Drug – bio-affecting and body treating compositions – Designated organic active ingredient containing – Sulfur – selenium or tellurium compound
Reexamination Certificate
1999-09-10
2001-08-14
O'Sullivan, Peter (Department: 1621)
Drug, bio-affecting and body treating compositions
Designated organic active ingredient containing
Sulfur, selenium or tellurium compound
C514S231200, C514S252120, C514S315000, C514S517000, C544S158000, C544S383000, C546S184000, C558S061000, C562S125000, C562S825000, C562S827000, C564S101000
Reexamination Certificate
active
06274632
ABSTRACT:
This invention relates to sulfur containing acids and their derivatives, and more particularly to sulfur-containing acids and salts, esters and amides thereof having utility as pesticidal agents.
In a first aspect the invention provides compounds of formula (I):
CF
2
═CX—CH
2
—CH
2
—S(O)—R (I)
wherein X represents hydrogen, halogen or lower alkyl, and R represents a group OR
1
or NR
2
R
3
wherein R
1
, R
2
and R
3
are each independently selected from hydrogen and alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, alkaryl, heteroaryl. and heteroaryalkyl groups, or R
2
and R
3
together with the adjacent nitrogen atom and wherein any of the groups represented by R
1
, R
2
and R
3
may optionally be substituted by one or more substituents selected from halogen, cyano, nitro, hydroxy, hydrocarbyloxy, amino, hydrocarbylamino, dihydrocarbylamino, carboxy, hydrocarbyloxycarbonyl, carboxamido, hydrocarbylaminocarbonyl, dihydrocarbylaminocarbonyl, hydrocarbylthio, hydrocarbylsulfinyl, and hydrocarbylsulfonyl, wherein any such hydrocarbyl groups may optionally be substituted by one or more substituents as aforesaid; and salts thereof.
Preferred compounds are those where X is hydrogen, fluorine or methyl.
Where any of R
1
, R
2
and R
3
represent groups comprising carbon atoms they prefereably contain up to 12 carbon atoms, and more preferably, except in the case of aryl, aralkyl and alkaryl groups, up to 6 carbon atoms.
Examples of groups of formula NR
2
R
3
which represent a nitrogen containing heterocyclic group which may contain a further heteroatom selected from oxygen, sulfur and nitrogen, include for example piperidine, piperazine, morpholine, thiazolidine, imidazoline, and the like.
Salts of the compounds of Formula (I) may be, in the case where R
1
is hydroxy, or where R
1
, R
2
or R
3
represents a group comprising an acidic hydrogen, metal salts, including for example, sodium, potassium, calcium, magnesium, copper, zinc or iron, or ammonium salts, amine salts or quaternary ammonium salts.
Specific examples of compounds according to the present invention include those set out in Tables I and IA below.
TABLE I
Compound no.
X
R
1
R
2
R
3
1
H
H
—
—
1A
H
Na
—
—
2
H
C
2
H
5
—
—
3
H
n-C
6
H
13
—
—
4
H
—
H
H
5
H
—
H
CH
3
6
F
H
—
—
7
F
n-C
4
H
9
—
—
8
F
—
H
H
9
F
—
C
2
H
5
C
2
H
5
10
CH
3
H
—
—
11
H
CH
2
C
6
H
5
—
—
12
H
n-C
8
F
17
—
—
13
H
cyclo-C
6
H
11
—
—
14
H
—
H
C
6
H
5
CH
2
15
H
—
3-Cl-C
6
H
4
H
16
H
CH
2
CF
3
—
—
17
H
(CH
2
)
2
CH═CF
2
—
—
18
H
CH
2
CH
2
OC
2
H
5
—
—
19
F
CH
2
CH═CH
2
—
—
20
F
—
H
C
6
H
5
CH
2
21
H
—
H
4-Cl-C
6
H
4
CH
2
TABLE I
Compound no.
X
R
1
R
2
R
3
1
H
H
—
—
1A
H
Na
—
—
2
H
C
2
H
5
—
—
3
H
n-C
6
H
13
—
—
4
H
—
H
H
5
H
—
H
CH
3
6
F
H
—
—
7
F
n-C
4
H
9
—
—
8
F
—
H
H
9
F
—
C
2
H
5
C
2
H
5
10
CH
3
H
—
—
11
H
CH
2
C
6
H
5
—
—
12
H
n-C
8
F
17
—
—
13
H
cyclo-C
6
H
11
—
—
14
H
—
H
C
6
H
5
CH
2
15
H
—
3-Cl-C
6
H
4
H
16
H
CH
2
CF
3
—
—
17
H
(CH
2
)
2
CH═CF
2
—
—
18
H
CH
2
CH
2
OC
2
H
5
—
—
19
F
CH
2
CH═CH
2
—
—
20
F
—
H
C
6
H
5
CH
2
21
H
—
H
4-Cl-C
6
H
4
CH
2
The compounds of Formula (I) may be prepared as follows. For convenience the group CF
2
═CX—CH
2
—CH
2
— is represented in the following description by Q.
Compounds where R represents hydroxy are sulfinic acids and may be prepared for example by reducing the corresponding sulfonyl chloride of formula Q—SO
2
Cl, or by reducing the corresponding benzthiazol-2-yl sulphone using the conditions described in
Chem.Lett.
2125 (1984) via the sodium salt. Another method of preparation involves reacting the Grignard reagent of formula Q—Mg—Cl with sulfur dioxide using the conditions set out in
Chem. Revs.
48 69 (1950).
Compounds where R represents OR
1
may be prepared by esterification of the sulfinic acids under mild conditions, such as those described in
Synthesis,
p441 (1978), or via the sulfinyl chlorides, prepared by treating the acids with thionyl chloride or oxalyl chloride, and reaction with alcohols of formula R
1
OH. Another method involves treating the disufide of formula Q—S—S—Q with a peroxy compound in in the presence of an alcohol as described in
Synthesis,
p252 (1988). A yet further process treats the sulfonyl chloride of formula Q—SO
2
Cl with an alcohol under reducing conditions, for example in the presence of trimethyl phosphinate, as described in
J. Org. Chem.
52 2598 (1987).
Compounds where R represents NR
2
R
3
may be prepared by reacting the sulfinyl chlorides of formula Q—S(O)Cl with a compound of formula NHR
2
R
3
.
The sulfinyl chlorides (and other halides) useful in the preparation of the compounds of formula (I) as described herein are novel compounds. In a further aspect the invention provides compounds of formula (II):
CF
2
═CX—CH
2
—CH
2
—S(O)—Y (II)
where X is hydrogen or halogen or lower alkyl, preferably hydrogen or fluorine, and Y is halogen, preferably chlorine, useful as intermediates for preparing the compounds of formula (I). Specific examples of compounds of formula (II) include 1-(4,4-difluorobut-3-ene)sulfinyl chloride and 1-(4,4,4-trifluorobut-3-ene) sulfinyl chloride.
Further information concerning the preparation of individual compounds may be ascertained from the Examples given hereinafter.
In a further aspect the invention provides a method of combating insect and like pests at a locus by applying to the locus or the pests an insecticidally-effective amount of an insecticidal composition comprising the compounds of Formula I or an acid addition salt thereof.
The compounds of Formula I and acid addition salts thereof may be used to combat and control infestations of insect pests such as Lepidoptera, Diptera, Homoptera and Coleoptera (including Diabrotica i.e. corn rootworms) and also other invertebrate pests, for example, acarine pests. The insect and acarine pests which may be combated and controlled by the use of the invention compounds include those pests associated with agriculture (which term includes the growing of crops for food and fibre products), horticulture and animal husbandry, forestry, the storage of products of vegetable origin, such as fruit, grain and timber, and also those pests associated with the transmission of diseases of man and animals. Examples of insect and acarine pest species which may be controlled by the compounds of Formula I include:
Myzus persicae
(aphid),
Aphis gossypii
(aphid),
Aphis fabae
(aphid),
Aedes aegypti
(mosquito), Anopheles spp. (mosquitos), Culex spp. (mosquitos),
Dysdercus fasciatus
(capsid),
Musca domestica
(housefly),
Pieris brassicae
(white butterfly),
Plutella xlostella
(diamond back moth),
Phaedon cochleariae
(mustard beetle), Aonidiella spp. (scale insects), Trialeurodes spp. (white flies),
Bemisia tabaci
(white fly),
Blattella germanica
(cockroach),
Periplaneta americana
(cockroach),
Blatta orientalis
(cockroach)
Spodoptera littoralis
(cotton leafworm),
Heliothis virescens
(tobacco budworm)
Chortiocetes terminifera
(locust), Diabrotica spp. (rootworms), Agrotis spp. (cutworms),
Chilo partellus
(maize stem borer),
Nilaparvata lugens
(planthopper),
Nephotettix cincticeps
(leafhopper),
Panonychus ulmi
(European red mite),
Panonychus citri
(citrus red mite),
Tetranychus urticae
(two-spotted spider mite),
Tetranychus cinnabarinus
(carmine spider mite),
Phyllcoptruta oleivora
(citrus rust mite),
Polyphagotarsonemus latus
(broad mite) and Brevipalpus spp. (mites).
In order to apply the compounds of Formula I to the locus of the nematode, insect or acarid pest, or to a plant susceptible to attack by the nematode, insect or acarid pest, the compound is usually formulated into a composition which includes in addition to the the compounds of Formula I suitable inert diluent or carrier materials, and/or surface active agents. The amount of composition generally applied for the control of nematode pests gives a rate of active ingredient from 0.01 to 10 kg per hectare, preferably from 0.1 t
O'Sullivan Peter
Zeneca Limited
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