Note: Descriptions are shown in the official language in which they were submitted.
~L2852~
The present invention relates to certain new N-(1,3-
azolyl)-alkyl-halogenoacetanilides, to a process for their
preparation and to their use as herbicides.
It has already been disclosed that 2,6-diethyl-N-methoxy-
methyl-chloroacetanilide can be used for selectively combating
weeds (see R. Wegler, Chemie der Pflanzenschutz- und
Il ll
Schadlingsbekampfungsmittel (Chemistry of Plant Protection Agents
and Agents for Combating Pests), volume 5, page 255, Springer-
Verlag (1977)). However, this compound is not always sufficiently
active and its selectivity is not always completely satisfactory.
The present invention now provides, as new compounds,
the N-~1,3-azolyl)alkyl-halogenoacetanilides of the general
f ormul~ CN ~
R2 1 ~ CH2 - z (I)
in which
A represents oxygen or sulphur
Rl represents hydrogen, alkyl or alkoxy,
R represents hydrogen, alkyl, al]coxy or halogen,
R3 represents hydrogen, alkyl, alkoxy or halogen,
R4 represents hydrogen or alkyl,
X represents hydrogen, alkyl, halogen, alkoxy,
alkylthio, halogenoalkyl, alkoxycarbonyl, dialkyl-
amino or cyano,
;
8524
X represents hydrogen, alkyl, halogen, alkoxy,
alkylthio, halogenoalkyl, alkoxycarbonyl, dialkyl-
amino or cyano, and
Z represents halogen,
and the azolyl radical is bonded via a carbon atom, and
acid addition salts and métal salt complexe.~, thereof.
The N-(1,3-azolyl)alkyl-halogenoacetanilides of the formula
(I) and acid addition salts and metal salt complexes thereof have
powerful herbicidal properties, in particular selective herbicidal
properties.
Preferably, in formula (I)1
Rl represents hydrogen or straight-chain or branched alkyl
or alkoxy with in either case 1 to 4 carbon atoms,
R2 and R3, which are identical or dierent, each represent
hydroyen~ straight-chain or branched alkyl or alkoxy with in either
case 1 to 4 carbon atoms, fluorine, chlorine or bromine,
R4 represents hydrogen or alkyl with 1 to 4 carbon atoms,
xl and X2, which are identical or different, each represent
hydrogen, straight-chain or branched alkyl with 1 to 4 carbon atoms,
straight-cha.in or branched alkoxy with 1 to 4 carbon atoms,
straight-chain or branched alkylthio with 1 to 4 carbon atoms,
alkoxycarbonyl with 1 to 4 carbon atoms in the alkoxy group,
fluorine, chlorine, bromine, halogenoalkyl with up to 2 carbon
atoms and up to 5 identical or diferent halogen atoms (preferred
halogens being fluorine, chlorine and bromine), dialkylamino with
1 to 4 carbon atoms in each alkyl part or cyano, and
Z represents chlorine, bromine or iodine.
.~,
:
'
i~L2~3~Z9L
The invention also provides a process for the preparation
of an N-(1,3-azolyl)-alkyl-halogenoacetanilide of the formula (I),
or an acid additio.n salt or metal salt complex thereof, in which
(a) an N-(1,3-azolyl)alkyl-aniline of the general formula
X
H (II),
R
in which
A, R , R , R , R , X and X have the meanings stated above,
is reacted with a halogenoacetic acid chloride or bromide or
anhydride of the general formula
Z-CH2-CO-Cl~Br) (IIIa)
and
(Z-cH2-c)2 (IIIb),
in which
Z has the meaning stated above,
in tne presence of a diluent and if appropriate in the presence of
an acid binding agent, or
(b) a halogenoacetanilide of the general formula
R3 ~ \ C - C}l2 - Z ~IV),
in which
Rl, R2, R3 and Z have the meanings stated abov~,
is reacted with an azolyl-alkyl derivative of the general formula
--3--
.
~, ' , ~ '
.
:,
1~852~
L. ~
- 4 -
Y - CH ~ (V),
in which
A, R4, Xl and x2 have the meanings stated above
and
Y represents halogen or the mesy:Late or tosylate
radical,
in the presence of an acid-binding agent and if appropriate
in the presence of an organic solvent, and
an acid or a metal salt is then optionally added
10 onto the compound (I) produced in either variant (a) or (b).
Surprisingly, the posslbilities of using the N-(1,3-
azolyl)alkyl-halogenoacetanilides according to the invention,
which ha~e a very good herbicidal action, as agents for
selectively combating weeds in important crop plants are
15 better than those of using 2,6-diethyl-N-methoxymethyl-
chloroacetanilide, which is known from the state of the art
and is an active compound of high activity and the same type
of action. The substances according to the invention
thus represent a valuable enrichment of the art.
Particularly preferred N-(1,3-azoIyl)alkyl-halogeno-
acetanilides of the formula (I) are those in which A
represents oxygen, sulphur or the grouping ~NR, R representing
methyl, ethyl, propyl or butyl; Rl represents hydrogen,
methyl, ethyl, isopropyl, sec.-butyl, tert.-butyl, methoxy,
; 25 ethoxy or isopropoxy; R and R3, which are identical or
different, each represent hydrogen, methyl, ethyl, isopropyl,
sec.-butyl~ tert.-butyl, methoxy, ethoxy, isopropoxy,
chlorine or bromine; R4 represents hydrogen or methyl;
xl and X2, which are identical or different, each represent
30 hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl,
sec.-butyl, tert.-butyl, methoxyl ethoxy, isopropoxy, methyl-
thio, ethylthio, isopropylthio, methoxycarbonyl, ethoxy-
:
Le A 19 123
~' ~ . . .
.: .
- . . . .
. ' . . . ' : ~.:
. ~, .
. , .
~1~8~;2
carbonyl, chlorine, bromine, chIoromethyl, bromomethyl,
dichloromethyl, trichloromethyl, trifluoromethyl, dimethyl-
amino, ethylmethylamino, cyano, phenyl which is optionally
substituted by chlorine and/or methyl, phenoxy which is
optionally substituted by chlorine and/or methyl, or
phenylthio which is optionally substituted by chlorine
and/or methyl; 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:
CX ~X~
C - CH2 - Cl (Br )
o
~ ~ '
CH3 CH3 H H H H
C2Hs CH3 H H H H
C2H, C2 H, H H H H
C(CH3)~ H H H H H
CH3 CH~ H CH~ H H
C2H~ CH~ H CH~ H H
C2H5 C2H, H CH~ H H
C(CH~)~ H H CH~ H H
CH~ H 3-CH3 H H H
3 5-CH3 H
CH Cl H H H H
Le A l9 123
1~8
- 6 --
R R2 R3 R4 X1 X2
C(C~3)3 Cl H H H B
CH3 CHI 3-CH~ H H H
OCH~ CH~, H H H H
OCH3 OCH3 H H H H
OCH3 Cz H!s H H H H
CH3 CH~ H H H CH3
C2 H3 CH.~ H H H CH3
H, C2~ H H H CH~
C(CH3 )~ H H H H CH~
CH~ CH~ H CH3 H CH~
C2 H~ CH3 H CH3 H CH~
C2 H~ C2 H, H CH~ H CH~
C(CHI )~ H H CH3 H CH3
CH3 H 3-CH3 H H CH~s
CH3 H 5-CH3 H H c~3
C~3 CI H H H C!H3 '~
C(CH3 )3 Cl H H H CH~
CH3 CH3 3-CH3 H H C~3
OCH3 CH3 H H H CH~
OCH3 OCH3 H H H CH3
OCH3 C2 H~ H H H CH3
CH~ CH3 H H H C2 H~ !
Cz H~ CH~ H H H C2 Hs
C2 ~ C2 H, H H H C2 H3
C~ Br H H H H
CH(CH~)2 CH~ H H H H . ~ -
'i .
I
Le A l9 123
:
8524
R R2 R3 R~ Xl X2
CH~ CH~ H H H CO2CH3
C2 H~ CH3 H H H CO2 CH3
C2 H, C2 H~ H H H COpCH3
CH3 CH3 H H H CO2C2 Hs
C2 Hs CH3 H H H CO2C2 Hs
Cz H~ C2 H5 H H H CO2Cz Hs
CH3 CH3 H H H Cl, Hg
C2H, CH~ H H H C4 Hs
C2 H5 C2H3 H H H C~Hg
CH3 CH3 H H H C3 H?
C2 H5 CH3 H H H C3 H7
Cz H5 C2H5 H H H C3 H7
CH3 CH3 H H H
C2 ~ CH3 H H H
C2 H~ C2 H~ H H H
CH3 CH3 H H Cl CH~
C2H5 CH3 H H Cl CH3
C2H~ C2 H~ H H Cl CH3
CH3 CH3 H H CH3 CH3
C2 Hs CH3 H H CH3 CH3
52 H~ C2 H5 H H CH3 CH~
CH3 CH3 : H H CH3 H
C2H~ CH3 H H CH3 H
C2H~ C2H5 H H CH3 H
CH3 CH3 H CH3 CH3 CH~
C2 H5 CH3 H CH3 CH3 CH3
C2H~ C2H5 H CH3 CH3 CH3
CH3 CH~ H H Br H
C2 H3 CH3 H H Br H
C2 Hg C2 Hg H H Br H
CX3 CH3 H H Cl H
C2Hg C~3 H H Cl H
C2H~ C2Hs H H Cl H
., ;
Le A 19 123 l`
~: .
' ' ,:
,:
- . - :
:
8 --
R' R2 R3 R4 X~ X2
CH3 CH3 H H Cl C~H
C2H5 CH3 H H Cl C4H
C2H5 C2H5 H H Cl C~H
~H3 CH3 H H Br C~3
C2H, CH3 H H Br CH3
C2Hs C2H, H H Br CH3
CH~ CH3 H H F C~H~
C2H~ CH3 H H F C~H
C2Hs C2Hs H H F C~H
CH3 CH3 H H F CH3
C2H, CH3 H H F CH3
C2H5 C2H, H H F CH3
R4 N ~ X~
R1 CH ~ S
N ~2 (Ib)
R2 C - CH2 - Cl(Br) .
a
R' R2 R3 R4 X' X2
:. .
CH3 CH3 H H H H
2Hs CH3 H H H H
CzH~ C2H~ H H H H
C(CH3)3 H H H H H
CH3 CH3 -- H CH3 H H
CzH5 CH3 H CH3 H H
C2H5 C2H5 H CH3 H H
C(CH3)3 H H CHj H H
CH3 H 3-CH3 H H H
CH3 H 5~CH3 H H H
CH3 Cl H H H H
Le A l9 123
~8~f.~
- g
R' RZ R3 R4 X~ X2
.__
C(CH3 )3 Cl H . H H H
CH3 CH3 3-CH3 H H H
OCH~ CH3 H H H H
OCH3 OCH3 H H H H
OCH3 C2Hg H H H H
CH~ Br H H H H
CH(CH3)2 CH3 H H H H
CH3 CH3 H H CH3 H
C2H~ Cl13 H H CH3 H
C2H5 CzHg H H CH3 H
C(CH3)3 H H ~ CY.3 H
CH3 CH~ H CH3 c~.3 H
C2H~ CH3 H CH3 CH3 H
C2H, C2H~ H CH3 CH3 H
C(CH3)3 H H CH~ CH3 H
CH3 H 3-CH3 H CH3 H
CH3 H 5-CH~ H CH3 H
CH3 Cl H H CH3 H
C(CH,)3 Cl H H CH3 H
CH3 CH3 3-CH3 H~ CH3 H
OCH3 CH3 H H ' CH3 H
OCH3 OCH3 H H CH3
OCH3 C2~s H H CH3 H
CH3 Br H H CH3 H
CH(CH3)2 CH3 H H CH3 H
C~3 CH3 H H C2H~ H
C2H~ CH3 H H C2Hs H
C2H, C2H, H H C2H~ H
C(CH3)3 H H H C2H~ H
CH~ CH3 H H C3H? H
C2H~ CH3 H H C3 H7 H
C2 Hg C2 Hs H H C3H7 H
C(CH3)3 H H H C3H7 H
1i
Le A 19 123
'' ', ' ' ~''~ . :
:
~ ~85~
-- 10 --
.
R1 R2 R3 R~ Xl x2
~__
CH3 CH3 H H C4 Hg H
C2H, CH3 H H C~ H9 H
CzH~ C2H5 H H Ch Hg H
C(CH3 )3 H H H C~Hg H
CH3 CH~ H H C6 H5 H
C2H, CH3 H H C6 H5 H
C2H5 C2 H5 H H C6H5 H
C(CH3 )3 H H H C6 H5 H
CH~ CH3 H H CO2CH3 H
C2 Hg CH3 H H CO2CH3 H
C2Hs C2Hs H H CO2 CH3 H
C(CH3 )3 H H H CO2 CH3 H
CH3 CH3 H H CO2 C2 Hs H
C2H~ CH3 H H CO2 C2 H~ H
C2H~ C2H5 H H CO2 C2 Hg H
C(CH3 )3 H H H CO2 C2Hs H
CH3 CH3 H H Cl H
C2Hs CH3 H H Cl H
C2H5 C2 H5 H H Cl H
C(CH3 )3 H H H Cl H
CH3 CH3 H H Br H
C2H, CH3 H H Br H
C2H~ C2 H~ H H Br H
C(CH3 )3 H H H Br H
CH3 CH3 H H F H
C~ H~ CH3 H H F H
C2H~ C2H5 H H F H
C(CH3 )3 H H H F H
CH3 CHs H H CH3 CH3
C2H~ CH3 H H CH3 CH3 :
C2H~ C2 H~ H H CH3 CH~
C(CH3 )3 H H H CH3 ~3
'.
Le A 19 123
:
8~;2~
R' R2 R3 R~ X' X2
__ __
CH3 CH3 H H CH3 ~ Cl
C2 H5 C~ H H C]~ Cl
C2 H, C2 H~ H H CH3 Cl
C(CH3 )3 H ~ H C]H~ Cl
CH~ CH3 H EI ClH~ Br
C2H, CH3 H H c~3 Br
C2 H, Cz Hs H H c~3 Br
C(CH3 )3 H H H c~3 Br
CH3 CH3 H H CH3 F
~2 H5 CH3 H H CH~ F
C2H3 C2 H~ H H CH3 F
C~CHs ~3 H H H CH3 F
CH3 CH3 H H H Cl
C2 H~ CH3 H H H Cl
C2 H~ Cz H~ H H H Cl
C(CHy )3 H H H H Cl
CH3 CH3 H H H Br
C2 Hs CH3 H H H Br
C2 H~ C2 H, H H H Br
C(CH3 )3 H H H H Br
CH3 CH3 H H H F
C2 H, C~3 H H H F
C2 H5 C2 H~ H H H F
C(CH3 ~3 H H H H F
CH3 CH3 H H C2 H3 Cl
C2 H, CH~, H H C2 H~ Cl
~2 H3 C2 H, H H C2 H3 Cl
C(CH~ )3 H H H C2H3 Cl
CH3 CH3 H H C2 H~ Br
C2 Hs CH3 H H C2 H~ Br
~2 H~ C2 H5 H H C2 I~, Br
C(CH3 )3 H H EI c2~ Br
CH3 c~3 H H c2~ F
C2 H~ H H C2 H~ F
C2 H5 C2 H~ H H C2 H~ F
C(CH3)3 H H H c2~ F
., . ~
Le A 19 12 3 l l
. . - . ,
:
~. . .
R3 R~ S`~/
\~ R' C~ N
~ R2 e- CH~ - Cl(Br)
o
R' R2 R3 R~ X~ X2
CH3 CH3 H H EI H
C2Hg CH3 H H H H
C2 H, C2 Hs H H H EI
C(CH~)3 H H H H H
C~13 CH3 H CH3 H H
C2 H5 CH3 H CHI H H
C2 H, C2 H, H CH3 H H
C(CH3 )3 H H CH3 H H
CH3 CH3 H H CH3 H
C2 Hs CH3 H H CH3 H
C2H5 C2H, H H CH3 H , ~ .
CH3 CH3 H H H CH3
C2 H~ CH3 H H H CH3
C2 H~ C2 H, H H H CH3
R' R /CH ~0 ~ X~ ¦
\R2 C - CH2 - Cl(Br)
r
Le A 19 12 3
6a~
- 13 -
~' .'
CH3 CH3 ~ H H H
C2 H~ CH~ H H H
C2 Hs C2 H~ H H H H
C(C~ )3 H H H H H
CH3 CH3 H CH~ H H
CH3 H CH3 H H
C2 ~ C2 H, H CH3 EI H
C~CH~ )~ H H CH3 H H
CH~ H 3-CH~ H H H
C~ H 5-CH3 H H H
CH3 Cl H H H H
C(CH~ )I Cl H H H H
CH~ c~3 3-CH~, H H H
OCH~ CH~ H H H H
OCH~ OCH, H H H H
OCH~ C2H~ H H H H
CH3 CH3 H H H CH3
C2 H~ CH~ H H H CH~,
C2 H~ C2 H~ H H H CH3
C(CH~, 3~ H H H H CH3
CH~ CH3 H CH3 H CH3
C2 H, CH3 H CH~ H CH3
C2H, C2H~ H CH3 H CH3
C(CH~)3 H H CH3 H C~3
CH3 H 3-CH3 H H CH~
CH~ H 5-CH3 H H CH3
CH3 Cl H H H 3 ,
C(CH3)~ Cl H H H CH3 .
CH, CH3 3-C~5 H H CH~ I
OCF~ CH3 H H H CH3
OCH3 OCH3 H H H CH~
OCH3 C2 ~ H H H CH3
CH~ C~ H H H C2 X5 J
C2 ~ CH~5 H H H C2 ~
C2 ~ C2 ~5 EI H H C2 H5
CH~ Br X H H H
CH(CH~)~ CH3 H H H X
., . I
Le A 19 lZ~ ¦
- 14 -
R' R2 R3 R4 X~ X2
CH3 CH~ H H H COzCH~
C2~ CH3 H H H CO2CH3
C2H, C2H~ H H H CO2CH3
CH3 CH3 H H H C02C2Hg
C2H, CH3 H H H CO2c2Hs
CzH~ C2H, H H H CO2C2H
CH3 CH3 H H H C~Hg
C2H5 CH3 H H H C~Hg
C2H5 C2Hs H H H C~H9
CH3 CHI H H H C~H7
C2H~ CH3 H H H C~H7
C2Hg C2Hg H H H C3H7
CH~ CH3 H H H
C2H, CH3 H H H
C2H, C2H, H H H
CH3 CH3 H H Cl CH~
CzH~ CH3 H H Cl CH3
C2H, C2H~ H H Cl CH3
CH3 CH3 H H CH3 CH3
C2Hs CH3 H H CH3 CH3
C2H, C2H, H H CH3 CH3
CH3 CH3 H H CH3 H
C2H, CH3 H H CH3 H
C2Hg C2H, H H CH3 H
CH3 CH3 H CH3 CH3 CH3
C2H~ CH3 H CH3 CHI CH~
C2H~ C2H, H CH~ CH3 C~3
CH3 CH3 H H Br H
C2H5 CH3 H H Br H
C2Hg C2H, H H Br H
CH3 CH3 H H Cl H
: C2Hs CH3 H H Cl H
C2H5 C2H~ H H Cl H
Le A-19 123
- 15 -
Rl RZ R3 R4 X' X2
. .
CH3 CH3 H H Cl C4 H9
C2 H, CH3 H H Cl C4 H9
C~ H5 C2 H~ H H Cl C4 Hg
CH3 CH3 H H . Br CH3
C2 H, CH3 H H Br CH3
C2 H~ C2 H5 H H Br CH
CH~ C~I3 H H F C" Hg :
C2 H, CH3 H H F Cs~ Hg
C2 H5 C2H~ H H F C~Hg
CH3 CH3 H H F CH3
C2H5 CH3 H H F CH3 -
C2 H5 C2 H5 H H F CH~
14 N~Xl
/R1 CH--~C)
R3~\ / I (Ie)
~ N xs
\
R2 C - CH2 ~ Cl (Br )
o
Rl R2 R3 R4 Xl X2
CH3 CH~, H H H H
Cz H~ CH3 H H H H
C2 M, C2 H, H H H H
C(C}~)3 H H H H H
CH~ CH3 H CH3 H H
C2 H5 CH3 H CH3 H H
C2 Hs C2 ~ H CH~ H H
C(CH3 )3 H H C~ H H
CH3 H 3-CH3 ~I H H
CH3 H 5-C~3 H H H
CH3 Cl H H H H
Le A l9 12 3
.
1~ ~85%~
- 16 -
R R2 R3 R4 xt X2
C~CH3)3 Cl H H H H
CH3 CH3 3-CH3 H H H
OCH3 CH3 H H H H
OCH3 OCH3 H H H H
OCH3 C2 H~ H H H H
CH3 ~r H H H H
CH(CH3)2 CH3 H H H H
CH3 CH3 H H CH3 H
C2 H5 C!i3 H H ~''H3 H
C2 H5 C2 H5 H H CH3 H
C~CH3 )3 H H H CH3 H
CH3 CH3 H CH3 CH3 H
C2H5 CH3 H CH3 CH3 H
Cz Hs C2 H5 H CH3 CH3 E~
C(CH3 )~ H H CH~ CH~ H
CH~ H 3-CH3 H CH~ H
CH3 H 5-CH3 H CH3 H
CH3 Cl H H CH3 H
C(CH3 )3 Cl H H CH3 H
CH3 CH3 3--CH3 H CH3 H
OCH3 CH3 H H c~3 H
OCH3 OCH3 H H CH3 H
OCH3 C2 H5 H H CH3 H
CH3 Br H H CH3 H
CH(CH3)2 CH3 H H CH3 H
CH3 CH3 H H C2 H5 H
C2 Hs CH3 H H C2 Hs H
C2 H5 C2 H, H H C2 H5 H
C(CH3)3 H H H C2Hg H
CH3 CH3 H H C3 H7 H
C2 H5 CH3 H H C3 H7 H
C2 Hs C2 H5 H H C3 H? H
C(CH3 )3 H H H C3H7 H
Le A l9 12 ~
.
~8~ :
- 1 7
R1 R2 R3 R4 X~ X
CH3 CH3 ~ H C4 Hg H
C~ H5 CH3 H H C4 Hg H
C2 Hg C2 H, H H C4 Hg H
C(CH3 )3 H H H C4H9 H
CH3 CH3 H H c6 H5 H
C2 H5 CH3 H H C6 H5 H
C2 Hs c2 H~ H H c6 H5 H
C(CH3 )3 H, H H C5 H5 H
CH3 CH3 H H CO2 CH3 H
C2 H5 CH3 H H C2 CH3 H
C2 H5 C2 H5 H H CO2 CH3 H
C(CH3 )3 H H H CO2 CH3 H
CH3 CH3 H H CO2 C2 H~ H
f'- T~ rlU U U n~ u L~ '
~2 n, ~113 1~ 1~ ~2 ~2 n~
C2 H~ C2 H~ H H CO2 C2 H~ H
C(CH3 )3 H H H COzC2Hs H
CH3 CH3 H H Cl H
C2 H, CH3 H H Cl H
C2 H5 C2 H5 H H Cl H
C(CH3 )3 H H H : Cl H : ¦
CH3 CH3 H H Br H ,
C2Hs CH3 H H Br H '.
C2 Hg C2 H, H H Br H
C(CH3 )3 H H H Br H
CH~ CH~ H H F H
C2H~ CH3 H H F H
C2Hs C2H, H H F H
C(CH3 )~ H H H F H
CH3 CH3 H H CH3 CH3
C2 H~ CH3 H H CH3 CH
C~ Hs C2 H~ H H CH3 CH3
C(CH3 )3 H H H CH3 CH3 ~ :
.
Le A 19 12 3
-
, ~ :
~ . ' ,
~- ,
~L2~5;Z9L
- 18 -
Q~ R2 R3 R~ X~ X2 ~:
CH~ CH3 H H CH3 Cl
C2 H5 CH3 H H CH~ Cl
C2 H5 C2 H5 H H CH3 Cl
C(CH3 )3 H H H CH3 Cl
CH3 CH3 H H CH3 Br
C2 H, CH3 H H CH3 3r
C2 H~ C2 Hs H H CH3 Br
C(CH~ )3 H H H CH3 Br
CH3 CH3 H H CH3 F
C2 H, CH3 H H CH3 F
C2Hg C2H5 H H CH3 F
C(CH3 )3 H H H CH3 F
CH~ CH3 H H H Cl
C2 Hs CH3 H H H Cl
C2 Hs C2 H~ H H H Cl
C(CH, )3 H H H H Cl
CH3 CH3 H H H Br
C2 H, CH3 H H H Br
C2 H, C2 H, H H H Br
C(CH3 )3 H H H H Br
CH3 CH3 H H H F :
C2 H~ C~3 H H H F
Cz Hs C2 H5 H H H F
C(CH3 )3 H H H H F
CH3 CH3 H H C2 Hg Cl
C2 H, CH3 H H C2 H5 Cl
C2 H, C2 H, H H C2 H~ Cl
C(CH3 )3 H H H C2H5 Cl
CH3 CH3 H H C2 Hs Br
C2 H5 CH3 H H Cz H~ Br
C2 H5 C2 Hg H H C2 ~ Br
C(CH3 )3 H H H C2H5 Br
CH3 CH3 H H C? H~ F
C2 Hs CH3 H H ~2 Hs F
C2 Hs C2 H5 H E~ C2 ~5 F
C ( CH~ ~ 3 H H H C2 Hs F
. .
Le A 19 123
.
- 19 -
R3\ ,~ R' R 0
~> e N / X2 ( If )
R2 C - CH~ - Cl(Br)
O
R' R2 R3 R~ X~ X2
CH, CH~ H H H H
C2 H~ CH3 H H H H
C2 H~ C2 H5 H H H H
C ( CH~ H H H H H
CH3 CHs H CH~ H H
C2 H l CH~ H CH~ H H
C~ H~ C2 H, H CH3 H H
CtCH, ~ H H CH3 H H
CH3 CH3 H H CH, H
C2 H5 CX3 H H CH~
C2 H~ C2 H, H H CH3 H
CH3 CH~, H H H CH~
C2 H, C~3 H H H CH3
C2 H~ Cz H~ H H H CH3
R3 R1 CR--
~R2 C - CH2 - Cl (Br )
O
Le A 19 123
. , :
~2~
- 20 -
CH3 CH3 CH3 H H H : H
CH3 C2H5 CH3 H H H H
CH3 C2H, C2H, H H H H
CH3 C(CH3)3 H H H H H
CH3 CH3 CH3 ~ CH3 H H
CH3 C2H5 CH3 H CH3 H H
CH3 C2H5 CzH~ H CH3 H H
CH3 C(CH3)3 H H C~3 H H
CH3 CH3 H 3-CH3 H H H
CH3 CH3 H 5-CH3 H H H
CH3 CH3 Cl H H H H
CH3 C(CH3)3 Cl H H H H
CH3 CH3 CH3 3-CH3 H H H
CH3 OCH3 CH3 H H H H
CH3 OCH3 OCH3 H H H H
CH3 OCH3 C2H~ H H H H
CH3 CH3 CH3 H H H CH3
CH3 C2Hg CH3 H H H CH3
CH3 C2H~ C2H~ H H H CH3
CH3 C(CH3)3 H H H H CH3
CH3 CH3 CH3 H CH3 H CH3
CH3 C2H, CH3 H CH3 H CH3
CH3 C2H, C2H5 H CH3 H CH3
CH3 C(CH3)3 H H CH3 H C~3
CH3 CH3 H 3-CH~ H H CH3
CH3 CH3 H 5-CH3 H H C~3
CH3 CH3 Cl H H H CH3
CH3 C(CH3)~ Cl H H H CH3
CH3 CH3 CH3 3-CH3 H H CH3
CH3 OCH3 CH3 H H H CH3
CH3 OCH3 OCH3 H H H CH3
CH3 OCH3 C2H~ H H H CH3
CH3 CH3 CH3 H H H C2H,
CH3 C2H5 C~3 H H H C2Hs
CH3 C2H~ C2Hs H H H C2HS
CH3 CH3 Br H H H H
CH~ C~(CH3)2 CH3 H H H H
Le A 19 123
. .
: '
~8~
- 21 -
CH3 CH3 CH, H H H CO2CH~
3 ccc-21~H3 CH~ hH H H COzCH~
CH3 CzH5 CH3 H H H Co2c2~ls
CH3 C2H5 CzH~ H H H Co2c2Hs
CH3 CH3 CH3 H H H C4 Hs
CH3 C2Hg CH3 H H H C~Hg
CH3 C2H5 C2H5 H H H C4 Hs
CH3 CH3 CH3 H H H C3 H7
CH3 C2H5 CH3 H H H C3H7
CH3 C2Hs C2Hs H H H C3H7
CH3 CH3 CH3 H H H
CH3 C2H, CH3 H H H
CCH3 C2H~ C2H5 H H H
CH3 CH3 CH3 H H Cl CH3
CH3 C2H, CH3 H H Cl CH~
CH3 C2H, C2H, H H Cl CH3
: CH3 CH3 CH3 H H CH3 CH3
CH3 C2H, CH3 H H CH3 CH3
CH3 C2H5 C2H, H H CH3 CH3
CH3 CH3 CH~ H H CH3 H
CH3 C2H5 CH3 H H CH3 . H
CH3 C2H5 C2H~ H H CH3 H
CH3 CH3 CH3 H CH3 CH3 CH3
CH3 C2Hs CH3 H CH~ CH3 CH3
CH3 C2H~ C2H5 H CH3 CH3 CH3
CH3 CH3 CH3 H H Br H
CH3 C2H~ CH3 H H Br H
CH3 C2H5 C2Hg H H Br H
CH~ CH3 CH3 H H Cl H
CH3 C2H~ CH3 H H Cl H
CH3 C2H~ C2H5 H H Cl H
Le A 19 123
52~
-- 22 --
R R1 R2 R3 R4 X' x2
CH3 CH3 C~3 H H Cl C4 Hg
CH3 C2H5 CH3 H H Cl C~Hg
CH3 C2Hs CzH5 H H Cl C4 H9
CH3 CH3 CH3 H H Br CH3
CH3 C2 H5 CH3 H H Br CH3
CH3 C2H, C2H, H H Br CH3
CH3 CH3 CH3 H H F C,,Hg
CH3 C2H~ CH3 H H F C~ H9
CH3 C2H, C2H5 H H F C~Hg
CH3 CH3 CH3 H H F CH3
CH3 C2Hg CH3 H H F C~3
CH~ C2H5 C2H5 H H F CH3
R4 N ~ X~
,R1 CH - ~ N ~ R
N X2 (Ih)
~R2 C ~ CH2 Cl(Br)
R R1 R2 R3 R4 X' x2
___ ~_
CH3 CH3 CH3 H H H H
CH3 CzH~ CH3 H H H H
CH3 C2 H, C2 H, H H H H
CH3 C(CH~ )3 H H H H H
CH3 CH3 CH3 H CH3 H H
CH3 C2 H3 CH3 H CHt H H
CH C2Hs C2H5 H CH~ H H
CH3 C(CH3 )3 H H CH3 H H
CH3 CH3 H 3-CH3 H H H
CH3 CH3 H 5-CH~ H H H
CH3 CH3 Cl H H H H
Le A 19 123
- 23 -
R R' R2 R~ R~ X' x2
CH3 C(CH, )3 Cl H H H H
CH3 CH3 CH3 ~-CH, H H H
CH, OCH3 CH3 H H H H
CH3 OCH3 OCHI H H H H
CH3 OCH3 C2H, H H H H
CH3 CH3 Br H H H H
CH3 CH(CH3)2 CH3 H H H H
CH3 C~3 CH3 H H CH3 H
CH3 C2H, C~i3 H H CH3 H
CHI C2H5 C2Hg H H CH3 H
CH3 C(cH3)3 H H H CH3 H
CH3 CH3 C~3 H CH3 C~.3 H
CH~ C2H~ CHi H CHy CH3 H
CH3 C2H~ C2H~ H CH3 CH, H
CH3 C(CH3 )3 H H CH~ CH, H
CH3 CH3 H ~-CH3 H CH3 H
CH3 CH3 H 5-CH3 H CH3 H
CH3 CH3 Cl H H CH3 H
CH3 C(CH3 )3 Cl H H CH3 H
CH3 CH3 CH3 3-CH3 H CH3 H
CH3 OCH3 CH3 H H C~.3 H
CH3 OCH3 OCH3 H H CH3 H
CH3 OCH3 C2H, H H CH~ H
CH3 CH3 Br H H CH3 H
CH3 CH(CH,)2 CH3 H H CH3 H
CH3 CH3 CH~ H H C2H~ H
CH, c2 H, CH3 H H c2 H~ H
CH3 C2H~ C2H, H H c2 H~ H
CH3 C(CH3 )3 H H H C2H~ H
CH3 CH3 CH3 H H C3 H7 H
CH3 C2H~ CH3 H H C3 H? H
CH3 c2 Hs C2 H, H H C3 H7 H
C~3 C(CH3)~ H H H C3H7 H
Le A 19 123
.
.' ' ' , ' , ' '
, ~ . ' ~ . . ,
.
.
8~%~
- 24 -
R Rl R2 R3 R4 X1 x2
CH3 CH3 ~H3 H H C4 Hg H
CH3 C2H5 CH3 H H C4 Hg H
CH3 C2~s C2Hs H H C4Hg H
CH3 C(CH3)3 H H H C4H9 H
CH3 CH~ CH3 H H C6H5 H
CH3 C2~I, CH3 H H c6~s H
CH3 C2~g C2H~ H H C6H~ H
CH3 C(CHI)3 H H H C6Hs H
CH3 CH3 CH3 H H C2 C~3 H
CH3 C2H~ CH3 H H CO2CH3 H
CH3 C2H5 C2Hs H H CO2CH3 H
CH3 C(CH3)~ H H H CO2CH3 H
CH3 CH3 CH3 H H CO2C2H~ H
CH3 C2H3 CH~ H H CO2C2H~ H
CH3 C2H~ C2H~ H H CO2C2H~ H
CH3 C(CH3)3 H H H CO2C2H~ H
CH3 CH3 CH3 H H Cl H
CH3 C2H, CH3 H H Cl H
CH3 C2H5 C2H~ H H Cl H
CH3 C(CH3)3 H H H Cl H
CH3 CH3 CH3 H H Br H
CH3 C2H, CH3 H H Br H
. CH3 C2H3 C2H5 H H Br H
CH3 C(CH3)3 H H H Br H
CH3 CH3 CH3 H H F H
CH3 C2 Hg CH3 H H F H
CH3 C2H~ C2H, H H F H
CH3 C(CH3)3 H H H F H
CH3 CH3 CH3 H H CH3 CH3
CH3 C2H5 CH3 H H CH3 CH3
CH3 C2H~ C2H5 H H CH3 CH3
~H3 C(CH3)3 H H H . CH3 CH3
Le A 19 12~
~,
.
- 25 -
R R' R2 R3 R~ X~ X2
~___________
CH3 CH3 CH3 H H CH3 Cl
CH3 C2H5 CH3 H H CH3 Cl
CH3 CzHs C2H5 H H CH3 Cl
CH3 C(CH3)~ H H H CH3 Cl
CH3 CH3 CH3 H H CH3 Br
CH3 C2H5 C~3 H H CH3 Br
CH3 C2Hs C?H5 H H CH3 Br
CH3 C(CH~)3 H H H CH3 Br
CH~ CH3 CH~ H H CH3 F
CH3 C2Hs C~3 H H CH~ F
CH3 C2H, C2H5 H H CH~ F
CH3 C(CH3)3 H H H CH3 F
CH3 CH3 CH3 H H H Cl
CH3 C2Hs CH3 H H H Cl
CH3 C2Hs C2H~ H H H Cl
CH3 C(CH3)~ H H H H Cl
CH3 CH3 CH~ H H H Br
CH3 C2Hg CH3 H H H Br
CH3 C2H, C2H, H H H Br
CH3. C(CH3)3 H H H H Br
CH3 . CH3 CH3 H H H F
CH3 C2H5 CH~ H H H F
CH~ C2Hs CzHs H H H F
CH3 C(CH3)~3 H H H H F
CH3 CH3 CH3 H H C2H5 Cl
CH3 C2H, CH3 H H C2Hs Cl
CH3 C2H~ C2~g H H C2Hs Cl
CH3 C(cH3 )3 H H H C2H~ Cl
CH3 CH3 CH3 H H C2H~ Br
- CH~ C2H, CH3 H H C2H, Br
CH3 C2H5 C2H5 H H C2H5 Br
CH3 C(CH3)~ H H H CzHs Br
CH3 CH3 CH3 H H C2~Is F
CH3 C2Hs CH3 H H c2~5 F
CH~ C2Hg C2H~ H H C2H5
CH3 C(CH3)~ H H H C2H~
. ' l
L~ A 19 1~3
.
. . .
- 26 -
R X'
R3 F(~ \N ~/ `
\~ R' CH---~N
~ R2 C - CH2 - Cl(:Br)
O ~,
R R1 R2 R3 R4 X1 X2
CH3 CH3 CH3 H H H H
CH3 C2H, CH3 H H H H
CH3 C2H~ C~H5 H H H H
CH3 C(CH3)3 H H H H H
CH3 CH~ CH3 H CHy H H
CH3 C2 H, CH3 H CH3 H H
CH3 C2 H~ C2 ~ H CH~ H H
CH~ C(CH~ H ~ ` CH~ H H
CH3 CH!, CHI H . H CH3 H
CH3 C~ H!~ CH5 H H CH3 H
CH3 C2 H~ C2 H~ H H CH3 H
~ CH3 CH3 CH3 H H H CH3
CH3 C2 Hs CH3 H H H C~3
CX3 C2 H~ C2 H~ H H H CH3
Further preferred compounds according to the in-
ve.ntio~ are also addition products of acids and those N-(1,3-
azolyl)al~yl.-halogenoacetanilides of the formula (I) in which
A, R, Rl, R2, R3, R4~ Xl, x2 and Z have the meanings which
have already been mentioned as preferred therefor. The
acids which can be added on include, as preferences, hydrogen
halide acids (for example hydrobromic acid and, in particular,
hydrochloric acid), phosphoric acid, nitric acid, sulphuric
acid~ monofunctional and bifunctional carboxylic acids and
hydroxycarboxylic acids(for example acetic acid, maleic
Le A 19 123
. . . !
~ '
' . ' ' .
, :
~ 5
- 27 -
acid, succinic acid, fumaric acid, tartaric acid~ citric acid,
salicylic acid, sorbic acid and lactic acid)~ and sul-
phonic acids (for example p-toluenesulphonic acid and
1,5-naphthalenedisulphonic acid).
Yet further preferred compounds according to the
invention are addition products of salts of metals of main
groups II to IV and of sub-groups I and II and IV to VIII
and those N-(1,3-azolyl)alkyl-halogenoacetanilides of the
formula (I) in which A, R, Rl, R2, R3, R4~ Xl, x2 and Z
have the meanings which have already been mentioned as
pre~erred therefor. Salts of copper, zinc, manganese,
magnesium, tin, iron and nickel are particularly preferred
here. Preferred anions of these salts are those which
are derived from those acids which lead to physiologically
acceptable addition products. In this connection,
particularly preferred acids of this type are the hydrogen
halide acids (for example hydrochloric acid and hydrobromic
acid), phosphoric acid, nitric acid and sulphuric acid.
If 2,6-dimethyl-N-(2'-methylthiazol-4'-yl-methyl)-
aniline and chloroacetyl chloride are used as starting sub-
stances in process variant (a)~ the course of the reaction
can be represented by the following equation:
--S
CH3 CH2 ~ N~ ~ CH3 + ClC0-CH2Cl
Q N ~
~CH3 H - HCl
CH3 CHz - ~NJ ~ ~H3
N\
CH3 C - CH2Cl
Le A l9 123
1~85~4L
-- 28 -
If 2-ethyl-6-methyl-chloroacetanilide and ~-bromo-
methyl-2-methyl-thiazole are used as starting substances in
process variant (b), the course of the reaction can be
represented by the following equation:
CH3 H
~ N / BrCH2' ~NJ`CH3 - H~r
~C~H5 C - CH2Cl
CH3 CH2 ~ ~N~ - CH3
- N\
C2H5 C - CH2Cl
o
The formula (II) provides a general definition of
the N-(1,3-azolyl)alkyl-anilines required as starking sub-
stances in carrying out process (a) according to the
invention. In this formula, A, Rl, R2, R3, R4, Xl and x2
preferably have those meanings which have already been
mentioned as preferred therefor in connection with the
description of the substances of the formula (I) accord-
ing to the invention.
The following compounds may be mentioned as specific
examples of compounds of the formula (II):
N ~' X
R~ C~ S~--
Le A 19 123
,
- 29 -
~ _} "
CH3 CH3 H H H H
C2H5 CH3 H H H H
C2H5 C2H~ H H H H
C(CH3)3 H H H H H
CH3 C~3 H CH3 H~ H
C2H, CH3 H CH~ H H
C2H, C2H, H CH~ H
C(CH3 )3 H H CH3 H H
CH~ H 3-CH~ H H H
CH3 H 5-CH3 H H H
CH3 Cl H H H H
C(CH3)3 Cl H H H H
CH3 CH3 3-CH3 H H H
OCH~ CH~ H H H H
OCH3 OCH3 H H H H
OCH~ C2H, H H H H
CH~ CH3 H H H CH3
C2H, CH3 H H H CH3
C2H, C2H, H H H CH3
C(CH3)3 H H H H CH~
.CH3 CH3 H C~3 H ~H3
C2Hg CH3 H C~3 H CH3
C2H~ C2H, H CH~ H CH3
C(cH3 )3 H H CH", H CH3
CH3 H ~-CH3 H H CH~
CH3 H 5-CH3 H H CH3
CH3 Cl H H H CH3
C(CH~)~ Cl H H H CH3
CH~ CH3 3-CH3 H H C~I3
OCH3 CH~ H H H CH3
OCH~ OCH3 H H H CH3 :
OCH3 C2H~ H H H CH3 :
CH3 CH3 H H H C2 H~
CzH~ CH3 H H H C2H~
C2H~ C2H, H H H C2Hg
CH3 Br H H H H
CH(CH3)2 CH3 H H H H
Le A 19 123
:
~ '
.
~z~
- 30 -
R' R2 R3 R~ X'
c~U~ Cll~ ,CII~
Ccc22HHH, CcH2HH~sH H }~ll Ccc~HH97
C2H5 CH3 H H H C3 H7
C2H5 C2H5 H H H C3H~
CH~ CH3 H H H
C2H, CH3 H H H
C2H, C2H, H H H
CH3 CH3 H H Cl CH3
C2H5 CH~ H H Cl CH~
Cc2H3H5 CCH3H5 HH HH Ccl3 CH3
C2H5 CH3 H H CH3 CH3
Cc2H3H, Cc2H3H,HH HH CcH3 CH3
C2H~ CH3 H H CH3 H
C H~ C2H~ H H CH3 H
c2H3 CH3 H CH3 CH3 CH
C2H~ CH3 H CH~ CH3 CH~
C2H, Cc2H3H5H CHH3 CBH3 CHH3
C2H5 CH3 H H Br H
C2Hs C2H5 H H Br H
CH3 CH3 H H Cl H
C2H, CH3 H H Cl H
C2H~ ~2 H5 H H Cl H
Le A 19 123
. '
,~
~,8~i;Z4
-- 31 -
Rl R2 R3 R4 Xl X2
CH3 CH3 H H Cl C4 H
C2 H3 CH~ H H Cl C,~ H
C2 H5 C2 H5 H. H C'l C~, H
CH3 CH3 H H ~r CH3
C2 H~ CH3 H H Br CH3
C2 H5 C2 H~ H H Br CH3
CH3 CH3 H H F C4 H
C2 H, CH~ H H F C4H
C2 H~ C2 Hs H H F C4 H
CH3 CH3 H H . F CH3
C2H5 CH3 H H F CH3
C2H5 C2H, H H F C~
R~ N=l~ X
R1 CH--~,~ S
R~--N/ l2 (IIb)
Rl R2 R3 R~ X~ X2
_
CH~ CH3 H H H H
C2H~ CH3 H H H H
C2 H~ C2 H, H H H H
C(CH3 )~ H H H . H H
CH3 CH3 H CH~ H H
C2 H~ CH3 H CH3 H H
C2 Hs C2 Hg H CH3 H H
C(CH3 ~3 H H CH3 H H
CH3 H 3-CH3 H H H
CH3 H 5-CH3 H H H
CH3 Cl H H H H
Le A 19 123
:
: - . , ~ :
.
.
.~
11 '12h5~2
-- 3~ -
R' R2 R3 R~ X' X2
___
C(CH3)3 Cl H H H H
CH3 CH~ 3-CH3 H H H
OCH3 CH3 H H H H
OCH3 OCH3 H H H H
OCH3 C2 H5 H H H H
CH3 Br H X H H
CH(CH3)~ CHt H H H H
CH, CH, H H CH~ H
Cz H~ ~13 H H CH~ H
C2~ C2H~ H H CH3 H
C(CH3)~ H H H CH3 H
CH3 CH3 H CH3 5~.3 H
C2H, CH3 H CH3 CH3 H
C2 H, C2 H, H CH3 CH3 H
C(CH3)3 H H CH3 CH3 H
CH3 H 3-CH3 H CH3 H
CH3 H 5-CH3 H CH3 H
CH3 Cl H H CH3 H
C(CH3)3 Cl H H CH3 H
CHt CH3 3-CH3 H CH3 H
OCH3 CH3 H H CH~ H
OCH3 OCH3 H H CH3 H
OCH3 C2H, H H CH3 H i :.
CH3 Br H H CH3 H
CH(CH3)~ CH, H H CH3 H
CHy CH3 H H CæH~ H
C2H, CH3 H H C2H~ H
C2H, C2H, H H C2H, H
C(CH3 )3 H H H C2H~ H
CH3 CHI H H C3H7 H
C2H, CH~ H H C3H7 H .
C2H, C2H3 H H C3H7 H
C(CHI)~ H H H C3H7 H
Le A 19 123
. .
:
. ~
~285; :4
- 33 -
R1 RZ R3 . R~ X' X2
CH3 CH3 H H C4 Hg
C2 H, C~3 H H C4 H9 H
C2 H~ C2H5 H H C4Hg H
C(CH3 )3 H H H C~Hg H
CH3 CH3 H H ~ C6 H5 H
C2Hg CH3 H H C6 H5 H
C2H5 C2 H5 H H C6 H5 H
C(CH3 )3 H H H C~ H5 H
CH3 CH3 H H CO2 CH3 H
C2 Hg CH3 H H CO2CH3 H
C2 H5 C2H~ H H CO2 CH3 H : -
C(CH3 )3 H H H CO2 CH3 H
CH3 CH3 H H CO2 C2 H~ H
C2 H, CH3 H H CO2 C2 H~ H
C2 H~ C2 H5 H H CO2 C2 Hg H
C(CH~ )~ H H H CO2 C2 Hg H
CH3 CH3 H H Cl H
C2 H~ CH3 H H Cl H
C2Hg C2 Hs H H Cl H
C(CH3 )3 H H H Cl H
CH3 CH3 H H Br H
C2 Hs CH3 H H Br H
C2 H9 Cz H5 H H Br H
C(CH3 )3 H H H Br H
CH3 CH3 H H F H
C2 Hg CH3 H H F H
C2 Hl C2 H~ H H F H
C(CH3 )3 H H H F H
CH3 CH3 H H CH3 CH3
C2 H5 CH3 H H CH3 CH3
C2 H, Cz H, H H CH3 CH3
C(CH3 )3 H H H CH3 CH
.,
Le A l9 123
. .
~'
` .
~8SZ~
_ 3Z~ _
R' R2 R3 R~ Xl X2
CH3 c~3 H H CH3 Cl
C2 Hs CH3 H H CH3 Cl
C2 H, C2H5 H H c~3 Cl
C(CH3 )3 H H H C~13 Cl
CH3 CH3 H H C~ Br
C2 H5 CH~ H H C~13 Br
Cz Hg C2 H~ H H c~3 Br
C(CH3)3 H H H CH3 Br
CH3 CH3 H H CH3 F
C2 H5 CH3 H H CH3 F
C2 H, Cz H5 H H ~H3 F
C(CH3 )~s H H H CH3 F
CH3 CH3 H H H Cl
C2 H~ CH3 H H H Cl
C2 H5 C2H~ H H H Cl
C(CH3 )3 H H H H Cl
CH3 CH~ H H H Br
C2 H~ CH, H H H Br
C2 H~ C2 H~ H H H Br
C(CH3 )~, H H H H Br
CH3 CH3 H H H F
C2 H, CH3 H H H F
C2 H~ Cz Hs H . H H F
C(CH3)3 H H H H F
CH3 CH3 H H C2 H, Cl
C2 H~ CH3 H H C2 Hg Cl
C2 H~ C2 H~ H H C2 H, Cl
C~CH3 )~ H H H C2H5 Cl
CH3 CH3 ~ H Cz H!S Br
C2H~ CH3 H H C2Hs Br
C2 Hs C2 H5 H H C2 Hg Br
C(CH3 )3 H H H C2H5 Br `
CH3 CH3 H H C2 H5 F
C2 H~ CH3 H H C2 H5 F ,~
C2 Hs C2 H5 H H C2 H5 F ~;~
C(CH3 )3 H H H C2Hg F
'.
Le A l9 12 3
,,
,
~" ' ':~ ' ' ' '
' ' . '
: ' ,
~lZ85~4
- 35 -
X1
R3 R~ S ~
IIc3 : :
\~ R
RZ \H
~-
R' R2 R3 R4 X~ X2
CH3 CH3 H H H H
C2 H, CH3 H H H H
Cz H~ C2H, H H H H :
C(CH3)3 H H H H H
CH3 CH3 H CH3 H H
C2H, CH3 H CH3 H H
C2Hg C2 H~ H CH3 H H
C(CH3 )3 H H CH3 H H
CH3 CH3 H H CH3 H
C2 H, CH3 H H CH3 H
Cz H~ C2 H3 H H CH3 H
CH3 CH3 H H H CH3
C2 H, CH3 H H H CH3
C2 H, C2 H, H H H CH3
1:
\~R <CN ~;3~,
R2 H
~.............. .
Le A 19 123
... . . . .
~2852
- 36 -
R' E~.2 R3 R~ X1 x2
CH3 CH3 H H H H
C2Hs C~3 H H H H : :
C2H3 C2H3 H H H H
C(CH3), H H H H H
CH3 CH3 H CH3 H H
C2H5 CH3 H CH3 H H
C2H5 C2H3 H CH3 H H
C(CH3 )3 H H CH~ H H
CH3 H 3-CH3 H H H
CH3 H 5-CH3 H H H
CH3 Cl H H H H
CtCH~)5 Cl H H H H
CH3 CH3 3-CHI H H H
OCH3 CH3 H H H H
OCH3 OCH3 H H H H
OCH3 CzH9 H H H H
CH3 C~3 H H H CH~
C2H~ CH~ H H H CH~
C2H~ C2H, H H H CH~
C(CH3)~ H H H H CH3
CH3 ~H3 H CH3 H CH3
C2H~ CH3 H CH3 H CH3
C2H, C2H, H CH3 H CH3
C(CH3 )3 H H CH3 H CH3
CH3 H 3-CH3 H H CH3
CH3 H 5-CH~ H H CH~
CH3 Cl H H H CH~ ~
C(CH3)3 Cl H H H CH3 ::
C~I3 CH3 3-CH3 H H CH~
OCH3 CH3 H H H CH3
OCH3 OCH~ H H H CH3
OCH3 C2H, H H H CH3
CH3 CH~ H H H CzH~ .
C2H5 CH3 H H H C2H~
C~H~ C2H~ H H H C2H~
CH3 Br H H H- H
CH(CH3)z CH3 H H H H
~ ., . ~
;
Le A 19 123
' ' . . ,
.
.
,
~285~L
- 37 --
R' R2 R3 R4 X' X2
___
CH3 CH3 H H H COz CH3
C2 H~ CH3 H H H CO2 CH3
C2 H5 ~2H~ H H H CO2 CH3
CH3 CH3 H H H COz C2H3
Cz H, CH3 H H H CO2 C2 H!l
C2 H5 C2 .~5 H H H CO2 C2 H5
CH3 CH3 H H H C4 Hs
Cz Hs CH3 H H H C4 Hg
C2 H5 C2 H5 H H H C4 Hs
CH3 CH3 H H H C3H7
C2H5 CH3 H H H C3H7
C2 Hs C2 H5 H H H C3 H7
CH3 CH3 H H H
C2 H, CH3 H H H
C2 H, C2 Hg H H H (~
CH3 C~3 H H C1 CH,
C2 H, CH3 H H C1 CH3
C2H, C2H, H H Cl CH3
- CH3 CH3 H H CH3 CH3
C2 H~ CH3 H H CH3 C~3
C2 H5 C2 H~ H H CH3 CH3
CH3 CH~, H H CH, H
C2Hy CH3 H H CH3 H
C2 Hs C2 H~ H H CH3 H
CH~ CH3 H CH3 CH3 CH3
C2 Hg C~3 H CH~ CH3 CH~
C2 H~ C2 H~ H CH3 CH3 CH,
CH3 CH3 H H Br H
C2 H, CH3 H H Br H
C2Hg C2H, H H Br H '.
CH3 CH3 H H Cl H .
C2 H, CH3 H H Cl H
C2 H5 C2 H, H H Cl H
Le A 19 lZ3
~X852
- 38 -
R1 R2 R3 R'~ X~ X2
CH3 CH3 H H Cl C4 Hg
C2 H5 CH3 H H Cl C4 Hg~ : ; .
Cz H5 C2 H, H H Cl C~, H~ ; :
CH3 CH3 H H ~3r CH3 :
C2 H5 CH3 H H Br . CH3
C~H5 C2H5 H H ~3r CH3
CH3 CH3 ~ H F C~ EI9
C2 H5 CH3 H H ~ C~ H~ ` :
C2 H... C2 H~ H H F C4 Hs
CH3 CH3 H H F CH3
C2 H, CH3 H H F ~H3 :
C2 H, C2 H~ H H F CH3
R~ N=~ X1 ~;
CH -~0
--N X2 (IIe)
R2 H
R~ R2 R3 R4 X~ ~2 ~:
CH3 CH3 H H H H :
C2H, CH3 H H H H
C2 H, C2 H, H H H H
C(CH~, )3 H H H H H :
CH3 CH~ H CH~ H H
C2 H, CH3 H CH3 H H
C2 Hs C2 ~ H CH~ H H
C(CH~ )3 H H CH3 H H
CH3 H 3-CH3 H H H
CH3 H 5-CH3 H H H
CH3 Cl H H H H
: .
Le A l9 123 l,
: . :
. -, ~ : ~ . ,
. '' ' . :
. ;~
.
: ............. . .
~L2852~
- 39 - :
R' R2 R3 R4 X' X2
C(CH3 )3 Cl H H H H
CH3 CH3 3-CH3 H H H
OCH~ CH3 H H H H
OCH3 OCH~ H H H H
OCH3 C2H5 H H H H
CH3 Br H H H H
CH(CH3)2 CH3 H H H H
C~ CH3 H H CH3 H
C2 H5 C!~3 H H CH3 H
C2 Hs C2H5 H H CH3 H
C(CH3 )3 H H H C~3
CH3 CH3 ~ CH3 CH H
C2 H5 CH3 H CH3 CH3 H
C2 H~ C2 Hs H CH3 CH3 H
C(CH3 )3 H H CH3 CH3 H
CH3 H 3-CH3 H CH3 H
CH3 H 5-CH3 H CH3 H
CH3 Cl H H CH3 H
C(CH3 )3 Cl H H CH3 H
CH3 CH3 3-CH3 H CH3 H
OCH3 CH3 H H CX3
CCH3 OCH3 H H CH3 H
OCH3 C2 H~ H H CH3 H
CH3 Br H H CH3 H
CH(CH3)2 CH3 H H CH3 H
CH3 CH3 H H C2 Hs H
C2 H~ CH3 H H C2H~ H
C2H5 C2Hg H H C2H~ H
C(CH3 )3 H H H C~ Hs H
CH3 CH3 H H C3 H? H
C2H~ CH3 H H C3 H7 H
C2H5 C2 H5 H H C3H7 H
C(CH3 )3 H H H C3H7 H
.
Le A l9 123
;~
. .
.
52~
- 40 -
R' R2 R3 R~ X' ~2
~ ____
__
CH3 CH3 H H C~Hg H
C2H~ CH3 H H C4H9 H
C2Hs C2Hs H H C~Hg H
C(CH3)3 H H H Cl,Hg
CH3 CH3 H H C6H, H
s CH~ H H C~sH~ H
CzHs C2H5 H H C6H5 H
C(CH3)3 H H H C6H5 H
CH3 CH3 H H CO2CH3 H
C2H5 CH3 H H CO2CH3 H
CzH5 C2H5 H H CO2C~3 H
C(CH~)3 H H H COzCH3 H
CH3 CH3 H H CO2C2H~ H
C2H, CH3 H H CO2C2H~ H
C2H, CzH~ H H CO2C2H~ H
C(CH~)~ H H H CO2C2Hs H
CH3 CH3 H H Cl H
C2Hs CH3 H H Cl H
C2Hs C2Hs H H Cl H
C(CH3)3 H H H Cl H
CH3 CH3 H H Br H
C2H~ CH3 H H Br H
CzH~ C2H~ H H Br H
C(CH3)3 H ~ H Br H
CH3 CH3 H H F H
C2H, CH3 H H F H
C2H, C2H~ H H F H
C(CH3)3 H H H . F H
CH3 CH3 H H CH3 CH3
C2H~ CH3 H H CH3 CH3 .
C2H~ C2H~ H H CH3 CH3
C(CH3)3 H H H CH3 CH3
Le A l9 12~
- .
~; ~
:
.: .
- 41 -
R' R2 R' R4 X' XZ
_________._
CH3 CH3 H H CH3 Cl
C2H5 CH3 H H ~H3 Cl
C2H, C2 H5 H H ~H3 Cl
C(CH~ )3 H H H (~H3 Cl
CH3 CH3 H H ~H3 Br
C2 H5 CH3 H H CH3 Br
C2H, C2H5 H H CH3 Br
C(CH3 )3 H H H CH3 Br
CH3 CH3 H H CH3 F
C2H5 CH3 H H CH3 F
C2 H5 C2 H5 H H CH3 F
C(CH~ )3 H H H CH3 F
C~3 CH3 H H H Cl
C2 ~5 CH3 H H H Cl
C2 H~ C2H5 H H H Cl
C(CH3 )3 H H H H Cl
CH3 CH3 H H H ~r
C2 ~5 CH3 H H H r
C2 H~ C2H~ H H H ~r
C(CH3 )~ H H H H Br
CH3 CH~ H H H F
C2 H~ CH~ H H H F
C2 H, C2 H, H H H F
C(CH~ )3 H H H H F
CH3 CH3 H H C2 H~ Cl
C2 H~ CH3 H H C2 H~ Cl
C2H5 C2H5 H H C2 H5 Cl
C(CH3 )3 H ~ H C2 Hs Cl
CH~ CH3 H H C2 H~ Br
CzH~ CH3 H H C2 H5 Br
C2 H, C2 H5 H H C2 Hs Br
C(CH3 )3 H ~ H C2 Hg Br
CH3 . CH3 H H C2 H5 F
C2H5 CH3 H H C2 Hs F
C2H5 C2H~ H H c2~ F
C(CH3 )~ H ~ H C2 ~ F
Le A 19 123
~ ~-2~35;~
-- 42 -
X~
R" R~ --~i/
R' CH ~N
~,)-- N ~ X2 ( I If )
R2 H
R1 R2 R3 R~ X' X2
CH3 CH3 H H H H
C2 H5 CH3 H H H H
C2 H~ C2 H~ H H H H
C(CH3)3 H H H H H
CH3 CH~ H CH3 H H
Cz H ~ CH~ . H CH~ H H
C2H, C2H~ H CH3 H H
C(CH~)~ H H CH~ H H
CH3 CH~ H H CH~ H
C2H, CH3 H H CH~ H
C2 H, C2 H, H H ~H3 ~ H
CH3 CH3 H H H CH.~ .
C2 H3 CH3 . H H H CH - -
C2 Hs C2 H~ H H H CH3
,~ . .
\~R' /CH~
( IIg )
R2 H
Le A 19 123
'' - . -
. . ~ ,
.
;
~ 43 -
CH3 CH, CH~ H H H H
CH3 C2H5 CH3 H H H H
CH3 C2H, C2H, H H H H
CH3 C(CH~ )3 H H H H H
CH3 CH3 CH3 H CH~ H H
CH3 C2H~ CH~ H CHI H H
CH3 C2H, C2H~ H CH3 H H
CH3 C(CH, )3 H H CH3 H H
CH3 CH, H 3-CH3 H H H
CH3 CH3 H s-CH3 H H
CH3 CH~ Cl H H H H
CH3 C(CH~)3 Cl H H H H
CH3 CH3 CH3 ~CH3 H H H
CH3 OCH3 CH3 H H H H
CH3 OCH3 OCH3 H H H H
CH~ OCH~ C2H~ H H H H
CH3 CH3 CH3 H H H CH3
CH3 C2H, CH3 H H H CH~
CH3 C2H, C2H3 H H H CH3
CH~ C(CH3)3 H H H H CH3
CH3 CH3 CH3 H CH3 H CH~
CH3~ C2H, CH3 H CH3 H CH~
CH3 C2H, C2Hg H CH3 H CH3
CH3 C(CH3 )~ H H CH~ H CH3
CH3 CH3 H 3-C~3 H H CH~
CH3 CH~ H 5-CH3 H H CH~
CH3 .CH3 Cl H H H C~3
CH~ C(CH3)~ Cl H H H CH~
CH3 CH~ CHI 3-CH~ H H CH3
~H3 OCH3 CH3 H H H CH3
CH3 OCH3 OCH3 H H H CH3
CH3 OCH3 C2H, H H H CH3
CH3 CH3 CH3 H H H C2HS
CH3 C2Hs CH3 H H H C2~
CH3 C2H3 C2H3 H H H C2Hs
CH3 CH3 Br H H H H
CH3 CH(CH3)2 CH3 H H H H
Le A 19 123
- 44 -
R R' R2 R3 R4 X' X2
CH3 CH3 CH3 H H H CO2CH3
CH3 C2Hs C~3 H H H CO2CH3
CH3 C2H5 C2H, H H H C02CH3
CH3 CH3 CH3 H H H C2CzHs
CH3 C2H5 CH3 H H H CO2C2Hs
CH3 C2H5 C2H5 H H H CO2C2H~
CH~ CH3 CH~ H H H C~Hg
CH3 C2Hs CH3 H H H C~Hg
CH3 CzH~ C2H, H H H C~Hg
CH3 CH3 CH3 H . H H C3H7
CH3 C2H, CH~ H H H C3 H7
CH3 C2Hs C2H5 H H H C3H7
C~3 CH3 CH3 H H H
CH3 C2H, CH3 H H H
CH3 C2H, C2H3 H H H
CH3 CH~ . CH3 H H Cl CH3
CH3 C2H, CH3 H H Cl CH~
CH3 C2H, C2K, H H . Cl CH~
CH3 CH3 CH3 H H ~H3 CH3
CH3 C2H, CH3 ~ H CH3 C~3
CH3 C2H, C2H, H H CH3 . CH3
CH3 CH, CH, H H CH3 H :
CH3 . C2H~ CH3 H H CH3 . H
CH3 CzH3 C2H~ H H CH3 . H
CH3 CH3 CH3 H CH3 CH~ C~3
CH3 C2H, . CH3 H CH3 CH~ CH3
CH3 C2H~ C2H, H CH3 CH3 CH3
CH3 CH3 CH3 H . H Br H
CH3 C2H5 CH3 H H Br H
CH3 C2H5 C2H~ H H Br H
CH3 CH3 CH3 H H Cl H
CH3 C2H, CH3 H H Cl H
CH3 C2Hg C2H, . H H Cl H
1e A 19 123
~.
.
- 45 -
R R~ R2 R3 R~ X~ ~c2
__
CH3 CH3 CH3 H H Cl C4 H
CH3 Cz H, CH, H H Cl C4H
CH3 C2 H, C2 H, H H Cl C4
CH3 CH3 CH3 H H Br ~ CH3
CH3 C2 H~ CH3 H H Br CH3
CH3 C2H~ CzH~ H H Br CH3
CH3 CH~ CH3 H H F C~ H
CH3 C2 H, CH3 H H F C4 Hs
CH3 C2 H~ C2 H3 H H .F C4 H
CH3 CH3 CH3 H H F CH3
CH3 C2 H~ CH3 H H F CH3
CH3 C2H, C2 H5 H H F ~H3
R4 N ~ X~
R~ CH ~ N ~ R
--N , X~
\ H (IIh)
R2
R Rl R2 R3 R~ X' x2
:
CH3 CH3 CH3 H H H H
CH3 C2 H~ CH3 H H H H
CH3 C2 H, C2 H, H H H H
CH3,, C(CH3 )3 H H H H H
CH3 CH3 CH3 H CH3 H H
CH3 c2 H~ CH3 H CH3 H H
CH3 C2 H, C2 H, H CH3 H H
CH3 C(CH3 )3 H H CH3 H H
CH3 CH3 H 3~CH~ H H H
CH3 CH3 H 5-CH~ H H H
CH3 CH3 Cl H H H H
Le A 19 123
- 46 ~
R Rl R~ R~ R~ X1 x2
__
CH~ C(CH~ )3 Cl H H H H
CH3 CH3 CH3 3-CH3 H H H :
f`l~Jt)r~u r tT tl ~T U ~
~113 ~ n~ ~I n L n
CH3 OCH~ OCH3 H H H H
CH3 OCH3 Cz H~ H H H H
CH3 CH~ 3r H H H H
CH3 CH ( CHs)z CH~ H H H H
CH3 CH3 CH3 H H CH, H
~H3 C2H, C!i3 H H CH3 H
C~I3 C2H, C2 H3 H H CH3 H
CH3 C(CH3 )3 H H H CY.3
CH3 CH3 CH3 H CH~ c~3 H
C~3 C2H5 CH3 H CH3 CH3 H
CH3 C2H, C2H, H CH3 CH~ H
CH3 C(c~3 )3 H H CH3 CH3 H
CH3 CH3 H 3-CH~ H CH3 H
CH3 CH3 H 5-CHs H CH3 H
~H3 CH3 Cl H H CH3 H
CH3 C~CH~ )3 Cl H H CH~ H
CH3 CH3 CH3 3-CH3 H CH3 H
CH3 OCH3 CH3 H H CH~ H
CH3 .OCH3 OCH3 H H CH3 H
CHs OCH3 C2Hg H H CH3 H
CH3 CH3 r Br . H H CH3 H
CH3 CH(CHI)z CH3 H H CH3 H
C~13 CH~ CH3 H H C2H5 H
CH3 C2Hg CH3 H H C2H, H
CH3 C2H, C2H, H H C2H, H
CH3 C(CH3)~ H H H C2Hg H
CH3 CH3 CH3 H H C3H7 H
CH3 C2H3 CHs H H C3 H7 H
CH3 CzH~ C2H9 H H . C3H~ H
CH~ C(CH3)~ H H H C3H7 H
Le A 19 123
.
~P~8~i2
-- 47 --
R R' R2 R3 R~ X1 x2
CH3 CH3 CH3 H H C4 H9 H
CH3 ~2H~ CH3 H H C4 H9 H
CH~ C2 H~ C2Hs H H C4 Hg H
CH3 C(CH3)~ H H H C4H~ H
CH3 CH3 CH3 H H . C6Hs H
CH3 C2H5 CH3 H H C6Hg H
CH3 C2H5 C2H, H H C6H~ H
CH3 C~CH3)3 H H H C6H~ H
CH3 CH3 CH3 H H CO2CH3 H
CH3 C2Hs CH~ H H CO2CH3 H
CH3 C2H5 C2H, H H CO2CH3 H
CH~ C(CH~)3 H H H CO2CH~ H
CH3 CH3 CH3 H H CO2C2H~ H
CH3 C2H, CH3 H H CO2C2H~ H
CH3 C2H, C2H~ H H CO2C2HI H
CH3 C(CH3)3 H H H CO2C2H~ H
CH3 C~3 CH3 H H Cl H
CH3 C2H, CH3 H H Cl H
CH3 C2H5 C2H, H H Cl H
CH3 C(CH3)y H H H Cl H
CH3 CH3 CH3 H H Br H
CH3 C2H5 CH3 H H Br H
CH3 C2H, C2Hs H H Br H
- CH3 C(CH3)3 H H H Br
CH3 C~3 CH3 H H F H
CH3 C2 H, CH3 H H F H
CH3 C2H~ C2H~ H H F H
CH3 C(CH3)3 H H H F H
CH3 CH3 CH3 H H CH3 CH3
CH3 CzHs C~3 H H CH3 CH3
CH3 C2Hg C2H, H H C~3 C~3
CH3 C(CH3)3 H H H CH3 CH3
Le A l9 123
.
~8~
_ 48 -
:: '
R1 R2 R3 Ri X' X~
_ _ _ _ ~
~H3 CH3 CH3 H H CH3 Cl
CH3 C2H5 CH3 H H CH3 Cl
C~3 C2H5 C2H5 H H CH3 Cl
CH~ C(CH3 )3 H H H CH3 Cl
CH3 CH3 CH3 H H CH3 Br
CH3 C2~5 CH3 H H CH3 Br
CH3 C2H, C2H5 H H CH3 Br
C~3 C(CH3)3 H H H CH3 Br
CH3 CH3 CH~ H H CH3 F
CH3 C2H, CH3 H H CH3 F
CH3 C2Hs C2Hg H H CH3 F
CH3 C(CH,)3 H H H CH3 F
CH3 CH3 CH3 H H H Cl
CH3 C2H, CH3 H H H Cl
CH3 C2 H, C2H~ H H H Cl
CH3 C(CH3)3 H H H .H Cl.
CH3 CH3 CHI H H H Br
CH~ C2Hg CH3 H H H Br
CH3 C2H, C2H, H H H Br
CH3 C(CH,), H H H H Br
CH3 CH3 CH3 H H H F
CH3 C2H, CH3 H H H F
CH3 C2H5 C2H, H H H F
CH3 C(CH3 )3 H H H H F
CH3 CH3 CH3 H H C2H, Cl
CH3 C2H, CH3 H H C2H, Cl
CH3 C2H, C2H, H H C2H5 Cl
CH3 C(CH,)3 H H H C2H, Cl
CH3 CH3 CH3 H H C2H9 Br
CH3 C2H~ CH3 H H C2H, Br
CH3 C2H5 CzH5 H H C2H5 Br
CH3 C(CH3 )3 H H H C2H5 Br
CH3 CH3 CH3 H H C2 H5 F
CH3 C2H~ CH5 H H C2H5. F
~ tr r~
~n3 "2 ~5 ~'2 ~ 1l n ~'2 rl5 r
1' 7 r r~ s tr tr r- tr ~
~n3 ~ ,rls ~ 2~ n n n ~'2 n~ r
Le A 19 123
:
.
Z8~
~ ~Xl
R2 H ~III)
R R R2 .R3 R4 X
. ~
CH3 CH3 CH3 H H H
CH3 C~H5 CH3 H H H H
CH3 C2H5 C2H5 H H H H
CH3 C(CH3)3 H H H H H
CH3 C~3 CH3 H OE13 H EI
CH3 C2H5 CH3 H CH3 H H
CH3 C2H5 C2H5 H CH3 H H
CH3 C(CH3)3 H H CH3 H H
CH3 3 C~13 H H CH3 H
C~I3 C2E15 ~E13 H H CH3 H
CH3 C2H5 C2H5 H H C~13 H
C~13 CH3 CH3 H H H CH3
CH3 C2H5 CH3 H H H CH3
CH3 C2H5 C2H5 H H H ~H3
The N-(1,3-azolyl)aLkyl-anilines of the formula (II) have
not hitherto been described in the literature. They are obtained
when anilines of the general formula
~ --NH2 (Vl )
in which
Rl, R2 and R3 have the mEanings stated above,
49 -
q~
~21~ 4
- 50 -
(a) are reacted with azolylalkyl derivatives Or the general
formula
R4
Y-C~X1 ( ) ~
~x2 ~',
in which
A, R , Xl, x2 and Y have the mea:nings stated above,
in the presence of an acid-binding agent and if appropriate
in the presence of a diluent, or
(~) are reacted with azole-aldehydes of the general formula
N
in which
A, Xl and x2 have the meanings stated above,
in the presence of an inert organic solvent and if appropri-
ate in the presence of a catalyst, and the imines formed,
of the general formula
R3 R
~ ~ ~ ~ X2 ;~
R2
in which
A, Rl, RZ, R3, Xl and x2 have the meanings stat,ed
above,~
are reduced, if appropriake in the presence of a polar
20 diluent. J
Only those compounds of the formula (II) in which R4
denotes hydrogen are formed in process (~
The anilines of the formula (VI) required as starting
Le A 19 123
, . .
- '
.
2~
substances in the preparation of the N-(1,3-azolyl)alkyl-
anilines of the ~ormula (II) are generally known compounds
of organlc 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-dimethylaniline, 2,5-dimethylanlline,
3,5-dimethylaniline, 2,6-diethylaniline, 2-ethyl-6-methyl-
aniline, 2~3,4-trimethylaniline, 2,4,6-trimethylaniline,
2,4,5-trimethylaniline, 2-ethyl-4,6-dimethylaniline, 2,6-di-
iO ethyl-4-methylaniline, 2,6-diisopropyl-4-methylaniline,
2,3,5-trimethylaniline, 2,3,6-trimethylaniline, 2-methyl-6-
chloroaniline, 2-tert.-butyl-6-chloroaniline, 2-methoxy-6-
methylaniline, 2,6-dimethoxyaniline, 2-methoxy-6-ethyl-
aniline and 2,6-diethoxyaniline.
The azole-aldehydes of the formula (VII) also required
as starting substances in the preparation of the N-(1,3-
azolyl)alkylanilines of the formula (II) are known (see,
for example, J. Am. Chem. Soc. 61, 891 (1939); Acta Chem.
Scand. 20, 2J600 (1966) and Helv. Chim. Acta 3L~, 147 (1959)),
or they can be obtained by the processes described in the
literature.
Any of the customary acid acceptors can be used as
acid-binding agents in the preparation of the N-(1,3-
azolyl)alkylanilines of the formula (II) by process ().
Alkali metal carbonates, such as potassium carbonate or
sodium carbonate, are preferably used.
Diluents which can be employed in process () are
any of the customary inert organic solvents. Dimethyl-
formamide and toluene are preferably used.
The reaction temperatures can be varied within a
substantial range in process (a). In general, the
reaction is carried out between 0C and 180C, preferably
between 20C and 160C.
In general, the anilines of the formula (VI) and
~5 the azolylalkyl derivatives ofthe formula (V) are employed
Le A 19 123
- 52 -
in equimolar amounts in the reaction in process (~).
However, it is also possible to employ one of the components,
preferably the aniline of the formula (VI), in excess.
Working up and isolation of the reaction products are
effected by customary methods (see the preparative examples
given later).
Inert or~anic solvents which can be used in the
first stage in the preparation of the N-(1,3-azolyl)alkyl-
anilines of the formula (II) by process (~) are any of the
customary solvents of this type. Aromatic solvents, such
as toluene, are preferably used.
Catalysts which can be used in the first stage in
reaction (~) are any of the reaction accelerators customary
for addition reactions of this type. Strong organic
acids, such as ~-toluenesulphonic acid, are preferably used.
Any of the inert polar organic solvents can be used as
the solvent in the second stage of process (~). Alcohols,
such as methanol, are preferably used.
Complex hydrides, for exampl0 sodium borohydride,
can preferably be used as the reducing agent in carrying
out the second stage of process (~).
The reaction temperatures can be varied within a
substantial range both in the first stage and in the
second stage in carrying out process (~). In the first
stage, the reaction is in general carried out at tempera-
tures between 40C and 140C, preferably between 60C
and 120C. In the second stage, the reaction is in
general carried out at temperatures between -10C and
+lQ0C, preferably between 0C and 80C.
In general, the anilines of the formula (VI) and
the azole-aldehydes of the formula (VII) are employed in
equivalent amounts in carrying out process (~). However,
it is also possible to employ one o~ the components,
preferably the aniline of the formula (VI), in excess.
The reducing agent required in the second stage is
Le A 19 ~23
~,
.
~L~2~352
- 53 -
appropriately employed in excess. Working up and isolation
of the reaction products are in each case effected by
customary methods (see the preparative examples given
later).
The formulae (IIIa) and (IIIb) provide general
definitions of the halogenoacetic acid chlorides and
bromides and anhydrides also to be used as starting sub-
stances for process variant (a) according to the invention.
In these formulae, Z preferably represents chlorine, bromine
and iodine.
The halogenoacetic acid chlorides and bromides and
anhydrides of the formulae (IIIa) and (IIIb) are generally
known compounds of organic chemistry. Examples which
may be mentioned are: chloroacetyl chloride, bromoacetyl
chloride, iodoacetyl chloride and the corresponding
bromides and anhydrides.
The formula (I~) provides a general definition of
the halogenoacetanilides required as starting substances in
carrying out process variant (b) according to the invention.
In this formula, Rl, R2, R3 and ~ pre~erably have those
meanings which have already been mentioned as preferred
therefor in connection with the description of the
substances of the formula (I) according to the invention.
The halogenoacetanilides of the formula (IV) are
generally known, or they can be obtained in a generally
known manner by reacting corresponding anilines with a
halogenoacetic acid chloride or bromide or anhydride of the
formula (IIIa) or (IIIb) in the presence of an inert
organic solvent, for example toluene or dimethylformamide,
if appropriate in the presence of an ac~d-binding agent,
for example potassium carbonate or triethylamine, at
temperatures between 0 and 100C (see also the pre-
parative examples given later in this text). Examples
which may be mentioned are the chloroacetanilides and
bromoacetanilides of the above-mentioned anilines of the
formula (VI).
Le A l9 123
: ,. ~
.
,.:: :.
.
. .
- 54 -
The formula (~) provides a general definition of
the azolylalkyl derivatives also to be used as starting
substances for process variant (b) according to the in
vention. In this formula, A, R , X and X preferably
have those meanings which have already been mentioned as
preferred in connection with the description of the
subs~ances of the formula (I) according to the in~ention~
Y preferably represents chlorine, bromine or the mesylate
or tosylate radical.
The azolylalkyl derivatives of the formula (V) are
known (see, inter alia, J. Am. Chem. Soc. 56, 470 (1934);
J. Am. Chem. Soc. 73, 2,935 (1951) and J. Org. Chem. 25,
1,151 (1960)) or they can be obtained in a generally known
manner, for example by halogenoating the corresponding
methyl derivatives by customary methods. The following
compounds may be mentioned as specific examples of compounds
of the formula (V):
x2
I ~ ~ (Va)
Y - CH - S X1
X1 X2 R4 y X' X2 R4 Y
~ . i .. . .. ~ _ ,.
H H H Cl(Br) CH3 CH3 HCl(Br)
H CH3 H Cl(Br) CH3 H HCl ( Br)
H CzHs H Cl(Br) CH3 CH3 CH3 Cl ( Br )
H C 6H ~ H Cl ( Br ) H H CH3 Cl ( Br)
Cl CH~ H Cl(Br) ,
- ~X' '
R4 N_
Y - CH ~~ S ( Vb )
X2
X' x2 R4 y Xl x2 R4 Y
_
CH3 H H Cl(Br) H C1 H Cl(Br)
H H H Cl(Br) CH3 Cl H Cl ( Br)
CH3 CH3 H Cl(Br) H H CH3 Cl(Br)
C6H5 H H Cl(Br~
Le A 19 12 3
'.
.
, , :
'
- 55 -
X'
R4 S l~/
Y - CH ~ N (Vc)
X' X2 R4 Y X' X2 R4 Y
. . _
H H HCl(Br) H CH3 ~ Cl(Br)
CH3 H H Cl(Br)
R4 N ~ X
~ ~ (~d)
Y - CH Q \X1
X' X2 R4 Y l X~ X2 R~ Y
. , ~
H H H Cl ( Br ) CH3 CH3 H Cl ( Br)
H CH3 H Cl(Br) CH3 H H Cl ( Br)
H C2 H~ H Cl ( Br) CH3 CH3 CH3 Cl ( Br)
H C6H, H Cl(Br) H H CH3 Cl(Br)
Cl CH3 H Cl ( Br)
R4 N~X~
Y - CH--~ (Ve)
X1 x2 R4 y X' x2 R4 Y
CH~ H H Cl ( Br ) H Cl H Cl ( Br)
H H H Cl(Br) CH3 Cl H Cl(Br)
CH3 CH3 H Cl (Br) H H CH3 Cl (Br)
C61i, H H Cl(Br) ¦
,.
Le A 19 123
~ ~-
: -
; . ~ ,
s~
N (Vf)
X2
X1 x2 R4 Y X~ X2 Rb y
. . .
H H H Cl(Br) H CH3 ~ Cl(Br)
CH3 H H Cl(Br)
R4 N ~ X2
Y ~ CH ~ ~ N ~ X' (Vg)
CH3
X~ X2 R4 y l X~ X2 R4 Y
__ __ , .... ~
H H H Cl(Br) ¦ CH3 CH3 H Cl(Br)
H CH1 H Cl(~r) I CH3 H H Cl(Br)
H C2H~ H Cl(Br) I CH3 C~3 CH3 Cl(Br)
H C6H, H Cl(Br) ¦ H H CH3 Cl(Br)
Cl CH3 H Cl(Br) ¦ .
~,X'
R4 N ~
Y - CH ~ ~ N`CH3 (Vh)
X~ X2 R4 Y I X~ X2 R4 Y
~ ._ . . _ _ :
CH3 H H Cl(Br) H Cl H Cl(Br) .
H H H Cl(Br) CH3 Cl H Cl(Br)
CH3 CH3 H Cl(Br) H H CH3 Cl(Br)
C6H5 H H Cl(Br)
Le A 19 123
'' '
'
'
,
- 5 1 -
CH~
N~
Y - ~H ~ N ~Vi)
x2
X~ X2 R4 Y I X~ X2 R4 Y
~ _ ____
H H H Cl(Br) H ~ H Cl(Br)
CH3 H H Cl(Br)
Preferred diluents for the reaction, according to
the.invention, in process variant (a) are inert organic
solvents. These include, as preferences, ketones, such as
di.ethyl ketone, and in particular acetone and methyl ethyl
ketone; nitriles, such as propionitrile, and in particular
acetonitrile; ethers, such as tetrahydro~uran or dioxan;
aliphatic and aromatic hydrocarbons, such as petroleum ether,
benzene, toluene or xylene; halogenated hydrocarbons, such
as methylene chloride,. carbon tetrachloride, chloroform or
chlorobenzene; and esters, such as ethyl acetate.
If appropriate, process. variant (a) according to the
invention can be carried out in the presence of an acid-
binding agent (hydrogen chloride acceptor). Any of the
customary acid-binding agents can be used here. These
include, as preferences, organic bases, such as tertiary
amines, for example triethylamine, or pyridine, and further-
more inorganic bases, for example alkali metal hydroxides
and alkali metal carbonates.
The reaction temperatures can be varied within a
substantial range in carrying out process variant (a)
according to the invention. In general, the reaction is
carried o.ut at from 0C to 120C~ preferably at from 20C
to 100C.
In carrying out process. variant (a) according to the
Le A 19 12}
.
: . .
,' ' ' ' :
.
- 58 -
invention, 1 to 1.5 moles of halogenoacetylating agent
and 1 to 1.5 moles of acid-binding agent are preferably
employed per mole o~ the compound of the formula (II).
Isolation of the compounds of the formula (I) is effected
in the customary manner.
Possible diluents for the reaction~ according to
the invention, in process variant (b) are all the inert 5
water-i~miscible, organic solvents. These include, as
preferences, ethers, such as diethyl ether; aromatic hydro-
carbons 5 such as ben~ene, toluene or xylene; halogenatedhydrocarbons, such as methylene chloride, carbon tetra-
chloride, chloroform or chlorobenzene; and esters, such as
ethyl acetate.
The reaction, according to the invention3 in process
variant (b) is carried out in the presence of an acid-
binding agent. Any of the customary acid-binding agents can
be used here. These include, as preferences, inorganic
bas0s, for example alkali metal hydroxides and alkali
metal carbonate~j ~or example sodium or potas~ium hydroxide
and sodlum or potassium carbonate.
The reaction temperatures can be varied within a
substantial range in carrying out process variant (b)
according to the invention. In general, the reaction is
carried out at from -70C to ~100C, preferably from -20C
to +80C.
In carrying out process variant (b) according to the
invention, 1 to 1.5 moles of azolyl-alkyl derivative of
the formula (V) are preferably employed per mole of halogeno-
acetanilide of the formula (IV). Isolation of the com-
pounds of the formula (I) is effected in the customarymanner.
In a preferred embodiment, the reaction3 according
to the invention, in process variant (b) 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
Le A 19 123 ,
. .
~2~3524
- 59 -
0.1 - 1 mol of a phase transfer cataly.st, for example an
ammonium or phosphonium compound, benzyl-dodecyl-dimethyl-
ammonium chloride (Zephirol) and triethyl-benzyl-ammonium
chloride being mentioned as examples (see also the pre-
parative examples herein).
The substances of the formula (I) accordi~g tothe invention, whether prepared by process variant (a) or
by process variant (b), can be converted into acid addition
salts and metal salt complexes.
The following acids are preferably used for the pre-
paration of physiologically acceptable acid addition salts
of the compounds of t~e formula (I): hydrogen halide
acids (for example hydrobromic acid and, in particular
hydrochloric acid), phosphoric acid, nitric acid, sul- - -
phuric acid,monofunctional and bifunctional carboxylic
acids and hydroxycarboxylic acids (for example acetic acid,
maleic acid, succinic acid, fumaric acid, tartaric acid,
citric acid, salicylic acid, lactic acid and sorbic acid)
and sulphonic acids (for example ~-toluenesulphonic acid
and 1,5-naphthalenedisulphonic acid).
The acid addition salts of the compounds of the
formula (I) can be obtai~ed in a simple manner by customary
salt formation methods, for example by dissolving a compound
of the form~la (I) in a suitable inert solvent and adding
the acid, for example hydrochloric acid, and can be
isolated in a known manner, for example by filtration, and
if appropriate purified by washing with an inert organic
so.lvent.
Salts of metals of main groups II to IV and of sub-
gr.oups I and II and IV to ~III are prèferably used forthe preparation of metal salt complexes of the compounds of
the formula (I), examples of metals which may be mentioned
being. copper, zinc, manganese, magnesium, tin, iron and
nickel. Preferred anions of the salts are those which are
deri.ved from the following acids: hydrogen halide acids
(for example hydrochloric acid and hydrobromic acid), l:
Le A l9 123
, : ~
.
~ . '' ' .
"
2g
- 60 -
phosphoric acid, nitric acid and sulphuric acidr
The metal salt complexes of compounds of the formula
(I) can be obtained in a simple manner by customary pro-
cesses, ~or example by dissolving the metal salt in
alcohol, for example ethanol, and adding the solution to
the compound of the formula (I). The metal salt complexes
can be purified in a known manner, for example by fil-
tration, isolation and, if appropriate, by recrystallisat-
ion.
The active compounds according to the invention
influence plant growth and can therefore be used as
defoliants, desiccants, agents for destroying grasses and
broad-leaved plants, germination inhibitors and, especially,
as weed-killers. By "weeds" in the broadest sense there are
meant plants growing in places where they are not desired.
Whether the compounds according to the invention
act as total herbicides or selective herbicides depends
essentially on the amount used.
The active compound~ according to the present in-
vention may be used, for example, to combat the followingplants:
dicotyledon weeds o~ the genera S'inapis, ~ ,
Calium, Stellaria, Matricaria, Anthemis, Gali~s'oGa
.. .... , ....,.,~_ ~
Chenopodium, U~t'i'ca, Senec'io,''~m~ra'n't'h'us,''Po'r't'ul'aca~
.. . .....
Xanthium, Con~olvulus, Ipomoea, Poly~onum, Sesbania
--Ambrosia, Cirsium, Ca~duus,'S'on'chus, Rorippa, Rotala
". .. _ ,,
Lindernia, La~ium,~ Veronica, Abutilon, Emex, Datura,
__ .. . . . _ . ..
' ~io-la,''Gale:o'psis,~Papa~er, Centaurea an~ So'l'an'um; and
monocotyledon weeds of the genera''E'ch'inoc'hl'oa,
Setaria, Pa~i~cum, Digitaria,~ Phleum, Poa, Festuca
.. . .
Eleusine 3' '~achi'aria, Lol'ium,' B~o'mus,' A~e'na~'Cy'pe'rus,
So~hum, Agropyron~ Cynodon, Monocho~ia, Fimbristylis,
. ~
S~gittaria, Eleoc'h:~is,' Scirpus, P~spalum, Ischaemum,
Sphenoclea, Dactyloctenium, Agrostis, ~ and
~5 Apera.
.
i
Le A 19 123
.
,~
~ .
~1~8~ii2
-- 61 --
The active compounds according to the pre.sent i.nvention
may be used, for e~ample, as selective herbicides in the
~ollowing cultures:
dicotyledon cultures of the genera ~ossypium,
Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum,
Ipomoea, Vicia, Nicotiana, Lycopersi~con, Arachis,
Bras-sica, Lactuca, Cucu~is and'Cucurbi'ta; and
monocotyledon cultures o~ the genera ~yza, Zea,
Triticum, Hordeum, Avena, Secale,' ~ hum, Panicum,
Saccharum, Ananas, Asparagus and Allium.
However, the use of the active compounds according
to the invention is in no way restricted to these genera
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,
for example afforestations, decorative tree plankings,
orchards, vineyards, cltrus groves, nut orchards, banana
plantations, co~fee plantations, tea plantations, rubber
plantations, oil palm plantations, cacao plantations, soft
fruit plantings and hopfields, and for the selective combating
of weeds in annual cultures. '
In addition to a very good action against graminaceous
weeds and against varieties o~ , the active compounds
according to the invention also exhibit, in particular, a
good herbicidal action on broad-leaved weeds. It is
possible to use the active compounds according to the
30 invention selectively, preferably on cereals, rape-seed, l:
cotton and sugar beet.
The active compounds can be converted to the custom- .
ary ~ormulations, such as solutions, emulsions, wettable
poweders, suspensions, powders, dusting agents, pastes,
soluble powders, granules, suspension-emulsion concentrates,
natural and synthetic materials impregnated with active
Le A 19 12~
~lZ~3~
- 62 --
compound, and very fine capsules in poIymeric substances.
These formulations are produced in known manner, for
example by mixing the active compounds with extenders, that
is to say liquid or solid diluents or carriers, optionally
with the use of surface-active agenks,that is to say
emulsifying agents and/or dispersing agents and/or foam-
forming agents. In the case of the use of water as an
extender, organic solvents can, for example, also be used
as auxiliary solvents.
As liquid diluents or carriers, especially solvents,
there are suitable in the main, aromatic hydrocarbons,
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
esters, ketones, such as acetone, methyl ethyl ketone,
methyl isobutyl ketone or cyclohexanone, or strongly
polar solvents, such as dimethylformamide and dimethyl-
sulphoxide, as well as water.
As solid carriers there may be used ground natural
minerals, such as kaolins, clays, talc, chalk, quartz,
attapulgite, montmorillonite or diatomaceous earth, and
ground synthetic minerals, such as highly-dispersed silicic
acid, alumina and silicates. As solid carriers for granules
there may be used crushed and fractionated natural rocks
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 sawdust,
coconut shells, maize cobs and tobacco stalks.
As emulsifying and/or foam-forming agents there
may be used non-ionic and anionic emulsifiers, such as
polyoxyethylene-fatty acid esters, polyoxyethylene-fatty
alcohol ethers, for example alkylaryl polyglycol ethers,
~,
Le A 19 123
~2~52
- 63 -
alkyl sulphonates, alkyl sulphates, aryl su~phonates as
well as albumin hydrolysis products. Dispersing agents
include, for example, lignin sulphite waste liquors and
methylcellulose.
Adhesives such as carboxymethylcellulose and natural
and synthetic polymers in the form of powders, granules
or latices, 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 example 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 according to the invention, as
such or in the form of their formulations, can also be
used, for combating weeds, as mixtures with other herbi-
cides, finished formulations or tank mixing being possible.
Mixtures with other active compounds, such as ~ungicides,
insecticides, acaricides, nematicides, bird repellants 3
growth factors, plant nutrients and agents which improve
soil structure, are also possible.
The active compounds can be used as such, in the
form of their formulations or in the use forms prepared
therefrom by further dilution, such as ready-to-use solutions,
suspensions,~emulsions, powders, pastes and granules. They
may be used in the customary manner, for example by watering,
spraying~ atomising and scattering.
The active compounds according to the invention can
be applied either before or after emergence of the plants.
They are preferably used before emergence of the plants,
that is to say by the pre-emergence process. They can
,
Le A l9 123
~ . . ' i
....
.' ,: ~.
., .
~2~3{;2~3L
- 64
also be incorporated into the soil before sowing.
The amount of active compound used can vary within
a substantial range. It depends essentially on the nature
of the desired effect. In general, the amounts used are
from Ool to 10 kg of active compound per hectare, preferably
from 0.1 to 5 kg/ha.
The present invention also provides a herbicidal
composition containing as active ingrecLient 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 com-
bating weeds which comprises applying to the weeds, 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
with a diluent or carrier~
The present invention further provides crops protected
f'rom 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 o~ 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,
3 which will be found later in this specification.
m e known comparison compound i8 identified as follows:
(A) - ~ ~Hs , CH2 - OCU~
Cz ~ C~2 Cl
~2,6-~iethyl)-N-methoxymethyl-chloroacetarilide .
Le A 19 123
Exampl'e A
Pre-emergence test
Solvent: 5 parts by weight of acetone
Emulsifier: l part by weight of alkylaryl polyglycol
ether
To produce a suitable preparation of active compo~d,
l part by weight of active compound Wa5 mixed with the
s~ated 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 plants were sown in normal soil
and, after 24 hours, watered with the preparation of
the active compound. It was expedient to keep constant
the amount of water per unit area. The concentration
of the active compound in the preparation was of no import-
ance, 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
compari~on to the development o~ ~he untreated control.
The figures denoted:
0% = no action (like untreated control)
100% = total destruction
In this test3 active compounds (1)~ (2) and (4)
exhibited a better selective activity than substance (A)
which is known from the prior art~
. ~ .
Example l 11 ~
/CH3 CH2 ~N ~ CH3
_ N \ (1)
CH3 C - CH2Cl
o
Process variant (a)
11.6 g (0.05 mol) of 2~6-dimethyl-N-(2'-methyI-thia-
zol-4'-yl-methyl)-aniline and 4 g (0.05 mol) of pyridine
- Le A 19 123
.
~;285Z~
- 66 -
were heated to the boil in 100 ml of absolute tetrahydrofuran,
and 5.7 g (0.05 mol) of chloroacetyl chloride were added
dropwise. After 15 minutes, the reaction solution was
concentrated in vacuo. Water was added to the residue and
the organic phase was extracted with methylene chloride.
After drying over sodium sulphate and distilling off the
solvent in vacuo, an oily residue remained which became
crystalline on trituration with petroleum ether. 12.5 g
(81% of theory) of 2,6-dimetnyl-N-(2'-methyl-thiazol-4'-
yl-methyl)-chloroacetanilide of melting point 60-62C were
obtained.
Preparation of~the st~artin~_mat'er'ial
N~`CH3
`CH3 H
Process ()
60.5 g (0.5 mol) of 2,6-dimethylaniline and 27.6 g
(0.2 mol) of finely powdered potassium carbonate were
heated to 100C in 100 ml of dimethylformamide, and 30 g
(0.2 mol) of 4-chloromethyl-2-methyl-thiazole were added
dropwise, whilst stirring~ The mixture was stirred at 100C
for 5 hours. Thereafter, the reaction mixture was poured
onto 300 ml of water and extracted with methylene chloride.
The organic phase was dried over sodium sulphate and
concentrated. The residue was distilled' in vacuo. 28.6 g
(63% of theory) of 2,6-dimethyl-N-(2'-methyl-thiazol-4'-yl-
methyl)-aniline of boiling point 128-130C/0.05 mm Hg were
obtained.
Le A 19 123
~2~5
- 67 -
Ex;a~ple ?
CH3 /CH2 N `CH3 (2)
- N\
'C2Hs C - CH2Cl
Process variant (b)
4.8 g (0.022 mol) of 2-ethyl-6-methyl-chloroacet-
anilide were dissolved in a two-phase mixture of 40 ml of
toluene and 20 ml of 50% strength sodium hydroxide solution,
after adding 0.1 g of triethyl-benzyl-ammonium chloride~ -
and 4.2 g (0.022 mol) of 4-bromomethyl-2-methyl-thiazole
were added dropwise, whilst stirring vigorously. The
mixture was subsequently stirred at room temperature for
3 hours. The toluene phase was then separated off, washed
several times with water and dried over ~odium sulphate.
After distilling off the solvent in vacuo, 6.3 g (93% of
theory) of 2-ethyl-6-methyl-N-(2'-methyl-thiazol-4'-yl-
methyl)-chloroacetanilide were obtained as a viscous oil
with a refractive index of n20 - 1.573.
Preparation o_ the 'startihg mat'erial
/CH3 H
(IV-l) ~ -N/
\C2H5 IC - CH2Cl
O
152 g (l.l mol) of potassium carbonate were added
to 135.2 g (1 mol) o~ 2-ethyl-6-methyl-aniline in 1,000 ml
of toluene. 113 g (1 mol) of chloroacetic acid chloride
were added dropwise to this mixture, whilst stirring.
When the exothermic reaction had subsided~ the mixture was
subsequently stirred under reflux for 2 hours. The
Le A l9 123
~ -
,
~ ~ 8
- 68 -
reaction mixture was then filtered and the filtrate was
concentrated to 500 ml in acuo. The crystals thereby
formed were filtered off and washed with petroleum ether.
189.6 g (98% of theory) of 2-eth~1-6-methyl-chloroacetanilide
were obtained in the form of white crystals of melting point
120C
Those compounds listed in Table l were obtained in a
corresponding manner.
T a b 1 e
R4 ~ X
R ~ \ X2 (I~)
X' Melting
No. R' R2 R3 R4 z ~N ~ X2 ~oint
. ¦ ca. C2 H~ H _ 5
4 C2H5 C2 H~ H ~ N~`CH3 62-65
C(CH3)3 H H H C1 1N~CH 85-86:
~ 6 CH3 H 3-CH3 H Cl ~ N~-CH3 72-74
7 C2H, C2H, H ~ ~ -CH3 95-96
; 8 C2Hs C2H~ H 1 l N~ 71-72
~ . --S . .
~ CH3 C2H, H H Cl ~ ~ 42-44
:
~ Le A l9 123
:'
~: :
~L12~i2
- 6 9 -
~ a ~ l e l (continued
Example 1 2 ~ 4 ~X Melting
No. R R R R Z t~ 3oint
10l CH3 CH3 H H Cl J~S~J`CH3 ~ isc~u~
ll~ CH3 CH3 H H Cl ~3 ¦ a
13 CH H 5_CH3 H 1~M~CH 76-77
~ '14 ¦ CH3 H 3-CH3 H C1 N~CH3 59-60
:~ ,
Le A 19 123 3.
... ~ - ,
~;'`' ' ' ~:
~'' ' ' ,
2 ~
- 70 -
The starting materials of the formula (II) listed in
Table 2 below were obtained by one or more of the processes
described in the foregoing specification and in a manner
corresponding to that described in Example l.
T a b l e 2
E~- R' R2 R3 R4 ~ Boiling
ample N
(II~2) CH3 C2H, H ~ -S 149C/
' N -CH3 0.05 mm Hg
(II-3) CH3 C2Hg H H ~ ~ _ ~ 188C/
N 0.015 mm Hg
(II-4) C2H~ C2H~ H H l gS l40-45C/
(II-5) C(CH3)3 H H H ~ ~ l53-60 C/
(II-6) CH3 H 3-CH3 H ~ l point
N CH3 73-74V
(II-7) c2 H, C2 H~ H l ~ 150-60C/
N -CH3 O.l mm Hg
Le A 19 123
. .
2~
T a b 1 e 2 ~continued)
Ex- Rl R2 R3 R4 ~ Boiling
ample N~ po m t or
No. melting
point
-
(II-8~ C2HS C2H5 H H J~N J 0.2 mn Hg
~II-9) OEI3 C2H5 H J~N J 128-32 C/
:
~II-10) CH3 CH3 H H ~ C 13 140-45 C/
~ ll) CH3 CH3 H N 142-45C/
(II-12 ) C~I3 C2H5 H H l~ 144-50 C/
S 0.2 Irlfl Hg
(II-13) CH3 H 5-OEI3 H ~N'lCH3 131-41 C/
~II--14) CH3 H 3-CH3 H l~ melting po~llt
S 85-86C
, .
- 71 -
'; ~'~''`'
.~ ~
~lZ~5Z~
-- 72 --
The starting materials of the formula (IV) listed
in Table 3 below were obtained by known processes~ and in
a manner corresponding to that described in Example 2.
T a b I e 3
R3 R~
C - CH2 - Z (IV)
R2 li
Example Meltin~
NoO p, _ p,2 _ _ R3 z point C
(IV^2) C~.3 C'.~.3 ~ C1 148
(IV-~) C2H~ C2Hs H Cl 1~3
(I~!-4) i-C~H7 H H Cl 79
(IV-5) tert.-C4 Hg H H Cl 96
(IV-6) C2H~ H H C1 103
(l~r_7) CH3 H H Cl 109
(IV-8) CH3 H 3-H3 C1 135
( T','_9 ) CH3 H 5~C~i3 Cl 154
(IV-10~ CH3 CH3 4-CH3 Cl }77
(IV-ll) C2H~ C~3 4-CH3 Cl 134
(IV-12) sec~-c4 Hg H H Cl Oil
(IV-13) H H H Cl 132
Le A 19 123
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