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Патент USA US3028431

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United States. Patentv
3',®Z8,li2l
"ice
Patented Apr. 3, 1862
2
1
acids, X being a lower alkyl radical, e.g., methyl, ethyl,
' propyl, butyl, and the like, or a halogen atom, as previ
3,028,421
POLYHALOGENATED TETRAHYDRO
ously de?ned; n being a number from 0 to 2, inclusive.
The following are illustrative of such compounds:
PHTHALAMIC ACID
Russell M. Bimher, Painesville, Ohio, assignor to Dia
mond Alkali Company, Cleveland, Ohio, a corporation
of Delaware
N - (2,2,2 - trichloro - 1 - hydroxyethyl) - tetrahydro
phthalamic acid
'
No Drawing. Filed Mar. 17, 1958, Ser. No. 721,685
4 Claims. (Cl. 260-514)
N - (2,2,3 - trichloro - 1 - hydroxybutyl) - tetrahydro~
phthalamic
This invention relates to tetrahydrophthalrnic acid de 10
rivatives represented by the structure:
acid
-
-
1
'
N - (2,2,2 - tribromo - 1,- hydroxyethyl) - tetrahydro
phthalamic
acid
'
~
N - ( 2,2,2 - trichloro - l - hydroxyethyl - 2 - methyltetra
hydrophthalamic acid
>
N - (2,2,3 - tribromo - 1 -t,hydroxypropyl) - tetrahydro~
15
phthalamic acid
N - (2,2,2 - trichloro - 1 - hydroxyethyl) - 3(or 6) —
chlorotetrahydrophthalamic acid
-
Compounds of‘this invention may be prepared by
chemically reacting a substituted tetrahydrophthalamic
wherein R1 is a halogen-substituted alkyl radical such as 20 acid of the structure:
'
trichloromethyl, trichloroethyl, 1,1,2-trichl0ropropyl, tri
bromomethyl, l-chloropropyl, and l-chloroethyl; R3, R4,
R5, R6, R7, R8, R9 and R10 are selected from the group
consisting of hydrogen atoms, alkyl radicals, such as
methyl, ethyl, propyl, butyl, octyl and the like, prefer
ably lower alkyl radicals; aryl radicals, such as phenyl or
naphthyl radicals; thienyl radicals, alkaryl radicals; such
as tolyl or xylyl radicals; aralkyl radicals, such as benzyl
wherein R3, R4, R5, R6, R7, R8, R9 and R10‘ are selectedv
or phenethyl radicals; halogen atoms, i.e., ?uorine, chlo
from the group consisting of hydrogen atoms, alkyl radi
' rine, bromine, and iodine, chlorine being preferred, and .80 cals, such as methyLethyl, propyl, butyl, octyl and the
substituted derivatives of the same, especially halogen
like, preferably lower alkyl radicals; aryl radicals, such
substituted derivatives, such as R’s preferably containing
as phenyl radicals and naph‘thyl radicals; thienyl radicals,
i.e., C4H4S1; alkaryl radicals, such as tolyl or Xylyl radi
cals; aralkyl radicals, such as benzyl and phenethyl radi
no more than 30 carbon atoms, and to the method of
preparing and using the foregoing.
,
More speci?cally, the present invention relates to novel
tetrahydrophthalamic acid compounds represented by the
structure:
_
‘
g
_
>O/ Rzm 0 .
cals; and substituted derivatives of the same, especially
' halogemsubstituted derivatives, e.g., ?uorine, chlorine,
, bromine, and iodine; such Rv’s preferably containing no
more than 30 carbon atoms, with an alpha vhalo'aldehyde,
e.g., an alpha halo acetaldehyde.
,
The expression “alpha halo aldehyde” as used in the
speci?cation and claims is intended to refer ‘broadly to a
compound of the structure ‘—-RCHO-- wherein R is an
Bin 0
0
6H
alpha-halogen-substituted alkyl vradical, especially a halo
/ \
45 gen-substituted lower alkyl radical, as previously de?ned.
wherein R1 is a halogen-substituted alkyl radical, e.g., tri
Exemplary alphahalo aldehydes are 2,2,3-trich1oropro4
chloromethyl, 1,1,2-trichloropropyl, tribrornomethyl, l
chloropropyl, and l-chloroethyl; R2 is hydrogen, R3 is
alkyl, e.g., lower alkyl radicals such as methyl, ethyl,
' pionaldehyde; 2,2,3-tribromopropionaldehyde; 2,2,2-tri
chlorobutyraldehyde; _ 2,2,3,3 - tetrachlorobutyraldehyde;
and 2,3-di?uorobutyraldehyde; speci?cally preferred alpha
halo aldehydes being alpha halo acetaldehydes, such as
propyl, butyl radicals, or the like; n equals 0 to 6; and m
equals
6-11.
1
’
~
.
'
chloral, 2,2-dichloroacetaldehyde, 2,2,2-tribromoacet'alde
_
Further exemplary of the above type compounds are
those having the structure:
hyde, 2,2-dichloro-2~bromoacetaldehyde. It is also in
tended that the above alpha halo aldehydes and speci?cal
ly the alpha halo acetaldehydes should include their re
55 spective hydrates, e.g., chloral hydrate, the hydrate of
2,2,3-trichlorobutyraldehyde, and the hydrate of 2,2-di
chloroacetaldehyde.
Morev speci?cally, novel compounds of this invention
may be prepared by chemically reacting a compound
Ran O
60 represented by the structure:
/
' -
wherein R2 is hydrogen; R3 is alkyl, e.g. lower alkyl radi
cal, such as methyl, ethyl, propyl, butyl radicals, or the
like, n equals 0 to 6; m equals 6-11; R1 is a halogen-sub
stituted methyl radical, erg.
65
X
I
—C|3—~Xa
X3
'
X being halogen or hydrogen, at least one X being halo
gen, i.e., ?uorine, chlorine, bromine, and iodine.
Speci?c preferred compounds of this invention are N
(trihalo-l-hydroxyloweralkyl)-Xn - tetrahydrophthalamic
wherein R2 is hydrogen, R3 is alkyl, e.g., lower alkyl
radical, such as methyl, ethyl, propyl, butyl radicals, or
the like; n equals 0-6; and m equals 6-11; with an alpha
halo aldehyde, e.g., an‘ alpha halo acetaldehyde, as pre
viously de?ned.
'
'
" 3,028,421 r
3
4
'
I
.
cally carried out at a temperature \above'0" C. up to the
decomposition temperature of chloral, e.g., at reflux tem
perature preferably in a range between 50'°-ll0° C. De
sirably, stoichiometric quantities of reactants are com
Still more speci?cally, novel compounds of this in
vention may be prepared by chemically reacting a lower
alkyl substituted tetrahydrophthalamic acid of the struc
bined; however, in certain instances, addition of a slight
excess of chloral is desirable. Preferably, the reaction
is carried to completion, e.g., for a time within the range
of from about 1 to 5 hours. Various solvents, previ
ously disclosed, may be employed to facilitate chemical
10
combination.
_
,
i
It will be understood that the reaction may be carried
out, when desirable, by employing the desired tetrahydro
wherein R2 is hydrogen, R3 is' alkyl, e.g., lower alkyl’
phthalic anhydride as the starting material, the anhydride
radical, such as methyl, ethyl, propyl, butyl radicals, or
being converted to the tetrahydrophthalamic acid which
the like; n=0-6;' m=6-n, with a compound represented 15 in turn reacts with the chloral. Various reaction condi
by the structure:
tions and solvents may be employed as previously dis
closed.
The compounds of this invention are useful in the ?eld
‘i X‘
HC- --X:
I
20
wherein ,X1, X2, and X3‘ are selected from the group
consisting of hydrogen atoms, and halogen atoms, as pre
viously de?ned, at least one X being halogen, e.g.,
X=chlorine, X=bromine.
Speci?c preferred N-(trihalo-l-hydroxy lower alkyl)
Xn-tetrahydrophthalamic acids of this invention may be
prepared by chemically reacting Xn-tetrahydrophthalamic
acid with an alpha halo aldehyde of the structure:
it’
of pharmaceuticals, chemical intermediates, and also show
biological activity such as the control of'plant growth,
e.g., pre- and post-emergent herbicidal activity, the con
trol of microorganism growth, e.g., the protection of
tomato foliage against blight fungi. While compounds of .
this invention may be employed in a variety of applica
tions, biologically or otherwise, when employed as bio
logically active materials it will be understood, of course,
that such compounds may be utilized in diverse formula
' tions, both liquid and solid, including. ?nely-divided
powders and granular materials, as Well as liquid, such
as solutions, concentrates, emulsi?able concentrates, slur
25
ries, and the like, depending upon the application intended
HC-Ri
wherein R1 is a halogenesubstituted methyl group; X
‘
being a lower alkyl radical, e.g., methyl, ethyl, propyl,
and the formulation media desired.
Thus, it will be appreciated that compounds of this
invention may be employed to form biologically active
butyl and the like, or a halogen atom as previously de
35 substances containing such compounds as the essential
?ned; n being a number from 0 to 2, inclusive.
active ingredients thereof which compositions may also in
Typically, the, above reactions are advantageously car
clude
?nely-divided dry or liquid diluents, extenders,
ried out below the decomposition temperature of the
?llers, conditioners, including various clays, diatomaceous
reactants, e.g., at re?ux temperature or less, 150° C. gen
erally being a practicable upper temperature limit in most 40 earth, talc, spent catalyst, alumina-silica materials, and
incorporating liquids, solvents,‘ diluents, etc., typically
instances. In general, it is preferred to employ substan
Water and various organic liquids such as kerosene, ben
tially stoichiometric ratios of‘ the reactants. However,
zene, toluene, carbon disul?de, carbon tetrachloride, chlo
considerable departure from these ratios can be tolerated
roform,
ethyl acetate, toluene, and other petroleum dis
in many. instances without serious detriments to either
fractions or mixtures thereof.
1
yield or quality of, product. The reaction chemical com 45 tillate
When liquid formulations are employed, or dry ma
bination is preferably" carried out until complete, e.g.,
terials prepared which are to be used in liquid form, it
reaction in the range of l to 5 hours. In certain instances,
is desirable in certain instances additionally to employ a
the reaction may be more easily eifected by bringing
wetting,
emulsifying or dispersing agent to facilitate use
together the two starting materials in the presence of a
solvent such as water, or an organic solvent such as 50 of the formulation, e.g., Triton X,-l55 (alkyl aryl poly
ether alcohol, U.S. Patent 2,504,064). Suitable surface
benzene‘, chloroform, heptane, ether, petroleum ether,
active agents are set out for example in a detailed list
hexane, carbon tetrachloride or- the like.
‘
in an article by McCutcheon in ‘_‘Soap and Chemical
Speci?c reactions falling within the scope of this in
Specialities,” vol. 31, No._7—l0 (1955).
vention are indicated in Table I in whichany compound
in column 1, i.e., the tetrahydrophthalamic acids, may be 55 The term “carrier” as employed in the speci?cation
and claims is intended to refer broadly to the materials
reacted with a compound in column 2, i.e., alpha halo
constituting a major proportion of a biologically active
aldehyde.
or other formulation, and hence includes ?nely-divided
materials, both liquids and solids as aforementioned con
TABLE I
Reactants
ventionally used in such applications.
60
7 Alpha Halo
'I‘etrahydrophthalamic acid Column 1
'
.
,
-
,3-methyl-tetrahydrophthalamic acid ___________________ __
Aldehyde,
Column 2
O13C~CHO
"d-chloro-tetrahydrophthalamic acid ____________________ __ 0151(131%?
tetrahydrophthalamic acid _____________________________ __
In order that those skilled in the art may more com
65 pletely understand the present invention and the preferred
methods by which the same may be carried into effect, the
OH3CH C1-
following speci?c examples areo?fered.
0012CEO
3,4-diethyl-tetrahydrophthalamic acid __________________ .i
GH201~
01101
CHO
The compounds of this invention may also be used in
combination with other known biologically active ma
terials such as organic phosphates, chlorinated hydro
carbons, and various pre- and post-emergent herbicides.
70
EXAMPLE I
Preparation of N-(2,2,2-Trich loro-I -Hydroxyez‘hyl ) -
Tetrahydrophthalamic Acid
Speci?cally exemplary of the above preparations is that
94.0 g. (0.6 mol) tetrahydrophthalic anhydride is stirred
of N-(2,2,2-trichloro-l-hydroxyethyl)-tetrahydrophthale
with 135.0 ml. of 28% NFL, in water solution. The re
amic acid which comprises chemically combining tetra
sulting solution, at 70‘_’ C., is then cooled to 10° C. and
hydrophthalamic acid and chloral. The reaction is typi 75 90 ml. of 37% HCl is added slowly with cooling. The
3,028,421
tetrahydrophthalamic acid.
7
6
tomato plants 5 _'to 7" high of the variety Bonny Best.
acidic solution is ?ltered and cooled to crystallize ‘the
100 ml. of a test formulation (2000 p.p.m. product of
g 7.:
Example I, 5% acetone, 0.01% Triton X-lSS, balance
55.8 g. of this tetrahydrophthalamic acid is then re
?uxed with 150 ml. of chloral for about 3 hours after
which the mixture is allowed to cool and the excess
water) are sprayed on the plants at 40 pounds air pres
sure while the plants are being rotated on a turntable
in a spray chamber. After {the spray deposit is dry,‘the
chloral ?ltered off. The solid product is triturated twice
treated plants and comparable untreated controls are
with petroleum ether and recrystallized from methanol
sprayed with about 20 ml. of spore suspension containing
and ethanol. ,A further puri?cation step is carried out
approximately 150,000 sporangi of P. infestans per ml.
comprising boiling the product for about 5 minutes, ?lter
Ming hot, and rinsing the undissolved powder with three 20 10 The plants are held in a ‘100%, humid atmosphere for 24
hours at 60° F. to permit spore germination and infec
ml. portions of methanol resulting in the desired
tion. After 2 to 4 days, lesion counts are made on the
C10H12Cl3NO4, M.P. 159-160.5° (3., indicated by the fol
three uppermost fully expanded leaves. Comparing the
lowing elemental analytical data:
number of lesions on the test plants and control plants
15 shows disease control of 28% at the above concentration.
E1ement
i ' percen
' Amp,’ y Calculagtgd,
pereen y
Wt.
C“ .
,
38. Q6
Fl‘
(‘l
3. 83
33. 7
EXAMPLE VI
Wt; .
'
A further fungicide test uses bean, variety Tendergreen,
and tomato, variety Bonny Best, plants growing in 4"
37. 95
3. 82
33. 6
20 pots which are treated by pouring a test formulation
(2000 ‘p.p.m. product of Example I, 5% acetone, 0.01%
Triton X-155, balance water) into the pots at a rate
The above product is less than 5% soluble in water,
equivalent to 128 pounds per acre (102 mg. per pot).
acetone, cyclohexanone, and xylene, and greater than 5%
The tomato plants are E3 to 4” tall and the trifoliant leaves
soluble in benzene, chloroform, and ethyl acetate.
just starting to unfold at the time of treatment. The bean
EXAMPLE II
plants are exposed to powdery mildew continuously after
To demonstrate insecticidal activity, male German
seedling emergence so that at the time of treatment infec
cockroaches, Blatella Germanica, 8 to 9 weeks old are
tion has occurred. The tomato plants are infected with
anesthetized with carbon dioxide to facilitate handling
the early blight fungus referred to in Example IV. Ob
and then dipped in a test formulation (2000 p.p.m. prod 30 servation of the tomato plants after 4 days indicates 41%
uct of Example I, 5% acetone, 0.01% Triton X-155, bal
disease control while observation after 14 days on the
ance water) for 10 seconds, removed, freed of excess
bean plants indicates very slight disease control of the
liquid, and caged. Two lots of 10 insects each are ex
posed to this formulation and mortality observations are
recorded after 3 days. Using the product of Example I
at the above concentrations, signi?cant mortality for the
powdery mildew.
EXAMPLE VII
35
To evaluate the effect of the product of Example I
upon the germination of seeds in soil, a mixture of seed
of six crop plants is broadcast in 8" x 8" X 2" metal
cockroaches is observed.
EXAMPLE HI
cake pans ?lled to within one half inch of the top with
Further insecticidal activity is shown against the bean 40 composted greenhouse soil. The seed is uniformly cov
aphid, Aphis fabae, which is cultured on nasturtium
ered with about one quarter inch soil and watered. After
plants. Nasturtium plants are infested with approximate
24 hours, 80 ml. of an aqueous test formulation con
ly 100 aphids at the time of treatment. The test plants
taining 320 mg. of the product of Example I is sprayed
are treated by pouring a formulation (2000 p.p.m. prod
at 10 pounds air pressure uniformly over the surface
uct of Example I, 5% acetone, 0.01% Triton X-l55, bal 45 of pans. This is equivalent to 64 pounds per acre. The
ance water) on the soil in which the plants are growing
seed mixture contains representative seeds of three broad
at a rate equivalent to 64 pounds per acre. Aphid mor
leafs:
turnip, ?ax, and alfalfa, and three grasses: wheat,v
tality of 60% is observed 24 hours after treatment.
millet, and rye grass. Two weeks after treatment, rec
EXAMPLE IV
50 ords are taken on seedling stands as compared to the con
Fungicidal activity is evaluated through a tomato foli
trols. Using this procedure, results show 100% stand
age disease test measuring the ability of the test com~
for the broadleaf and 75% stand for the grasses, thus
pound to protect tomato foliage against infection by the
early blight fungus, Alternaria solani. Tomato plants 5
indicating selective herbicidal activity.
plants are'sprayed with 100 ml. of test formulation (2000
p.p.m. and 400 p.p.m. product of Example I, 5% ace
tone, 0.01% Triton X-155, balance water) at 40 pounds
bodiments thereof, it is not to be so limited since changes .
It is to be understood that although the invention has
to 7 " high of the variety Bonny Best are employed. The 55 been described with speci?c reference to particular em
and alterations therein may be made which are Within
the full intended scope of this invention as de?ned by
air pressure while being rotated on a turntable in a spray
the appended claims.
chamber. After the spray deposit is dry, the treated
plants, and comparable untreated controls, are sprayed
with about 20 ml. spore suspension containing approxi
mately 20,000 conidia of A. solani per ml. The plants
What is claimed is:
1. Compounds represented by the structure:
are held in a 100% humid atmosphere for 24 hours at 70°
F. to permit spore germination and infection. After 2 65.
to 4 days, lesion counts are made on the three upper
most fully expanded leaves. Data based on the number
of lesions obtained on the control plants show 36% and
21% diease control at the 2000 and 400 p.p.m. concentra
tions, respectively.
70
EXAMPLE V
wherein R1 is a halogen-substituted lower alkyl radical;
and
R3, R4, R5, R8, R7, R8, R9 and Rm are selected
of N-(2,2,2-tricloro-1 Qhydroxyethyl) - tetrahydrophthal
from .the group consisting of hydrogen atoms, lower
amic acid to protect tomato plants against the late blight
fungus, Phytophthora infestans. The method employs 75 alkyl radicals and halogen atoms.
Further fungicidal utility is demonstrated ,by the ability
3,028,421
8
,2. Compounds represented by the structure:
wherein R2 is hydrogen, R3 is lower alkyl, R1 is ahalogen
substituted methyl group, n=0—6, and m=6—n.
4. N-(2,2,2-trichloro-l-hydroxyethyl) -tetrahydrophthal
amic acid.
5
7
References Cited in the ?le of this patent
UNITED STATES PATENTS
H
2,695,225
wherein R1 is a halogen-substituted lower alkyl radical, 1'0
R2 is hydrogen, R3 is lower alkyl, n=0-6, and m=6—n.
3. Compounds represented by the structure:
Witman _____________ __ Nov. 23, 1954
Kenney et a1 __________ __ Nov. 30, 1954
Geschicker __________ __ Dec. 18, 1956
2,695,839 '
2,774,787
2,844,505
' 2,847,460
Trapp et a1 _________ __‘___ Aug. 12, 1958
2,850,425
Gaertner _____________ __ Sept. 2, 1958
15 ‘
Miller et al. __________ __ July 22, 1958
OTHER REFERENCES‘
Vavon et a1.: “Bull. Soc. Chem,” France, vol. 45
(1929), pages 298-9. (Copies in Scienti?c Library.)
Degering. et- al.: “An Outline of Organic Nitrogen
Compounds” (1945), page 426. (Copies in Scienti?c
20 Library.)
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