Organic compounds -- part of the class 532-570 series – Organic compounds – Nitriles
Reexamination Certificate
1999-02-26
2002-04-30
Higel, Floyd D. (Department: 1626)
Organic compounds -- part of the class 532-570 series
Organic compounds
Nitriles
C564S027000, C564S029000
Reexamination Certificate
active
06380422
ABSTRACT:
The invention relates to a compound of the formula I
and the disulfide thereof and salts thereof, processes for the preparation thereof and the use thereof for the preparation of compounds having a microbicidal and plant-immunizing action, of the formula III
in the compounds of the formulae I and III:
X is halogen,
n is 0, 1, 2 or 3;
Z is CN, CO—A or CS—A,
A is hydrogen, OR
1
, SR
2
and N(R
3
)R
4
;
R
1
to R
4
are hydrogen, a substituted or unsubstituted, open-chain, saturated or unsaturated hydrocarbon radical containing not more than 8 carbon atoms, a substituted or unsubstituted cyclic, saturated or unsaturated hydrocarbon radical containing not more than 10 carbon atoms, substituted or unsubstituted benzyl or phenethyl, a substituted or unsubstituted alkanoyl group containing not more than 8 carbon atoms, a substituted or unsubstituted benzoyl group or a substituted or unsubstituted heterocyclyl radical; or R
3
and R
4
, together with the nitrogen atom to which they are bonded, are a 5- or 6-membered, substituted or unsubstituted heterocyclic radical having 1-3 heteroatoms O, S and/or N.
The compounds of the formula I have at least one basic group and can thus form acid addition salts. The se are formed, for example, with mineral acids, for example sulfuric acid, a phosphoric acid or a hydrogen halide acid, with organic carboxylic acids, for example acetic acid or oxalic, malonic, maleic, fumaric or phthalic acid, with hydroxycarboxylic acids, for example ascorbic, lactic, malic, tartaric or citric acid, or with benzoic acid, or with organic sulfonic acids, for example methane- or p-toluenesulfonic acid. On the basis of the SH group or an acid group in the substituent Z, compounds of the formula I can furthermore form salts with bases. Suitable salts with bases are, for example, metal salts, such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as morpholine, pipesdine, pyrrolidine, a mono-, di- or ti-lower al kylamine, for example ethyl-, diethyl-, tethhyl- or dimethyl-propyl-amine, or a mono-, di- or trihydroxy-lower alkylamine, for example mono-, di- or triethanolamine. If appropriate, corresponding inner salts can furthermore be formed.
Unless defined otherwise, the general terms used above and below have the meanings given below:
Hydrocarbon radicals can be saturated or unsaturated and open-chain or cyclic, or a mixture of open-chain and cyclic, for example cyclopropyl methyl or benzyl.
Alkyl groups are straight-chain or branched, depending on the number of carbon atoms, and are, for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert- butyl, sec-amyl, tert-amyl, 1 -hexyl or 3-hexyl.
Unsaturated hydrocarbon radicals are alkenyl, alkynyl or alkenynyl groups with at least 3 multiple bonds, for example butadienyl, hexatrienyl, 2-penten-4-ynyl.
Alkenyl is to be understood as meaning straight-chain or branched alkenyl, for example allyl, methallyl, 1-methylvinyl or but-2-en-1-yl. Alkenyl radicals with a chain length of 3 to 4 carbon atoms are preferred.
Alkynyl can likewise be straight-chain or branched, depending on the number of carbon atoms, f or example propargyl, but-1-yn-1-yl and but-1-yn-3-yl. Propargyl is preferred.
Cyclic unsaturated hydrocarbon radicals can be aromatic, for example phenyl and naphthyl, or non-aromatic, for example cyclopentenyl, cyclohexenyl, cycloheptenyl and cyclooctadienyl, or partly aromatic, for example tetrahydronaphthyl and indanyl.
Halogen or halo and Hal are fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.
Haloalkyl can contain identical or different halogen atoms, for example fluoromethyl, difluoromethyl, difluorochloromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2,2,2-trichloroethyl and 3,3,3-trifluoropropyl.
Alkoxy is, for example, methoxy, ethoxy, propyloxy, i-propyloxy, n-butyloxy, iso-butyloxy, sec-butyloxy and tert-butyloxy; preferably methoxy and ethoxy.
Haloalkoxy is, for example, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy and 2,2-difluoroethoxy.
Cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
Alkanoyl is either straight-chain or branched. Examples are formyl, acetyl, propionyl, butyryl, pivaloyl or octanoyl.
A heterocyclyl radical is understood as meaning 5- or 6-membered aromatic and non-aromatic rings with heteroatoms N, O and/or S. An unsubstituted or substituted benzo group can furthermore be fused onto such a heterocyclyl radical bonded to the remainder of the molecule. Examples of heterocyclyl groups are pyridyl, pyrimidinyl, imidazolyl, thiazolyl, 1,3,4-thiadiazolyl, triazolyl, thienyl, furanyl, pyrrolyl, morpholinyl, oxazolyl and the corresponding partly or totally hydrogenated rings. Examples of heterocyclyl groups with a fused-on benzo group are quinolyl, isoquinolyl, benzoxazolyl, quinoxalinyl, benzothiazolyl, benzimidazolyl, indolyl and indolinyl.
Compounds of the formula III having a microbicidal and plant-immunizing action and processes for the preparation thereof are known, for example, from EP-A-313,512. The processes described therein are not suitable for industrial preparation, since they comprise many reaction stages, some of which are complex, and thus overall result in an unsatisfactory yield.
There is therefore a need for a novel, industrially more advantageous synthesis for such compounds.
The compounds of the formula I according to the invention allow a novel access to the compounds of the formula III, which is shown in Equation 1. This synthesis is distinguished by easy accessibility of the percursor, use of customary reactants and good yields, even in cases where an intermediate product is not isolated. The present invention likewise relates to this synthesis.
In the formulae of Equation 1,
X, n and Z are as defined for formula I and
T is hydrogen, C
1
-C
12
alkyl, in particular C
1
-C
6
alkyl, C
3
-C
6
alkenyl, C
3
-C
6
alkynyl, C
3
-C
6
cycloalkyl or substituted or unsubstituted phenyl, benzyl or phenethyl.
The precursors of the formula V are compounds which are obtainable industrially or can be prepared by known methods, for example by reduction of the corresponding nitro compounds.
In detail, the reaction stages can be carried out as follows:
(1) SCN-T/for example methyl isothiocyanate/inert solvent/if appropriate in the presence of acid or base; or SCN salt.
(2) Oxidizing agent, for example SO
2
Cl
2
or Br
2
or H
2
SO
4
/bromide or Cl
2
.
(3) Strong aqueous base, for example potassium hydroxide solution, preferably under an inert atmosphere.
Reactions (1), (2) and (3) as such are described, for example, in
Org. Synthesis, Coll.Volume III, page 76;
J. Het. Chem. Volume 17, page 1325, (1980);
U.S. Pat. No. 5,374,737;
Ukrain.Khim.Zhur. Volume 22, 363, 1956; cited in Chem.Abstr. 22, 4358b, (1957).
(3a) Diazotization/H
3
PO2(Synth. Comm. Volume 10, page 167 1980)
(4) Diazotization with cyclization, for example with nitrous acid (═HONO) or with an inorganic or organic nitrite, for example sodium nitrite or isoamyl nitrite (for example EP A 313,512).
(4a) For example hydrazine/ethanol or basic hydrolysis, or such as 4) (Synth. Comm. Volume 10, page 167 1980).
(4b) For example Zn/acid or Fe/acid (Heterocyclic Compounds, Volume 7, page 541 et seq.); or H
2
/catalyst
(5) The conversion of the group COOH into a group Z where Z is as defined for formula I can be carried out by known methods, as shown in Equation 2.
Preferred compounds of the formula I are
(1) Compounds in which:
X is fluorine;
n is 0, 1, 2 or 3;
Z is CN, CO—A or CS—A,
A is OR
1
, SR
2
or N(R
3
)R
4
; and in which
R
1
, R
2
and R
3
are hydrogen, C
1
-C
8
alkyl, which is unsubstituted or substituted by 1-5 halogen atoms, C
3
-C
6
cycloalkyl, C
1
-C
4
alkoxy, phenoxy, benzyloxy C
1
-C
4
acyloxy, benzoyloxy, hydroxyl, nitro, cyano, C
1
-C
4
alkanoyl, benzoyl, carboxyl, C
1
-C
4
alkoxycarbonyl, benzyloxycarb
Jau Beat
Kunz Walter
Higel Floyd D.
Sackey Ebenezer
Syngenta Investment Corportion
Teoli, Jr. William A.
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