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Патент USA US3037917

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United States Patent 0 ” 1C6
Patented June 5, 1962
‘ may be incorporated into commercially useful resins, and
Edward D. Weil, Lewiston, N.Y., assignor to Hooker
‘ Chemical Corporation, Niagara Falls, N.Y., a corpo
ration of New York
No Drawing. Filed Jan. 17, 1961, Ser. No. 83,148
4 Claims. (Cl. 167-30)
may also be reacted with compounds and polymers having
—OH, —N-H, —SH and PH groups.
Similarly, because of the reactive vinyl grouping of the
molecule, the inventive compounds have utility as or
ganic intermediates for the preparation of derivatives,
many of which are pesticidal.
The compound of this invention in the technical state,
-is a low-melting, colorless solid, the recrystallized mate
. This invention concerns‘a new and valuable sulfur-con
taining organic compound which lends itself for use as
a biocidal product, organic intermediate or polymerizable
10 rial is a crystalline solid, melting between ninety-four and
ninety-six degrees centigrade. It may be prepared, among
other ways, by the Diels-Alder reaction of an excess of
divinyl sulfone with hexachlorocyclopentadiene. The use
More speci?cally, this invention comprises a composi
of no less than one mole of divinyl sulfone per mole of
tion of matter consisting of vinyl 1,2,3,4,7,7-hexachloro 15 hexachlorocyclopentadiene is preferred since it avoids the
bicyclo(2.2.1)-hept-2-ene-5-yl sulfone (hereinafter called
formation of substantial amounts of the di-adduct, bis
vinyl hexachlorobicycloheptenyl sulfone), which is a po
(hexachlorobicycloheptenyl) sulfone, as a by-product. A
convenient preparation is to heat the two reactants to
tent fungicide, bactericide and nematocide at low levels
gether at ?fty to two hundred and ?fty degrees centigrade
of application, which may be employed for disease con
trol in commercial crops, both vegetable or ornamental. 20 for a period ranging from one hour to several days, pref
The formula of the subject compound is as follows:
01 l —SOzCH=CHz
l C1:
or |
_ » While there is no dearth of fungicides, bactericides or
nematocides or intermediates, few compounds have the
A advantage of possessing all of these qualities, thus allow
' ing a single compound to be used in many dilferent com
erably at about one hundred and twenty to one hundred
and eighty degrees centigrade. At lower temperatures
(below one hundred degrees centigrade), the reaction is
inconveniently slow, and at higher temperatures resinous
25 by-products predominate. Solvents such as petroleum
hydrocarbons may be used. While atmospheric pressures
_ are commonly used where the equipment is available and
‘it is convenient, sub or super-atmospheric temperature
may be used without detriment. Polymerization inhibi
30 tors such as phenols, quinones, and the like may be added
to reduce the tendency towards polymerization. A more
detailed description of the synthesis of the inventive com
, pound, as well as its formulation ‘and use, are described
positions for a variety of uses.
in the examples which follow. '
An additional advantage of this inventive composition 35
is that unlike many of the commercially available nema
tocides, fungicides and bacteriocides, the compound of
A mixture of one hundred parts of divinyl sulfone and
- this invention functions for all of these purposes at low
?fty parts .of hexachlorocyclopentadiene were heated for
rates of administration. A further advantage is the sur
twenty-four hours at one hundred and ?fty degrees cen
prisingly low phytotoxicity of the compound of the inven 40 tigrade. The mixture was then fractionally distilled to
tion, which permits its application to the foliage of a wide
remove unreacted starting materials, until a pot temper
variety of crops, including those extremely sensitive to
ature of one hundred and forty-three to one hundred and
damage by chemicals.
?fty-six degrees centigrade at 0.1 millimeter was reached.
Still another valuable characteristic of this compound
The residual syrup was then warmed and stirred with
is that it readily may be compounded for agricultural use 45 heptane until no further material appeared to go into solu
in a great variety of formulations each possessing a par
tion, then the heptane solution was decanted from the
ticular advantage for a particular use. For instance, the
insolubles and chilled. The precipitated solid thus ob
active fungicidal and nematocidal compound is a crystal
tained had the correct elemental analysis for vinyl hexa
line solid, that being non-hygroscopic by its nature, may
chlorobicycloheptenyl sulfone. It could be crystallized
readily be granulated or ground to a ?ne powder which 50 from heptane to obtain crystals melting at ninety-four to
can be conveniently spread either by hand or by a fer
ninety-six degrees centigrade. A second crop of crystals
tilizer spreader or a seed planter without caking up or
having a lower melting point could be obtained by concen
clogging the mechanical spreading device. In the alterna
trating the mother liquor.
for CQHGOBSCIB: Cl, 54.5. Found:
tive the pesticidal solid may be pelletized and used as such '
or admixed with the soil using a plow or disc or spade. 55 Cl, 54.2.
If it is required, the pesticidal component may be diluted
with a solid diluent such as clay, vermiculite, silica, solid
Divinyl Sulfone Giving Diadduct
fertilizer, saw dust or the like. An additional advantage
of the inventive compound is that it is stable and soluble
In a similar experiment employing one hundred and
in a great variety of common, inexpensive, organic solvents 60 ?fty parts of hexachlorocyclopentadiene and twenty-?ve
such as xylene or toluene or petroleum fractions. These
parts of divinyl sulfone heated for two hours at one hun
solutions may be used to produce emulsions with Water us—
dred and forty to one hundred and seventy degrees cen
ing the usual wetting, surface active, suspending, sequester
ing and emulsifying agents. When the pesticide or fungi—
tigrade the principal product isolated was ?fty parts of
a heptane-insoluble solid, which when recrystallized from
cide is formulated as an emulsion, it may be watered into
the soil or may be applied immediately before a rainfall.
benzene had a melting point of 239.5 to two hundred and
forty degrees centigrade. This was shown to be the di
The subject compound having a reactive vinyl group
adduct by analysis.
Cl, 63.7.
In another series of tests on control of late blight of
Analysis.—Calcd. for C14H6O2ClmS: CI, 64.1. Found
tomatoes (Phytophthora infestans), ninety-eight percent
Formulation of Vinyl Hexachlorobicycloheptenyl Swlfone
control was obtained at one hundred parts per million, as
compared to ninety percent control with an equal con
centration of N-(trichloromethylthio) phthalimide, a
as an Emulsion '
The following were weighed out:
commercial fungicide.
Tests were run on the inhibition of germination of
Vinyl hexachlorobicycloheptenyl sulfone _________ __ 10
_________________________ __'____s ____ __ 15
Polyoxyethylene sorbitan laurate (emulsi?er) ____ __
Sclerotiam rolfsii (southern blight), by applying the
These ingredients were blended to make asolution
chemical at various concentrations (in water dispersion),
to black blotting paper, applying sclerotia to the treated
paper, and incubating in closed vials. Substantially com
plet inhibition of germination was observed with the
emulsi?able with water.
chemical of the invention at concentrations as‘ low as ?fty
Formulation as a Dust
One part of vinyl hexachlorobicycloheptenyl sulfone
'was ground’ with nine parts‘ of Microcel E (a synthetic
'clay), to prepare a pesticidal dust.
Formulation. as a Wettable Powder
‘ Threeparts of vinyl hexachlorobicycloheptenyl sulfone
vwas ground. with 0.9 space part'of Microcel E, 0.08 part
parts per million.
disease, whereas. cucumber: seedlings transplanted into
similarly infested‘ hut-untreated‘ soil developedsevere root
of VMarasperse N (a. lignin sulfonate dispersing‘ agent),
damage caused by nematodev galls.
and 0.02 part of Sorbit P (a Wetting agent) to prepare
a wettable powder.
In nutrient agar, the compound of the invention at two
hundred and ?fty-?ve parts per million gave marked re
pression of the growth of Staphylococcus aureus (a com
' Use as a Fungicide
Soil infested. with Me'loidogyne incognz'ta var. acrita,
the nematodecausative- of root knot disease, Was admixed
with- the compound of the: invention at 0.5 gram per gal
lon of soil. Cucumber seedlings transplanted. into this
treated; soil developed only; trace symptoms of root‘ knot
>A suspension-of the compound of Example 1 was made
v‘by grinding it with Microcel‘ E, etc., as in‘ Example 5,
and dispersing this powder in. water. It was sprayed at
various concentrations on tomato plants inoculated with
spores of Alternaria'solani (early blight‘ disease). When
' untreated’ controls had‘ developed severe symptoms of the
' disease;_ the percent’ control of the disease (judged by‘the
mon bacterium).
I claim:
1. Vinyl 1,2,3,4,7,7-hexachlorobicyclo(2.2.l)hept-Z-en
S-yl sulfone.
2. A pesticidal composition‘ consisting of vinyl l,2,3,4,
7,7-hexachlorobicyclo(2.2.1)hept-Z-en-S-yl sulfone plus a
‘ carrier.
percent reduction of thenumber of foliar lesions" relative‘ 40 3. The composition of claim 2 wherein the inactive
to thecontrols)_rwas estimated.- Therdata is given in the 0 component‘ oftiie compositionv is ‘a solid carrier.
4. The. composition of claim 2 wherein the inactive
i following table.
component oflthe' composition is apsolvent.
Concentration (p.p.m.):
100 ________ _____..._-.._V___V _______ _; ______ _.
_ _ __ _
_ _ _ __
12s____V_~____>__v ______________ _-. _______ ____
"References Cited in the‘ ?le of'this‘ patent
Winterstein ; ________ __ Apr. 20, ‘1.954
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