series of known proces~ steps, starting from hlown
intermediate~ .
The hydroxylamine~ IV in which A ie a substituted
or un~ubstituted but-2-enylene bridge are s~nthesized in
accordance with the reaction ~cheme below, s~ar~ing from
aniline derivatiYes VIIX, by diazo ization and ~ub~equent
coupling of the diazoniu~ salt to a corre~pondingly
sub~tituted butadiene IX. The re~ulting mixture of Xa
and Xb i9 coupled to a cyclic hydroximide XI, and the
protected hydroxyl~mine derivative XII obtained i~
cleaved with 2-aminoethanol to give the free hydroxyl-
amin~ IV.
~n~ ¦ ) Diazotlzation /Hal~ Xn
2-- - D ~C~12--CR~=CRb~ /RC-H~31
\~ 2) Cil2=CR~CR~:CHRC ~=~
VI I I IX Xa
Xn Rd
~H 2--C~Rb--C~RC
)1~I Xh
J~ Xn
xa ~ Xb ~ o~N~H ~ O~N~CHRC--CRb=CRa-C~I2~<
0 XI 0 XII
X I I ~ H 2N~ OH ~ I v
: ~ :
'
. :
.'
2~2~
- 6 - O.Z. OOSO/41599
R~, Rb and Rc independently of one another are hydrogen,
C1-C3-alkyl and/or halogen. Hal is halogen, preerably
chlorine.
E~ampl~ of suitable cycli~ hydroximides are the
S following substance~s
~'`IOH ¢~N--OH ~N~OH
O O O
O O O
~NOH ~N--aH ¢¢N--3H
O O O
o
~<H{:)H
~a
.
The halids Xa required for the ~ynthesi~ of the
novel hydroxylamine~ of the formula IV can be prepared,
as a mixture with Xb, by method~ known from the litera-
ture, for example by reacting a diazonium salt of an
:~ 10 aromatic or heteroaromatic aniline with a diene. The
range of application~ of the reaction i~ di~cu~ed in
Organic Rea~tionc 11 (1960), 189 and 24 (1976), 22!j.
Coupling of the isomeric halides Xa and Xb to a
cyclic hydroximide o~ the onmula XI results exclu~ively
in the cyclic imidoethers of the formula XII, which give
the hydroxyl~nine~ IV after the protective group on the
nitrogen atom has been eliminated.
The reaction of the mixture o~ Xa and Xb with a
hydroximide XI i8 carried out in the presence of an acid
acceptor and of a solvent. For re~ons of co t, a
preferrod hydroximide XI i8 hydroxyph~halimide.
Suitable acid acceptor~ are alkali metal
~: :
. ~
: . .
.
_ 7 o.Z. 0050/4159g
carbonate~, such a~ pota~i~m carbonat~ or sodium car-
bonate, alkali metal bicarbonates, such as potassium
bicarbonate or sodium bicarbonate, tertiary amines, ~uch
as trimsthylamine or triethylamine, and basic hetero
cycle~, such as pyridine. For rea~on~ of cost, pota~ium
carbonate and sodium carbonate are preferred.
Suitable solvents are aproti.c dipolar organic
solvents, for example dimethylformam:ide, dLmethyl sul-
foxide and/or sulfolane.
Alkylation under phase transfer condition~ is
also pos~ible. The organic solvents used here are water-
immiscible compounds, ~uch as hydrocarbons or chloro-
hydrocarbons. Suitable phase transfer catalysts are
qua~ernary ammonium and phosphonium salts.
The cyclic imidoeth~r3 XII are cleaved by a
proce~s similar to that described in EP-A-244 7861 using
alkanolamines. The hydroxylamines IV can ba i~olated as
free ba~e~ after thi~ proce~ or a salts after precipi-
tation with acids. Readily cry~talli2ing salt~ are
obtained by reacting the base3 wi~h o~alic acid.
With regard to the biological c~i~ity, preferred
cyclohexenones of the formula II are those in which the
sub~tituent~ hav~ the following meaninys:
Rl i3 branched or straight~chai~ Cl-C6-alkyl, such a~
methyl, et~yl, propyl~ methylethyl, butyl, l~methyl-
propyl, 2-methylpropyl, l,1-dimethylethyl, pentyl,
l-methylbutyl, 2-methylbutyl, 3-mathylbutyl, l,l-di-
met~ylpropyl, 1,2-di~ethylpropyl, 2,~-dimathylpropyl,
l-ethylpropyl, hexyl, l-methylpentyl, 2 methylpentyl,
3-mathylpentyl, 4-methylpentyl, 1~1-dimethylbutyl,
1,2-dimethylbutyl, 1,3-dimethylbutyl, 2 t 2 dimethylbutyl,
2,3-dimethylbutyl, 3,3-dimethylbutyl, l-ethylbutyl,
2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2 trimethyl-
pxopyl, l-eth~l-l-methylpropyl or 1-ethyl-2-methylpropyl,
in particular ethyl or propyl;
A is C4-alkylane or C4 alkenylen0, ~uch a~ butylene, but~
2-enylene or but-3-enylene, whi.ch may be monosubs~ituted
~ 8 ~ O.~. 0050/41599
to trisubstituted by, in particular, methyl or ethyl
and~or fluorine or chlorine; in the case of the unsatu-
ratPd chains, both the cis and the trans form can occur;
but-2-enylene is particularly preerred;
X is halogent such a3 fluorine, chlorine, bromine or
iodine, in particular fluorine or chlorine;
Cl-C4-alkyl, such a~ methyl, ethyl, propyl, l-methylathyl,
butyl, l-methylpropyl, 2-methylpropyl or l,1-dimethyl-
~thyl, in particular methyl or l,1-dLmethylethyl,
0 Cl C4 alkoxy, such as methoxy, ethoxy, propoxy, l~methyl~
ethoxy, butoxy, l-methylpropoxy, ~-methylpropo~y or 1,1~
dLmethylethoxy, in particular methoxy, ethoxy, 1-methyl-
ethoxy or l,1-dimeth~l~thoxy~
Cl-C4-alkylthio, such a~ methylthio~ e~hylthio, propyl-
thio, 1-mathylethylthio, butylthio, l-methylpropylthio,
2-methylpropylthio or l,1-dlmethylethylthio, in par-
ticular methylthio or ethylthio,
partly or completely halogenated Cl-C4-alkyl, such as
fluoromethyl, difluoromethyl, trifluoromethyl, chlorodi-
; 20 fluoromethyl, dichlorofluoromethyl, trichloromethyl, 1
; fluoroethyl, 2-fluoroe~hyl, 2,2-difluoroethyl, 2,2,2-
tri~luoroeth~l,2-chloro-2,2-difluoroethyl,2,2-dichloro-
2-fluoroethyl, 2,2,2-trichloroeth~l or penta~luoroethyl,
in particular difluoromethyl r tri1uoromethyl, 2,2,2-
trifluoroethyl or pentafluoroethyl,
partly or completely halogenated C1-C4-alkoxy, such as
difluorom~thoxy,trifluorome~hoxy,chlorodifluorsmethoxy,
dichlorofluoromethoxy, 1-fluoroethoxy, 2-fluoroethoxy,
2,2-difluoroethoxy, 1,1,~,2-tetrafluoroethoxy, 2,2~2-
trifluoroetho~y, 2-chloro~1,1,2-tri~luoroetho~y or
penta1uoroethoxy, in par~icular tri~luoromethoxy,
C1 C,4-alko~yearbonyl, ~uch as methoxyearbonyl, etho~y
carbonyl, propoxycarbonyl, l-methylethoxycarbonyl,
butoxyearbonyl or 1,l-dimethyletho~yearbonyl, in par-
tieular ~ethoxycarbonyl, ethoxycarbonyl or 1,3. dimethyl-
ethoxycarborl~l, e~peeially me~hoxycarbonyl, or
; hydrogen, ni~ro, cyano, carboxyl
2 ~
- 9 - O.Z. 0050/~1599
ben2yloxycar~0nyl or phenyl, where the aromatic radicals
in turn may carry from one to thrPe of tha following
radical~: nitro, cyano, carboxyl, benzyloxycarbonyl,
halogen as ~tated in general and in particular for X,
alkyl as stated fox Rl, in particular methyl, ethyl or 1-
methylethyl, alko~y a~ staked above, in particular
methoxy or ethoxy, alkylthio as ~tated above, in par~
ticular methylthio, haloalkyl a~ s ated above, in par-
ticular trifluoromethyl, haloalkoxy a~ stated above, in
particular difluoromethoxy or trifluorometho~y, andJor
alkoxycarbonyl a~ stated above, in particular methoxy~
carbonyl or ethoxycarbonyl.
Un~ub~tituted or monosub~titutPd aromatic radi-
cals o thi~ type are particularly preferred.
lS n i3 1, 2 or 3, in particular l or 2. Where
there is a plurality of radicals X, the sub~ituen~s may
be identical or different.
R2 is alkyl as ~tated under Rl, whîch may carry
one of tha alkoxy or ~lkylthio group~ stated under X,
preera~1y in the l-, 2- or 3 po~ition, in particular 2-
ethylthiopropyl,
5 me~bered heterocycloalkyl, ~uch as tetrahydrofuranyl r
tetrahydrothienyl, dioxolanyl, dithiolanyl or oxathiolan-
yl, in particular tetrahydrofuranyl, tetrahydroth.ienyl or
dioxolanyl, where these ring~ may carry ~ro~ one to three
of khe Cl-C4-alkyl, Cl-C4-alko~y, Cl-C4 allylthio and/or
Cl C4 haloalkyl groups 3tated under X,
5-mcmbered hetaryl, such as pyrrolyl, pyrazolyl, Lmidaz
olyl, i~oxszol.yl, oxazolyl, i~othiazolyl, thiazolyl,
furanyl or thienyl, in particular isoxazolyl or furanyl,
a 6-membered or 7-membered heterocyclic ~tructure, quch
a~ ~etrahydropyran-3-y~, dihydropyran-3 yl7 tetrahydro-
pyran~4-yl, dihydropyran-4-yl, tetrahydrothiopyran 3-yl,
dihydrokhiopyran-3-yl,tetrahydrothiopyran-4-yl,dihydro-
th~opyran-4~yl or dioxepan-5-yl, in particular tetra-
hydropyran-3-yl, tetrahydropyran-4-yl or tetrahydrothio-
pyran-3~yl,
2~2~ ~
- 10 - O.Z. 0050~41599
phenyl or pyridyl,
where the cyclic radical~ may carry from one to three of
the alkyl, alkoxy, alkylthio and/or haloalkyl group~
~a~ed under X.
Tha 5-membered heteroaroma~ic radical~ R2 may
carry the following radical~ a~ substituent~:
halogen as ~tated under X, in particular fluorine or
chlorine~
alkoxyalkyl, such a~ metho~ymethyl, 2-methoxyethyl, 2
metho~ypxopyl, 3-methoxypropyl, 2-metho~y-1-methylethyl,
ethoxymethyl, 2-ethoxye~hyl, 2-ethoxypropyl, 3-etho~y-
propyl, 2-ethoxy-1-methylethyl or 1-etho~y-1-methyllethyl,
in particular methoxyethyl or ethoxyethyl,
~lkenyl, such a~ ethenyl, 1-propenyl, 2-propenyl, 1-
methylethe~yl, 1-butenyl, 2-butenyl t 3-butenyl, 1-mlethyl-
l-pxopenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl, 2-
mathyl-2-propenyl, l~pentenyl, 2-pentenyl, 3-pentenyl, 4-
pentenyl, l-methyl-l-butenyl, 2-methyl-1-buteny:L, 3-
methyl-l~butenyl,1-methyl-2-butenyl,~-methyl-2-butenyl
3-methyl 2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-
butenyl, 3-n~ethyl-3-butenyl, 1,1-dimethyl-2~propenyl, 1-
dimethyl-1-propenyl, 1,2-dimethyl-2-propen~l, 1-ethyl-1-
propenyl, 1-ethyl-2-propenyl, l-haxenyl, 2-hexenyl, 3-
hexenyl, 4-hexanyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-
methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl~l-
pentenyl, l-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-
: methyl-2-p2n~enyl r 4-meth~1-2 pentenyl, 1-methyl-3-
pentenyl, 2-meth~1-3-pentenyl, 3-methyl-3-pentenyl, 4-
methyl-3-pante~yl, 1-methyl-4-pentenyl, 2~met~lyl-4-
pentenyl, 3-meth~1-4-pantenyl, 4 methyl-4-pen~eny~0 1,1-
dimethyl-2-butenyl,l,l-dimathyl-3-butenyl,1,2 dimethyl-
l-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-
butenyl, 1,3-dimethyl-1-butanyl, 1,3-dimathyl-2-butenyl,
1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-
dimethyl-1-butenyl,2t3-d~nethyl-2-butenyl,2,3-dimethyl-
3-butenyl, 3l3-dimathyl-1-bute~yl, 1-ethyl-1-butenyl, 1-
eth~l-2-butanyl, 1-ethyl-3-butQnyl, 2-ethyl-1-butenyl,
~ ~., ., .;,.,
,. .
:' .
2~
~ O.Z. 0050/~1599
2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1 r 1,2-trim thyl-2
propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-
l-propenyl or l-ethyl-2-methyl-2-propenyl, in particular
l-methylethenyl or corresponding alkenylo~ and/or halo-
alkenyl.
Th~ 6-membered and 7-membered heterocyclic
structures may also carry hydroxyl group~ in addition to
the abovementioned substituent~.
Suitable substituents for the phenyl or pyridyl
radical , in addition to the abovementioned groups, are
~he following radical~
alkenyloxy, such as 2-propenyloxy, 2-butenyloxy, 3-
buten~loxy, l-methyl-2-propenyloxy, 2-methyl-2-propenyl-
oxy, 2-pente~ylo~y, 3-pentenyloxy, 4-pentenyloxy, 1-
methyl-2-but~nyloxy, 2-methyl-2-butenyloxy, 3-methyl-2
butenyloxy~1-methyl-3-hutenyloxy,2 methyl-3-butenyloxy/
3-m~thyl-3-butenyloxy, 1,1-dimekhyl-2-propenylo~y, 1,2-
dimethyl 2~propenyloxy,1-ethyl-2 propenyloxy,2-hexenyl-
oxy, 3-hexenyloxy, 4-hexenyloxy, 5-hexenyloxy, l-methyl-
2-pentenyloxy,2-methyl-2 pentenylo~y,3-methyl 2-penten-
yloxy, 4-methyl-2-pentenyloxy, 1-methyl-3-pentenyloxy,
2-methyl-3-pentenyloxy,3-methyl-3-pentenyloxy,4-methyl-
3-pentanyloxy,1-me~hyl-4-pentenyloxy,2-me~hyl-4-penten-
yloxy, 3-m~thyl-4-pent~nyloxy, 4-methyl-4-pentenyloxy,
1,1-dimethyl~2-butenylo~y, 1,1 dimethyl-3-butenyloxy,
1,2 dimethyl-2 butenyloxy, 1,2-dLmethyl-3-butenyloxy
1,3-dimethyl-2-butenyloxy, 1,3-dimethyl-3-butenyloxy~
2,2-dimethyl-3-butenyloxy, 2,3 dimethyl-2-butenylo~y,
2,3-dimethyl-3-butenylo~y,l-ethyl-2-butenyloxy,l-el:hyl-
3-butenyloxy,2-ethyl-2-butenylo~,2-ethyl-3-buten~loxy,
1,1,2-trimethyl~2-propenyloxy, 1-othyl-1-methyl-2-propen-
yloxy or l-ethyl-2-me~hyl-2-propenyloxy, in particular 2-
propenyloxy or 2-butenyloxy,
alkynyloxy, such as 2-propynyloxy, 2-butynyloxy, 3-
butynyloxy, }-methyl-2-propynyloxy~ 2-pentynyloxy, 3-
pentynylo~y, 4-pentyny7Oxy, l-methyl-3-butynyloxy, 2-
methyl-3-butynylo~y,1-m2thyl-2-bu~ynyloxy,1,1-dimethyl-
2~3~21~
- 12 - O.Z. 0050/41599
2-propynylo~y, 1 ethyl-2-propynyloxy, 2-hexynyloxy, 3-
hexynylo~y, 4-hexynyloxy, 5-hexynyloxy, 1-methyl-2-
pentynyloxy,l-methyl-3-pentynyloxy,l-methyl~4-pentynyl-
oxy, 2-methyl-3-pentynyloxy, 2-methyl-4-pentynyloxy, 3-
methyl-4-pentynyloxyt 4-~ethyl-2-pentynyloxy, 1,1-
dimethyl-2-butynyloxy, 1,l-d ~ethyl-3~butynylo~, 1,2-
dimethyl-3-butynyloxy, 2,2-dimethyl--3-butynyloxy, 1-
ethyl-2~butynyloxy, 1-ethyl~3~butynyloxy, 2-ethyl-3-
butynyloxy or l-ethyl-l-methyl-~-propynyloxyI in par-
ticular 2-propynyloxy or 2-butynyloxy~
amino which may carry one or two of the following
radicals: alkyl as ~tated for Xl in particular methyl or
ethyl, o~ alkenyl as stated above, in particular 2-
propenyl or 2-butenyl,
al~ynyl, such as ethynyl, l-propynyl, 2~propynyl, 1-
butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propyny.l, 1-
pentynyl, ~-pentynyl, 3-pentynyl, 4-pentynyl, l-methyl-
3-butynyl, 2-methyl-3-butynyl, 1-methyl-2-butynyl, 3-
methyl-l-butynyl, l,l-dimethyl-2-propynyl, 1-ethyl-2~
propynyl, 1-he~ynyl, 2-he~ynyl, 3-hexynyl, 4-al}~ynyl, 5-
hexynyl, 1-methyl-2-pentynyl, l-methyl-3-pentynyl, 1-
meth~l-4~pentynyl, 2-methyl-3-pentynyl, 2-methyl-4
pentynyl, 3-methyl-1-pentynyl, 3-methyl-4-pentynyl r 4~
methyl-1-pentynyl, 4-methyl-2-pant~nyl, 1,1-dLmethyl-2
butyn~l, 1,1-dimethyl 3-butynyl, 1,2-dLmethyl-3-butynyl,
2,2-dimethyl-3-butynyl, 3,3-dimethyl-1-butynyl, 1 ethyl-
2-but~nyl, 1-ethyl~3-buty~yl, 2-ethyl-3-butynyl or 1-
ethyl-1-methyl-2-propynyl, in particular 2-propynyl or
2-butynyl and/or
acyl, such as acetyl, propionyl, butyryl, 2-me~hyl-
propionyl, pen~anoyl, 2-methylbutyryl, 3-methylbut~yryl,
2,2-dimethylpropionyl, hexanoyl, 2-methylpentanoyl, 3-
methylpentanoyl, 4-methylpentanoyl, 2,2 dimethylbutyryl,
2,3-dimethylbu~yryl, 3,3-dimethylbutyryl or 2-ethyl-
butyryl~ in particular acetyl, propionyl or benzoyl.
Specific e~ample~ of cyclohexenone~ of the
ormula II who~e toleration by crop~ carl be improved by
- 13 - O.Z. 0050/41599
naphthalene derivakive~ of the formula I are sho~ in
Tablas A and B below:
: , " ~, : .
,~ . : ~ : ',.. - '.'
2~'~2 ~
900243
14 O.Z. 0050/41599
Table A
NO-A
~5 Rl
o
Rl A Xn
CH2CH3 (CH2~4 H
(CH2)2CH3 (CH2)4 H
CH2CH3 (cH2)2cH=cH H
(CH2)2CH3 (CH2)2CH=CH H
CH2CH3 (CH2)4 4-CF3
(CH2)2CH3 (CH2)4 4-CF3
CH2CH3 (CH2)4 3-F
(CH2)2CH3 (CH2)4 3-F
CH2CH3 (CH2)4 4-F
(CH2)2CH3 (CH2)4 4-F
CH2CH3 (CH2)4 3-CH3
(CH2)2CH3 (CH2)4 3-CH3
CH2CH3 (CH2~4 4-OCH3
~CH212CH3 (CH2)4 4-OCH3
CH2CH3 (CH2)4 3-N02
(CH2) 2CH3 (CH2)4 3-N02
CH2CH3 (CHz)4 3-CN
(CH2)2CH3 (CH214 3-CN
CH2CH3 (CH2)4 3-cO2cH3
(CH2)2CH3 (CH2)4 3-cO2cH3
CH2C~3 ~CH2¦4 3-CO2Ph
(cH2l2cH3 (CH2)4 3-C02Ph
CH2CH3 (CH2)4 4-OCHF2
(CH2)2CH3 (CH2)4 4-OCHF2
CH2CH3 (CH2)4 3-CH3,4-CI
(C~12)2CH3 (CH2)'~ 3-CH3,4-Cl
. . :
: `, . : ' .'.. - ' ', '
-
. . -, . ~ :
, .. ,
. . ~ . , .
~2~
900243
O.Z. 0050/41599
Table B
X
R2 ~ / H2CH CH CH2 ~ (n = 1)
R~ R2 __ __ X
CH2CH3 ~ H
(CH2)2CH3 ~ O H
CH2CH3 ~ 0 4-F
~CH2)2C~l3 ~ O 4-F
CH2C~13 ~ O 3-CH3
(CH2~2CH3 ~ O 3-CH3
CH2CH3 ~ O 3-CF3
(CH2)2CH3 ~ 0 3-CF3
CH2C~13 ~ O 4-C(CH3)3
(C~12)2CH3 ~ 1O 4-C(CH3)3
CH2CH3 ~ 0 3-Cl
(CH2~2CH3 ~ O 3-Cl
,
- : .
' . '.: :
.
.
:
.
2~l~2~
900243
16 O.Z. 0050/41599
Table B (contd.)
Rl R2 _ X
CH2CH3 ~ S H
(CH2)2CH3 ~ S H
CHzCH3 ~ S 4-F
(CH2)2CH3 ~ S 4-F
CH2CH3 ~ 3-CH3
(CH2)2CH3 ~ 3-CH3
CHzCH3 ~ S 3-CF3
(CH2)2CH3 ~ S 3-CF3
CHzCH3 ~ 4-C(CH3)3
(CH2)2CH3 ~ S 4-C~CH3)3
CH2CH3 ~ S 3-CI
(CH2)2C~3 ~ S 3-CI
CH2C~l3 ~ H
(CHz~zcH3 l o~ H
`.~
: . .
~2 l:~
900243
17 O.Z. 0050/41599
Tab I e B ( c ontd . j
Rl R2 X
CH 2CH 3 l~ 4-F
tCH2) 2C~3 l~ ~-F
CH2CH3 1 O~ 3-CH3
(~H2)2CH3 ~ 3-CH3
CH2CH3 1 O~ 3-CF3
(CH2)2CH3 ~ 3-CF3
CH2CH3 ~ 4-C(CH3)3
(CH2)2CH3 ~ 4-C(CH3)3
CH 2CH 3 ~ 3-CI
(CH2) 2CH3 ~ 3-Cl
CH3
CH 2C~I 3 1 ~ CH3 H
(CH2)2C~I3 1 ~ C~3 H
CH3
CH2CH3 1 ~ CH3 4-F
2 ~
900243
1 ~ O . Z . 0050/4 1 599
Tab 1 e B ( c ontd . ~
Rl R2 _ _ X
(CH2)2CH3 1 O 1 CH3 4~F
C~3
CH 2CH 3 1 O 1 CH3 3-CH 3
CH3
(C~l2)2CH3 1 ~ CH3 3_CH3
CH2CH3 CH3 3-CF3
CH3
(CH2)2CH3 1 ~ CH3 3-CF3
CH3
CH2CH3 1 ~ CH3 4-C(CH3)3
CH3
(CH2)2C~3 1 ~ CH3 4-C(CH3)3
CH3
CH 2CH3 1 ~ CH3 3-CI
CH3
(CH2)2CH3 1 ~ CH3 3-CI
CH2CH3 1 ~
(C~12)2CH3 1~ H
CH2CH3 1 ~ 4-F
:
`- ~ . , ' . ' ~'. ~ `
L 2 ~
900243
19 O.Z. 0050/41599
Table B (contd. )
Rl , _R2 _ _ _ ,, _ _ X _
~CH2) 2CH3 S~ 4-F
CH 2CH 3 l~ 3-CH 3
(CH2) 2CH3 S~ 3-CH3
CH 2Clt 3 l~ 3-CF 3
( CH 2 ) 2CH 3 5~ 3-CF 3
CH2CH3 l~ 4-C(CH3) 3
(CH2)2CH3 S~ 4-C(CH3)3
CH2CH3 l~ 3-Cl
~ctl2) 2CH3 1~ 3-CI
C~ 2C~ 3 ~? H
~CH2) 2CH3 ~ H
CH 2CH 3 ~) 4-F
~CH2) 2CH3 {0 4-F
.
~2~
930243
O.Z. 0050/41599
Table B (contd.)
R1 . R2 _ _ X
CH2CH3 ~? 3-CH3
(CH212CH3 ~ 3-CH3
CH2CH3 ~? 3-CF3
(CH2)2CH3 ~ ? 3-CF3
CH2CH3 ~ 4-C(CH313
(CH2)2CH3 ~ ? 4-C(CH3)3
CH2CH3 ~ ? 3-CI
(CH2)2CH3 ~ ? 3-Cl
Br Br .
CH2CH3 ~ ? H :~
: Br Br
(CH2)2C~13 ~ ? H
Br Br
CH2CH3 ~? 4-F
Br Br
(CH2)2CH3 ~ ? 4-F
Br Br
CH2CH3 ~? 3-CH3
- ,
~2~
900~43
21 O.Z. 0050~l~1599
Tabl~ B (contd. )
Rl , R 2, ,_ _ X
Br Br
(CH2) 2CH3 ~ 3-CH3
Br Br
CH 2CH 3 ~? 3-CF 3
Br Br
(CH2) 2CH3 ~? 3-CF3
Br Br
CH2C113 ~ 4--C(CH3) 3
Br Br
(CH2) 2CH3 ~ 4-C(CH3) 3
Br Br
\~\ 3-C 1
CH 2CH 3
Br Br
(CH2) 2CH3 ~ 3-Cl
CH 2CH 3 ~S--N
(CH2) 2CH3 ~I~N H
CH2C1~3 ~S--N 4-F
~CH2) 2CH3 ~N 4-F
CH 2CH 3 J S~--N 3 -CH 3
.
: , . ~-... `' ~ :
~2~
900243
22 O.Z. 0050/41599
Table B (contd.)
Rl -- R2 X
(CH2)2CH3 ~ ~S-I 3-CH3
CH2CH3 ~S~N 3-CF3
(CH2)2CH3 ~ -N 3-CF3
CH2CH3 ~ -N 4-C(CH3)3
(cH2~2cH3 ~S-N 4-C(CH3)3
CH2CH3 ~ ~N 3-CI
(CH2)2CH3 ~S-N 3--CI
o
CH2CH3 ~ ~ CH3 3-CF3
(CH2)2CH3 ~0 ~ CH3 3-CF3
CH2CH3 ~ ~ CH3 4-C~CH3)3
(CH2)2CH3 ~0 ~ CH3 4-C(CH3)3
CH2CH3 ~o~ ~CH3
(C~l2)2cH3 ~O ~ C~13 H
CH2CH3 ~oJ H
2~2~
900243
23 O.Z. 005~/41599
Table B (contd.~
R1 _ R2 _ _ X
( CH 2 3 2CH 3 ,rOJ
CH2CH3 ~ J 3-CF3
(CH2)2CH3 ~oJ 3-CF3
CH~CH3 ~ J 4-C(CH3)3
(CH2)2CH3 ~oJ 4-C(CH3~3
CH2CH3 O
(CH2) 2CH3 0 H
CH2CH3 O 3-CF3
(CH2)2CH3 O 3-CF3
; CH2CH3 O 4-C(CH3)3
(CH2)2CH3 O 4-C(CH3)3
CH2CH3 ~ H
~CH2)2CH3 ~ H
CH2CH3 ~ 3-CF3
(CH2)2CH3 _ ~ 3--CF3
CH2CH3 ~ 4-C(CH3)3
(CH2)2CH3 ~ 4-C(CH333
2~121~:~
900243
24 O.Z. 0050/41599
The herbicidal cyclohexe~one derivatives of the formula II are predom-
inantly used for combating unwanted grasses in dicotyledonous crops and in
grasses which do not belong to the Gramineae family. Depending on the
structure of the substituents and the application rate, compounds from
this class may also be used for selectively combating unwanted grasses in
graminaceous crops such as wheat and rice.
Naphthalene derivatives have been described in the literature both as
herbicides and as antidotes of the formula I
R ~COR I ',
where the substituents have for example the following meanings:
R' is hydrogen, halogen, nitro, C1-C5-alkyl or phenyl and
R is hydroxy, alkoxy, alkylthio, amino or substituted amino
(HU-A 21 318, HU-A 21 319, HU-A 21 320, Hl)-A 21 321, HU-A 21 322,
HU-A 21 323 and BE 884 634). These antidotes are recommended for reducing
damage caused by herbicides of the following classes: ureas, thio-
carbamates, triazines, and chloroacetanilide and uracil derivatives.
The object of the present invention was therefore to provide compounds
able to reduce the damage to crop plants caused by herbicides of the
cyclohexenone type II.
We have now found that naphthalene derivatives cf the formula I
~I Rm I,
where the substituents and the index have the following meanings:
R is C1-C4-alkyl, C1-C4-alkylthio, C1-C4-haloalkyl, C1-C4-alkoxy,
halogen, hydroxy, nitro or benzyl;
"., . , :
' : . .. .
: .,
,
..
-- 2 ~
9002~3
3.Z. 0050/41599
m is 0, 1, 2 or 3, the radicals R being identical or different when m is
2 or 3;
R3 is -CN; -C(NH2)NOH; -c(z~-rR5;
O O N O
-C-Azol , -C-o-N=cRllRl2 , ~ N ~ R6 ;
R4 is halogen; -NR7R~; -N=CH-R7; -NR7-502R9; CooR5; OH
~lo R10
I I or -NR7-C-B and
O ¦ O O
Z is oxygen or sulfur;
10 T is oxygen or -NR5;
R5 is hydrogen,
C1-C6--alkyl which is unsubstituted or ~ono- to trisubstituted by
haloyen, C1~C4-alkylamino, di-(C1-C4-alkyl)amino, Cl-C4-alkoxy or
C1-C4-alkylthio;
phenyl or benzyl which may bear one to three of the ~ollowing gro~ps:
C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-haloalkyl, cyano,
nitro and/or halogen;
R6 is phenyl which may bear one or two of the Following groups: halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-haloalkyl, cyano
and/or nitro;
25 R7 is hydrogen;
C1-C6-alkyl which is unsubstituted or mono- to trisubstituted by
halogen, C1-Cb,-alkylamino, di-(C1-C4-alkyl)amino, C1-C4-alkoxy,
C1-C4-alkylthio, phenyl and/or (C1-C4-alkyl~oxycarbonyl;
phenyl which is unsubstituted or mono- to trisubstituted by halogen,
Cl-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, Cl-C~-haloalkyl, cyano
and/or nitro;
R8 is hydrogen;
3S Cl-C6-alkyl which is unsubstituted or mono- to trisubstituted by
halogen, Cl-C4-alkylamino, di-(Cl-C4-alkyl)amino, Cl-C4-alkoxy,
Cl-C4-alkylthio and/or phenyl;
. : .. : : ,
~ ~3 ~
900243
~6 O.Z. 0050/41599
R9 is C1-C6-alkyl which is unsubstituted or mono- to trisubstituted by
C1- C4-alkoxy, C1- C4-alkyl~hio, C1-C4 alkylamino, di-(C1-C4-
alkyl)amino, phenyl and/or one to five halogen atoms;
phenyl or 5- or 6-membered hetaryl, and these rings may bear from one
to three of the following yroups: C1-C4-alkyl, C1-C4-alkoxy,
Cl-C4-alkylthio, C1-C4-haloalkyl, nitro, cyano and/or halogen;
R10 is C1-C6-alkyl or C2-C6-alkenyl, these groups being unsubstituted or
mono- to trisubstituted by: halogen, C1-C4-alkoxy, Cl-C4-alkylthio
and/or phenyl;
phenyl which is unsubstituted or mono- to trisubstituted by Cl-C4-
alkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-haloalkyl, nitro, cyano
and/or halogen;
or RlO...Rlo together
form a C2-C4-alkylene or C2-C4-alkenylene chain, and these bridges may
bear fro~ one to three of the following substituents: C1-C~-alkyl,
C1-C4-alkoxy, C1-C4-alkylthio, halogen and/or phenyl, or
form a fused ben~ene ring which may bear ~rom one to four halogen
~ atoms and/or from one to three of the following radicals: C1-C4-alkyl,
: 25 C1-C4-alkoxy, Cl-C~,-alkylthio, C1-C4-haloalkyl, cyano, nitro and/or
phenyl;
R1l,R12 are each C1 C4-alkyl or, together with the carbon atom to which
they are bonded, form C3-C6-cycloalkyl;
B is hydrogen,
C1-C6-alkyl which is unsubstituted or mono- to trisubstituted by
halogen, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkylamino,
di--(C1-C4-alkyl)amino, phenyl and/or C1-C4-alkoxycarbonyl;
C1-C4-alkoxycarbonyl;
-NR~RS- or
phenyl which may bear from one to five halogen atoms and/vr from one
to three of the following substituents: C1-C4-alkyl, Cl-C4-alkoxy,
Cl-C4-haloalkyl, cyano and/or nitro;
. .
~2~
900243
27 O.Z. 0050/41599
provide excellent protection for crop plants from the Gramineae family and
improve the tolerance of herbicides of the cyclohexenone type II specific-
ally in crops such as milletr rice, Indian corn, cereals (wheat, rye,
barley, oatS), cotton, sugarbeets, sugarcane, soybeans and sorghum. The
5 damage to crop plants is reduced or completely suppressed. Unwanted grassy
species are combated, it being irrelevant for the action whether -these
herbicidal agents consiSting of herbicidal active ingredient and safener
are formulated and applied together or separately, and irrelevant, when
the active ingredient and safener are applied separately, in which order
10 they are applied.
The compounds I are manufactured in accordance with methods generally
known in the literature.
15 Derivatives I in which R3 and R4 occupy adjacent ring positions are
obtained for instance by reacting a corresponding nitronaphthyl derivative
XIII under conditions analogous to those described by Y. Tomioka ~Chem.
Pharm. Bull. 33 (4), 1360-1366 (1985)~ to give the cyanonaphthylamine Ia
(R3 = CN, R4 - NH2). This reaction seqUence is shown below for the
20 synthesis of 2-aminonaphthalene-1-carbonitrile derivatives:
,~ " ~'`~NO2 base
m ~ + NC ~ C02CH2CH3
XIII
CN CN
m ~ N ~ CO2CH2CH3~ N ~ co2cH2cH3
NC C02CH2CH3
CN
hydrolysis
R ~ NH2
la
The corresponding compounds I can be synthesized by methods described in
the literature from the derivatives Ia ~derivatives of the cyano group:
Methoden der organ. Chem. (Houben-Weyl) V01. E5, pp. 263 et seq.,
25 pp. 710 et seq., pp. 790 et seq., pp. 941 et seq., pp. 1242 et seq.,
pp. 1313; Vol. X/4 (1968), pp. 209 et s0q.; derivatives o~ the amino
group: Methoden der organ. Chem. (Houben-Weyl) Vol. XI (2), pp. 3 et Seq.,
Vol. V (2) p. 846),
3~ Numerous methods have been described in the literature of synthesizing
naphthalene derivatives I in Which R3 and R4 do not occupy adjacent ring
positions. The literature citations are listed together With the corres-
ponding compounds in Tables 8 and 9 a~ter the synthesis examples.
, . . ~ .
; .
.
~2~
9002~3
BASF AktiengesellschaFt 28 O.Z. 0050/41599
With regard to biological activity, those naphthalene derivatives are
preferred in which the substituents have the following meanings:
R is alkyl such as methyl, ethyl, propyl, 1-methylethyl, butyl,
l-methylpropyl, 2-methylpropyl and 1,1-dimethylethyl, especially
methyl and ethyl;
haloalkyl such as fluoromethyl, difluoromethyl, trifluoromethyl,
2,2-difluoroethyl, 2,2,2-trifluoroethyl and 1,2,2-trifluoroethyl,
especially trifluoromethyl and 2,2,2-trifluoroethyl;
alkoxy such as methoxy, ethoxy, propoxy, isopropoxy and tert-butoxy,
especially methoxy and ethoxy;
alkylthio such as methylthio, ethylthio, isopropylthio and tert-butyl-
thio, especially methylthio;
halogen such as fluorine, chlorine, bromine and iodine, especially
fluorine, chlorine and bromine; hydroxyl; nitro or benzyl;
m is 0, 1, 2 or 3, R baing identical or different when m is 2 or 3;
R3 is cyano; a carboxaminoxime, a carboxylic acid, a thiocarboxylic acid,
a carboxamide, a thiocarboxamide, oxadiazole, an oxime ester group,
where R11 and Rl2 are methyl, ethyl, propyl, butyl, cyclopentyl or
cyclohexyl, or a radical -C(0)-azole, where azole is a l-imidazolyl,
1-pyrazolyl and especially a 1-triazolyl radical.
Where R3 denotes an acid or an acid amide function, this radical may
30 additionally be substituted by one of the abovementioned alkyl groups, a
phenyl radical or a benzyl radical.
The following are particularly preferred:
35 - cyano,
~ carboxamide and thiocarboxamide radicals which are unsubstituted or
substituted by methyl, ethyl, phenyl and/or benzyl, and
. :
~2~
900243
29 0.~. 0050/41599
- 3-oxadiazolyl radicals substituted in the 5-position by a phenyl ring,
and this phenyl substituent may in turm bear up to three substituents.
Suitable substituents are the halogen atoms, alkyl, alkoxy, alkylthio,
haloalkyl and/or cyano or nitro groups already mentioned for R.
R4 may denote halogen, as under R, fluorine, chlorine and bromine being
preferred.
R4 may also be a carboxylic acid group, a hydroxyl group, an amino
group or a derivative of a hydroxyl or an amino group. The following
are particularly preferred:
- dialkylamino, such as dimethylamino and diethylamino
15 - diacylamino, such as diacetylamino, maleimino, dichloromaleimino, methylmaleimino, phthalimino, tetrabromophthalimino and
3,4,5,6-tetrahydrophthalimino,
- acylamino, such as acetylamino, glutarylamino, benzoylamino and
ethyloxaloylamino
- sulfonylamino, such as phenylsulfonylamino and N-(phenylsul-
fonyl)-N-(1-carboxylyl)-methylamino
- imino, such as benzalimino.
Suitable derivatives of hydroxy groups are salts such as alkali metal
salts or esters with inorganic or organic acids such as alkylsulfonic
acids, phosphoric acids and carboxylic acids.
Particularly preferred compounds I are those in which the radicals R3 and
R4 occupy adjacent ring positions.
Examples illustrating the synthesis of the cyclohexenone deriYatives of
35 the formula II
Manufacturing instructions for Example 3.2
a) At 0C, 69.1 9 (1 mol) of sodium nitrite in 100 ml of water was added
to a solution o~ 93.1 g ~I mol) of aniline in 340 ml of water and
225 ml of concentrated sulfuric acid.
2 ~
900243
30 O.Z. 0050/41599
b) At -15C, 67.6 9 (1.25 mol) of butadiene was gassed into 840 ml of
acetone and 50 ml o~ water. 15.5 9 of copper(II) chloride and 22.5 9
of calcium oxide were added and the diazoniu~ salt prepared under a)
was introduced over a period of 2 hours. This reaction mixture was
allowed to heat up to 25C. After it had been stirred for 6 hours, it
was extracted with methyl-t-butyl ether, the organic extract was
evaporated down and distilled in a thin~film evaporator (0.2 mm Hg;
80C). There was obtained a mixture of 1-chloro--4-phenylbut-2-ene and
3-chloro-4-phenylbut-1-ene (78:22) in a total yield of 55%.
c) 78.3 g (0.48 mol) of N-hydroxyphthalimide and 44.2 g (0.32 mol) of
potassium carbonate were added one after the other to 480 ml of
anhydrous N-methylpyrrolidone. At an internal temperature of 40C,
88.8 g (0.54 mol) of the chloride mixture obtained in accordance with
example b) was dripped in. The mixture was heated to 60C and stirred
for a further 6 hours. After the mixture had cooled it was poured into
2 liters of ice water and filtered. Washing and drying gave 9ah of
theory of (E)-N-(4-phenyl-2-butenyloxy)-phthalimide.
Mp.: 70-71C (isopropanol)
d) At 60C and while stirring, 11.6 9 (0.19 mol) of ethanolamine was
added to 55.5 g (0.19 mol) of the phthalimid ether e) in 190 ml of
ethyl acetate. After 5 hours the precipitated N-(hydroxyethyl)-
phthalimide was filtered off and 18.8 g of oxalic acid in 30 ml of
ethyl acetate was added to the filtrate. there was obtained 95% of
theory of (E)-4-phenyl-2-butenyloxy amine as the oxalate salt.
Mp.: 127-129C.
e) 4.3 g (0.016 mol) of 2-propionyl-5-(3-tetrahydrothiopyranyl)-cyclo-
hexane-1,3-dione, 4.5 g (0.018 mol) o~ 4-Phenyl-but-2-enyloxyammonium
oxalate and 3.0 g of sodium bicarbonate were stirred for 16 hours in
100 ml of methanol at 25C. The solvent was distilled off under
reduced pressure and the residue was chromatographed on silica gel
using a mixture of toluene and ethyl acetate in a volume ratio of 8:2.
After removal of the solvent, there was obtained 2.2 g (34.3% of
theory) of 3-hydroxy-2-~1-(4-phenyl-but-2 enyloximino)-propyl]-
5-(3-tetrahydrothiopyranyl~-cyclohex-2-en-1-one as a resin.
40 Unless stated otherwise in the tables below, the alkenyl radicals are in
the E configuration. The IH-NMR details relate to characteristic signals.
:
.
goo243
31 O.Z. 0050/41599
Manufacturing instructions for example 5.26
a) 71.5 9 (0.23 mol) of N-(4-(4-fluorophenyl)-3-butenyloxy)phthalimide
(prepared as in DE-OS 38 38 310) is dissolved in 300 ml of tetrahydro-
furan. 2 9 of palladium on activated carbon is added, followed by
hydrogenation at slightly superatmospheric pressure until 1.2 times
the theoretical amount of hydrogen has been consumed.
The mixture was filtered through kieselguhr, evaporated down and
recrystallized from isopropanol.
Yield: 62.8 g (87%); mp.: 67-68C
250-MHz 1H-NMR (DMSO-d6)
3 (ppm) = 1.8-1.9 (m,4H); 2.65 (t, 2H); 4.15 (t,2H)
7.0-7.35 (m, 4H); 7.86 (s,4H).
b) 61.8 ~ (0.197 mol) of the chlorophthalimide prepared above is added in
portions to 92 ml of ethanolamine. The mixture is heated for 3 hours
at 60C, cooled, poured into 400 ml of ice water, and extracted three
times with 100 ml of dichloromethane. The combined or~anic phases are
washed with saturated sodium chloride solution, dried and evaporated
down under reduced pressure.
4-(4-Fluorophenyl)-butyloxyamine is isolated as an oil.
250-MHz IH-NMR (CDC13)
(ppm) = 1.5-1.75 (m,4H); 2.61 (t,2H); 3.68 (t,2H);
5.4 (broad s, 2H), 6.9-7.2 (m,4H)
3 g (11 mol) of 2-butyryl-3-hydroxy-5-tetrahydrothiopyran-3-yl-cyclohex-
2-enone is dissolved in 100 ml of anhydrous methanol, and 2.2 9 (12 mmol)
of 4-(4-fluorophenyl)-butoxyamine is added. The mixture was stirred for
16 hours at room temperature and evaporated to dryness under reduced
35 pressure. The residue is taken up in diethyl ether and chromatographed on
silica gel. There is obtained 3.6 g (~0% of theory) of the title compound
2-(1-[4-(4-fluorophenyl)-butyloximino]-buty1-5-tetrahydrothiopyran-3-yl-
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900243
44 O.Z. 0050/~1599
Examples illustrating the synthesis of naphthalenes of the formula I
Example 8.008
5 2-Benzoylaminonaphthalene-l-carbonitrile
~H~
3.0 9 (17.8 mmol) of 2-aminonaphthalene-1-carbonitrile (Chem. Pharm. BUll.
33 (4), 1360-1366 (1985)) was stirred with 2.5 9 (18.1 mmol) of benzoyl
chloride and 4 ml of triethylamine in 100 ml of toluene for 15 hours at
10 80C. Upon completion of the reaction the product was filtered off and
dried. There was obtained 1.5 g (31% of theory) of the title compound of
mp. 205C.
Example 9.010
1-(N-Phthalimido)naphthalene-2-carbonitrile
~0
IN
~ CN
3.0 g (17.9 mmol) of l-aminonaphthalene-2-carbonitrile (Chem. Pharm. Bull.
33 (4jj 1360-1366 (1985~) and 2.7 g (17.9 mmol) of phthalic anhydride were
boiled for 15 hours in 40 ml of concentrated acetic acid. Upon completion
20 of the reaction the mixture stirred into 200 ml of wa$er, and the precipi-
tate was isolated and dried. There was obt~ined 3.5 g (66% of theory) of
the title compound of melting point 196C.
Example 9.069
2S
5-(3-Chlorophenyl)-3-(1'-aminonaphth-2'-yl)-oxadiazole
NH2 Nl
NJ~C I
,
,:
~ ~ '
-:
'~ ', ' : '`'
900243
O.Z. 0050/~1599
a) 1~Aminonaphthal~ne-2-carboxamide oxime
NH2
¦ ~N-OH
~C~NH
33.6 9 (0.20 mol) of 1-aminonaphthalene-2-carbonitrile ~Chem. Pharm.
8ull. 33, 1360-1366 (1985)), 18.8 g (0.27 mol) of hydroxylammonium
chloride and 22.7 g (0.27 mol) of sodium bicarbonate were refluxed for
lS hours in 300 ml of ethanol/water (3:2). After cooling, suction
filtration was effected and the filter ca.~e was washed with n-propan-
ol. Yield: 30.0 g (75%) of the title compound of m.p. 178-180C
(active ingredient example g.031).
` '
b) 6.0 g (30 mmol) of the compound obtained under a), 6.9 ml (50 mmol) of
methyl 3-chlorobenzoate and 3.2 9 (60 mmol) of sodium methylate were
boi1ed for 15 hours in 70 ml of methanol. Upon completion of the
reaction the mixture was stirred into 500 ml of water, the precipi-
tated product was filtered off and dried. There was obtained 5.4 9
(56% of theory) of the title compound of melting point 160C (active
ingredient example 9.069).
Example 8.001
,
2-Chloronaphthalene-1-carborlitrile
CN
~ ~Cl
33.6 g t0.2 molj of 2-aminonaphthalene-1-carbonitrile ~cf. Example 1) in
250 ml (abs.) of acetonitrile were added, at 65C, to a suspension of
32.3 g (0.24 mol) of anhydrous copper(II~ chlorid and 30.9 g (0.3 mol) of
tert-butylnitrile in 800 ml ~abs.) of acetonitrile. Upon cornpletion o-f gas
25 evolution the reaction mixture was allowed to cool, 2000 ml of 20%
strength hydrochloric acid was added, and the precipitate was isolated,
washed and dried. There was obtained 31.7 g (70% of theory) o~ the title
compound of melting point 82-83C.
.
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~00243
58 O.Z. 0050/41599
Examples demonstrating biological action
The influence of various representatives of the herbicidal a~ents, or
combinations of herbicide and safening compound, according to the
5 invention on the growth of crop and unwanted plants compared with that of
the herbicidal active ingredient alone is demonstrated by the following
examples in the greenhouse:
The vessels employed were plastic flowerpots having a volume of 300 cm3
10 and filled with a sandy loam containing about 3.~/O humus. The seeds of the
test plants were sown separately, according to species. The vessels were
then covered with transparent plastic hoods until the seeds had unifor~ly
germinated and the plants had taken root.
15 For the postemergence treatment, the plants were grown, depsndiny on
growth form, to a height of 3 to 20 cm before being treated with the com-
pounds, suspended or emulsified in water, by spraying them through finely
distributing nozzles.
20 The cyclohexenone derivative II used in the experiments was compound 3.34.
The herbicidal active ingredients and safening compounds may be applied
together or separately to the leaves and shoots of the crop plants and
unwanted grasses. Preferably, the safener is applied together with the
25 herbicidal active ingredient. Separate application is also possibie, in
which case the safener is applied first to the field, followed by the
herbicidal active ingredient. The herbicidal active ingredient and the
safener may be formulated, together or separately, as a spray liquor in
the form of a suspension, emulsion or solution.
It is also possible to treat the seed of the crop plants with the safener
before sowing, The herbicidal active ingredient is then applied on its own
in the usual manner.
35 For the same cyclohexenone derivative II, different amounts of safener are
required, depending on the crop in which it is to be used. rhe ratio of
cyclohexenone derivative II to naphthalene derivative I may vary within a
wide range, and is dependent on the structure of the cyclohexenone and
naphthalene derivatives, and on the crop involved. Suitable ratios of
~0 herbicidal active ingredient to safener are from 1:40 to 1:0.1, and
preferably from 1:4 to 1:0.25, parts by weight.
The novel herbicidal active ingredients may contain, in addition to the
naphthalene derivative I as safener and the herbicide from the group of
cyclohexenones II, further herbicidal or growth-regulating active ingredi-
en-ts of different chemical structure, without losing the safening effect.
`' : ' , '
. ~
,
:~ , " ' ' , '
- . :
59 OOZ. 0050/41599
The agents according to the invention, or, when applied separately, the
herbicidal active ingredients and the safener, may be applied for instance
in the form of directly sprayable solutions, powders, suspensions (includ-
ing high-percentage aqueous, oily or other suspensions), dispersions,
5 emulsions, oil dispersions, pas$es, dusts, broadcasting agents, or
granules by spraying, atomizing, dusting, broadcasting or watering. The
forms of application depend entirely on the purpose for which the agents
are being used.
10 For the preparation of solutions, emulsions, pastes and oil dispersions to
be sprayed direct, mineral oil fractions of medium to high boiling point,
such as kerosene or diesel oil, further coal-tar oils, and oils o~ vege-
table or animal origin, aliphatic, cyclic and aromatic hydrocarbons such
as ben~ene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated
15 naphthalenes and their derivatives, methanol, ethanol, propanol, butanol,
chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chloro-
benzene, isophorone, etc., and strongly polar solvents such as N,N-di-
methylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water, etc. are
suitable.
Aqueous formulations may be prepared from emulsion concentrates, pastes,
oil dispersions, wettable powders or water-dispersible granules by adding
water. To prepare emulsions, pastes and oil dispersions the ingredients as
such or dissolved in an oil or solvent may be homogenized in water by
25 means of wetting or dispersing agents, adherents or emulsifiers. Concen-
trates which are suitable for dilution with water may be prepared from
active ingredient, wetting agent, adherent, emulsifying or dispersing
agent and possibly solvent or oil.
30 Examples of surfactants are: alkali metal, alkaline earth metal and
ammonium salts of ligninsulfonic acid, phenolsulfonic acid and
naphthalenesulfonic acid, alkylaryl sulfonates, alkyl sulfates, alkyl
sulfonates, and alkali metal and alkaline earth metal salts of dibutyl-
naphthalenesulfonic acid, lauryl ether and fatty alcohol sul-fates, fatty
35 acid salts of alkali metals and alkaline earth metals, salts of sulFated
hexadecanols, heptadec~nols and octadecanols, salts oF sulfated fatty
alcohol glycol ethers, condensation products of sulfonated naphthalene and
naphthalene derivatives with formaldehyde, condensation products of
naphthalene or naphthalenesulfonic acids with phenol and formaldehyde,
l~0 polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol, ethoxyl-
ated octylphenol and ethoxylated nonylphenol, alkylphenol polyglycol
ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols,
isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated
castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene,
lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite
waste liquors and methyl cellulose.
,
2 ~
O.Z. 0050/41599
Powders, dusts and broadcasting agents may be prepared by mixing or
grinding the active ingredient and/or safener with a solid carrier.
Granules, e.g., coated, impregnated or homogeneous granules, may be
5 prepared by bonding the active ingredients to solid carriers. Examples of
solid carriers are mineral earths such as silicic acids, silica gels,
silicates, talc, kaolin, a-ttapulgus clay, limestone, lime, chalk, bole,
loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium
sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium
lO sulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetable
products such as grain meals, bark meal, ~ood meal, and nutshell meal,
cellulosic powders, etc.
The formulations contain from 0.1 to 95, and preferably 0.5 to 90, % by
15 weight of active ingredient and safener. The application rates of
herbicidal active ingredient are from 0.05 to ~ kg/ha.
The herbicidal active ingredient Il is formulated as a 10 to 20wt% emul-
sion concentrate (EC) and employed in the spray liquor ~ogether with a
20 solvent system used in the same amount in ~hich the safener is applied in
the tables.
All safening compounds are formulated in a mixture consisting of 80% of
solvent (cyclohexenone) and 20% of surfactant (Emulphor~ EL = ethoxylated
25 castor oil), together wi~h lOwt% of active ingredient.
The vessels were set up ir. the greenhouse - heat-loving species at 18 to
35C, and species from mors moderate climates at 10 to 25C.
30 The experiments were carried out for from 3 to 5 weeks. During this time,
the plants were tended and their reactions to the various treatments
assessed. Damage by the chemical agents was evaluated on a 0 to 100% scale
(compared with untreated control plants), 0 denoting no damage and 100
denotiny complete destruction of the plants.
The plants employed were Setaria viridis (green foxtail), Zea mays (Indian
corn) and Sorghum vulgare (shattercane).
The tables below demonstrate the safeniny action of compounds nos. 3.003
40 and ~.094 and the tolerance of cyclohexenone derivative no. 3.34 by crop
p I ants .
- ~ : ,: :
.
- -.' . ,, ' :
. . ~ . .
~ ~3
900243
61 O.Z. OOS0/~1599
Tab1e lO Improved tolerance of herbicide no. 3.34 by Indian corn
as a result of adding safening compound no. 8.094;
postemergence application in the greenhouse
5 Appl. rate [kg/ha] Test plants and damage [%]
Herbicide Safener Crop plant Unwarted plant
No. 3.34 No. 8.094 Zea mays Se-taria viridis
0.25 -85 100
0.25 0.75 10 98
Table 11 Improved tolerance of herbicide no. 3.34 by Indian corn as a
result of adding safening compounds nos. 8.003 and 8.094;
postemergence application in the greenhouse
Appl. rate [k~/ha] Test plants and damage [%]
Herbicide Safener Safener Crop plants Unwanted plant
No. 3.34 No. Zea Sorghum Setaria
mays vulg. viridis
_ _ _ _ _ _ _
0 . 25 - - 90 1 00 1 00
0.25 0.75 B.003 10 20 100
0 . 25 0 . 75 8.094 20 65 98
l~O
