Use of 2-(n-phenylamino)pyrimidines as fungicides, and novel...

Details Use of 2-(n-phenylamino)pyrimidines as fungicides, and novel... Use of 2-(n-phenylamino)pyrimidines as fungicides, and novel...

2000-12-05

2003-05-13

Rao, Deepak (Department: 1624)

Drug, bio-affecting and body treating compositions

Designated organic active ingredient containing

Having -c-, wherein x is chalcogen, bonded directly to...

C544S330000, C544S332000

Reexamination Certificate

active

06562833

ABSTRACT:

The present invention relates to the use of 2-(N-phenylamino)pyrimidines of the formula I,
where:
R
1
, R
3
independently of one another are cyano, C
1
-C
8
-alkyl, C
2
-C
6
-alkenyl, C
2
-C
6
-alkynyl, where the radicals alkyl, alkenyl and alkynyl may be substituted by cyano, halogen, C
1
-C
4
-alkoxy or C
1
-C
4
-alkoxycarbonyl, or are C
3
-C
8
-cycloalkyl or a group C(═NOR
x
)R
y
;
R
x
is hydrogen, C
1
-C
8
-alkyl, C
2
-C
6
-alkenyl, C
2
-C
6
-alkynyl, where the radicals alkyl, alkenyl and alkynyl may be substituted by cyano, halogen, C
1
-C
4
-alkoxy or phenyl;
R
y
is hydrogen, C
1
-C
8
-alkyl, C
2
-C
6
-alkenyl, C
2
-C
6
-alkynyl, where the radicals alkyl, alkenyl and alkynyl may be substituted by cyano, halogen or C
1
-C
4
-alkoxy;
R
2
is halogen, C
1
-C
8
-alkyl, C
2
-C
6
-alkenyl, C
2
-C
6
-alkynyl, where the radicals alkyl, alkenyl and alkynyl may be substituted by cyano, halogen, C
1
-C
4
-alkoxy or C
1
-C
4
-alkoxycarbonyl; or
R
1
and R
2
together with the two linking carbon atoms form a fused-on partially unsaturated 4- to 8-membered ring which may be up to trisubstituted by identical or different substituents selected from the group consisting of C
1
-C
4
-alkyl, halogen and C
1
-C
4
-alkoxycarbonyl, which may contain a carbonyl group and/or, in addition to the multiple bond of the pyrimidine ring, a double bond and/or which may be interrupted by O, S or N—(C
1
-C
4
-alkyl);
R
4
to R
8
independently of one another are hydrogen, cyano, halogen, R
a
, R
a
O, R
a
S(O)
m
, R
a
O—(C═O), R
a
(C═O), R
a
R
b
N—(C═O), R
a
HN—(C═O), H
2
N—(C═O), R
a
—(C═O)—NH, R
a
—(C═O)—NR
b
or R
a
O—N═C(R
b
);
R
a
, R
b
are C
1
-C
4
-alkyl, C
3
-C
6
-alkenyl or C
3
-C
6
-alkynyl, each of which may be substituted by cyano, halogen, C
1
-C
4
-alkoxy, C
1
-C
4
-alkoxycarbonyl or phenyl, or are phenyl which may carry one to three substituents selected from the group consisting of halogen and C
1
-C
4
-alkyl;
m is 0, 1 or 2;
as fungicides.
Fungicidal 2-(N-phenylamino)pyrimidines carrying a hydrogen atom in the 5-position of the pyrimidine ring are known from EP-A 224 339, EP-A 270 111, EP-A 310 550, EP-A 457 726, DD 151404 and JP 03/271278.
2-(N-phenylamino)pyrimidines substituted in the 5-position have been described as intermediates for herbicidally active compounds (EP-A 337 944) and as pharmaceutics (WO-A 97/19065).
Finally, fungicidal 2-(N-phenylamino)pyrimidines which may be substituted in the 5-position and which carry a specific 2-nitrophenyl radical at the amino function are known from EP-A 172 786.
However, the compounds mentioned in EP-A 172 786 do not always fully meet the requirements which have to be met by active compounds in practice.
It is an object of the present invention to provide fungicidally active compounds having improved properties.
We have found that this object is achieved by the abovementioned compounds, some of which have already been mentioned in the publications EP-A 337 944 and WO-A 97/19065, which are outstandingly suitable for controlling harmful fungi. In addition, we have found novel 2-(N-phenylamino)pyrimidines having improved fungicidal activity.
It is a common feature of all aminopyrimidines according to the invention, both the novel aminopyrimidines and those known from EP-A 337 944 and WO-A 97/19065, that they carry hydrophobic substituents in each of positions 4, 5 and 6.
The novel 2-(N-phenylamino)pyrimidines can be prepared similarly to methods known from the literature. Particularly suitable are the process routes shown in Schemes 1 and 2.
The condensation reaction of the guanidines II with 1,3-dicarbonyl compounds of the formula III to give the 2-(N-phenylamino)pyrimidines I can be carried out as described in EP-A 337 944 and the literature cited therein.
With regard to the synthesis of the guanidines II, reference is made to Houben-Weyl, Methoden der Organischen Chemie, Stuttgart, Vol. VIII pp. 98, 180 to 189. The 1,3-diketones III can be prepared, for example, either by a) Claisen condensation or by b) alkylation or halogenation of a 1,3-diketone which is unsubstituted in the 2-position (Organikum, 1993 Barth Verlagsgesellschaft Leipzig, a) p.487 b) p. 536).
The preparation of the 2-(N-phenylamino)pyrimidines I starting from aniline derivatives of the formula IV and pyrimidine derivatives of the formula V where X is a nucleophilically replaceable group, such as halogen or C
1
-C
4
-alkylsulfonyl, is described in EP-A 337 944.
The compounds I according to the invention in which R
3
is C(═NOR
x
)R
y
are preferably prepared from the aldehydes VI (see Scheme 3), and the aldehydes VI for their part can be synthesized similarly to EP-A 457 726.
Compounds Ia in which R
3
is CH(═NOR
x
) are obtained by reacting the aldehydes VI with the alkoxyamines VII under conditions known per se (Scheme 3).
Moreover, the aldehydes VI can be converted under conditions known per se with organometallic reagents, such as Grignard reagents VIII (R
y
—Mg—X; X═Cl, Br, I), into the secondary alcohols IX.
The oxidation of these alcohols IX, preferably according to Swern using oxalyl chloride/DMSO, gives the ketones X which for their part can be reacted with alkoxyamines VII to give the compounds Ib according to the invention.
The active compounds Ic in which R
3
is cyano (Scheme 4) can preferably be prepared by reacting the aldehydes VI with hydroxylamine, followed by dehydration of the resulting oximes XI (similarly to EP-A 457 726).
In the definition of the compounds I given at the outset, collective terms which represent individual enumerations of each of the group members were used for the radicals R
1
to R
8
, R
x
and R
y
and R
a
and R
b
. The radicals alkyl, alkoxy, alkoxycarbonyl, alkenyl and alkynyl can be straight-chain or branched.
Examples of meanings are:
halogen: fluorine, chlorine, bromine or iodine;
C
1
-C
4
-alkyl: methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl or 1,1-dimethylethyl;
C
1
-C
8
-alkyl: C
1
-C
4
-alkyl, as mentioned above, and also pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-3-methylpropyl, heptyl, octyl or 2-ethylhexyl;
C
1
-C
2
-haloalkyl: a C
1
-C
2
-alkyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, i.e. for example chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl or pentafluoroethyl;
C
1
-C
4
-alkoxy and the alkoxy moieties of C
1
-C
4
-alkoxycarbonyl: methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy or 1,1-dimethylethoxy;
C
1
-C
2
-haloalkoxy: a C
1
-C
2
-alkoxy radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, i.e. for example fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, bromodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromomethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, pentafluoroethoxy;
C
2
-C
6
-alkenyl: ethylene, prop-1-en-1-yl, prop-2-en-1-yl, 1-methylethenyl, buten-1-yl, buten-2-yl, buten-3-yl, 1-methylprop-1-en-1-yl, 2-methylprop-1-en-1-yl, 1-methylprop-2-en-1-yl and 2-methylprop-2-en-1-yl, penten-1-yl, penten-2-yl, penten-3-yl, penten-4-yl, 1-methylbut-1-en-1-yl, 2-methylbut-1-en-1-yl, 3-methylbut-1-en-1-yl, 1-methylbut-2-en-1-yl, 2-methylbut-2-en-1-yl, 3

Affiliated with

Also associated with

Rating

Use of 2-(n-phenylamino)pyrimidines as fungicides, and novel... does not yet have a rating. At this time, there are no reviews or comments for this patent.

If you have personal experience with Use of 2-(n-phenylamino)pyrimidines as fungicides, and novel..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Use of 2-(n-phenylamino)pyrimidines as fungicides, and novel... will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFUS-PAI-O-3088651