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Патент USA US3052713

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United States Patent O?ice
3,052,703
Patented Sept. 4, 19,62
2
1
such as tolylene, phenylene, naphthylene, or an-thrylene
group, or an aralkylene group, the alky-lene portion of
which contains 1-10 carbon atoms and the aryl portion
of which is a tolyl, phenyl, naphthyl or an anthryl group.
Of the polyhalogenopolycycloalkenes which occupy one
3,052,703
N-ACYLATED-AMINO DERIVATIVES OF HALO
GENATED BICYCLO (2,2,1) I-IEPT - 5 - EN - 2 - YL
COMPOUNDS
Juan G. Morales and Samuel Barney Soloway, Modesto,
Calif., assignors to Shell Oil Company, a corporation of
terminal position ‘of the compounds encompassed by the
present invention, halogenated bicyclo(2.2.l)hept~5-ene
Delaware
No Drawing. Filed Dec. 30, 1957, Ser. No. 705,782
14 Claims. (Cl. 260-438)
rings as shown in the following structural formula are
preferred
10
The present invention is concerned with organic com
pounds wherein one terminal position is occupied by a
polyhalogenopolycycloalkene and the other terminal po
sition is occupied by an amide or amide derivative. These
compounds have been found to possess signi?cant toxicity
toward and inhibition of a wide variety of fungi.
The need for ef?cient and economical fungicidal and
Of equal interest is the dimethanonaphthalene ring
fungistatic compositions has long been manifest. In spite
structure shown in the ‘following structural formula:
of this fact, however, -a number of the compounds em
ployed ‘as fungicides, have generally been found lacking 20
in one or more of the basic requirements of a satisfactory
fungicide. In order to be commercially useful a fungi
cidal composition must be compatible with adjuv-ants and
other active ingredients; it must be economical; it should
be soluble in common solvents ‘and stable; and most im 25
portant, it must not be toxic to the plants to which it is
The present invention also encompasses the polycyclic
applied or to animal life. A prohibitive degree of phytoa
structures shown in the following general formula:
toxicity under the conditions utilized for fungus control
and toxicity toward Warm blooded animals are among
the most common shortcomings of present fungicides.
It is consequently the principal object of the present
invention to provide new and novel compounds which
are effective as fungicides yet do not manifest prohibi
tive phytotoxicity ‘or toxicity toward warm blooded ani
mals such as man.
35
In these (formulae X represents hydrogen or halogen
(preferably chlorine) ‘and X’ represents hydrogen, halo
gen or an alkoxy (preferably met-boxy) group. At least
Another object of the present invention is to provide
one X should be a halogen.
new and novel fungicidal compounds which can be eco
R may be a straight chain, branched chain or cyclic
Yet another object of the present invention is to pro 40 alkylene group of from 1—10 carbon atoms both substi
tuted and unsubstituted, ran arylene group such as a
vide economical and stable fungicidal compositions con
tolylene, phenylene, naphthylene or anthrylene or an
taining these compounds.
aralkylene group wherein the alkylene portion contains
Still ‘another object of the present invention is to pro
1-10 carbon atoms and the aryl portion is chosen from
vide a method of combating fungi by applying these
groups such as tolyl, phenyl, naphthalenyl or anthracenyl.
compositions to plants.
Other objects, features and ‘advantages will be apparent 45 Of these »R is preferably a straight chain alkyl group of
1—10 carbon atoms. y is O to 10. When y is 0 the poly
from the following description read in conjunction with
cyclic ring structure will be connected directly to the
the appended claims.
nitrogen atom.
Generally speaking the present invention is concerned
Z is carbon, ‘S0 or P((_O alkyl)2). An example of a
with ‘organic compounds wherein one terminal position
is occupied by a polyhalogenopolycycloalkene and the 50 compound wherein Z is S0‘ is N-(l,4,5,6,7,7~hexachloro
bicyclo(2.2.1)hept - 5-en-2-ylmethyl)benzenesulfonarnide.
other terminal position is occupied by an amide or amide
An example of a compound wherein Z is Pi((O alkyl)2)
derivative. More speci?cally, the present invention re
is diethyl(1,4,5,6,7,7-hexachlorobicyclo (2.2.l)'hept-5-en
lates to polyhalogenopolycycloalkenes containing a
nomically prepared, distributed and ‘applied to plants.
i’
_N_._Z_..
group wherein the nitrogen atom lies between the atom
attached to the oxygen atom and the polyhalogenopoly
55
2-ylmethyl)phosphoramidate. Z is preferably carbon.
R’ may be hydrogen, ‘a straight chain, branched chain
or cyclic alkyl group of from 1-10 carbon atoms, both
substituted and unsubstituted, an aryl group such as
benzyl, tolyl, phenyl, naphthyl or anthryl or an 'aralkyl
group, the alkyl portion of which has 1-10 carbon atoms
cycloalkene portion of the molecule. In other words,
the nitrogen atom is proximate to the polyhalogenopoly 60 and the aryl portion of which is a benzyl, tolyl, phenyl,
naphthyl or ‘anthryl group. In one example one of the
cycloalkene portion of the molecule. The second valence
substituted alkyl groups which may be employed is the
bond of the nitrogen atom and the \free valence bond of
group CHg‘OHzCN. R’ is preferably hydrogen.
the carbonyl group are occupied by groups defined below.
R" may be a substituted or unsubstituted aliphatic or
Z, ‘the atom attached to the oxygen atom, is preferably
ole?nic radical, preferably of 1-18 carbon atoms. Straight
carbon 'but may also ‘be a S0 or P((O' alky=l)) group. 65
chain alkyl and ole?n radicals are of particular interest.
Hence, sulfonamides and phosphoramide are also en
R"
may also be a substituted or unsubstituted aryl radical
compassed by the present invention.
such as a tolyl, phenyl, naphthyl, or anthryl group or sub
The halogenated cycloalkene portion of the molecule
stituted or unsubstituted aralkyl group wherein the alkyl
may be attached directly to the nitrogen of the amide
portion of the molecule, or alternatively the terminal 70 portion contains 1-10 carbon atoms and the aryl portion
is chosen ‘from groups such as tolyl, phenyl, naphthyl or
portions of the molecule may be separated by ‘an alkylene
radical of ‘from 1-10 carbon atoms, an arylene radical
anthryl group. The groups which may be substituted on
3,052,703
t»
sponding acetonitrile in acetic anhydride to ‘form the
R" include the halogens as in the case of 2-chloro-N
( 1,4,5 ,6,7,7 - hexachlorobicyclo(2.2.1)hept-S-en-Z-ylmeth
amide. For example, hydrogenation of 1,4,5,6,7,7-hexa
yl)acetamide and 2-chloro-N-(‘1,4,5,6,7,7-hexachlorobicy
clo ( 2.2.1 ) -hept-5-en-2-ylmethyl) maleamic acid. When
chlorobicyclo (2.2.1)hept-S-ene-Z-acetonitrile in acetic an
R" has substituted thereon a carboxylic group (—COOH)
the compound may be considered an acid derivative. Of
particular interest in this connection are the compounds
wherein R” is a (—CH=CHCOOH) group. Also of in
terest are compounds wherein R" is a
(—CH: CHCOOR’”)
hydride yields n-(2- ( 1,4,5 ,6,7,7-hexachloro-bicyclo(2.2. 1 ) hept-5-en-2-yl)ethyl)acetamide. The amine salts may be
made by reacting the amides with the appropriate acids.
Thus, N-(1,4,5,6,7,7-hexachlorobicyclo(2.2.1)hept-5-en-2
yl) acetamide forms the hydrochloride salt of the amine
when reacted With HCl. The maleamic acids of the pres
10 ent invention may be made by addition of an inorganic
base to the amine salt in alcohol to form the free amine
and reacting the ‘free amine so formed with the appro
R'” representing an alkyl radical or metallic ion. In other
priate acid anhydride. N-(1,4,5,6,7,7-hexach1orobicyclo
words, the present invention encompasses, among other
acids, certain maleamic acids and the corresponding esters
and metallic salts.
Examples of speci?c compounds encompassed by the
(2.2.1)hept-5-en-2-ylmethyl) maleamic acid may thus be
15 made by treating the amine sulfate with NaOH in alcohol
and reacting the free amine so formed with maleic an
hydride. It will, of course, be readily understood that the
present invention follow:
salts and esters of these maleamic acids are easily made
N - (1,4,5 ,6,7,7 - hexachlorobicyclo (2.2. 1 ) hept-S-en-Z-yl
by reaction with the appropriate base or alchol. A de
tailed description of the preparation of the amines and
amine salts is to be found in copending application, Serial
Number 705,781, ?led December 30, 1957.
methyl] maleamic acid
Methyl N-( 1,4,5,6,7,7-hexachlorobicyclo(2.2. 1 )hept-5-en
2-ylmethyl) maleamate
N - (1,4,5,6,7,7 - hcxachlorobicyclo(2.2.1)hept-S-en-Z-yl
Examples of preparations of compounds encompassed
methyl)maleamic acid cupric salt
by the present invention follow:
N - (1,4,5,6,7,7 - hexachlorobicyclo(2.2.1)hept-5-en-2-yl
methyl) acetamide
25
EXAMPLE I
2 - chloro-N-(1,4,5,6,7,7-hexachlorobicyclo(2.2.1 )hept-S
N- [1,4,5,6,7,7-Hexachl0r0bicycl0 (2.2.1 )Hept-5-En-2
en-2-ylmethyl) acetamide
Ylmethyl ] Maleamic Acid
N - (2 - (1,4,5,6,7,7-hexachlorobicyclo(2.2.1)hept-5-en-2—
yl)ethyl) acetamide
A solution of 106 g. of 1,4,5,6,7,7-hexachlorobicyclo
N - (2 - cyanoethyl) - N - (1,4,5 ,6,7,7-hexachlorobicyclo
(2.2.1)hept-S-ene-Z-methylamiue sulfate made in accord
ance with Example III of copending application, Serial
Number 705,781, ?led December 30, 1957, in 100 ml. of
(2.2.1 )hept-S -en-2-y1methyl) acetamide
N - ( 1,4,5 ,6,7,7-hexachlorobicyclo (2.2.1 )hept-5-en-2-yl) -
acetamide
N - ('l,4,5,6,7,7 - hexachlorobicyclo(2.2.1)hept-5-en-2-yl)
maleamic acid
2 .- chloro-N-(1,4,5,6,7,7dhexachlorobicyclo(2.2.1)hept-S
methanol was treated with 26 g. of NaOH in 200 ml. of
35 methanol until the solution of the free amine was con
centrated under vacuum at 30° and the residue extracted
extracted with benzene at 30°. The benzene solution of
amine was added to 28 g. of maleic anhydride in 100 ml.
N - (1,4,5,6,7,7 - hexachlorobicyclo(2.2.l)hept-5-en-2-yl~
of benzene with cooling. The maleamic acid which vfell
methyl) stearamide
out was collected and washed with benzene. The crude
N - ( 10-( 1,4,5 ,6-tetra?uoro-7,7-dimethoxybicyclo ( 2.2. 1 ) - 40 melted at 168-171". Recrystallization from acetone gave
hept-S-en-Z-yl) decyl) -caproamide
25 g. of N-(1,4,5,6,7,7-hexachlorobicyclo(2.2.l)hept-5
en-2-ylmethyl)maleamic acid
N - ( 10-(1,4,5,6,7,7-hexabromobicyclo(2.2.1)hept-5-en-2
3n-2-ylmethyl)maleamic acid, M.P. 182-184". Workup of
yldecyl ) phenyl) decylbenzlamide
N - (1,4,5,6,7,7 - hexachlorobicyclo(2.2.1)hept-S-en-Z-yl
tolyl)toluamide
the mother liquor gave an additional 59 g. of crude prod
45 uct.
Total yield 70% .
Analysis:
N - (1,4,5 ,6,7,7 - hexabromobicyclo(2.2.1)hept-S-en-Z-yl
anthryl)naphthamide
01
2 - ?uoro - N-(1,4,5,6,7,7-hexa?uorobicyclo(2.2.1)hept-S
en-2-yln aphthyl) acetamide
2 - bromo-N- ( 1,4,5,6,7,7-hexabromobicyclo(2.2. l ) hept-S
50
Acid eq.
Calc’d for CuHgOaN G15 _______________________ _ _
49. 8
428
Found ________________________________________ __
49. 0, 49. 4
418
en-Z-yl) -ethyl) acetamide
EXAMPLE II
N - methyl ~ N - 2-((1,4,5,6,7,7-hexachlorobicyclo(2.2.1)
hept-S-en-Z-yl) -ethyl) acetamide
Methyl N-(],4,5,6,7,7-Hexachlorobicyclo(2.2.1)Hept-S
N - ( 2-decyl) -N-10-( 1,4,5 ,6,7,7-hexachlorobicyclo (2.2. 1 ) -
hept-S-en-Z-yl) decyl) acetamide
'- A solution of 42.8 g. of N-(1,4,5,6,7,7-hexachloro
b1oyclo(2.2.1)-hept-5-en-2-ylmethyl)maleamic acid in 100
N - (decylphenyl) - N - (5,6,7,8,9,9-hexachloro-1,2,3,4,4a,
5,8,8a - octahydro - 1,4,5,8-dimethanonaphthalen-Z-yl)
methyl) acetamide
N - (benzyl) - N-I0-(5,6,7,8,9,9-hexachloro-1,2,3,4,4a,5,8,
8a-octahydro-1,4,5,8'dimethanonaphthalen-2-yl)decyl)
En-2-Ylmethyl)Maleamate
55
ml. of methanol was re?uxed with 5 g. of silica gel cata
' lyst containing sulfuric acid for 16 hours. Filtration of
60 the catalyst and concentration of the ?ltrate under vacuum
gave a sticky semi-solid. Recrystallization from heptane
gave 25 g. of methyl n-(1,4,5,6,7,7-hexach1orobicyclo
acetamide
N - (tolyl) - N - 10-(5,6,7,8,9,9-hexabron1o-1,2,3,4,4a,5,8,
( 2.2.1 )hept-S-en-Z-ylrnethyl)maleamate, M.P. ll9‘—121 °
and 5 g. of solid, M.P. 1117-120“. Total yield 67%.
8a-octahydro-1,4,5,8-dimethanonaphthalen-2-yl) decyl) acetamide
N '- (2 - anthrYD-N-(5,6,7,8,9,9-heXabromo-1,2,3,4,4a,5,8, 65
Analysis:
Cl
8a - octahydro - l,4,5,8 - dimethanonaphthalen - 2-yl)
methyl) acetamide
Calc’d for C13H11NO3C16 ____________________ __ 48.2
Found
N -' (2 - naphthyl)-N-3-(5,6,7,8,9,9-hexabromo-l,2,3,4,4a,
propyl) acrylamide
Generally speaking the amides of the present invention
___________________________________ __ 48.4
EXAMPLE III
5,8,8a - octahyd-ro - 1,4,5,S-dimethanonaphthalen-Z-yl)
70
N-(I,4,5,6,7,7-Hexachlor0bicycl0(2.2.1 )Hep‘t-S-En
2-Ylmethyl)Maleamic Acid Cupric Salt
may be made by the addition of corresponding ole?nic ni~
32 ‘g. of N-(1,4,5,6,7,7-hexachlorobicyclo(2.2.1)hept-S
trogen compounds to a hexahalocyclopenta‘diene. It is
en-2-ylmetl1yl)rnaleamic acid was dissolved in dilute
also possible in certain cases to hydrogenate the corre 75 NaOH until the solution was alkaline. A solution of 13
8,052,703
5
6
g. of cupric sulfate pentahydrate in 400 m1. of water was
added and the resulting precipitate Was collected'and
water-washed. After drying the blue precipitate, 30‘ g.
of green N-(l,4,5,6,7,7-hexachlorobicyclo(2.2.1)hept-S
sure (120° C. and 0.5 mm). Analysis or the residue
showed a carbon content of 35.1%, hydrogen content of
2.92%, and a chlorine content of 55.2%. Calculated
carbon, hydrogen and chlorine content of the above acet
en-2-ylrnethyl)maleamic acid cupric salt, M.P. 197—198°
was obtained in 85% yield. Analysis:
amide being 34.2%, 2.85% and 55.2%, respectively.
Crystallization of the residue from pentane and ethyl
Cu
acetate produced a ‘white powdery solid with a melting
point of 119-20° 0.
EXAMPLE VII
CalC’d 'fOl' C24H16Cl12O6N2Cll _________________ __ 7.0
Found
______________________________ __V____ __
7.4
10
EXAMPLE IV
N - ( 1 ,4,5,6,7,7-Hexachlor0bicycl0‘(2 .2 .1 )Hept-5-En
N-(1,4,5,6,7,7-Hexa‘chlorobicyclov(2.2.1)Hept-S-En
Z-Yl) Acetamide
2-Ylmethyl) Acetamide
1,4,5,6,7,7 - hexachlorobicyclo(2.2.1)hept - 5 - en-2-yl
methyl ketone oxime was prepared by re?uxing a mixture
of 300 g. of the ketone, 70 g. of hydroxylamine hydro
Hexachlorocyclopentadiene (81.9 g, 0.3 mole) and N
allylacetamide (29.7 g., 0.3 mole) were mixed together
chloride, 81 g. of anhydrous sodium acetate .110 ml. of
water and 450 ml. of methanol on the steam bath for 16
hours. While hot the solution was decanted from the
and heated for 40 hours in the presence of a small amount
of ditertiarybutyl hydroquinone. The temperature of the
reaction mixture was maintained at approximately 125°
NaCl which had precipitated. The decantate was cooled
C. throughout the reaction period. Methanol was added 20 to 25° and the crude product collected on a ?lter and
to dissolve the reaction mixture and the solution was
washed with water until free of salt. The product had a
treated with charcoal. After removing the charcoal by
melting point of 132—3° and weighed 313 g. (100%
?ltration, 91.7 g. of crude product was obtained ‘from the
yield). 117 g. of the oxime was slowly added to 110
methanol solution. This represented an 82% yield of
g. of polyphosphoric acid at 100° C. The mixture was
N[1,4,5,6,7,7 - hexachlorobicyclo(2.2.l)hept - 5-en-2-yl
25 then warmed to 150°.
methyl]acetamide based on the theoretical amount possi
ble from the above reactants. Subsequent recrystalliza
tion produced a product having a melting point of 170‘
171° C. and a chlorine content of 57.1 percent, the the
oretical chlorine of the above named acetamide being 30
57.3 percent.
The mixture was maintained for
3 hours ‘at 140°, allowed to stand overnight at 40°, and
poured into 2000 ml. of water. The crude product was
collected and recrystallized from benzene to give 43 g.
of solid, M.P. l65—78. Recrystallization from CCL; and
benzene gave 22 ‘g. of solid, M.P. l81—2°. Analysis:
N- [1,4,5,6,7,7 - hexachlorobicyclo(2.2.1)hept-5-en-2
0
ylmethyl1-acetamide, propionamide and butyramide are
illustrative of compounds that may be prepared by the ad
dition of the corresponding N-allyl-substituted amides to 35
hexachlorocyclopentadiene.
Oalc’dior C9H7NOO16 .................. _.
Found .................................. ._
30.2
31.2
H
2.0
2.5
01
59.2
59. 7, 59.8
The corresponding bromo-eompounds may be prepared
EXAMPLE VIII
by using hexabromocyclopentadiene as one of the start
ing materials. Thus, N~[1,4,5,6,7,7-hexabromobicyclo
(2.2.1)hept-S-en-Z-yhnethyl]acetamide may be prepared
by reacting hexabromocyclopentadiene and N-allyl-aceta
40
N - (‘1,4,5,6,7,7 - hexaehlorobicyclo(2.2.l)Hept - 5 - en
mide.
2-yl)~acetamide (140 g.) was ‘dissolved in 500 ml. of
hot methanol and 350 ml. of aqueous HCl was added
to the solution. The homogeneous solution was re?uxed
EXAMPLE V
Z-Choloro-N- ( 1 ,4 ,5 ,6,.7,7-Hexachlorobicyclo (2 .2 .1 ) Hepit
5 -En—2 Yl-Methyl ) Acetamide
45 for 4 hours, then cooled, and the precipitated hydrochlo
ride salt of the amine was collected. The crude salt was
A toluene solution (50 ml.) of 110 g. (0.3 mole) of
suspended in 500 m1. of hot water and treated with 20%
the isothiocyanic acid ester of 1,4,5,6,7,7-hexachloro
NaOH solution until the mixture was alkaline to phenol
bicyclo(2.2.l)hept-S-en-Z-ethanol and 30 g. (0.3 mole)
ph-thalein. The liberated ‘amine was dissolved in hexane
of chloroacetic acid with 0.5 g. of p-toluene~sulfonic acid
as catalyst was refluxed ‘for 17 hours. The toluene was 50 and the hexane extract was concentrated to give 123 g.
of crude amine. A solution of 45 g. of maleic anhydride
removed under vacuum and the residue Was recrystal
in 300 ml. of benzene was added slowly with cooling to
the amine to give the maleamic acid which came out at
'once. After ?ltration and recrystallization from acetone
Cl 55 vthe product 157 -g., was dried in an oven, M.P. 195-6°
lized from CCl4 to give 65 g. of solid; recrystallization
from ethanol yielded a pure product, M.P. 136—137°.
Analysis:
(dec.). Analysis:
Calc’d for CmHgClqNO _____________________ __ 61.0
Found
Cl
___________________________________ __ 60.6
Calcd’d for C11H5Cl6NO3 ____________________ __ 51.7
EXAMPLE VI
N-(2-(1,4,5,6,7,7-Hexachlorobicycl0 (2.2.1 )Hept-5-En
'
2-Yl) Ethyl)Acetamide
Found ______________ _.______, ________________ __
51.2
60
EXAMPLE IX
Z-Chloro-N-(1,4,5,6,7,7-Hexachl0r0bicycl0(2.2.1 ) -
1,4,5,6,7,7 - hexachlorobicyclo(2.2.l)hept - 5-ene - 2 -
acetonitrile was used as the starting material in the prep
aration of
N-(Z-[l,4,5,6,7,7-hexachlorobicyclo(2.2.1)
hept-S-en-Z-yl]ethyDeacetamide. 68.0 g. of the above
acetonitrile were hydrogenated under pressure for a period
of four days in the presence of acetic anhydride (125
ml.) and reduced platinum oxide as catalyst. The initial
pressure of the hydrogenation bomb was 61 pounds
Hept-5-En-2-Ylmethyl)Maleamic Acid
1,4,5,6,7,7 - hexachlorobicyclo(2.2.1)hept - 5 — ene - 2
methylamine sulfate (158 g.) made in accordance with
Example III of copending application Serial No. 705,781
?led December 30, 1957, was dissolved in 100 m1. of
methanol and a solution of 17 g. of NaOH in 500 ml.
H2O was added to the solution until a penmanent red
color to phenolphthalein was obtained. The combined
benzene extracts were dried over Na2SO4 and then treated
with 5 6 g. of chloromaleic anhydride; an exothermic re
action resulted. The benzene was. boiled oil and the
(gauge) and the external temperature of the vessel was
maintained at 35° C. Total pressure drop over this period
was 36 pounds. Theoretical pressure drop for the desired
reaction being 32 pounds. The volatile materials were
then removed from the reaction mixture at reduced pres 75 residue was boiled with hexane and ?ltered hot to give
3,052,703
7
8
200 g. of product, M.P. 135-45" dec. The product was
dissolved in acetone and the acetone was displaced by
benzene and cooled to give 48 g. of product M.P.
C1
The compounds‘ for the present invention possess fungi
cidal activity for a wide variety of plant pathogens. In
the foliage fungicide screen three varieties of bean plants
and tour foiliage fungus diseases were employed. Em
52.3
ploying these hosts and pathogens the chemicals were
screened for general as well as speci?c control activity
and for phytotoxicity.
148-5 0'’. Analysis:
Calc’d for C12H8C17NO3 _____________________ ..... 5
Found
_
___
Diseases and hosts are shown below:
EXAMPLE X
Bean hosts:
10
Phaseolus vulgaris var. Pinto
N- (2-Cyanoethyl ) -N-(1 ,4,5 ,6,7,7-Hexach lorobicyclo
(2.2.1 )Hept-5-En-2—Ylmelhyl) Acetamide
P. vulgaris var. Black Valentine
P. linensis var. Fordhook 242
A solution of 146 g. (0.81 mole) of N-allyl-N-(Z
cyanoethyl)—acetarnide and 220 g. (0.81 mole) of hexa
chlorocyclopentadiene containing 0.1 g. tert-butylhydro~
Uromyces phaseoli var. typica (rust)
quinone was heated at 95 ° for 7 days. The crude product 15
was dissolved in benzene, the solution was treated hot
Erysiphe polygoni (powdery mildew)
Colletotrichum lindemuthitmumi (anthracnose)
Plzytophthora phaseoli (downy mildew)
with charcoal, and ?ltration and concentration of the
These four bean pathogens are of economic importance
The solid was collected and
and represent each of the four classes of fungi. P. phaseoli
recrystallized from benzene-hexane to give 144.5 g. of
product, M.P. l28—30°. Stripping the ?ltrates of un 20 is closely ‘allied with P. infestans, the important potato
and tomato pathogens. Thus, with the above selection,
reacted hexachloro cyclopentadiene in vacuo and re
?ltrate gave crude solid.
chemicals can be routinely screened for general or speci?c
crystallizing the residue from methanol gave an additional
disease control activity and for phytotoxioity on a sus
34 g. of product, M.P. 127—9° (total yield 49%).
Analysis:
ceptible plant type.
25
The test is carried out according to the following pro
cedure. Test chemicals are prepared as 1% w./v. stock
solutions in a solvent. The stock is diluted for spraying
using a diluent consisting of distilled water+solvent
("1:1) or with distilled water-i-two solvents (2:121).
Oalc’d for CraHrzNaOClu ____________________ _.
Found
30 Triton X-155, at 0.005% 'W—0.1% w. is used as a wetting
agent for each concentration of toxicant. All chemicals
EXAMPLE Xl
are initially tested at a single concentration of 1000 ppm.
If acceptable disease control is shown, chemicals are re
tested at 1000 ppm. and the next lowest dilution of 500
An aqueous solution of 73 g. of 1,4,5,6,7,7-hexachloro 35 ppm. Chemicals continuing to show disease control
are retested in this fashion until the
effective
bicyclo(2.2.1)hept-5-ene - 2 - rnethylarnine hydrochloride
Diethyl(1,4,5,6,7,7-Hexachlorobicycl0(2.2.1 )Hept-5
'
'
'
En-Z-Ylmethyl)Phosphoramidate
concentration is determined.
prepared in accordance with the method described in
copending application Serial No. 705,7 811 ?led December
Phytotoxicity assessments
‘are expressed as the maximum “safe” concentration.
30, 1957, was treated with 20% NaOH and hexane until
Spray applications are made using a laboratory sprayer.
alkaline. The hexane layer was dried and 14.1 g. of 40 The bean plants are selected ‘for use at a stage when the
diethyl chlorophosphate added to give an exothermic
two primary leaves are about three-quarters expanded.
reaction and a heavy precipitate. Filtration of the solu
To facilitate deposit the primary leaves are oriented to a
tion after the completion of the ‘addition gave 30 g. of
vertical position by pinning them to a small Wire stall.
the amine hydrochloride. Concentration of the hexane
Either the upper or lower epidermis of the leaf is exposed
?ltrate gave an oil which on cooling solidi?ed to give 45 to the spray stream, depending on the surface to be inocu
two crops 7 g. of solid M.P. 94-98, 4.7 g. of solid M.P.
lated.
92—8°, and 2.7 g. of solid M.P. 85-98"; total yield 31%.
With the mist type spray and the diluent mixture which
Recrystallization of the 94—98° product gave 5.5 g.
is applied, a drying interval of 1-2 hours in su?icient be
M.P. 96-98 ° . Analysis:
P
50
Calc’d
Found ‘£01’ C12H15C16NO3 ____________________
.._
_.... 6.10
fore inoculation with spore suspensions using a specially
constructed atomizer. Inoculations with bean mildew
are made by dusting conidia over treated plants in the
greenhouse.
EXAMPLE XII
‘ After 24 hours’ incubation at 19° C. and 100% humid
55 ity, the plants are removed to the controlled-environment
N-(1,4,5,6,7,7-Hexachlorobicyclo(2.2 .1 )Hept-S-Ene
2-Ylmethyl)Benzenesulfonamide
greenhouse for symptom development. Disease control
and phytotoxicity assessments are made within 7 days.
A hexane solution of 1,4,5,6,7,7-hexachlorobicyclo
The e?fectiveness of the present compounds as fungi
cides is further evidenced by the following tests.
with the disclosure in copending application Serial No.
705,781, ?led December 30, 1957, was treated with 22 60 To obtain disease control data, chemicals were sprayed
g. of benzenesulfonyl chloride to give a mildly exothermic
as emulsions, solutions or suspensions using concentra
(2.2.1)hept-5-ene-2-methylamine prepared in accordance
reaction and a gummy precipitate.
The hexane super
tions of 0.24% w., 0.12% w, and 0.06% W.
natent was decanted and the precipitate extracted with
boiling hexane to leave 36.5 g. of l,4,5,6,7,7-hexachloro
bicyclo(2.21)hept - 5 - ene-Z-methylamine hydrochloride.
The combined hexane extracts and decantate was dried
to yield 42 g. of solid M.P. 95~99° (90% yield). Re
crystallization from hexane and ethane gave 30 g. M.P.
96—98 ° .
Analysis:
70
01
S
Calc’d f0!‘ CuHuClaNSOz ___________________________ ._
45. 3
6. 8
45. 0
6. 7
l
icity development.
Crops and diseases used were tomato or potato blight
(Phytophthora infestans), celery blight (Septoria apii
Fnrmrl
_____ __
These cor
respond respectively to 2, 1, ‘and 0.5 lbs. toxicant per 100
gallons of spray. Plants were sprayed to the runoff stage,
dried for 24 hours, and inoculated with test fungus spores.
After inoculation, the plants were held for 24-48 hours
in a humidi?ed incubation chamber at 19° C. They were
then removed to the greenhouse for disease and phytotox
graveolenwtis), bean mildew (Erysiphe piolygoni) bean rust
(Uromyces appendiculatus), and cucumber anthracnose
75
(Collototrichum lagenarium').
3,052,703
FOLIAGE FUNGICIDE SCREEN
Disease Control, Min. Effective Cone.
_
Phytotoxicity, Max. “Safe” Conc.
(p-p-m.)
(op-m)
Chemical Compound
Pp.“
E4).
Up.
01.
Lb
P.
BV
>1, 000
>1, 000
>1, 000
500
>1, 000
l, 000
l, 000
250
500
32
16
500
250500
1, 000
500-1, 000
>1, 000
125-250
125-250
>1, 000
>1, 000
>1, 000
250-500
500
500
1, 000
>1, 000
500-1, 000
>1, 000
>1, 000
>1, 000
>1, 000
>1, 000
>1, 000
>1, 000
>1, 000
>1, 000
N - [1,4,5,6,7,7-Hexachlorobicycl0(2.2.1) - hept - 5 -
en-lylmethyllmaleamic acid _________________ -_
Methyl N - (l,4,5,6,7,7 - hexachlorobicyclo(2.2.1)
'
hept-S-en-Z-ylmethyl)maleamatc ______________ __
N(l,4,5,6,7,7 - Hexachl0robicyc1o(2.2.l)hept - 5 -
en~2-ylmethyl)maleamic acid cupric salt ______ __
2-Chl0r0 -N - (1,4,5,6,7,7-hexachlor0bicyclo(2.2.l)
hept-5-en-2-ylmethyl) acetamide ______________ _N - (2 - Cyanoethyl) - N - (1,4,5,6,7,7 - hexachloro -
bicyclo(2.2.1)hept-5-en-2-ylmethyl)acetamide-..
N - (1,4,5,6,7,7 - Hexachlorobicyclo(2.2.l)l1ept - 5 -
en-2-yl)acetamide ____________________________ _ _
>1, 000
>1, 000
>1, 000
>1, 000
>1, 000
>1, 000
>1, 000
>1, 000
1, 000
>1, 000
>1, 000
1,000
>1, 000
1, 000
>1, 000
500
125
500-1, 000
500-1, 000
500~l, 000
N - (l,4,5,6,7, - Hexachlorobicyclo(2.2.1)hept - 5 -
en-2-yl)maleamic acid ________________________ __
2- Chloro -N - (1,4,5,6,7 ,7-hexacl1lorobicyclo(2.2.1)
hept-5-en-2-ylmethyl)maleamic acid __________ ._
a P4). =Ph1/tophthora phaseoli (downy mildew of lima bean); E.p.=Erysiphe polyqom' (bean powdery mildew); U.p. = Uromyces
phaseoli (bean rust); C’.Z.= Colletotrichum Zindemuthianum (bean anthracnose).
b L=Lima bean; P=Pinto bean; BV=Black Valentine bean.
From four replicated plants per concentration, a per
tritives, plant hormones and the like. Wetting agents,
centage disease control ?gure was obtained, which was
and if necessary or desirable, stickers such as the heavy
based upon the improvement shown over the untreated 25 hydrocarbon oils with a minimum viscosity of 10° Engler
at 50° C. can be present. Any conventional wetting
checks as follows:
(disease rating
agent, for example, alkyl sulfate salts, alkyl aryl sulfon-ate
salts, sulfosuccinate salts, ethers from polyethylene gly
disease rating)
(of untreated check
of treatment or standard)
disease rating of untreated check
cols and alkylated phenols, and the like can be employed.
30 If the toxic agents are employed in the form of emulsions
The percent disease control for a treatment was next
or suspensions, for example, in Water, solvents such as
compared with the percent control for the standard fungi
oils, emulsi?ers, emulsion stabilizers, and the like may be
cide (captan at 0.24% w. of formulated chemical) as fol
added. Materials which suppress phytotoxic action may
lows:
'
also be added if desired. For example, glucose is known
35 to protect tomato plants against damage by certain sub
Foliage-Fungicide __Percent control for treatment
stances having a phytotoxic effect when employed in
Activity Index — Percent control for standard X100
concentrated form.
(F-F. A. I.)
The compounds of the present invention may be ap
Where disease control for the test chemical and stand
plied by means of spraying. Spraying of the plants to
ard was equivalent, the index value was (100). Values
40 be treated may be performed with aqueous emulsions,
above 100 indicated superiority.
solutions, or suspensions of the active agents. The spray
In most cases comparisons were made at the 0.24% W.
liquid is generally applied at a rate of from about 75 to
(2 lbs/100 gal.) concentration.
150 ‘gallons per acre. If spraying is eifected with smaller
Readings for plant injury were obtained on tomatoes,
quantities of liquid as in low volume spraying, high con
beans, celery and cucumber. Both chronic toxicity (yel
lowing, distortion, etc.) and acute toxicity (tissue death) 45 centrations of the active agents should be employed. If
were recorded. The scale used was 0-4000 represented
no visible poisoning and 400‘ was the most severe mani
desired, a minor amount of the order of about 0.01 to
festation.
The following table summarized the results of these
to aid in forming a suspension of toxicant in the aqueous
tests.
about 0.05% by weight, of a wetting agent may be added
medium. Any of the conventional Wetting agents can be
50 employed. Particular suitable wetting agents are the
FOLIAGE FUNGICIDE TEST
Activity Index at 0.24% Cone. (Upper
?gure) and percent control at 0.06%
Chemical Compound
(lower ?gure)
P.z'.e
Sta
N-(l 4 5 6 7 7-Hexachlorobicyc1o (2.2.1) kept-5
ene-2'—ylin’ethyl)maleamic acid _______________ __ { 1,15% 1%
N - (1 4 5 6, 7, 7-Hexachl0robicycl0 (2.2.1) hept
?-en-i-yl’methyl)acetamide ................... _. {
N- (2- (1,4,5,6,7,7-Hexachlor0bicyc1o(2.2.1)hept-
*“gé‘
E47.
U.a.
1% “fa
83
100
125
5'en'2'Y1>ethy1) acetam‘de -------------------- -- { 100
57
70
100
N-(2-Cyanoethyl)-N-(l,4 5 6, 7 7-hexachlorobi—
0.1.
Combined
Index
Phytotoxicity at 0.24% (upper
?gure and 0.06% cone. (lower
?gure) respectively
'1‘b
C
B
On
12 II: 2% IIII: 10% 108 $22 108
120
-
‘
.,
cyclo(2.2.l)hept-5-en-2~yl1ncthyl)acetamide____{ 128 59
175
_____ ":1? 108
3
108
1g?
100
100
100
400
0
0
100
150 ________ __
-------------- --
100
Com
bined
35
108
g 10g 108
81
175
75
11 P.i.=Phytophthora infestans (late blight of tomato); S.a.=Septoria apz'i-graveolentis (late blight of Celery); E.p.=Er1/siphe
polygom' (bean powdery mildew); U.a.=Uromyces appendiculatus (bean rust); C.Z.=COZlectotrichum Zagenarz'um (Cucumber
Anthracnose) .
b T=T0mato; C=Celery; B=Bean; Cu=Cucumber.
The active compounds of the present invention may be
used alone or in combination with other fungicidal, ver
s-odiuin salts of a mixture of secondary heptadecyl sul
fates, sold commercially under the trade name of
“Teepol” and polyethylene glycol ethers of alkyl phenols
icidal, insecticidal or acaricidal materials, the action on
which may ‘be either internal or external, with plant nu 75 sold under the trade name of “Triton X4100” and “Triton
3,052,703
l2
11
X-155.” Preferably concentrate compositions comprising
carbon atoms, tolyl, phenyl, naphthyl and anthryl,
an active compound of the present invention and a suit
alkenyl of 1 to 18 carbon atoms —COOH,
able wetting agent are prepared, and the concentrate is
then dispersed in water prior to use.
A further ‘form in which the fungicidal compounds of
the present invention may be applied consists of solu
tions of the active ingredient in suitable inert liquid or
semi-solid diluents, in which the active ingredient is pres
ent in molecularly dispersed form. The form in which
the agents to be employed are applied to the objects
treated depends on the nature of the object and the pur
pose of the application.
Suitable inert solvents for the manufacture of liquid
preparations should not be readily in?ammable, as odor
—CHICHCOOH
and —CH=CHCOOR”’ wherein R'” is cupric ion.
2. A polychloro compound of the formula
01
01
wherein R is alkylene of 1 to 10 carbon atoms.
3. A polychloro compound of the formula
less as possible and without any toxic effect on humans 15
C
and animals when properly used. Neither should they
have a corrosive e?ect on the ‘components of the prep
arations or the material of the storage vessel. Examples
of suitable solvents are high boiling oils, e.g., oils of
vegetable origin such as castor oil, etc, and lower-boil
ing solvents with a ?ash point of at least 301° 0., such as
wherein R is alkylene of 1 to ‘10 carbon atoms.
4. A polychloro compound of the formula
carbon tetrachloride, ethylene dichloride, acetylene tetra
chloride, hydrogenated naphthalene, sorbent naphtha, etc.
01
Non-aromatic petroleum oils and Xylene are commonly
used. Mixtures of solvents may also be used.
25
The active compounds of the present invention may
also be applied in the form of dusts utilizing as the inert
vehicle such materials as tricalcium phosphate, precipi
tated chalk, bentonite, kaolin, and kieselguhr, etc.
These compounds may also be employed in the form
of aerosols. For this purpose the active ingredient is
dissolved, or dispersed in a solvent boiling below room
temperature at atmospheric pressure.
01
wherein R is alkylene of 1 to 10 carbon atoms and R"
is alkyl of 1 to 18 carbon atoms.
5. A polychloro compound of the formula
HO
0
We claim as our invention:
1. A polyhalo compound selected from the group con
0‘
III
\R— —(J-R"
~ C1-— —01
C1
sisting of
C1
wherein R is alkylene of 1 to 10 carbon atoms and R”
is alkenyl of 1 to 18 carbon atoms.
6. A polychloro compound of the formula
\Ol
wherein R is alkylene of 1 to 10 carbon atoms and R"
is alkyl of 1 ‘to ‘18 carbon atoms.
7. A polychloro compound of the formula
50
55
r
wherein R is alkylene of 1 to 10 carbon atoms and R"
, is alkenyl of 1 to 18 carbon atoms.
8. A polychloro compound of the formula
or
El 0
60.
wherein X is halogen, X’ is selected from the group con
/
sisting of hydrogen, halogen and lower alkoxy, R is se
lected ‘from the group consisting of alkylene, tolylalkyl- ,
ene, phenylalkylene, naphthalenylalkylene and anthra 65 wherein R” is alkenyl of 1 to 18 carbon atoms.
9. A polychloro compound of the formula
cenylalkylene in which alkylene is in each case alkylene
of 1 to 10 carbon atoms ‘and tol'ylene, phenylene, naph
01
HO
II
thylene and anthryllene, R’ is selected from the group
consisting of hydrogen, alkyl, benzylalkyl, tolylaikyl,
phenylalkyl, naphthylalkyl and anthrylalkyl in which 70
ailkyl in each case contains 1 to 10 carbon atoms and
01
benzyl, tolyl, phenyl, naphthyl and anthryl, and R” is
selected from the group consisting of alkyl of 1 to 18 car
bon atoms, tolylalkyl, phenylalkyl, naphthylalkyl and
wherein R" is alkyl of l to 18 carbon atoms.
10. N - (1,4,5,6,7,7 - hexachlorobicyclo(2.2.1)hept - 5
anthrylalkyl in which alkyl in each case contains 1 to 10 75 en-2-ylrnethyl)maleamic acid.
2,052,703
13
14
2,516,674
11. Methyl N - (1,4,5,'6,7,7 - hexachlorobicyclo(2.2.1)
hept-5-en-2-y1methy1)mxaleamate.
2,635,977
2,635,979
2,638,431
12. N - (1,4,5,6,7,7 - hexachlorobieyc1o(2.2.1)hept - 5
2,642,373
2,673,172
Polen et a1. __________ __ Mar. 23, 11954
2,717,851
2,771,479
10 2,872,483
2,875,123
2,912,459
Lidov ______________ __ Sept. 13, 1955
Block ______________ __ Nov. 20, 1956
Block ________________ __ Feb. 3, 1959
13. 2 - chloro - N - (‘1,4,5,6,7,7 - hexachlorobicyclo
(2.2.1 )hept-S-en-Z-ylmethyl)‘acetamide.
14. 2 - chloro-N - (1,4,5,6,7,7 ~ hexachlorobicyclo
References Cited in the ?le of this patent
UNITED STATES PATENTS
2,015,045
2,186,976
2,456,590
Lidov ______________ __ Apr. 21, 1953
Lidov ______________ __ Apr. 21, 1953
Harry ________________ _ May 12, 1953
Dazzi _______________ __ June 16, 1953
en-Z-yhnethyDmaleamic a'cid cupric salt.
(‘2.2.1)hept-5—en-2-y1methyl)maleamic acid.
H
Bruce _______________ _._ July 25, 1950
Teichmann __________ _._ Sept. 17, 1935
Junkmann ___________ __ Jan. 16, 1940
Morey ______________ __ Dec. 14, 1948 15
Wygant _____________ -_ Feb. 24, 11959
Boehme etlal __________ __ Nov. 10, 1959
FOREIGN PATENTS
207,369
Australia _____________ __ Dec. 1, 1955
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