CA1137086A - Oxime ethers, processes for their preparation and their use as herbicides - Google Patents

Abstract

Abstract of the Disclosure New oxime ether compounds of the formula (I) wherein R1 is hydrogen, alkyl or alkoxy, R2 is hydrogen, alkyl, alcoxy or halogen, R3 is hydrogen, alkyl, alkoxy or halogen, R4 is hydrogen or alkyl, R5 is hydrogen, alkyl, aryl or substituted aryl, and R6 is hydrogen, alkyl, alkenyl, alkynyl, alkoxyalkyl, alkyl-thioalkyl, dialkylaminoalkyl, haloalkyl, alkoxycarbonyl-alkyl, aryl, substituted aryl, aralkyl, substituted aralkyl, or R5 and R5 together represent an alkylene group, and Z is halogen.
are outstandingly effective as herbicide.

Description

- ~3~ 6 ' .

The present invention relates to certain new oxime ethers, ~- to a process for their preparation and to their use as herbicides.
It has already been disclosed that 2,6-diethyl-M-methoxymethyl-chloroacetanilide can be used for selectively combat-ing weeds (see R. Wegler, Chemie der Pflanzenschutz-und ~ ,.
Schadlingsbekampfungsmittel (Chemistry of Plant Protection Agents and Agents for Combating Pests), Volume 5, page 255, Springer-Verlag ~`~ (1977) and United States Patent Specification 3,442,945). However, this compound is not always sufficiently active and its selectivity , 10 is not always completely satisfactory ~'; The present invention now provides, as new compounds, the ; oxime ethers of the general formula ~ r R l H--C = N - O - R6 - CH2 - Z (I) The oxime ethers of the formula (I) have powerful herbicidal properties, in particular also selective herbicidal properties.
In formula (I~, Rl represents hydrogen or straight-chain -~ or branched alkyl or alkoxy with in either case 1 to 4 carbon atoms~
,.:
"
. ~, ~
y ' --1--i;', ~ ~ .

:

. . .

~37~6 ~., ;~ R2 and R3 are identical or different and each represent ;~ hydrogen/ straight-chain or branched alkyl or alkoxy with in either ;~ case 1 to 4 carbon atoms, fluorine, chlorine or bromine, R4 represents hydrogen or s~raight-chain or branched alkyl . with 1 to 4 carbon atoms, ~. . R5 represents hydrogen, straight~chain or branched alkyl ;~ with 1 to 4 carbon atoms or optionally substituted aryl with 6 to .~; 10 carbon atoms (especlally phenyl or naphthyl), thè substituent(s) being selected from halo~en, straight-chain or branched alkyl with ~: 10 1 to 4 carbon atoms/ halogenoalkyl with 1 to 2 carbon atoms and

2 to 5 haloqen atoms ~preferred halogens being fluorine and ~- chlorine), alkoxy and alkylthio with in either case 1 or 2 carbon ~ atoms, cyano and nitro, and es~ ~ R6 represents hydrogen, straight-chain or branc~ed alkyl , with 1 to 4 carbon atoms, alkenyl or alkynyl with in each case 2 to 4 carbon atoms, alkoxyalkyl with 1 to 4 carbon atoms in the alkyl part and 1 to 4 carbon atoms in the alkoxy part, ~.
alkylthioalkyl with 1 to 4 carbon atoms in the alkyl part and 1 to 4 carbon atoms in the alkylthio part, dialkylaminoalkyl ~' 20 with 1 to 4 carbon atoms in each alkyl part, halogenoalkyl with 1 to 2 carbon atoms and 1 to 5 halogen atoms (preferred halogens being fluorine and chlorine)~ alkoxycarbonylalkyl with 1 to 4 carbon atoms in the alkyl part and 1 to 4 carbon atoms in the alkoxy part, optionally substituted aryl with 6 to 10 carbon atoms (especially phenyl or naphthyl) or optionally substituted aralkyl with 6 to 10 carbon atoms in the aryl part and 1 to '`~
,~ 2-`; . - : .

., .

4 ~370~36 ., 2 carbon atoms in the alkyl part (such as be'nzyl)g the substituent(s) in either case being selected from halogen straight-chain or branched alkyl wi'th 1 to 4 carbon atoms, halogenoalkyl with 1 to 2 carbon atoms and 2 to 5 halogen atoms (preferred halogens being fluorine and chloririe), ' alkoxy and alkylthio with in either case 1 or 2 carbon -.~ atoms, cyano and nitro~ or X5 and R6 together represent a two-membered to four~
membered alkylene group and Z represents ch]orine, bromine or iodine.
The compounds of the formula (I) can exist in the syn-form or anti-form; they are predominantly obtained as `~ mixtures of the two forms.
The inventlon also provides a process for the pre-paration of an oxime ether of the formula (I) in which ,~ (a) an anilinomethyl oxime ether of the general f'ormula ~ -- N ~ 11 _ o _ R6 `, .:
' in which ~ ' -' R1, R2, R3~ R4, R5 and R6 have the meanings indicated ?~: 20 above, '~$` iS reacted with a halogenoacetic acid chloride or bromide ' or anhydride of the general formula ~ or Z-CH2-C0-Cl(Br) (IIIa) ;''l 25 (Z-CH2-Coj2o (IIIb)~
` l in which '~ I Z has the meaning indicated above, ~',,' ~ in the presence of a diluent and if appropriate in the I presence of an acid-binding agent, or (b) a halogenoacetanilide of the general formula ~,`", 1 , ,,, j.
... :, ;~ ~ eit;~
.`,~ I
~ Le A 19 240 .... . .
'.': - :
, :, .
:. , . , :

37~i~6 .. -- 4 --~ (IV), :~ O
in which lg ~2, R3 and Z have the meanings indicated above~
~. is reacted with a substituted oxime ether of the general :'. 5 formula R4 R5 ~ Y_cH_c_N_o_R6 (~f)~ :
~ ~ .
in which R4, R5 and R6 have the meanings indicated above and Y represents halogen or the mesylate or tosylate radical, in the presence o~ an acid-binding agent and if appropriate : in the presence of a diluent, or , ~ . (c) an N-substituted halogenoacetanilide:of the -.. `s ~ .
~: general formula : ~ ~4 R5 ~,~ R3\ / Rl ~ CH - C =
~:~ 15 ~ - N tVI), ~: : R2 G ~ CHz - Z
O
~'~ in which ~:s Rl, R2~ R3~ R43 R5 and Z have the me~nin~ indicat(?d 5: ~ ~ above, is reacted with a salt of hydroxylamine or a derivative ~ 20 thereo~ Or the general:formula :f;~ H2N-0-R6: (VII)~
in which R has;the meaning indicated above~, . ~ in the presence of a diluent and in the presence of an acid-, 25 bindin~ agent, or :. I ' A
*~
Le A 19 240 ~: , (d) an alkali metal salt of an oxime of the general formula ,,.CH - 1 = NOM (VIII), in which R , R2, R3, R4, R5 and Z have the meanings indicated above, is reacted with a halide of the general formula X-R (IX), .
: in which R7 has any of the meanings defined for R6 other than a . ~ hydrogen atom, and X represents~chlorine or ~rominej in the presence o an organic diluent ox in the presence of an organic-inorganic two-phase system in the presence of a phase ; ,i ~
transfer catalyst, the alkali metal salt of the oxime of the formula ;: (VIIIj being produced in situ.

Surprisingly~ the oxime ethers acco~ding to the invention, . which have a~very good herbicidal action~ show, in particular, ~;~ : better possibilities for use as agents for selectively combating ,t, weeds in important crop plants than 2~6-diethyl-N-methoxymethyl-.: .
:~: chloroacetanilide, whi.ch is known from the state of the art and is ~ .
an ac~ive compound of high activity and the same type of action.

.~; The suhstances~according to the invention thus represent an enrich-~: ment of herbicidal agents for selectively combating weeds.

.~. Particularly preferred oxime ethers of the formula ~

`~i are those in which Rl represents hydrogen, methyI, ethyl/~.
. ~ .
.. :
,............................................................... : ~

~.. ,............................. ; :

", ,,~ ~ ~
',,",'''. . ' ' "'' ' ' ' . ~ ~

isopropyl3 sec.-butyl, tert.-butyl, methoxy, ethoxy or isopropoxy; R2 and R3 are identical or different and each represent hyd~ogen~ methyl, ethy~l, isopropyl, sec.-butyl, tertO~butyl, methoxy~ ethoxy, isopropoxy, chlorine or bromine; ~I represents hydrogen, methyl or et~lyl; R5 represen~s hydrogen, methyl3 ethyl, isopropyl or a phenyl ; or naphthyl radical which is op~ionally substituted by chlorine and/or methyl and/or methoxy and/or methylthio and,'or trifluoromethyl; R6 represents hydrogen, methyl3 ;~ 10 ethyl, isopropyl, n-propyl~ n-butyl, ~ert.-butyl~ vinyl, allyl, propargyl, methoxymethyl, ethoxymethyl? ethoxy-ethyl ,methylthiomethyl, chloromethyl, chloroethyl, dimethylaminomethyl, ethylmethylaminomethyl,~ diethyl-;~ aminomethyl, methoxycarbonylmethyl or a phenyl, naphthyl or benzyl radical which is optionally substituted by chlorine and/or methyl and/or methoxy and/or methylthio andior trifluoromethyl; or R5 and R6 together represent the dimethylene or trimethylene group; and Z represents chlorine or bromine.
The following compounds of the general formula (I) , may be mentioned specifically, in addition to the compounds mentioned later in the preparative examples:
": :.
R~ R~
~, R3 R1 ~ ~
CH - C = N - 0 - R6 - R2 C - CH2 - Cl(Br) ? 0 ~ R1 R2 R3 R4 R5 R6 H H H H H H
CH~ CH3 H H H H
J`, '

3 C2 Hs H H H H
; C2Hs C2Hs H H H ~ `~
CH~ CH3 H H H CH3 /,. . .
~ C2H~ C2H~ H H H CH3 ; ~.. ;
Le A 19 240 .~ ' ' , .. : , ~ : - . : . .
. .

~37 Rl R2 R3 R4 ............... R5....... R6 ~ ............................................... .

C2 ~ H H H H CH3 ~; C(CH3 )3 H ~ H H CH3 CH3 Cl H H H CH3 CH3 0-CH3 H H H C~13 CH3 Br HEI H ~
~ C(CHs )~ Cl H H H CH3 ;' OCH3 OCH3 H H H
~; CH, H 3~CH3 H C~3 ~xl i-C~, H~ C2 H!sH H H C~3 ~-~ ; CH~ H H H H CH3 CH~ CH~ H H H C2~5 2 H~ H H
è~ C2 ~ C~ H ~ C2 H~s 2 H~ H ~ H 8 ~ ~ C2 Hs C(CH~ )~ H H H H C2 H
,~.... . ~ CH~ Cl E~. ~I H C~ H5 ~: :v~
3 ~ 0'CH~ H ~i H C2 Hs CH~ Br: H H H C2 Hs C~CH3 ~j Cl H H H C2H5 OCH~ OC~ H H . H C2 ~3 - CH3 H ~ 3~ H H Cz H5 s i-C3 H7 C2 H~s ~ C2 H~s ' ~", :
.~
e .,~
t.'.' ^-~ Le A 19 240 - .
. ~ , -: . - ~ .
:. ~ . . :
:;' .' . - ' : ` ~ : . . ' . ' , : . . . :

~37~6 ` - 8 - :
. ,, Rl R~ R~ R~ R5 ~.~
.. ; ~ - .
,7 :
3 GH,CHq H H H n~C3 H7 ` ~ CH,C2H~ H H H n-C3H7 C~ H3 C2 H~, EI H H n~C.~ H7 .' :
C(CH~ ~s H H H ~I n~C3H7 CH~CH~ 8 H H n-C4 H~
CHyC2H~ H H H n-c4~Is C2 H3 C2 H~ H H H
C~CH~ 3~ H H H H H
~3C~ ~ H H H t-C4 H~ :
C~C2 H~ H ~ H E~ t-C4 Hs 2 H~ ~2 H5 H H H t-C,~ H9 C(CH3 )~ H H EI H t-C4Hs CH3CH3 H H H ~ -CH2 -C-- CH ~ ~
CH3 C2 ~ H H H CH2 -C- CH : ~:
C2H~ CZHs ~ H : H ~ ~ H -CH2-C--CH
C(C~ I :: H:~ H ~: : CH2-~--CH
CH3 ~ ~ CH H ~ H H -CH2 -CH=CH2 .
CH3: C2 H~ : H ~ H ~CH2 -CH=CH2 :
2 H3 ~ Cz H, . H: H H ~CH2 -CH=CH2 C(CH3 )y H H H H ~CH2-CH-CH2 ... . .
CH3 C~ ~ H H H C6 H5 ~ ~ CH3: ~ ~ C2 H~ H H: H C5 H5 ; . C2 H5 ~2 ~ H H H : Cs Hs `'` C(CH~ ~ H H ~ H H C6srI5 :

:;
.7 ~' .'' : ` , ~.
Le A 19 240 .: : ': ,. :, ~" 11370B6 R1 R2 R3 F~ Rs ~
.,~. ~ ,.

~ ~ CH~ C2 H3 H H H -C~z -0-CH3 ``i; ~ C2 H~ C2 H~ H H H -CH2 -O~CH3 t ~ C ~ CH~ H H H H -CH2 -0-CH3 ~ ~ CH3 CH3 ~ H H -CH2 S -c~3 `~ CH3 C2H, H H H ~CH2 -S-CH
~2~ CzH!~ H H H CH2-S-CH3 C(CH3 ~ H~ H H H CEI~ -S-CH3 `~; CH3 CH3 H H H -C~I2 -C6 H5 .~ CH3 C2 H3 H H H -CH2 -C6 H5 C2 H~ c2 H~ H H H -CH2 -C6 H5 C(CH~ )~ H H H H -CH2 ~C6Hs .: .~ CH3 : CH3 H H H -CH2 -CH2 Cl -CH3 ~ C;~H3 H H ~ -CH2 ~CH2 Cl Cz H~ C2 H5 ~ H H -CH2 -CH2 Cl C(CH~ ~3 H H H H -CH2 -CH2 Cl ~; ~ CH3 CH3 H H GH3 n-C3 H7 . ~ .
CH, C2 H~ H H CH3 n-C3 H7 C2 H~ ~C2 H5 H H C~I3 n-C3 H7 C(C-rI3 ~ H H C~I3 ~-C3 H7 CH3 . CH3 . H H CH~ n~C"Hg CH3 ~2 H, H H CH~ n-C4 H9 C2 H~ C2 H~ H H CH3 n-C"~ Hg C(CH~ H H H CH3 n~C4Hg .
~ , :
,:
,~
~,,.. ~ ~, .
~ 1 Le A 19 240 , ,, ~ . , .

:s.
,' ~ :
~, ~
. . .

``` ` ~370B6 .;
R1 R2 R3 R4R3 ~6' ~: ~ $
: ~ CH~ CH3 H H CH3 t-C4 H3 CH~ C2H, H H CH3 t~C4 H9 , ~. C2 H3 C2 Hg H H CH3 ~C~ ~9 ;~ C(CH3 )~ H H H C~I3 t-C~Hg ~;; CH3 CH~ H H CH3 ~CH2 -C- CH
CH3 C2 Hg H H CH3 -CH2 -C~ CH
.. , ~ .
~' C2H3 C2Hg H H CH3 -CH2~C-CH
~r, C ( CH3 )!!1 H H H CH3 ~CH2--C - CH
CH3 CH~ H H ;~3 -CHz-CH-~H2 ,' ~ CH~ C2 H~ H H CH3 -CH2 -CH=CH2 `: i C2H~ c~s H H CH3 -CH2-CH-CH2`? ~ , C ( CH~ H H H CEI3 ~CH2 -CH=CH2 CHI C~ H H CH3 C6 ~5 ~; ~ CH3 C2H3 H H CH3 C6H~
H~ C2H3 H ~ H CH3 C6H5 C(CH3 )3 H H H C~3 C6Hs CH3 CH3 ~ H CH~ -CH2-0-CH3 , ~ CH3 ~2 ~ H H CH3 -CH2 -0-CH3 C2 ~g C2 H5 H H (: H3 -CH2 -0 CH3 C(C~ ~3 H ~I H C~3 -CH2 ~0-CH
CH~ : ~3 H H CH3 -CH2-S-CH3 CH3 C2 ~9 H H CH3 -CH2 S~H3 C2H C2H~ H H CH3 ~CH2 ~ S-CH
.; f~. C~CH3 )~ H H H CH3 -CH2-s-cH3 ~, .~,~, .

r ~ Le A 19 240 ~ . .

~- :$:

~ . .
;,- : '~

~3~70i!3~ ~

R1 R2 R3 R~ R~ . ~6 .~f ~
s, f CH~ c~3 H H CH3 -CH2 -C6 Hs : CH s C2 H~ H H CH~ ~CH2 ~C6 Hg :~: C2 H~ C2 H~ H H CH3 -CH2 -C6 ;` C(CH~ )3 H H H CH3 -CH2 -C6H~
CH~ CH3 H H CH3 -CH2-CH2-Cl CHI ~2 H3 H H CH3 -CH2 -C~2 -C~
C2 H~ C2 H, H H: ~ :CH3 -CH? -CH2 -Cl C(CH~ H ~ ~ H H CH3 -CH2 -CH2 Cl ~;
CH~ H3 : ~ ~I H -(C~l2 )2 - :
~r ~ ~H3 C2~5 H H :--(CH2 )2 -:;f~ . C2H, C2H~, ~ H H ~ -(CH2 )2 ~ ~ :
C(CH3 3!S H :~ H H -(CHz )2 ~
H~ CH3 ~ : H~ ~ H (CH?. )3 - ~ ' :
CH3 ~ CeH~ H~ H :~ -(CH2 )3 - ~ ~
C2H!~ C2H9 ~:H H - (CH2 ~3 - :
::~: .: .
~- C(c~I3 )~5 ~ H H H -(CH2 )3 -.~ ~ CH3 , CH~ H E~3 _(CH2 )z ~
CHI C2H~ H C~3 : -(CHz )2 ~ : : .~:
2N~ C2~ H C~H3 ~ (CH2 )2 -.f ~ ' C(CH3 j~ H ~ H CH3 : ~~CH2 )2 - ~
CH3 ~ CH3 ~ H CH3 -(CH2 )3 - ::
CH3 ~ C2~H~ H CH3~ ~-(CH~ )3 ~ :
~:g ~ ~ ~ C2H~ C2~ H ~H3 _~CH2 33 ~
t~ 3 3~ ~ ~ H ~ CH~ )3-'",~
L~ A l 9 2 4 0 ~, ~

:,~, . :: ~ . , :
,~

... :

., ., ~, ~: R1 R~ R3 R~ R9 R~ , :.$
.,,t~
. CH~ H H C2 H~ H
CH~, ~2 H~ H H C2 H5 H
,~;, (~2 ~C2 ~ C2 H!~ ~
C(CH, ~j~ H H H C2H~ H
CH~ CHj~ H H C2 H3 CH3 CHS ~2 Hs H H C2H9 CH3 ;............................................................... , ~. C2 H~ C2 ~s ~ ~ C2 H~ CH3 ;~ ~ C~CH3 )~ H H H C2H5 C~3 CH~, CH3 : H H C2Hs C2 H3 H H Cz H5 ~ C2 H5 Cz Hs C2 H!~ H H C2 EI~ C2 H5 C ( CH~ H H H C2 Hg C2 H5 ..... ..
CH3 ~H3 H ; H C6H5 H
t ~ CH~ C2 H H H C6 H3 H
~2 Ms ~ C2 H9 H H C6 H~ H

CH~ ~ H H C6 H5 ~3 ,-~ " H H H C6 H5 CH3 "2 ~ ? C2 H, C2 H~ H H C6 H5 CH s : : < C(CH~ ~3 H H H C6H~
CHg Cl H H C6 ~5 CH3 CH3 Br H H C6 H5 CH3 i OCH3 CH3 H H Cs H5 CH3 ~ti~ , i .~ ~.: '' :
: . . :

.,, ~, ,: Le A 19 240 ?, ~ ' . .
` ' ' ' ' '` ' ' ,' ~ ,, . ~ ' ~$ ~ ; ;
' L37~36 - R' R2 R3 R4 R5 R6 :
'r CH3 H H H ~6 Hs CH3 CH3 H 3-CH H C6 ~5 CH3 ~
CH3 H 5-CH~ H C6 H~ C~I3 CH~ CH3 H H C6 Hg C2 H5 CH3 ~2 H5 H H C6 H5 C2 H5 C2 Hs C2 H5 H H C6 H5 C2 Hs ~:~
C(C~I3 )3 H: H H c6 H5 C2 H5 CH3 CH3 H H c6 H5 n-C3 H~r ~;
CH3 : ~ C2 Hs H H c6 H5 n-C3 ~7 C2 H5 : C2 Hs H H C6 H5 n-C3 H7 C(CH3 )3 H H H C6 H5 n-C3 H7 CH3 c~3 H CH3 H CH3 CH3 C2 ~s H ~ CH3 H CH3 C2 H5 C2 H5 ~ H : ~ CH3~ H CH
C(CH3 )3~ ~ H ~ H CH3 H CT~3 CH3 : ~: CH3 H CH3 ~ CH3 ~
CH3 :~ ~ C8 ~5 H CH5 CH3 CH3 C2 Hs ~ C2H5 H CH3 CH3 CH3 C(CH3 )3 H H CH3 CH3 CH3 CH3 CH3 H CH3 H C2 ~Is CH3~ ~ : CzH~ ~ H~ ~ CH3 H C
C2 Hs : C2 H5 H CH3 : H C2 H5 C(CH3 )3 H H CH3 H C2 Hs "
CH3 C~H~ : H C~3 CH3 C2 H5 ,, ?, - CH3 : c2 H~ H CH3 C~13 ~, , .
~ C2 H5 : C2 H5 H CH3 CH3 C2 H5 ., ~ C(CH3 )3 H:: H CH3 CH3 C2 H5 ,,, ~, .
-, Le A l9 240 .:-f~ .
;, ~' :~'. ` . .. .:
~- - :
;~ ' ' '-' : ~ :
,~,, . ~ , 'S .- ~ , :
".'' ' ' ` ~ : ' L3yj~
.. ;
; 14 -`', ' -. R~ R2 R3 R4 R5 R6 .
. .
CH3 CH3 H CH3 H n-C~H~
. CH3 C2H5 H CH3 H n~C3H7 C ~ ~2 H3 H CH3 H n~C3H7 ,~ 5 C(CH3)3 H H CH3 EI n-C3H7 CH3 CH3 H CH3 CH3 n~C3 H7 ~;{ C2H5 H CH3 CH3 ~ n-c3 H7 C~H~ C2H5 H CH3 CH3 n-C3H7 ` C(CH3)~ H H CH3 CH3 ~ ~-C3H7 CH3 CH3 ~ CH3 H n-C~Hg ~'5~` :
; ~ CH3 C2H3 H CH3 H n~C4 Hg C2H~ ~ C2H~ H CH3 H n-C4Hg C(CH3 13 H H CH3 H : n-C4Hs ~, :
If 2,6-dimethylanilinomethyl methylketoxime methyl ether and chloroacetyl chloride are used as starting sub- :
stances in process~va~iant (a) 3 the course of the reaction can be represented by the following equation:

CH2-C-N-0-CH3 t Clr~ ~EI c ~ :

~ ~ -N / 4 ~=N---H3 , ~, :

~- Le A 19 240 :

' ~ ' , :

`-``` 1~37~

If 2-ethyl-6-methyl-chloroacetanilide and c'nloro-methylaldoxime :methyl ether are used as starting sub- ~:
. stances in process. variant :(b)~ the.course of the reaction s can be represented by the following equation:
~$
C2H~ H + ClCH2-CH-N-0-CH3 ( ~ N ~ ----------___ CH3 ~-CH2Cl - HCl ~: 5 . ,.:'` ;
~ ~ C2H~ 2-C~=N~}~3 :: ~ N\
CH~ C-CH2Cl O
If 2,6-dimethyl-N-acetyl~ethyl-chloroacetanilide and ~: 0-methyl-hydro~ylamine-hydrochlo~ide are used as starting substances in process variant (c), the course of the reaction:can be represented by the following e~uation:

~CE~, C~ O ~
N : 2 _ CH3 C-cH2~cl ~ H20 _ HCl O

,~ ~ CH2-C=N-O-CH3 :. . ~CH3 ;I~-CH Cl If the sodium salt of 2,6-dimethyl-chloroacetanilido-~: methyl methylketoxime and benzyl chloride are used as starting substances in process variant (d) 5 the course i~ . of the reaction can be represented by the following .~ 15 equation-: ~ :
~:~'-, ,.I Le A 19 240 , . :

,~ : :: ' . ' ~ :

.3 `. , . `

CH~ CH2-C-NONa + Cl-C~
. ~ N\ :~
CH3 ~-CH~Cl -N~Cl s o CH~

'~ ' ~ H, ~-CH2Cl ,.: The ~ormula (II~ provide~s a general definition o~
the anllino-ketoxime ethers~required as starting substances carrying out:process variant (a). In this formula to R6 pref0rably have those meanings which have already ,; been mentioned as preferred in connection with the descrip-. ~ tion of the substances of the formula (I).
:, , ~:~ The following~compounds may be:me~ntioned as specific examples~of~compounds:of the formula (II): :
.

10 ` ~ ~ CH - C =~ N - O - R6 R2:: H

' . :
t ~ ~ R2 ~ R' R4 R5 R6 ~ ~ ;

H H H H ` H H
: CH~, CH3 ~ H H: H ~ H
~H3 C2 H~, ~ H ; ` H H H
` d~ ' C2H~ C2 H5 H H , ! ~ H H
CH3 CH H: H H CH

'` . : : ~:
,: ~-" I Le A 19 240 ~`~;3 l `` : :
` ~

3~

R2 R~ R~ ......... R
: .
~ CH, c2 H,H H H :CH
C~ E~3 C2 HgH EI H CHI;
Cz H~ H H H H CE15 3 C(CHg )~ ~I H H EI C~
CH3 Cl H EI H CH;
CH~ O-CHI H H H CH3 ~r~"~,~ CH~s Br H H H : CH~ `
C(CH; )~ Cl H H H ~ , OCH, OGH3~H ~ H H ~H~; :
CH3 H : 3-~ H H CH3 ~ ;
C~ N7 ~ ~2 H~~ H H H c~3 s ~ CH3~ H ~ H H H CE.13 CH~ CHc H H ~I G2Hs ;
, ..
CH3 C2 ~SH ~ H ~ : ~ C2 H5 C2 H~j C2 H5~ H ~ H ~ Cz H
CzH~ ~ N ~ H~ H ~ C2 H5 ~:
C(CH~ H~ ~ H ~ H C2Hs CH~, Cl H: H ~ C2H5 CH~ O~ H H H ~2 Hs CH~: Br H H H C2 ~1, C(~Hy ~ Cl ~ C2H5 ~ :
~ OCH~ ~ 05N~ ~ H H . ~ ~ : C2 H
CN~ H 3~ H H C2 C~ HT C2 ~: ~ H }~ ~ C2 Hs . ;
~: I CH3 H H H ~ : C2 H~
,~,. .. .

` ~ Le A 19 240 ~ ~

r, ~ , :

',',', '" ,. ~ ' ~: ~ - , , .

`

~ ~3i~7~86 R1 R2 R~ R4 R9 R~

CH3 CH3 H H Hn C3 H
CH, C2 H, H H Hrl-C3 H7 C2 ~Ig C2 H~ H H Hn~3 H7 C(CH~ )~ H H H H n-C3H7 CH~ H H Hn~C4 H9 CH, C2H9 H H ~ Hn~C4H~
2 Hs C2 ~ H H Hn~C4 Hg C(CH~ 3~ H H H H ~ n-C~Hs, C~ CH3 ~ : H ~ H H t-C4H~
CH3 C2~ H H H t ~C~ 9 :~ ,:;,; , , C2 H~ C~ H~ H H H t-C4 Hg C(CH, )~ H H ~ H H t-C,~H~ :
CH~ H H H~ -CH8 -C_ CH
CH~ : ~ C2 X~ ~ CH2 -C~CH
C2~ ~ ~ C2H~ ~ H; H~ ~ H ~ ~CH2-C~CH
C(CH5 ~ H :H ~I H-CH2 -C_CH
CH3 CH3 H H H~CH2 - C~=CH2 CH3 C2 H, H H HCH2 CH=CH2 ~2 H!s C2 H~ H H H-CH2 ~ J2 C~C~ ~3 ; X ~ H ~ 2-~H-CH2 ~ ~
CH3 ~ ~ CH~ ~ H H EI C6 H5 ~ ;
CH3 C2 H, H H H C6 Hg ~ ~.
~2 ~ C 2 H~, H H H C6 ~19 C(CH~ H H H H C6~5 : ~ :
~,v ~
., - :
;,i~ ;

Le A 19 240 : :' : . .., ~ . . :
. . . . . . .

:; . : , , ,. . . . . ~ :
. - . . . . . .

~ 1~L37~

:~ - 19 ,~
.~ :
~.~ R2 R3 R~ ~9 ~
'.';~ ' ,~, ' CH3 GH~ H H H -CHz~O~CH3 :~ CH~ C2 H!, H H H -CH2 -O-CH3 Hs ~2 Hg H H H -CH2 -O~CH3 C(CH~ ~ H H H ~I -CH~ -O ~CH
.
CH~ CH!, H H ~I -CH2-S-CH3 CH~ C2 H~, H H H -CH~ -S-CH3 ., ~ C2 H~ 2Hy H H H -CH2~S-CH3 C(CH3 )~3 H H H H CH~S~CH3 .~ ~
C~ CH3 ~ H H--CH2 ~C6 Hs CH3 C2 ~ H H H-CH2 -C6 Hs C2 1~ c2 H, H : H H-CH2 -C~j H
C(CH )~ H ~ H H: ~ HCH2 C6Hs `~
GH~ H H-CH2 ~CHz Cl CH3 C2 Hg H H H-CH2 -CH2 Cl C2 ~ C2 H~ ~ H H H-CH2 ~CH2 Cl C~CH~ )3 H H H H-CH2 -CH2 Cl . .~, . . .
~ CH~ CH!, H H CH3 n-C~ H7 ~ i CH3 . C2 Hg ~ n-C~ H7 C2 H~ ~2 H H : H CX3 Il C3 H
. C ~ CP~ H H H C~ n-C~ H7 .~ CH3 CH3 ~ . H H CH~; n~C~H9 ` CH3 C2H~ H H CH3 n-C,~ H9 ~r ~2H~ C2H9 H H ~3 n-Cb.~s '~
CtCH~ ~3 H H H CH~ n C~,H9 ~,~

.
''.i ~= :
"., ; Le A l9 240 .~ ~ .. . .. . .

... .
, .
, ~ 1~7~

~1 R2 R~ R4` - R~ R6, ~ .
... ~ .

CH~ 5 H H C~H3~-C4 H9 ~H3 C2 H3 H H ~H3t-C~ ~3 ,~ C2~I~ C2H~ H H C~C~ H9 C(C~ )3 ~I H ~ CH3t -C,,,H9 CH3 ~H~, H H CH~~CH2 -C~- C~
CH~ C2 H.. H ~ CH5-CH2 -G~- C~
'~ C2 H~ C H~ H H CH3-CH2 -C~ C~I
~ C(CH~ ~" H H H CH[3-CH2 -C-CH
i~
: ~H3 CH~ ~ H t~3U-CH2 --CH=CH~
CH3 ~2 H3 H H CH3-C~2 ~C~ H2 ~: .: C2 H3: C2 H~ ~ H ~ H C~3-CEI2 ~C~I=CH2 C~CH3 )~ ~ H ~ CH2 -CH=~H2 ; ~ CH3 ~ ~ C~ H ~ C6H5 CH!~ ~ C~H~ ~ H H ; CH~ C6H5 : C2 H~ C2 ~ ~ H ~H~CG H3 .- C(CH~ ~ H ~I H C~13CGH~
/ CH3 CH~ ~ H CH3-CH~O~C~
.~ CH3 ~- C2~H~ H H . CH3--CH2~0~CE~3 :
:~ ~ 5 ~ : C~ H~ H ~ ~H3-GH2 -~ s C(CH~ H H H (~3~C~I2 ~ CE~
: ~ ~H3 CH~ 3~CH2 S_CH3 :; ~H3 ~2 H~ H ~3~H2 ~S~C~3 2 E~5 ~ H5 H ~ CH3~CH~ S~CH3 : : C ( C~: )~ H ~ H : H ~3-CH2 S~C~
..
,'~, . ~

.i, ;~ ~ ~ r~
~,' :

~ ,~ Le A 19 2 4 0 ~ :
~ ..

.: - , . , , :.
: ' ' ~ . : .. .

1~37~6 .,. ~

. . .

R1 R2 R3 R~ R~ ' R~
., ~_ ,~ 3 ~H3 H H CH3 -~CH2 -C6 H5 CH!, c2 ~ H H ~CH2 -'C6 ~5 ~ ` C2 H ~2 H~ H H CH3 -CH2 C6 H~ :
C(CH3 ), ~ H H CH3 ~CH2~C~H~
,. CH, CH~ H H CH3 -CH2CH2-CI
`~. CH~, C2 H9 H H CH3 CH2 -CH2 ~51 .~ ..
~s~ C2 H~~2 H~ H H CH3 -CH2 -CH2 -Cl .~ ' Y~ ~ C ( CH~ i El H H CH3 ~ -CH2 ~CH2 -C1 CH3 CH~; H H-(CH~ ~2 -CH~ C2~ H H-(CH2 )2 - :
C;!H, ~H9 H H ~(CHZ )2-C(CH~ H H H -¦CH2 )2 - ~
CH~ : ~H3~ (CH2 )3 - ;:
~: C~ 2H~ H ~ H-~CH2 )3 -C2 H~ 2 g ( C 2 ) 3 C ( CH~ )3 H H ~ ~ ( CHZ )3 CH3 C~3 H c~3- (CH2 )2 ~
: I . C'H3 C2~ H C~3(C~IZ )2 ~ :
~2H5 ~C2E~ H C~3'-~CE-~2 jZ_ C~CH3 ~3 H H C~3 -(C~2 )2 - ~
CH3 CH H ~H3 ~(CH~ )3- -CH3 C2H~ H C~3 -( CH2 ~3 - ~ ¦
~-: C2HS C2H~ ~ H CH3 _(CH2 )~
~¦ ~ C~CH3 ~, H ~ c~3 (CH2 )3 -., '"
::i ~ _.
-~ Le A 19 240 5 ~ , ...
, -,: . , . ........................ .

i - . ~ . . .
:s' ~ . :

~ ~ 3~7~8~

R1 R~ ~ R~ .6 :
'i ~' :~ , CH3 CH, H H C2EI5 H
CH, c2 H~ H H C2 H3 C2 lI~ C2 E~ H H c2 H~ H
C ( CH~ H ~ H C2 H~ H
` CH, ~H3 H H C2 HgCH3 ca3 : ~2 H9 H : H Ca H~C~
C2 ~ C2 H!;H H C2 ~ 3 C ( CH3 ~ )~ H H H ~2 H5 ~H3 ~; ~CH CH3 ~ ~ H H : Cz H5 Cz H5 : -: ~ ~ CEI~: : C2 H~; H H C2 H~ C2 Hs : C2H C2H~ ~: H H C2H~ C2H~
~: t::(CH3)3 H ~: H ~: C2H!~ ~Hs ;~`; ~: ~C~ CH3 ~~ 8~ C6~5 ' H
~ ~H~ ~ ~ CeH~ C6H5 ~ ; H
~ ~ ~ C2H~ : C2~ ~~ ~H ~ C6~ ~

~ CH~ H ~ C6 H5 CH~;
:;~ CH~ ~ C,~ H~ CH3 ~ ~ C2H5 ~ CzH~ C~;H3 CH3 -` C ( CH~ H : H : H C6 H~ CH~
:.~. CH~ Cl . H H ~ ~6 H5 CH3 CH3 : Br H H C~ H5 C~3 , :
: ~ OCH~ CH3 ~H N C6H~ C~j;
~ - :' , : ~:

. ..., ', ' Le A l 9 21~ o . . : :
... .
:, . . :
. " ~ . ,.

~L3~36 . ~:

CH3 H H H C6 H5 ~H3 ~`
;~' CH, H 3-CH H C~; H~ CH3 CH~ H 5-CH~ H C6 Hs CH~, , ~ CH~ CH3 H H C6 H5 C2 ~5 ~1 `~ ~ CH~, C2 H~ H H C~s H5 C2 ~5 C2 Hs C2 H5 H H C6 H~ C2 Hg C ( CH~ H H C~ H5 C2 ~s CH.!~ CH~ H E~ C6 H~ n-C3 H7 . ~ ~, CHs c2~ H H C6Hz;s n-C3H7 ~I3 C2Hs H H C6H~ n-C3H7 ` ~ C ( CH~ H H H C6 ~s n-~c~5 H7 CH~ ~H3 H CH, H CH3 CEI3 c2 H~ H CH3 H CH3 : ~ C2 H5 ~2 H~ H CH~ H CH
C(CH~ j3 H H ~H3 H CE~
,; CH3 CH!~ H CH3 CHI CH
.i CH3 C2 H~ H CH3 CH3 CH3 C2 H~ C2 H~ H CH3 CH~ CH3 C~CH3 ) }~ H CH3 c~3 CH3 , CE~3 CH3 H CH~, H CzH.
CH.~ C2H~ H CH3 H ( 2~I3 ~: C2 H3 C2 H~ H CH ~ H C2 Hs C (CH3 )3 H H CH~ H C2~5 s CH3 CEI3 El CH~ C~ C2 H3 ,~ C H3 C2 H~ ~ CH~ c~3 C~ H5 :.~ ` , . C2 ~5 c2 H5 H ~ ~H3 C~ c2 H3 C(CH3 ~3 H EI CE~3 CH3 C2H~

; Le A 19 240 .., ' .,. ~ , .
... . .
, .
i ~L~3~
. .

' ~: R~ R2 R~R~ Ri~ R~

CH3 CH3 HCH3 H n-C3H7 :
~ :;
CH3 c2 H~ HCH3 H ~-C3 H7 ' C2H~ C2H3 HCH3 H n ~3 ~l7 ~ ' C(CH3)~ H HCH3 ~ ~C3H7 . CH3 CH3 HCH3 CH3 n-C~H7 CH3 C2H~ H:CH CH ~ n-C3H7 C2H~ C2H, HCH3 CH3 n-C3H7 C(CH~)3 H HCH3 CH3 n-C3H7 10 CH~ CH HCH3 H n C~Hg CH3 C2H~ HCH~ H n-C4H~
C2H~ C2H~ H. ~H3 H n~C4H~
;~ C(CHI)~ H ~ HCH3 H ~ ~C4Hs The anilinomethyl oxime ethers~of the formula (II) ..
. 15 have not hitherto been disclosed in the literature.
Compounds of the formula (II)`are obtained when (e) anilines of the general formula .. `' :~

~ , ~ NH2 ~ (X)g :~

~ !,: ~ ~,2 `:~: . in which :. 20 Rl, R2 and R3 have the meanings indicated above, l (a) are reacted with substituted oxime ethers of the general ;'l formula R4 R5 ~ Y-CH-~-N-0-R (V) j7 ~,. .
,',.~.

, . .. .

' ~S~
- Le A 19 240 ~'"

:. .
i -;
:: .

7~86 in which R4, R5, R6 and Y have the meanîngs indicated above~
~3 in the presence of an acid-binding agent and if appropriate . in the presence of a diluent, or :~ 5 (~) are reacted wîth proargyl halides of the general ~r` ~0 rmu:La :~ Y-CH-C-CH (XI), in which ~ R and Y have the meanings indicated above, i:: 10 ln the presence of an acid-bindi.ng agent and if appropriate in the presence of a diluent, the propargyl-anilines fornied~
~ of the general formula :~ R4 R5 R2 H ~XI:[), ~;t,,~' in which Rl~ R2, R3 and R4 have the meanings indicated above, are hydrated in the customary manner and the aniline derivatives formed, of the general formula . R3 R1 R~ CH3 R2 .H 'XIII), : .
.. in which ~
.t~ ~ . 20 Rl, R2, R~ and R4 have the meanings indicated aboveg are reacted with salts of hydroxylamine or deri.vatives thereof of the general formula ; H2N-0-R (VII), ~,;
I,~t ~' ' ~: Le A 19 240 , ,t ' : ' ' :
3, .s, . ` ,,~ ' .
., ~ '7 in which R6 has the meaning indicatéd above~
in the presence of a diluent and in the presence of an acid-binding agent, or 5 (r) are reacted w.ith keto derivatives of the general -~ formula ~ R4 R5 , Y-CH~C=0 (XIV), in which R4, R5 and Y have the meanings indicated above~
lQ in ~he presence of an acid-binding agent and if appropriate ~:
in the presence of a diluent 3 and the substituted aniline ` derivatives formed, of the general formula 1~ ~

N
~ R2 H
:Z~
. in which c;~ 15 Rl, R2, R3, R4 and~R5 have :the meanings indicated above, are reacted with~salts of hydroxylamine or derivatives . ;~
: thereof of the general formula ` : H2N-0-R (VII)~
in which , R6 has the meaning indicated above, in the presence of a diluent and in the presence of an acid-binding agent, or when : (f), provided compounds of the formula ~II) in which R6 does not represent hydrogen are to be obtained~ aniline derivatives~of the general formula ~Ir Cll - C - O )' .;
~ ~ Le A l9 240 '"~':
'' -'' ' ' ' ` : .

-s. : ... . :
',s~

, ~L~3~8 in which Rl, R2~ R3, R4 and R5 have khe meanings indicated above~
s. are reacted with salts Or hydroxylamine iII the pres~nce of~
a diluent and in the presence of` an acid-binding agent, and p the oximes thereby formedg of the general formula N (XVI), i in which Rl~ R2, X3, R4 and R5 have the meanings indicated above~
~:~ are reacted9 in the form of their alkali metal saIts~ wlth dimethyl sulphate or with halides of the formula X - R7 (IX), in which R7 and X have the meanings indicated above, j~`` in the presence of an organic diluent or in the presence of ;-;` an organic-inorganic two-phase system in the presence o~ a ~-; phase transfer catalyst, the alkali metal salts of the il oximes of the formula (XVI) being produced in situ.
j~i 20 The anilines of the formula (X) required as starting `. substances~in the preparation of the anilinomethyl oxime - ethers of the formula (II) are generally ~nown compounds of !'. ' ~ organic chemistry. Examples which may be mentioned are:
,~ aniline, 2-methylaniline, 2-ethylaniline~ 2-isopropyl-aniline~ 2-sec.-butylaniline, 2-tert.--butylaniline, 2,6-dimethylaniline, 2,3-dimethylanillne, 2~5-dimethylaniline, 3,5-dimethylanilineg 2,6~diethylaniline, 2-ethyl-6-methyl-aniline ~ 2,3,4-trlmethylaniline, 2,4,6-trimethylaniline~
~ 2,4,5-trimethylaniline, 2-ethyl-4,6-dimethylaniline, 2~6-r~ 30 diethyl-4-methylaniline, 2,6-diisopropyl-4-methylaniline, t ~ 233,5-trimethylaniline, 2,3,6-trimethylaniline, 2-methyl-z~" ,.
t,~
.. ..
'`'~',';' ..'' j 1 "
Le A 19 240 $:
' ~V : ' ' ' ~ ' ~7Q~6 6-chloroaniline, 2-tert. butyl-6-chloroaniline3 2-mekhoxy-6-methylaniline~ 2,6-dimethoxyaniline, 2-methoxy-6-ethyl-aniline and 2,6-diethQxyaniline.
The substituted oxime e-t~lers Or the formula (V) also required as starting substances in the preparakion of the anilinomethyl oxime ethers Or the formula (II) by process (e)g variant ~a) are known (see, for example~ U.S.
Patent Specification 3~896,189), as are khe propargyl halides of the formula (XI) (see Houben-Weyl~ Methoden der organischen Chemie (Meth~dsof Organic Chemistry)~
~ Volume V/3 and 4) required for proce3s (e) variant (~
; and also the keto derivatives of khe formula (XIV) (see Houben-Weyl3 Methoden der organischen Chemie (Methods of Organic Chemistry), Volume ~II/2 a, b3 c) and the hydroxyl~
amine (derîvatives) of the formula (VII) (see ~ouben-Weyl, Methoden der organischen Chemie (Methods of Organic Chemistry), Volume X/l) required for process (e), variant (y); or the particular compounds can easily be prepared by the processes given in khe likerature sources mentioned.
Any of the customary acid accepkors can be used as acid-binding agents~in the preparation of~khe anilinomekhyl oxime ethers of the formula (II)~by process (e), variants ) and (y)~ An alkalI metal carbonate~ such as potassium carbonate or sodium carbonate~ is preferably `~
25 used. ~ ;
Any of t~e customary inert organic solvents can be ~i employed as diluents in process (e), variants (), (~) and - (y). An aromatic solvent, such as toluene~ or dimethyl-formamide, is preferably used. Preferred solvents in khe ~;~ 30 second stage of process (e), variant (~) are alcohols, ~;~ such as methanol.
~- The reackion temperatures can be varied within a substantial range in process (e), variants (a)~ (~) and (X)-~- In general,~the reaction is carried out between 0C and 180C, preferably between 20 C and 16QC.
"., ~ :
:: .
~ ' ~
: r ~:'i ' ,. : ' .
Le A 19 240 ."::' ~
;
:, .-.
..... ~ ~

-.. i, . ' :
- ~ . , .~ ,. . .

. 113708G
;. - 29 -Equimolar amounts of the react`ants are pre~erably used s in the reaction according to process (e~, variants (~), ) and (y). However, it is also possible to employ one of the components, preferably the aniline of the formula (X), in excess. Working up and isolation of the reaction products are effected by customary methods.
The oximes of the formula (XVI) required as starting ~ substances in carrying out process (f) have not hltherto `~ been described in the literature. However, they can be prepared in a simple manner by process (e)~ variant (y).
The formula (IX) provides a general definition of the halides also required as starting substances in proce~s (r) In this formula, R7 and X preferably have those meanings which are mentioned as preferred in con-;,; 15 nection with the description of process variant (d).
Possible diluents in p~ocess (f) are any of the inert organic solvents. These include, as preferences, ethers~
such as diethyl ether and dioxanj aromatic hydrocarbons, ... .
such as toluene and benzene~ in specific cases also ; 20 chlorinated hydrocarbons, such as chloroform~ methylene chloride and carbon tetrachloride; and hexamethylphosphoric acid triamide.
~;'s~. The reaction temperatures can be varied within a substantial range in carrying out process (f)~ In general9 s;~ 25 the reaction is carried out between 20 and 150C, prefer-ably at roo~ temperature. In speci~ic cases it is advan-tageous to carry out the reaction at the boiling point of the ' ~ solvent, for example between 60 and I00C.
$~ In carrying out process (f), l to 3 moles of halogen ~3 of~the formula (IX) are prererably employed per mole of ;j; al~ali metal salt of an oxime of the formula (XVI).
Working up and isolation of the reaction products are ' ~ effected by customary methods.
In a preferred embodiment of process ~f), the procedure 35 is appropriately to use an axime of the formula (XVI) as . . ~ ,.
~5'~ Le A l9 240 ~ 30 ~
the starting material, to convert the la~ter into the salt by means of an alkali metal hydride or amide in a suitable inert organic solvent and to react the salt ~ immediately, without isolation, with a halide of the forrnula ; 5 (IV), the compounds of the formula (II) being obtained in one operation with elimination o~ an alkali metal halide.
In a further preferred embodiment of process (f)~
; - the preparation o~ the salts of the oximes of the formula ; (XVI) and the reaction are appropriately carried out in a ~; 10 two-phase system, for example aqueous sodium hydroxide solution or potassium hydroxide solution~toluene or methylene chloride, with the addikion of 0.01 - 1 mol of a phase transfer catalyst, for example an ammonium or !' phosphonium compound-.~ 15 The ~ormulae (IIIa) and (IIIb) provide general definitions of the halogenoacetic acid chlorides and ~i ~ bromides ard, respectively, anhydrides also to be used as starting substances for process variant (a). In these formulae, Z preferably represents chlorine, bromine or iodine.
;Y The halogenoacetic acid chlorides and bromides and anhydrides of the formulae (IIIa) and (IIIb) are generally known compounds of organic chemistry. Examples which may ~ 25 be mentioned are: chloroacetyl chloride, bromoacetyl `~ chloride3 iodoacetyl chloride and the corresponding bxomides : . ~
~ and anhydrides.
; ~ The formula (IV) provides a general definition of the halogenoacetanilides required as starting substances in carrying out process variant (b3 according to the invention.
~1 In this formulag Rl, R29 R3 and Z preferably have those ¦ meanings which-have already been mentioned as preferred in connection with the description o~ the substances of the ; ~ormula (I).
~ 35 The halogenoacetanilides of the formula (IV) are ,,:r ~ generally known~ or they can be obtained in a generally ' :.,.': ,, ~', '~ ~` Le A 19 240 ,, ~, ..
,. . . , . . ~ .

.~ . . - . . : .: .
,;,:, . ..
.,,~. ` , . .

`~ : ~ : ' : -' :,.~ - ~:
;:' : '' ~ : , ., ~

. known manner by reacting corresponding anilines with a halogenoacetic acid chloride or bromide or anhydride of , . the formula (IIIa) or ~IIIb) respectively in t~le presence : of an inert organic solvent, for example toluene or `~ 5 dimethylfor~amide, if appropriate i.n the presence of an acid-binding agent, for example potassium carbonate or triethylamineg at temperatures between 0 and 100 C.
~- . Examples which may be mentioned are the chloroacetanilides and bromoacetanilides of the above-mentioned anilines of the formula (X).
he formula (V) provides a general definition of the substituted oxime ethers also to be used as starting substances for process variant (b). In this formula~ R4 R5 and R6 preferably have those meanings wh;.ch have al--~ 15 ready been mentioned as pre~erred in connection with the description of the substances of the formula (I). Y pre-ferably represents chlorine, bromine or the mesylate or ~:~ tosylate radical.
: The substituted oxime ethers of the formula (V) are ~s 20 known (see, for example, U.S. Patent Specification ~ 3,896,1893 or they can be obtained in a generally known .~ manner, by reacting corresponding carbonyl compounds with .~ ; hydroxylamine (or a derivative thereof~ in the presence o~
. a solvent, preferably an alcohol or an aqueous alcohol, at ~: 25 temperatures between 20C and 100C~ preferably between . ~ 50 C and 80 C ~he hydroxylamine (derîvative) is pre-c ferably employed in this process in the form of a salt, in particular as the hydrochloride, if appropriate in the presence of an acid-binding a~ent, for example sodi.um 3 acétate. Isolation of the end products is effected in the customary manner~
The formula (VI) provides a general definition of the N-substituted halogenoacetanilides required as starting ;.~ substances in carrying out process variant (c). In this ~ .35 formula, R , R , R3, R4, R5 and Z preferably have those ~:

~ . Le A 19 240 ~?

"~ ' , '` ~ ', ` ` ` ~

~7~36 ~ .
: - 32 - :
meanings which have already been mentioned as preferred in connection with the descrip~tion of the substances: of the . formula (I).
The N-substituted halogenoacetanilides of the formula (VI) have not hitherto been described in the literature However, they can be prepared in a simple manner by several processes. Thus~ N-substituted halogeno-acetanilides of the formula (VI) are obtained when (g) halogenoacetanilides of the general formula R3 R~ / ~ (IV)~

.~; 10 ~ R2 C - CH2 - Z

;~ O
. in which Rl, R2, R3 and Z have the meaningsindicated above, () are reacted with keto derivatives of the general -~ formula R4 R5 ~: . 15 Y-CH-C=0 (XIV), . in which -. R4, R5 and Y have the meanings indicated above, - in the presence of an acid-binding agent and if appropriate .~.: in the presence of a diluent, or (~) are reacted with propargyl halides of the general !.
'. ~ormula R4.
Y CH-C-CH (XI)~
- ;~. . ~
~ - in which -~ R4 and Y have the meaningsindicated above, ~ . 25 in the presence of an acîd-binding agent and if appropriate ::. in the presence of a diluent 9 and the propargyl halldes ~! formed3 of.the general formula .. `';~ . 1~4 . R~ ~ R1 ~H - C - CH
> - N ~XVII) ~;J~ 2 C--CH2--Z

':~ O
i Le A 19 240 .i, .

~ 33 ~
- in which R~, R2~ R3, R4 and Y have the meanings indicated above, are hydrated in the customary manner, or when (h) aniline derivatives oi the general formula R3 R1 ~ CH - C ~ 0 (XV), H

in which Rl, R2~ R3, R4 and R5 have the~meanings indicated above, are reacted with~known~halogenoacetic acid chlorid?s or bromides of the g~eneral formula Z-CH2-C0-Cl(Br) (IIIa)~
~-~ in which ~ ` Z has~the meaning indicated above, $~ 15 in the presence of a diluent; and~if~appropri~a~te in the ; presence of an acid-binding agent.
The aniline derivatives of th~e~formula~(XV) required as startlng~substances~in the~preparation of the N- ' -substituted halogenoacetanilides~of the ~ormula (V-I) can ~;, 20 be obtained according to the first stage of process ~e), variant (y)~. ~
Any of the customary acid acceptors can be used as . acid-binding~agents in the preparation of the N-substituted ;~
halogenoacetanilide~s of~the formula (VI) by processes (g) and (h). ~An alkali metal carbonate, such as potassium ~? ~ carbonate or sodium ~carbonateg~is preferably used.
Any of the customary inert organic solvents can be~
- - employed~as dlluents;in~pro~cesses (gj~ variants () and (~
~ and (h).~ Aromatic solvents, such as toluene~ or dimethyI--~¢~ ~ 30 formamide is~preferably used.
,,, : ' : :~
~: : ~ ::
~: . ' : ~ , :
,, . , ~.~s '~,. ' ' '''~!`, ' ~ Le A 19 240 " : . - , ': ' , :
:; , : , -. ~37 In a pre~erred ernbodiment, the reaction according to process (h) is carried out in a two-phase system, for example aqueous sodium hydroxide solution or potassium hydroxide solution/toluene or methylene chloride~ if appropriate with the addition of 0,1~1 mol of a phase transfer ca~alys-t, for example an ammonium or phosphonium compound.
The reaction temperatures can be varied within a substantial range in processés (g)3 variants (a) and (~), 10 and (h). In general, the reaction is carried out between - 0C and 180C, pre~erably between 20C and 160C.
Equimolar amounts~of the reactants are preferably used in the reaction according to process (g), variant () and (~)l and process ~h)~. Working up and isolation 15 o~ the reaction products is effected by customary methods.
The fbrmula (VII) provides a gener~l definition of the hydroxylamine tderivativ`es) also to ~be used ~in form of their salts) as starting substances ~or process variant tc) according tQ the invention. In this formula, R6 pre-~' . 20 ferably has those meanings which have already been mentionedA
as preferred in connection with the description of the sub-stances of the formula (I)~. ~The compounds~of~the formula (~II) are preferably~employed in the form of their hydro-; halldes, especially as the hydrochloride.
The formuIa (IX) provldes a general definition of the halides re~uired as starting substances in carrying out process variant (d). In this ~ormula, R7 preferab1y re-presents straight-chain or branched alkyl with 1 to 4 carbon atoms, alkenyl or alkynyl with in either case 2 to 4 30carbon atoms3 alkoxyalkyl or alkylthioalkyl with in each case 1 to 4 carbon atoms in the alkyI part and 1 to 4 carbon atoms in the alkoxy or alkylthio part, dialkylamino-alkyl with 1 to 4 carbon atoms in each alkyl part, halogeno-alkyl with 1 to 2~carbon;atoms and 1 to 5 halogen atoms, 35preferred halogens which may be mentioned being fluorine and chlorineS alkoxycarbonyl~alkyl with 1 to 4 carbon atoms ....
:
~ Le A 19 240 : .
. - ~` ., .

7 ~ ~6 in the alkyl part and l to 4 carbon atoms in the alkoxy part, or optionally substituted aryl or optionally substituted aralkyl with in each case 6 to lO carbon atoms in the aryl part and l to 2 ~arbon atoms in the alkyl part, specific aryl or aralkyl xadicals which may be mentioned being phenyl, naphthyl and benzyl~ and preferred substituents being the substituents for aryl already mentioned as pre-ferred in the case of R5.
The hydroxylamine (derivatives) of the formula (VII) and the halides of the formula (IX) are generally known compounds of organic chemistry.
Preferred diluents for the reaction in process variant (a) are inert organic solvents. These include~ as preferences, ketones, such as diethyl ketone, and in particular acetone and methyl ethyl ketone; nitriles~ such as propionitrile, and in particular acetonitrile; ethers~
such as tetrahydrofuran or dioxan; aliphatic and aromatic hydrocarbons, such as petroleum ether, benzene~ toluene or xylene; halogenated hydroearbons 3 such as methylene chloride~
20 carbon tetrachlorideg chloroform or ehlorobenzene; and ~;~
esters~ such as ethyl acetateO
If appropriate, process variant (a) can be carried out in the presence of an acid-binding agent (hydrogen halide acceptor). Any of the eustomary aeid-binding agents can be usedi these include, as preferences, organic bases, sueh as tertiary amines, for example triethylamine or pyridineg and furthermore inorganic bases~ for example alkali metal hydroxides and alkali metal carbonates.
The reaetion temperatures ean be varied within a substantial range in carrying out process variant (a). In general~ the reaetion is carried out at from 0C to 120C, preferably at from 20 to 100C
In carrying out process variant (a), l to 1.5 moles of halogenoacetylating agent and l to 1.5 moles of acid-binding - 35 agent are preferably employed per mole of the compound of `, ! ~e A l9 240 i .

~:
. . .
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~1370B6 - 36 ~
the formula (II), Isolation of the'compound of the formula (I) is effected in the customary manner.
Preferred diluents for the reaction in process variant (b) are inert organic solvents. These include, as prefer-ences, the solvents already mentioned in the ca~;e of proccssvariant (a).
Preferred acid-binding agents in process variant (b) are the acid acceptors already mentioned in the case of`
process variant (a).
~he reaction temperatures can be varied within a substantial range in carrying out process variant (b), In general~ the reaction is carried out between 0C and 150C, preferably between 20C and 100C.
Equimolar amounts of the reactants are preferably used in carrying out process variant (b). However~ it is also ~; possible to employ one of the reactants in excess. Working - up and isolation of the reaction products are effected by customary methods.
In a preferred embodiment~ the reaction in process (bj is carried out in a two-pha'se system, for example aaueous sodium hydroxide solution~or potassium hydroxide solutioni toIuene or methylene~chloride~l~if appropriate~with the addition of 0.1-1 mol~of a phase transfer catalyst3 for example an ammonium or phosphonium compound; benzyl dodecyldimethyl-ammonium chloride (Zephirol) and triethyl-benzyl-ammo~ium chloride may be mentioned as examples' (see ' also the preparative examples)~
r~ Preferred diluents for the reaction in process variant (c) are alcohols or aqueous~alcohols.
¦ 3Q ' As the compounds o`f the formula (VII) are employed in the form of.their salts, preferably as the hydrochlorides~
in carrying out process (c), the process i5 carried out in the presence of an acid-binding agent. Acid-binding agentsl, I include~ as preferences, alkali metal carbonates and acetates, , 'I' .

he A 19 24 ;
.
~ -~137~6 - 37 - :
The reaction temperatures: can be varied within a substantial range in carrying out process (c). In general~
the reaction is carried out at from 20 to 120C, prefer-ably at from 40 to 100C.
Equimolar amounts of the reactants are preferably used in carrying out process variant (c). However~ it is also possible to employ one of the reactants in excess.
Working up and isolation of the reaction products are effected by customary methods.
Possible dlluents for the reaction in process variant (d) are any of the inert organic solvents. These include~
as preferences, ethers, such as diethyl ether and dioxan;
aromatic hydrocarbons, such as toluene and benzene, in specific cases also chlorinated hydrocarbons~ such as 15 chloroform, methylene chloride and carbon tetrachloride; ;
~- and hexamethylphosphoric acid triamide.
The reaction temperatures can be varied within a substantial range in carrying out process variant (d).
In general, the reactrion is carried out at from 20 to `~ 20 150C~ preferably at room temperatureO In specific cases j it is advantageous to carry o~t the reaction at the boiling point of the solvent; for example from 60 to 100C.
In carrying out process variant (d), 1 to 3 moles of -~ - halide of the~formula (IX) are preferably employed per mole of alkali metal salt of an oxime of the formula (VIII).
orking up and isolation of the reaction products are - effected by customary methods.
In a preferred embodiment of process variant (d)~ the ; appropriate procedure is to use an oxime of the formula 3 (VIII) as the starting material, to convert the latter into the salt by meQns of an alkali metal hydride or amide in a suitable inert organic solvent, and to react the salt ~- immediately, without isolation, with a halide of the formula ~IV~, the compounds of the formula (I) being obtained in one i~ 35 operation with elimination of an alkali metal halide.
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~37~6 In a further preferred er,bodiment of process variant (d)~ the preparation of the salts of the oximes of the formula ('~rIII) and the reaction according to the invention are appropriately carried out in a two-phase system~ for example aqueous sodium hydroxide solution or potassium hydroxide solution/toluene or methylene chloride, with the addition . of 0.01 - 1 mol of a phase transfer catalyst, ~or example an ammonium or phosphonium compound.
The active compounds according to the in~ention influence plant growth and can therefore be used as defoliants, desiccants, agents for destroying broad-leaved plants, germination inhibitors and~ espec;.ally, as weed-killersO By "weeds" in the broadest sense there are meant pl:ants growing in places where they are not desired.
- Whether the compounds according to the invention ''~ act as total herbicides or selective herbicides depencls ~: essentially on the amount:used.
' The active compounds according to the present in-; 20 vention may be used~ for example~ to combat the following~:; plants:
.
dicotyledon weeds of the genera Slnapis, Lep~ldium, Gallum, Stellaria3 ~la~trIcar1ag Anthemis, Gallnsoea, -':
~: ' ' Cheno~odium, Urtica, Senecio,'A~ar'anthus, Portulaca, : 25 Xanthium, Convolvulus, Ipomoea~ Poly~onum, Sesbania, ~: Ambrosia,~Cirsium, Carduus, Sonchus, Rorippa,'Rotalag Lindernia~ Lamium, Veronica, Abutilon, Emexg Datura~
Viola, Galeopsis, Papaver,~ Centaurea an~ Solanum; and monocotyledon weeds of tl~e ~enera ISchinocl~lo~
; 30 Setaria, Panicu_~ ~ , Phleum, Poa, Festuca~
Eleusine,:Brachi~ria, Lolium~ Bromus, Avena3''~ erus, Sorghum, Agropyron, Cy~odon, Monochori~,'Fimb'riSt'yl'iS~
___ _____ Sagittaria~ Eleocharis, Scirpus 9' PaspaIum,~ Is aemum~ ..
: Sphenoclea, Dacty~octeniumg Agrostis, Alop'e'curus and : 35 ''~pera ,'' :

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~ 39 -The active compounds according to the pres'ent invention may be used, for example,~ as selective herbicides in the following cultures:
dicotyledon cultures of the genera'~Gos'syplum, Glycine, Beta, _aucus, Ph~seolus,'Pi's'um,''S'o'lan'um,''I;i'n'um, Ipomoea, Vicia, ~icotiana,'Ly'c'o'p'e'~s'i'con,''~'r'ac'h'iS, Brassica~'Lact'uca,' Cucu~is and Cucurbita; and monocotyledon cultures of the genera''O'ryza,''Zea, 1.
Triticum, Hordeum, Avena,'Secale,''S'orghum,''Pani'cum~
Saccharum~ A~a~as, ~ and Allium.
However, the use of the active compounds according to the invention is in no way restricted to these ~enera but also embraces other plants, in the same way.
Depending on the concentrations, the compounds can be used for the total combating of weeds, for example on industrial terrain and railway tracks and on paths and squares with or without trees. Equally, the compounds can be employed for combating weeds in perennial cultures, ~or example afforestations, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards~ banana ~- '' plantations, coffee plantations, tea plàntations, rubber plantations~ oil palm plantations, cacao plantations, soft fruit plantings and hopfields, and for the selective ~ combating of weeds in annual cultures.
I 25 In addition to a very good action against graminaceous weeds and against''Cype'rus varieties~ the active compounds according to the invention also display a good herblcidal ; action in the case of broad-leaved weeds. It is possible tlo use the active compounds according to the invention selectively, preferably in cereals~ cotton and su~ar beet, or also in oth~r crops.
The active compounds can be converted into the custom-ary formulations, such as solutions, emulsions, wettable powders, suspensions~ powders, dusting agents, pastes~ ' 135 soluble powders, granules, suspension-emulsion concentrates~
'1natural and synthetic materials impregnated with active com-.

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pound, and very fine capsules in polymeric substances.
These formulations are produced in known manner~ for example by.mixing the active compounds with extenders~ that is, liquid solvents and/or solid carriers~ optionally with the use of surface-active agents, that is to ~ay emulsifying agents and/or dispersing agents and/or ~oam-forming agents.
In the case of the use Or water as an extender~ orgallic solvents can, for example, also be used as auxiliary solvents.
~` 10 As liquid dlluents or carriers~ especially solvents, there are suitable in the main, aromatic hydrocarbons 3 such as xylene, toluene or alkyl naphthalenes, chlorinated~
aromatic or chlorinated aliphatic hydrocarbons~ such as ... chlorobenzenes, chloroethylenes or methylene chloride~
aliphatic or alicyclic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols~
such as butanol or glycol as well as their ethers and : esters3 ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, or strongly polar solvents, such as dimethylformamide and dimethylsulphoxide, as well as water. .
As solid carriers there may be used ground natural minerals, such as:kaolins, clays, talc, chal.k, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly-dispersed silicic acid, alumina:and si.licates. As solid carriers for granules there may be used crushed and fractionated natural rock.s . such as calcite~ marble, pumice, sepiolite and dolomite, ~`~ as well as~synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust3 coconut shells, maize cobs and tobacco stalks.
As emulsifying andlor foam-forming agents there may be used non-ionic and anionic emulsifiers 3 such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycol ethers~

: l .
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alkyl sulphonates', alkyl sulphates, aryl sulphonates as well as albumin hydrolysis products. Dispersin~ agents include, for example, lignin sulphite waste liquors and methylcellulose.
Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granule~
or laticesg such as gum arabic, polyvinyl alcohol and polyvinyl acetate, can be used in the formulations.
It is possible to use colorants such as inorganic pigments, for exam.ple iron oxide, titanium oxide and Prussian Blue~ and organic dyestuffs~ such as alizarin dyestuffs, azo dyestuffs or metal phthalocyanine dyestuffs~
and trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain from 0.1 to 95 per cent by weight of active compound, preferably from 0.5 to 90 per cent by weight.
The active compounds a'ccording to the invention9 as ' such or in the form of their formulations, can also be used for combating weeds as mixtures with othe~ herbicides~
finished formulations or tank mixing being possible.
Mixtures with other active compoundsg such as fungicides~
insecticides, acaricides~, nematicides, bird~repellants, growth factors~ plant nutrients and agents which improve ~; 25 soil struc~ure, are also possible.
The ac.tive compounds can be used as such3 in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solu-tions, suspensions, emulsions, powders, pastes arld ~ranules.
3 They may be used in the customary manner~ for example by watering, spraying, atomising or scattering.
The active compounds according to the invention can be applied either before or after emergence of the plants.
They are preferably applied before emergence of the plants, that is to say by the pre-emergence ~ethod. They can ; ~:

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also be incorporated into the soi1 be;fore sowing.
The amount of active compound used can vary ~rithin a substantial range. It depends essentially on the nature of the desired effect. In general, the amounts used are from 0.1 to 10 kg of active compound per hectare9 preferably from 0.1 to 5 kg/ha.
When used in accordance with the post-emergence method, the active compounds according to the invention exhibit growth-regulating properties.
The present invention also provides a herbicidal composition containing as active ingredient a compound of the present invention in admixture~with a solid diluent - or carrier or in admixture with a liquid diluent or carrier -~
containing a surface active agent.
The present invention also provides a method of combating weeds which comprises applying to the weeds 3 or to a habitat thereof, a compound of the present invention alone or in the form of a composition containing as active ingredient; a compound of the present invention in admixture ; 20 with a diluent or carrier.
The present invention further provides crops protecte~
from damage by weeds by being~grown in areas in which immediately prior to and/or during the time~of the growing - ~ ~ a compound of the present invention was applied alone or in admixture with a diluent or carrier.
. It will be seen that the usual methods of providing a harvested crop may be improved by the present invention.
The herbicidal activity of the compounds of this invention is illustrated by the following biotest Example.
~ In this Example, the compounds according to the - present invention are each identified by the number ~given in brackets) of the corresponding preparative Example~
which will be found later in this specification.
The known comparison compound is identified as follows:
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(A)= ~ - N / 2 0 - CH3 CpH, C - C~2Cl .. ...
2,6-Diethyl-N-methoxymethyl-chloroacetanilide.
Examp'le A
Pre-emergence test Solvent: 5 parts by weight of acetone EmulsifierO 1 part by weigh't of alkylaryl polyglycol ether To produce a suitable preparation of acti~e compound, 1 part by weight of active compound was mixed with the stated amount of solvent, the stated amount of emulsifier was added and the concentrate was diluted with water to the desired concentration.
Seeds of the test plant:s were sown in normal soil and, after 24 hours, watered with the preparation of the ; 15 active compoundO It was expedient to keep constant the ; amount of water per unit area. m e concentration of the active compound in the preparation was of no importance, '~
only the amount of active compound applied per unit area being decisive. After three weeks, the degree of damage to the plants was determined in % damage in comparison to the deveiopment of the untreated controlO 'rhe figures denoted:
0% = no action (like untreated control) 100% = total destruction In this test~ the active compound (1) showed a better ;
selective activity than the substance (A) known from the ;-prior art.
' 'Læ`~=~
~- Example 1 CH3 ~0 ~ / CH2 - ; N - 0~l Le A 19 240 :, ~ . : . - - , , . . - ~ , - . . , ~ ' : ~ - :-- .

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~ 70 - l14 -Process variant (c) A mixture of 14.1 g (0.05 mol) of 2,6-diethyl-N-(2'-oxo)-propyl-chloroacetanilide, 4.2 g (0.05 mol) of O~methyl-hydroxylammonium chloride and 7 g (0 05 mol) of powdered potassium carbonate was stirred at 20C for 24 hours.
T~lereafter~ t~e reaction mixture was concen~rated by d;.s-tilling off the solvent in vacuo The residue was partitioned between water ~nd methylene chloride and the~
organic phase was separated off, dried over sodium sulphate and concen~r-ated. The crystalline residue was recrystallised from petroleum ether at -10C. 8.5 g (56% of theory) of 2,6-diethyl-N-(2 t -methoxyimino)-propyl-chloroacetanilide of melting point 56-57C were obtained.
Preparation of the precursors ~ .
; 15 (VI-l) .. O
C2H~ ~' C2H ~ - CH2Cl '~ O

Process (g), variant (~) ~
39.5 g (0.15 mol) of 2,6-diethyl-N-propargyl-chloroacetanilide~were introduced in portions into 85%
-~ 20 strength formic acid at 80C. After stirring the reaction ~ mixture at 80C for two hours, it was poured onto saturated - ammonium sulphate solution and extracted with ether and the product phase was neutralised with sodium carbonate. After drylng over sodium sulphate, the product phase was concen-trated in ~vacuo and the residue was made to crystallise by~ trituration w~ith petroleum ether. 35.7 g (85% of theory) of 2,6-diethyl-N-(2'-oxo)-propyl-chloroacetanilide of melting point 65-67C were obtained.

N~ 2 _ CH

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112.7 g (0.5 mol) of 2,6~diethyl-chIoroacetanilide were stirred at high speed in a two phase mixture of 500 ml of methylene chloride and 250 ml of 50% strength sodium hydroxide solution/water, after adding 1.5 g of triethyl-benzyla~monium chloride (TEBA), and 59.5 g (0.5 mol) ofpropargyl bromide were added dropwise at 25-35C. The ~i mix~ure was stirred at 20C for a further four hours and the organic phase was separated off~ washed several times with water, dried over sodium sulphate and concentrated in vacuo.
The residue was recrystallised from isopropanol. 67.8 g (51.5% of theory) of 2,6-diethyl-N-propargyl-chloroacetanil-ide of melting point 57-58C were obtained.
.. ~ ~
f C~3 CH2 - CH = N - OCH3 - N~ (2) CH3 C - CH2Cl O
Process variant (a) 6 g (0.03 mol) of 2,6-dimethyl-N-(2'-methoxyimino-ethyl)-aniline and 2.8 g (0 0~5 mol) of pyridine were heated to the boil in 80 ml of anhydrous tetrahydrofuran~ and 4 g (0.035 mol) of chloroacetyl chloride were added. After heating the reaction mixture under reflux for 15 minutes, it was cooled and concentrated in vacuo. The residue was .... .
partitioned between water and methylene chloride and the organic phase was separated off, dried over sodium sulphate and concentrated. After treatment with petroleum ether~
the oily r~sidue crystallised. 4.8 g (60% of theory) Or 2,6-dimethyl-N-(2'-methoxyimino-ethyl)-chloroacetanilide of meltin~ poink 56-58C were obkained ' ~ ~ ~'.
(II-l) .: `

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Process (e), variant '(a) 48.4 g (0.4 mol) of 2,6-dimethylaniline and 27.6 g (0.2 mol~ of f`inely powdered potassium carbonate were heated to 100C in 80 ml of dimethylformamide, whilst stirring~ an~
5 21.5 g (0.2 mol) of chloroacetaldehyde oxime 0-methyl ether were added dropwise. After stirring the mixture at 100C
for 3 hours, the inorganic salt was fil.tered off. 250 ml of methylene chloride were added to the filtrate~ the mix-ture was extracted several times by shaking with water and the product phase was dried over sodium sulphate and concen-trated in vacuo. The residue was distilled. 14.2 g (37%
___ _._ : o~ theory) of 2j6-dimethyl-N-(2'-methoxy-imino-ethyl)--aniline of boiling point 105 110C/0.1 mm Hg and of refrac-~
tive index nD: 1.537 were obtained.
x`amp'le 3 .,' '~ ~
~ , CH2; c F N OCH3 (3) CH3 IC - CH2Cl :
Process variant (a) 13.4 g (0.05 mol) of a-(2,6-dimethylphenylamino)- ..
acetophenone oxime 0-methyl;ether were dissolved in 200 ml - 20 of toluene, 4 ml (0.04 mol) of chloroacetyl chloride were '~ added and t~e mixture was heated under reflux for 6 hours until the evolution of gas had ended. The mixture was allowed to cool and was concentrated by distilling off the so]vent in 'vacuoO The residue was purified by chromatography. 3.1 g (18% of theory) of a-[(2,6-dimethylphenyl)-N-chloro-acetyl-'' amino]-acetophenone oxime 0-methyl ether of melting point 80C were obtained.
Prep-aration of the~pre'curs'ors .' (II-2) ~ .

3 ~ ~ N ~ :

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Process (f) 31.2 g (0.11 mol) of ~-(2,6-dimethylphenylamino)-acetophenone oxime hydrochloride and o~6 g (0.176 mol) of benzyldimethylammonium chloride were dissolvec1 in 110 ml of methylene chloride and, after adding 110 ml of concentrate,d sodium hydroxide solution and 6.9 g (0.055 mol) of dimethyi-sulphate, the mixture was stirred at 20C for 6 days.
After pouring t~e mixture onto ice, the organic phase was separated off, washed with water, dried over sodium sulphate and evaporated. 25.7 g (87% of theory) of ~-(2,6-dimethyl-phenylamino)-acetophenone oxime 0-methyl ether of refractive index nD : 1.5877 were obtained.
(II-3) - ~

CH3 ~ CH2 - C - N - OH
N
CH3 ~ x HCl 15 Process (e), variant (y~ ;
59.7 g (0.3 mol) of phenacyl bromide (for the preparation, compare Org. Syntheses Volume II3 page 480) and 7}.2 g (o.6 mol) of 2,6-dimethylaniline were heated to 80C in 100 ml of ethyl alcohol for 10 minutes and the mix-ture was then concentrated in vacuo. The residue was taken up in toluene and the mixture was filtered. The filtrate was diluted with ethyl alcohol3 and 20.8 g (0.165 mol) of hydroxylammonium chloride and 22.6 g (0.165 mol) of powdered . potassium carbonate were added. After stirring the mixture at room temperature for 20 hours, it was filtered and the filtrate was concentrated. The residue was made to crystal-- lise by tritur~ation with a little ethyl alcohol. 33.9 g (40% of theory) of ~-(2,6-dimethylphenylamino)-acetophenone oxime hydrochloride of melting point 200C were obtained.
The compounds of the formula (I) listed in Table 1 below were obtained by one or more of the processes described in the foregoing description and analogously to Examples 1 to 3.

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R3 R1F~4 R5 ( I ) ~ ~ CH - C = N - 0 - R6 ~ R Q ;:
Me1tin g~
Example R.1 R2 R3 R~ R5 R6 Z point (' C) No . or re frac~
t ive inde x

4 CH3 CH3 H H CH3 C~13 Cl 61 75 CH3 C2 H5 H H c~3 CH~ Cl 5~
6 CH3 CH3 H H CH3 C2 H~ Cl 70--82 7 C2 Hg CH, H H CH3 C2 H5 Cl 62 8 C2 H5 C2 H~; H H CH3 n-C4 H9 Cl nD 13 520 9 CH3 ~ C~ HS H H : CH3 n-C4 Hg Cl nD :1~ 523 10 C2 Hg C2 H, H H H CH3 C1 49-50 11 CH3 C2 H~ H ~ H ~ ~ H ~ ~ CH3 : Cl nD :1, 541 , 12 C2H!~ C2H~ H H~ H ~ C2Hs Cl: 51Ydg 13 ~CH3 C2H~ H H ;: H C2H5 ~ Cl nD:1~5336 14 C2 Hs C2 H5 H H:: CH3 H Cl 139~ 40 15 CH3 . CzHs H H c~3 H Cl 111-13 16 C2H5 C2H~ EI H H n-C4Hg Cl nD3:1~521 ~: :

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T a b l e 1 (continued) Example ~ 2 R3 ~ F.5 R6 M lt ~ngO
or ref rac~
-t ive index -- ;

17 CH3 Cl ~LI E! C~3 Ci~3 Cl 77_78 `
-: 18 H CH3 H H C~3 CH3 Cl nD=1,5402 19 H C (C~3) 3 H H C:~3 CH3 Cl 95-101 ~0 CH3 CH3 H H CH3 C3H7 Cl cryd ?1 CH3 H 3-CEI H C~3 CH3 C1 48-52 ' 2 C~,Ei C2H5 H 3 H Ci3 C~H5 Cl n~, =1,5282 23 c.~3 2 ~ }~ C'I3 C3~7 Cl nD =1,5276 2~ CH3. CH3: :H H CH3 H Cl 123-12 C;i3 CE~3 1l ~ CE13 Crl3 CH3 ~Cl n~ =1 J 5388 ~, C~-!3 CH :E~ C-~3 ~ Ci~3 Cl. n~ =1,5333 :
27 CH3 CH3 H ~ H C2H5 Cl n~ =1,5369 :~ 23 C- 3 C2 5 ~ ~ 3 Cil3 CH3 Cl n~ -1,5298 2 5 ~ C2H5 ~ H rl C~3 ~ C3~I7 Cl n =1 52~2 C2H5 C2H5 ~ 3 CH3 CH3 Cl n~? =1,5300 CH3~ C~3 ~ H ~ ~ ~ H C3H7 Cl n~0-1,531_ ~; ~ 32 ; CH3 C2H5 H ~ ~ ; H ; H ~ C3~7 Cl n~ =1,5155 33 C2 5 2 5 ~ H C3H7 Cl rl~O 1,52 9 3~ CH3 . CH3 H 3 C2'H5 Cl nD =1 ~53~8 ~: 3~ CH3 C2H5 C13 H CH3 Cl crystal 36 CH3 ~C2H5~ ~ ~H C 3 C2~5 Cl n~ =1 /s2go 37 C 2 H 5 2 5 ~ C ~ 3 ~ C 2 H ~ C l n ~ 273 38 CE~3 ~13 C~3 CLi.3 C2~I5 Cl nD0 1,5-2539 CH3 C2~ 5 H CH3 C~ 3 2 5 ~0 CH3 C~3 Ei C2 5 Ei C~3 Cl r.~ =1,5372 '_1 CH3 ~CH3 ~ ~ CT~3 C~Hg Cl nD =1,5299 The starting materials of the formula (II) in Table 2 : ::
.` ~ below were obtained by one or more of the pro~esses described ~`~ 30 in the foregolng description, and analogously to Examples 2 and 3.

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CH - C = N - o - D6 ( II ) '' ~2 Bgiling point Example : ( C)/mm Hg or No. R1 R2 R3 R~ R5 R6 nD ~ .

~ 4) C2H3 CH3 H H H CH3 120-25/0~1 :~ 1,531 (II-5) C2H~ C2Hs H ~ H H CH3 112-17/OD1 .

6) CH3 C2H5 H~ H; H ~ C2H5 I20-21/0~1

7~ C2HS C2Hs H ;H H~ C2H5 13552~45/gl ' (II~83 C2H5 : C2H~ H~ H ~ H~ n-Cs~H9 120-35/0~

The startlng~materlals of the formula (VI) in Table 3 : 10 below were obtained by ~one~ or more of the proce~ses described in the foregoing description, and analo;gously to Example 1.
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Claims (17)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. Oxime ethers of the general formula (I) in which R1 represents hydrogen or straight-chain or branched alkyl or alkoxy with in either case 1 to 4 carbon atoms, R2 and R3 are identical or different and each represent hydrogen, straight-chain or branched alkyl or alkoxy with in either case 1 to 4 carbon atoms, fluorine, chlorine or bromine, R4 represents hydrogen or straight-chain or branched alkyl with 1 to 4 carbon atoms, R5 represents hydrogen, straight-chain or branched alkyl with 1 to 4 carbon atoms or optionally substituted aryl with 6 to 10 carbon atoms, the optional substituent(s) being selected from halogen, straight-chain or branched alkyl with 1 to 4 carbon atoms, halogenoalkyl with 1 to 2 carbon atoms and 2 to 5 halogen atoms, alkoxy and alkylthio with in either case 1 or 2 carbon atoms, cyano and nitro, and R6 represents hydrogen, straight-chain or branched alkyl with 1 to 4 carbon atoms, alkenyl or alkynyl with in each case 2 to 4 carbon atoms, alkoxyalkyl with 1 to 4 carbon atoms in the alkyl part and 1 to 4 carbon atoms in the alkoxy part, alkylthioalkyl with 1 to 4 carbon atoms in the alkyl part and 1 to 4 carbon atoms in the alkylthio part, dialkylaminoalkyl with 1 to 4 carbon atoms in each alkyl part, halogenoalkyl with 1 to 2 carbon atoms and 1 to 5 halogen atoms, alkoxycarbonylalkyl with to 4 carbon atoms in the alkyl part and 1 to 4 carbon atoms in the alkoxy part, optionally substituted aryl with 6 to 10 carbon atoms or optionally substituted aralkyl with 6 to 10 carbon atoms in the aryl part and 1 to 2 carbon atoms in the alkyl part, the optional substituent(s) in either case being selected from halogen, straight-chain or branched alkyl with 1 to 4 carbon atoms, halogenoalkyl with 1 to 2 carbon atoms and 2 to 5 halogen atoms, alkoxy and alkylthio with in either case 1 or 2 carbon atoms, cyano and nitro, or R5 and R6 together represent a two-membered to four-membered alkylene group, and Z represents chlorine, bromine or iodine.

2. Compounds according to claim 1 wherein R1 represents methyl or ethyl, R2 represents methyl or ethyl, R3 represents hydrogen, R4 represents hydrogen, R5 represents hydrogen or methyl, R6 represents alkyl with 1 to 4 carbon atoms, and Z represents chlorine.

3. 2,6-Diethyl-N-(2'-methoxyimino-propyl)-chloroacetanilide of the formula

4. 2,6-Dimethyl-N-(2'-methoyimino-ethyl)-chloroacetanilide of the formula

5. 2,6-Dimethyl-N-(2'-methoxyimino-propyl)-chloroacetanilide of the formula

6. 2,6-Diethyl-N-(2'-n-butoxyimino-propyl)-chloroacetanilide of the formula

7. 2,6-Diethyl-N-(2'-n-butoxyimino-ethyl)-chloroacetanilide of the formula

8. A process for the preparation of an oxime ether according to claim 1, characterised in that (a) an anilinomethyl oxime ether of the general formula (II), in which R1, R2, R3, R4, R5 and R6 have the meanings indicated in claim 1, is reacted with a halogenoacetic acid chloride or bromide or anhydride of the general formula (IIIa) or (IIIb), in which Z has the meaning indicated in claim 1, in the presence of a diluent, or (b) a halogenoacetanilide of the general formula (IV), in which R1, R2, R3 and Z have the meanings indicated in claim 1, is reacted with a substituted oxime ether of the general formula (V), in which R4, R5 and R6 have the meanings indicated in claim 1 and Y represents halogen or the mesylate or tosylate radical, in the presence of an acid-binding agent, or (c) an N-substituted halogenoacetanilide of the general formula (VI), in which R1, R2, R3, R4, R5 and Z have the meanings indicated in claim 1 above, is reacted with a salt of hydroxylamine or a derivative thereof of the general formula H2N-O-R6 (VII), in which R6 has the meaning indicated in claim 1, in the presence of a diluent and in the presence of an acid-binding agent, or (d) an alkali metal salt of an oxime of the general formula (VIII), in which R1, R2, R3, R4, R5 and Z have the meanings indicated in claim 1, is reacted with a halide of the general formula X-R7 (IX), in which R7 has any of the meanings defined for R6 other than a hydrogen atom, and X represents chlorine or bromine, in the presence of an organic diluent or in the presence of an organic-inorganic two-phase system in the presence of a phase transfer catalyst, the alkali metal salt of the oxime of the formula (VIII} being produced in situ.

9. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a compound according to claim 1.

10. A method according to claim 9 wherein the compound is applied in the form of a composition containing said compound as active ingredient in admixture with a suitable diluent or carrier.

11. A method according to claim 9 in which the compound is applied to an area of agriculture in an amount of 0.1 to 10 kg per hectare.

12. A method according to claim 9 in which the compound is applied to an area of agriculture in an amount of 0.1 to 5 kg per hectare.

13. A method according to claim 9 or 12 wherein the compound is the compound according to claim 3.

14. A method according to claim 9 or 12 wherein the compound is the compound according to claim 4.

15. A method according to claim 9 or 12 wherein the compound is the compound according to claim 5.

16. A method according to claim 9 or 12 wherein the compound is the compound according to claim 6.

17. A method according to claim 9 or 12 wherein the compound is the compound according to claim 7.