close

Вход

Забыли?

вход по аккаунту

?

Патент USA US3094573

код для вставки
United States Patent 0
3,094,560
M
lC€
Patented June 18, 1963
2
1
ie derivatives of the arylamine. The desired products of
3,094,560
this invention will ?nd a wide variety of uses in the chemi
cal ?eld, foremost of which will be their use as pesti
N-HALOCYCLOALKENIC DERIVATIVES
ologically active agents and speci?cally as insecticides or
fungicides. For example, the reaction product which re
sults from the condensation between hexachlorocyclopen
tadiene and methyl vinyl ketone followed by reacting the
OF ARYLAMINES
John P. Luvisi, Park Ridge, and James J. Louvar, River
side, Ill., assignors to Universal Oil Products Company,
Des Plaines, 1th, a corporation of Delaware
No Drawing. Filed Mar. 9, 1959, Ser. No. 797,890
resultant condensation product with p-phenylenediamine,
12 Claims. (Cl. 260-566)
namely, N,N'-bis- [ 1-( 1,4,5 ,6,7,7-hexachloro-5-norbornen
2-yl)ethylidene]-p-phenylenediamine may be used as an
This invention relates to new compositions of matter 10 insecticide, especially against house-?ies. In addition the
which are useful as pestiologically active agents and to a
reaction products of this invention may also be used as
method for the preparation thereof. More speci?cally,
oxidation inhibitors or as intermediates in the preparation
7' the invention relates to 1a method for the preparation of V
N-halocycloalkenic derivatives of arylamines.
An object of this invention is to prepare halocyclo
' of resins, pharmaceuticals, plastics, etc.
The process of this invention 1n which the haloalkai
15
alkenic derivatives of arylamines.
A further object of this invention is to prepare new
diene or halocycloalkadiene of the type hereinafter de
scribed is condensed with a ketone containing an ole?nic
linkage will take place at a temperature in the range of
from about room temperature, that is, 25° C., to about
compositions of matter comprising N-substituted halo
cycloalkenic derivatives of arylamines, said new compo
150° C. or more, the temperature at which the reaction
sitions of matter being useful a pestiologically active com 20 proceeds depending upon the reactants which are used
pounds.
therein.
In addition, if so desired, higher temperatures
One embodiment of this invention is found in a process
for the formation of an N-halocycloalkenic derivative of
an arylamine which comprises condensing a halo substi
may be employed along with superatmospheric pressures
group consisting of haloalkadienes and halocycloalka
rials in the liquid phase.
dienes with a ketone containing an ole?nic linkage, and re
fected in the presence of water and a small amount of a
ranging from about 2 atmospheres to about 100 atmos
pheres or more, the particular pressure used being su?i
tuted conjugated unsaturated compound selected from the 25 cient to maintain at least a portion of the starting mate
In addition, the reaction is ef
polymerization inhibiting compound such as t-butyl-cate
acting the resultant condensation product with an aryl
ch01, for example. These reactants, namely, the halo
amine to form the desired product.
A further embodiment of this invention is found in a 30 alkadiene or halocycloalkadiene and the ketone contain
ing an ole?nic linkage are usually reacted in the 1:1 mo
process for the formation of an N-halocycloalkenic de
rivative of an arylamine which comprises condensing a
lecular ratio.
halo substituted conjugated unsaturated compound se
lected from the group consisting of haloalkadienes and
The resultant condensation product which comprises
a halocycloalkenyl alkyl ketone is further reacted with
halocycloalkadienes with a ketone containing an ole?nic 35 an arylamine at an elevated temperature, usually in the
range of from about 75 ° to about 150° C. or more and
linkage at a temperature in the range of from about 25°
at pressures ranging from ‘atmospheric to about 100
atmospheres or more, said pressure being su?icient to
product with an arylamine in the presence of an inert or
ganic diluent and a catalyst containing a metal of the
maintain a major portion of the reactants in the liquid
40 phase. In addition the second step of the process of
platinum group of group VIII of the periodic table at a
this invention may, if so desired, be effected in the pres
temperature in the range of from about 75° to about
ence of an inert organic solvent or diluent, said solvents
150° C. to form the desired product.
including saturated paraf?ns such as pentane, hexane,
Yet another embodiment of the invention resides in an
N-halocycloalkenic derivative of an arylamine.
45 heptane, etc.; aromatic hydrocarbons such as benzene,
to about 150° C., and reacting the resultant condensation
A speci?c embodiment of the invention is found in a
toluene, o-xylene, m-xylene, p-xylene, ethyl benzene, etc.;
process for the formation of N,N'-bis-[l-(l,4,5,6,7,7
alcohols such as methyl alcohol, ethyl alcohol, propyl
alcohol, etc.; ethers such as dimethyl ether, diethyl ether,
hexachloro - S-norbornen-Z-yl)ethylidene]-p-phenylenedi
amine which comprises condensing hexachlorocyclopenta
dipropyl ether, etc., or acetone, acetic acid, dioxane, etc.
diene with methyl vinyl ketone at a temperature in the 50 A catalyst is also present in the second step of the reac
tion ‘for purposes of aiding in the removal of water
range of from about 25° to about 150° C., and reacting
the resultant 1,4,5,6,7,7 - hexachloro-S~norb0rnen-2-y1
which is formed during said reaction. This catalyst
contains-a metal of the platinum group of group VIII
methyl ketone with p-phenylenediamine at a temperature
of the periodic table such as platinum, palladium, osmium,
in the range of from about 75° to about 100° C. in the
presence of benzene and a catalyst containing platinum
iridium,
rhodium, ruthenium, either alone or composited
55 on a solid support. A particularly suitable catalyst which
to form said N,N’-bis-[1,4,5,6,7,7-hexachloro-5-norbor
may be used in this invention comprises platinum com
nen-Z-yl ) ethylidene] -p~phenylenediarnine.
posited on a solid support such as alumina and contain
Yet another speci?c embodiment of the invention re
ing combined halogen such as chlorine or ?uorine. The
sides in an N,N'-bis-[l-(l,4,5,6,7,7-hexachloro-S-norbor
nen-2‘y1) ethylidene] -p-phenylenediamine.
halocycloalkenyl alkyl ketone and arylamine are reacted
Other objects and embodiments referring to alternative 60 in a ratio of from 1 to 2 molecular proportions of the
halocycloalkenyl ‘alkyl ketone to 1 molecular proportion
haloalkadienes, halocycloalkadienes and arylamines will
of arylamine, the molecular ratio being dependent upon
be found in the following further detailed description of
the particular arylamine which is used in the reaction.
the invention.
Halo substituted conjugated unsaturated compounds
It has now been discovered that N-halocycloalkenic de
rivatives of arylamines may be prepared by condensing a 65 which may be reacted with the ketone containing an
ole?nic linkage in the process of the present invention
halo substituted alkadiene or cycloalkadiene with a ketone
containing an ole?nic linkage and reacting the resultant
include straight chain diole?ns having the general for
condensation product with an arylamine to thus prepare
the desired product. For purposes of this invention the
term “halocycloalkenic” when used in the speci?cation 70
and appended claims will refer to halocycloalkenic, poly
in which X is independently selected from the group
mula:
haloalkenic, halobicycloalkenic, and polyhalobicycloalken
’
'
3,094,560
4
consisting of hydrogen, alkyl, haloalkyl or halogen radi
vinyl ketone, isopropyl vinyl ketone, n-butyl vinyl ketone,
isobutyl vinyl ketone, t-butyl vinyl ketone, n-arnyl vinyl
cals having an atomic weight of from 35 to 127 (Le.
chlorine, bromine or iodine), 1at least one X being halogen
or haloalkyl, and Y is independently selected from the
ketone, isoamyl vinyl ketone, n-heXyl vinyl ketone, iso
hexyl vinyl ketone, etc., methyl allyl ketone, ethyl allyl
ketone, propyl allyl ketone, isopropyl allyl ketone, n-butyl
group consisting of alkyl, haloalkyl, and hydrogen radi
cals; or polyhalocycloalkadienes having the general ‘for
mula:
X
\
X
10
(XOX)n
W
X
allyl ketone, isobutyl allyl ketone, t-butyl allyl ketone, n
amyl allyl ketone, isoamyl allyl ketone, n-hexyl allyl ke
tone, isohexyl allyl ketone, etc., methyl crotonyl ketone,
ethyl crotonyl ketone, propyl crotonyl ketone, isopropyl
crotonyl ketone, n-butyl crotonyl ketone, isobutyl crotonyl
ketone, t-butyl crotonyl ketone, n-amyl crotonyl ketone,
isoamyl crotonyl ketone, n-hexyl cotonyl ketone, isohexyl
crotonyl ketone, etc.
_
Arylamines which may be condensed with the resultant
in which X has the same meaning as above and n is 1
halocycloalkenyl alkyl ketone include arylamines contain~
or 2. Examples of these compounds include haloalkadi
ing only nitrogen, carbon and hydrogen atoms such as V
enes such as l- and 2-chloro-l,3-‘butacliene, 1,3-, 2,3
aniline, o-toluidine, m-tolnidine, _p-toluidine, o-ethylanil
and 1,4-dichloro-1,3-butadiene, 1- and 2-bromo-1,3-tbuta- '_' ~ line, m-ethylaniline, p-ethylaniline, o-propylaniline, m—
diene, 1,3-, 2,3- and 1,4-dibromo-1,3-butadiene, 1,3-, 2,3
propylaniline, p-propylaniline, o-phenylenediarnine, m
ene, 1,2,3-tribromo-1,3-butadiene, 1- and 2-iodo-l,3
phenylenediamine, p-phenylenediamine, Z-me't'hyI-p-phen
ylenediamine, 2-ethyl~p-phenylenediamine, 2-propyl-p
butadiene,
1,2-diiodo-l,3-butadiene,
phenylenediamine, etc.
butadiene,
l,2,4-trichloro-l,3-1butadiene,
and 1,4-diiodo-1,3-butadiene, 1,2,3-trichloro-1,3-butadi
20
1,2,3 - triiodo - 1,3
1,2,4-tribromo- ' *
1,3dbutadiene, 1,2,4-triiodo-1,3abutadiene, 1,2,3,4-tetra
chloro-1,3--butadiene, l,2,3,4-tetrabromo-1,3-butadiene, 1,
2,3,4-tetraiodo-1,3~butadiene, 1,3-dichloro-2-methyl-1,3
ibutadiene, 1,4-dichloro-2-methyl—l,3-butadiene, 1,3,4-tri
25 Varylarnines are only representatives of the classes of com
pounds which may be used and that the present invention
chloro-2-methyl~1,3-butadiene,
methyl-1,3-bu-tadiene, 1,4-dichloro-2-dichloromethyl-1,3
1,4 - dichloro - 2 - chloro- " '
is not necessarily limited thereto.
An example of the condensation reactions of the present
invention may be illustrated by the following equations in
:butadiene, 1,3-dibromo-2-methyl-1,3-butadiene, 1,4-di
bromo-Z-methyl-1,3-butadiene,
It is to be understood that the
aforementioned halo substituted conjugated unsaturated
compounds, ketones containing an ole?nic linkage and
30 which the haloalkadiene to be used is 1,2,3,4-tetrachloro
1,4-dibromo - 2 - bromo
1,3-butadiene and the ketone is methyl vinyl ketone, said
methyl-1,3-rbutadiene, 1,4-dibromo-Z-dibromomethyl-l,3
reactants being used in a 1:1 molecular ratio:
butadiene, 1,3,4-tribromo-2-methyl-1,3-butadiene, 1,3-di
1,4-diiodo - 2 - methyl - 1,3
butadiene, 1,4-diiodo-2-iodomethyl-1,-3-butadiene, 1,4-di
iodo-Z-rnethyl-1,3-butadiene,
35
iodo-2-diiodomethyl-1,3-butadiene, 1,3,4-triiodo-2-methyl
1,3-butadiene, etc.; and halocycloalkadienes such as halo
genated 1,3-cyclopentadienes which for purposes of this _
invention will be ‘designated as halogenated cyclopenta
dienes including l-chlorocyclopentadiene, 1,2-and other
dichlorocyclopentadienes, 1,2,3- and other trichlorocyclo
pentadienes, 1,2,3,4- and other tetrachlorocyclopentadi~
enes, 1,2,3,4,5- and other
pentachlorocyclopentadienes,
hexachlorocyclopentadiene, the corresponding bromo
This intermediate ketone is then reacted with p-phenyl
40 enediamine in a mole ratio of 2 molecular proportions of
ketone per molecular proportion of diamine according to
the following equation:
' '
and iodo- derivatives, etc. It is also contemplated with
in the scope of this invention that polyhalo substituted
conjugated \cyclohexadienes such as 1,2-dichloro-l,3
cyclohexadiene, 1,2,3-trichloro-1,3-cyclohexadiene, octa
chloro-1,3-cyclohexadiene, etc., 1,'2-dibromo-l,'3-cyclo
hexadiene, 1,2,3-tribromo-1,3-cyclohexadiene, octabromo
1,3-cyclohexadiene, 1,2~diiodo-1,3-cyclohexadiene, 1,2,3
60
triiodo-1,3-cyc1ohexadiene, octaiodo-l,3-cyclohexadiene,
‘etc., may also be used. Furthermore, it is contemplated
within the scope of this invention that ‘?uorine analogs
of the aforementioned unsaturated compounds such as 55
hexa?uorocyclopentadiene or 2,3-di?uoro-l,‘3-butadiene
may also be used, although not necessarily with equiv
alent results. Generally speaking the iodine, bromine '
and chlorine containing compounds are preferred be
cause of their relatively vgreater availability and lower 60
cost. In addition, it is also contemplated that polyhalo
alkadienes and polyhalocycloalkadienes which are used
in this process may contain more than one species of
halo substituents, such as, for example, 1,2-dichloro-3
If a halocycloalkadiene such as hex-achlorocyclopenta
br0mo-1,‘3-:butadiene, 1-chlor0-3-bromo-1,3-butadiene, 1
iodo-3-chloro~1,34butadiene, 2-‘bromo~34chloro~1,3-buta
diene, l,4-,dichloro-2-‘bromomethyl-1,3-hutadiene, 1,4-di
65 diene is condensed with methyl vinyl ketone the reaction
is illustrated as follows:
chloro-Z-iodomethyl-1,3-butadiene, l-chloro - 2 - bromo
cyclopentadiene, 1,2-dichloro ~ 3 — bromocyclopentadiene,
1,2-dichloro-5,S-dibromocyclopentadiene, etc., although
not necessarily with equivalent results.
Examples of ketones containing an ole?nic linkage
which may be condensed with the halo substituted conju
gated unsaturated compound hereinbefore set forth in
70
Two molecular proportions of'the resultant 1,4,5,6,7,7
clude methyl vinyl ketone, ethyl vinyl ketone, *n-propyl 75 .hexachloro-S-norbornen-Z-yl
methyl ketone may then be
3,094,560
reacted with one molecular proportion of p-phenylenedi
amine to form the desired product N,N’-bis-[l-(1,4,5,6,7,
7-hexachloro-5-norbornen - 2 - yl)ethylidene]-p-phenyl
enediamine according to the following equation:
IV
components. The latter solvents and dispersants may
also be employed for the speci?c purpose of reducing the
01
01
l
2 1 01001
01 01l
(I)
0-0Hs+NHr©'NH1 -——>
concentration of insecticide to the desired level in a
speci?c insecticide formulation, the particular formula
tion of active components in combination with the solvent
or dispersant will depend upon its application. Composi
tions containing as high as 20% of active component
may be preferred, in some instances Where deep pentra
01
01
01
~ 01001
l
-C~—GH:
01
15 tion of the insecticide is desired, as in the treatment of
l
?brous material, such as wood, for extinction of a particu
lar infestation, for example, wood termites. For other
purposes, the required concentration of action compo
+ 21120
nents in the formulation may be as low as 0.1%, as for ex
20 ample in the treatment of fabrics for destroying moth
01
larvae. In utilizing the present insecticidal compounds
01
l
I 01001
01
N
(Li-0H3
01
Accordingly, if the arylamine comprises aniline or a
substituted aniline, one molecular proportion of the inter
mediate ketone product of the condensation reaction be
tween the haloalkadiene or halocycloalkadiene and the
ketone containing an ole?nic linkage willbe reacted with
one molecular proportion of the aniline. An example of
this is the reaction between 1,4,5,6,7,7-hexachloro-5-nor7
bornen-2-yl methyl ketone and aniline to form N-[1-(1,4,
5,6,7,7 - hexachloro-S-n0rbomen-2-yl)ethylidene]-aniline
"
against most insects, a composition containing from about
0.1% to about 5% by weight of the active component is
highly effective. The choice of the most desirable solvent
or dispersant further depends upon the method utilized
to apply the insecticidal composition to the infested
article. For example, a low molecular weight, normally
gaseous carrying agent for the active insecticidal com_
ponent, with as propane, butane, the Freons, etc., may be
compressed and lique?ed into a small bomb containing
the insecticide. Upon release of pressure from the bomb,
according to the equation:
01
\ 01001
0il\|
..
C1
O
the lique?ed carrier vaporizes and suspends a quantity
of the active component therein, thus providing a con
venient spraying method of applying the insecticide. The
active component may also be dissolved in a liquid car
rier, such as kerosene, an alcohol, ester, ketone, etc.,
and the resulting solution atomized by a suitable spraying
v
0/‘
6
suitable high boiling solvent, such as a mineral or vege
table oil, petroleum, etc; a Wax, such as para?in wax,
beeswax, etc., a high molecular weight alcohol or ether
such as myricyl alcohol, dibutyl ether, etc.; or they may
be emulsi?ed with water by the addition of an emulsifying
agent, such as surface active agent, to the mixture of
device.
..
ii-onw @arrn __-»
.
01
01/
01 1
I
01
The process of this invention may be effected in any
suitable manner and may comprise either a batch or a
continuous type operation. For example, when a batch
type ‘operation is used, a quantity of the starting materials
comprising the haloalkadiene or halocycloalkadiene and
the ketone containing an ole?nic linkage along with the
o-om-l- H10 . ~ desired amount of water and the polymerization inhibit
ll,
4 ing compound are placed in a condensation apparatus
provided with heating and mixing means. The apparatus,
along with the contents thereof, is heated to the desired
temperature for a predetermined period of time, at the
end of which time the apparatus and contents thereof
are allowed to cool to room temperature.
The physical properties of the present N-halocyclo
alkenic derivatives of arylamines and the elfects they have
on entomological vforms of life make them particularly _,
desirable as insecticides and insect repellents, the com
pounds having many of the features desired of materials
‘of this purpose. They are, for example, toxic to insects
which are destructive to plant life and materials nor
The desired
reaction product comprising the halocycloalkeny-l alkyl
ketone is separated from unreacted starting materials
and/or by-products by conventional means such as frac
tional distillation, crystallization, etc. The aforemen
tioned halocycloalkenyl alkyl ketone is then placed in a
separate condensation apparatus along with the aryl
amine, the catalyst and, if so desired, the inert organic
diluent.
The apparatus is then heated to the desired
mally subject to insect infestation, their toxic effects be- , _ temperature and maintained thereat for a predetermined
ing manifested by contact of the poison with the insect. 60 period of time, the water which is formed by the reaction
The insecticides comprising the present com-pound are
being continuously removed therefrom. At the end of
thus. effective against chewing as well as sucking types of
insects. The compounds are sui?ciently volatile so that
the desired residence time the apparatus and contents
when applied to plant life intended for subsequent human ‘ ,
consumption, the plants when harvested and after allow 65
product, comprising the N-halocycloalkenic derivative of
the arylamine is separated from the unreacted starting
ing a reasonable time for evaporation of the applied in
thereof are cooled to room temperature and the desired
materials and/ or by-products by conventional means here
inbefore set forth.
Another method of effecting the condensation reactions
other hand,‘ the compounds are of su?iciently limited
of the present invention is by a continuous type operation.
volatility to be retained on the insect for the time required 70 In this type of operation the starting materials comprising
toaccomplish the toxic eifects of the compounds. The
the halocycloalkadiene or haloalkadiene and the ketone
volatility and retentive capacity of the compounds may
containing an ole?nic linkage are continuously charged to
be varied at will by combining them with suitable ?xing
a reactor which is maintained at the proper operating con
agents‘ which reduce or promote their volatilization, as
ditions of temperature and pressure. The reactor may
75
desired. Thus, the compounds may be dissolved in a
secticide therefrom retain nose of the toxicant to pre
vent use of the plant for consumption as food. [On the
7
3,094,560
comprise an unpacked vessel or coil or may be lined with
an adsorbent packing material such as ?re brick, alumina,
dehydrated bauxite or the like. The water-and polymer
ization inhibitor are also continuously charged through
separate lines or, if so desired, may be admixed with one
or both of the starting materials prior to entry into said
reactor and charged thereto in a single stream. The con
densation product from the ?rst step of the reaction,
8
tion. The desired product, which comprised 151 g. of a
pearly off-white, crystalline material having a melting
point of 271--272‘l C. Was subjected to analysis with the
following results:
‘
Calcd. for: CMHIGCIHNZ: C, 38.03; H, 2.12; N, 3.69;
CI, 56.14. Found: C, 38.73; H, 2.46; N, 3.97; Cl, 56.14.
Example II
In
this
experiment
a
mixture of 190g. of (1.0 mole) of
withdrawn from the reactor,’separated from reactor ef?u 10
1,2,3,4-tetrachloro-l,3-butadiene
and 60 g. (1.0‘ mole) of
ent and continuously charged to a second reactor, the
methyl vinyl ketone along with approximately 10' g. of
effluent being separated and recycled to form a portion
water and .1 g. of t-butylcatechol is slowly heated at a tem
namely, the halocycloalkenyl alkyl ketone is continuously
of the starting materials. The second reactor is similar
to the ?rst reactor and is also maintained at the proper
perature ranging from about 24° C. to about 140° C. for
a period of about 10 hours. At the end of this time the
operating conditions of temperature and pressure. The 15 flask and con-tents thereof are allowed to cool to room
arylamine is continuously charged to the second reactor
temperature and the desired ketone, namely, 2,3,4,5-tetra
through a separate line or, if so desired, may be admixed
chloro-3-cyclohexenyl methyl ketone is separated and re
with the halocycloalkenyl alkyl ketone prior to entry into
covered.
said reactor and charged thereto in a single stream. Ad
A mixture of 104 g. (0.4 mole) of the ketone and 21.5
ditional means are also’provided for the continual entry 20 g. (0.2 mole) of p-phenylenediamine along with 300 cc.
of the ‘inert organic solvent if one is used in the reaction.
of benzene and 10 g. of a platinum containing catalyst is
The second reactor is provided with the catalyst, the use
heated at a temperature of about 85 ° C. for a period of
of a catalyst comprising a metal of the platinum group of
about 23 hours. At the end of this time the ?ask and con
group VIII of the periodic table either alone or com
tents thereof are allowed to cool to room temperature
posi-ted on a solid support is particularly effective for a 25 and the desired product, comprising crystalline N,N’-bis
?xed bed type of continuous operation. In this type of
operation the catalyst is positioned as a ?xed bed in the
[1 - (2,3,4,5 - tetrachloro - 3 - cyclohexenyl)-ethylidene]
p-phenylenediamine is separated and recovered.
reactor and the reactants pass over said catalyst in either
Example III
an upward or downward ?ow. In addition, the second
reactor is also provided with means for continuously with 30
In this experiment a mixture of 285 g. (1.0 mole) of
drawing the Water which is formed during the reaction.
hexachlorocyclopentadiene and 84 g. (1.0 mole) of ethyl
As in the case of the ?rst reactor the desired reaction
vinyl ketone is slowly heated at a temperature of from
product, comprising an N-halocycloalkenic derivative of
about 24° C. to about 140° C. for a period of about 10
the arylamine is continuously withdrawn from the reactor
hours, the condensation taking place in the presence of
and separated from the reactor effluent, the latter being 35 about 12 g. of water and l g. of a polymerization inhibi
recycled to form a portion of the starting materials, while
tor comprising t-butylcatechol. At the end of this time
the former is puri?ed and recovered by conventional means
the ?ask and contents thereof are allowed to cool to room
hereinbefore set forth.
temperature and the resulting ketone, comprising 1,4,5,6,
In addition to the ?xed bed type of operation which may
7,7-hexach1oro-5-norbornen-2-yl ethyl ketone is separated
be used in the second step of this process, other types of 40 and recovered.
continuous operation such as the compact moving bed type
A mixture of this ketone (156.2 g.) and 21.5 g. of
in which the bed of catalyst and the reactants pass either
p-phenylenediamine is heated at a temperature of about
concurrently or countercurrently to each other and the
85° C. for approximately 23 hours in the presence of
slurry type operation in which the catalyst is carried into
300 cc. of benzene ‘and 10 g. of a platinum containing
the reactor as a slurry in one of the reactants may also 45 catalyst. At the end of the aforementioned period of
be used.
time the ?ask and contents thereof are cooled to room
‘The following examples are given to illustrate the proc
temperature and the desired product, comprising N,N'-bis~
ess of the present invention, which, however, are not in
[1 - (1,4,5,6,7,7 - hexachloro - 5 - norbornen - 2 - yl)prop
tended to limit the generally broad scope of the present
ylidene]-p-phenylenediamine is separated and recovered.
50
invention in strict accordance therewith.
Example IV
Example I
A mixture of 285 g. (1 mole) of hexachlorocyclopenta
diene and 60 g. (1 mole) of methyl vinyl ketone was slowly
, -In this experiment the starting materials comprise 285
g. (1.0 mole) of hexachlorocyclopentadiene and 60 g.
(1.0 mole) of methyl vinyl ketone. T'he reactants are
heated in a condensation ?ask along with 12 g. of water 55 treated in a manner similar to that set forth in the above
and 1 g. of t-butylcatechol for a period of about 10‘ hours
examples and the intermediate product, comprising 1,4,5,
at a temperature ranging from about 24° C. to about
6,7,7-hexachloro-S-norbornen-Z-yl methyl ketone is sep
arated and recovered.
140° C. At the end of this time the ?ask and contents
thereof were cooled to room temperature and the desired
This ketone in an ‘amount of 75.5 g. (0.2 mole) and
ketone, namely, 1,4,5,6,7,7~hexachloro-5-norbornen-Z-yl 60 18.5 g. (0.2 mole) of aniline are heated to a temperature
methyl ketone in a 70% yield was recovered.
of about 85° C. in the presence of 300 cc. of toluene and
The aforementioned ketone was then reacted with
10 g. of a platinum containing catalyst. At vthe end of
p-phenylenediamine by heating 151.5 g. (0.4 mole) of the
the residence time the ?ask and contents thereof are
halocycloalkenyl alkyl ketone with 21.5 g. (0.2 mole) of
cooled to room temperature and the desired product, com~
the arylamine in 300 cc. of benzene and 10 g. of a plati 65 prising N - [1 - v(1,4,5,6,7,7 - hexachloro - 5 - norbornen
num containing catalyst. The mixture was maintained at
2-yl)-ethylidene] aniline is separated and recovered.
a temperature of about 85° C. for a period of approxi
mately 23 hours, the water which was formed during the
reaction (7 cc.) being continuously removed from the
solution. At the end of this time the condensation flask
and contents thereof were allowed to cool to room tem
perature and the desired reaction product comprising
Example V
In this example 190 g. (1.0 mole) of 1,2,3,4-tetrach10ro
1,3-butadiene and 84 g. ( 1.0 mole) of ethyl vinyl ketone
are treated in a manner similar to that set forth in the
above examples. The intermediate ketone comprising
N,N'-bis-[l-(1,4,5,6,7,7-hexachloro-5 - norbornen - 2 - yl)
2,3,4,5-tetrachloro-3-cyclohexeny1 ethyl ketone is further
ethylidene]-p-phenylenediamine was recovered, washed
condensed
with aniline in equimolecular proportions in
with water, dried and subjected to fractional crystalliza 75 the presence of toluene and a platinum containing catalyst.
3,094,560
10
_
_
.
VIII of the periodic table at a temperature in the range
The desired product,’ comprising N-V[1->(2,3,4,5-tetra
chloro-3-cyclohexenyl)propylidene]aniline is separated
of from 75° to about 150° C. ,
and recovered.
prepared by condensing hexachlorocyclopentadiene with
3. An N-halocycloalkenic derivative of an arylamine
Example VI
an alkenyl alkyl ketone having from 2 to 4 carbon atoms
in the alkenyl group and from 1 to 7 carbon atoms in the
alkyl group at a temperature in the range of from about
25 ° to about 150° C., and reacting the resultant halo
Equimolecular proportions of hexachlorocyclopenta
diene ‘and N-propyl vinyl ketone are condensed in the
presence of water and a polymerization inhibitor in a
manner similar to that set forth in the above examples.
cycloalkenyl alkyl ketone with an arylamine containing
The intermediate ketone comprising 1,4,5,6,7,7-hexachlo 10 up to 9 carbon atoms per molecule in the presence of
a metal of the platinum group of group VIII of the
periodic table at a temperature in the range of from about
75° to about 150° C.
ro-5-norbornen-2-yl 'propyl ketone is further condensed
with p-pheny-lenediamine in a molecular ratio of 2 moles
of ketone to 1 mole of the p-phenylenediamine under
conditions similar to that set forth in the above examples.
The desired reaction product, comprising N,N'-[1-(1,4,
4. An N-halocycloalkenic derivative of an arylamine
15
prepared by condensing 1,2,3.4-tetrachloro-1,3-butadiene
20
halocycloalkenyl alkyl ketone with an arylamine contain
5,6,7,7 - hexachloro - 5 - norbornen - 2 - yl)butylidene]
p-phe’nylenediamine is separated and recovered.
Example VII
A mixture of equimolecular proportions of 1,2,3,4
tetrachloro-1,3,butadiene ‘and methyl allyl ‘ketone are con
densed in a manner similar to that set forth in the above
examples. The intermediate ketone is further condensed
with aniline in a 1:1 molecular ratio under conditions
also set forth in the above examples. The desired prod 25
uct, comprising N-[1-(2,3,4,5-tetrachloro-3-cyclohexenyl
methyl)ethylideneJaniline is separated and recovered.
Example VIII
In this example equimolecular proportions of hexa
5. An N-halocycloalkenic derivative of an arylamine
prepared by condensing a halo substituted conjugated un
saturated compound selected from the group consisting
hexadienes with methyl vinyl ketone at a temperature in
the range of from about 25° to about 150° C., and react
ing the resultant halocycloalkenyl alkyl ketone with an
arylamine containing up to 9 carbon atoms per molecule
densed in a manner similar to that set forth in the above
in the presence of a metal of the platinum group of
group VIII of the periodic table at a temperature in the
examples. The intermediate ketone is further condensed
with p-phenylenediamine in a molecular ratio of 2 molec
ular proportions of the ketone to 1 molecular propor
tion of the p-phenylenediamine under conditions similar
to that hereinbefore set forth. The resultant product,
diamine is separated and recovered.
ing up to 9 carbon atoms per molecule in the presence of
a metal of the platinum group of group VIII of the
periodic table at a temperature in the range of from about
75° to about 150° C.
of halogenated butadienes, cyclopentadienes and cyclo
chlorocyclopentadiene and ethyl allyl ‘ketone are con
comprising N,N’ - bis - [1 - (l,4,5,6,7,7 - hexachloro
5 - norbornen - 2 - yl methyl)propylidene] - p - phenylene
with an alkenyl alkyl ketone having from 2 to 4 carbon
atoms in the alkenyl group and from 1 to 7 carbon atoms
in the alkyl group at a temperature in the range of from
about 25° to about, 150° C., and reacting the resultant
range of from about 75 ° to about 150° C.
6. An N-halocycloalkenic derivative of an arylamine
prepared by condensing a halo substituted conjugated un
saturated compound selected from the group consisting of
halogenated butadienes, cyclopentadienes and cyclohexa
40 dienes with ethyl vinyl ketone at a temperature in the
Example 1X
range from about 25° to about 150° C., and reacting the
resultant halocycloalkenyl alkyl ketone with an arylamine
containing up to 9 carbon atoms per molecule in the pres
ence of a metal of the platinum group of group VIII of
of N,N’ - bis - [1 - (1,4,5,6,7,7 - hexachloro - 5 - nor 45 the periodic table at a temperature in the range of from
bornen-Z-yl)ethylidene]-p-phenylenediamine in 2 cc. of
about 75° to about 150° C.
benzene and adding 100 cc. of water using Triton X-100
7. An N-halocycloalkenic derivative of a p-phenylene
as an emulsifying agent. This solution is sprayed into
diamine prepared by condensing a halo substituted con
An insecticidal solution is prepared by dissolving 1 g.
a cage containing common house?ies and causes a 100%
knockdown. Similar tests using other compounds set
forth in the above examples will show similar results.
We claim as our invention:
jugated unsaturated compound selected from the group
consisting of halogenated butadienes, cyclopentadienes
and cyclohexadienes with an alkenyl alkyl ketone having
from 2 to 4 carbon atoms in the alkenyl group and from
1. An N-halocycloalkenic derivative of an arylamine
1 to 7 carbon atoms in the alkyl group at a temperature
prepared by condensing a halo substituted conjugated un
in the range of from about 25° to about 150° C., and
saturated compound selected from the group consisting of 55 reacting the resultant halocycloalkenyl alkyl ketone with
halogenated butadienes, cyclopentadienes and cyclohexa
paphenylenediarnine in the presence of a metal of the plati
dienes with tan alkenyl alkyl ketone having from 2 to 4
num group of group VIII of the periodic table at a tem
carbon atoms in the alkenyl group and from 1 to 7 car
perature in the range of from about 75° to about 150° C.
bon atoms in the alkyl group at a temperature in the
8. A process for the formation of N,N’-bis-[1-(1,4,5,
range of from about 25 ° to about 150° C., and reacting
6,7,7-hexachloro-5-norbornen-2-yl)ethylidene] - p-phenyl
the resultant halocycloalkenyl alkyl ketone with an aryl
enediamine prepared by condensing hexachlorocyclo
amine containing up to 9 carbon atoms per molecule in
pentadiene with methyl vinyl ketone at a temperature in
the presence of a metal of the platinum group of group
the range of from about 25 ° to about 150° C., and react
VIII of the periodic table at a temperature in the range
ing the resultant 1,4,5,6,7,7-hexachloro-S-norbornen-Z-yl
65 methyl ketone with p-phenylenediamine at a temperature
of from about 75 ° to about 150° C.
2. An N-halocycloalkenic derivative of aniline pre
in the range of from about 75 ° to about 100° C. in the
pared by condensing a halo substituted conjugated un
presence of platinum.
saturated compound selected from the group consisting of
9. A process for the formation of N,N’~bis-[1-(2,3,4,5
halogenated butadienes, cyclopentadienes and cyclohexa
tetrachloro-3-cyclohexenyl)ethylidene] - p - phenylenedi
dienes with a ketone having from 2 to 4 carbon atoms in 70 amine prepared by condensing 1,2,3,4-tetrachloro~1,3
the alkenyl group and from 1 to 7 carbon atoms in the
butadiene with methyl vinyl ketone at a temperature in
alkyl group at an alkenyl alkyl temperathre in the range
the range of from about 25° to about 150° C., and react
of from about 25° to about 150° C., and reacting the
resultant halocycloalkenyl alkyl ketone with aniline in
ing the resultant 2,3,4,5-tetrachloro-3-cyclohexenyl meth
yl ketone with 6-phenylenediamine at a temperature in
the presence of a metal of the platinum group of group 75
3,094,560
11
the range of from about 75° to about ‘100° C. in the
presence of platinum.
condensing 1,2,3,4-tetrachloro~1,3!butadiene with ethyl
V
vinyl ketone at a temperature in the range of from about
- >10. A process for-the formation of N,N’~bis-[1-(1,4,5,
6,7,7-hexachloro-5-norbornen - 2 - yl)-propy1idene]
25° to about 150° C., and reacting the resultant 2,3,4,5
tetrachIoro-3-eyclohexenyl ethyl ketone with aniline at a
- - -
phenylenediamine prepared by condensing hexaehloro
cyclopentadiene with ethyl vinyl ketone at a temperature
5 temperature in the range of from 75 ° to about 100° C.
in the range of from about 25° to about 150° (3., and
reacting the resultant 1,4,5,6,7,7-l1exachloro-5-norbomen
2-y1 ethyl ketone with p-phenylenediamine at a temper
ature in the range of from about 75 ° to about 150° C.
in the presence of platinum.
References Cited in the ?le of this patent
UNITED STATES PATENTS
in the presence of platinum.
11. A process for the formation of N-[1-(l,4,5,6,7,7-v
2,198,260
2,616,928
2,744,137
hexachloro-S-norbornen-Z-yl ) ethylidene] aniline prepared
2,773,799
by condensing hexachlorocyclo-pentadiene with methyl‘
vinyl ketone at a temperature in the range of from about 15 2,798,094
25° to about 150° C., and reacting the resultant 1,4,5,6,7,
100° C. in the presence of platinum.
, 12. A process for the formation of N-[1-(2,3,4,5-tetra~ 20
chloro~3-cyclohexeny1)propylidene]aniline prepared by
Fan _________________ __ Dec. 11, 1956
Shepard et al ___________ __ July 2, 1957
FOREIGN PATENTS
7-hexachloro-S-norbornen-Z-yl methyl ketone with aniline
at a temperature in the range of from about 75° to about
Van Melsen __________ __ Apr. 23, 1940
Gilbert et al. __________ __ Nov. 4, 1952
Grewe _______________ __ May 1, ‘1956
786,215
' Great Britain ________ __ Nov. 13, 1957
OTHER REFERENCES
Prill: Jour. Amer. Chem. Soc,. vol. 69 (January 1947),
pages 62-63 (2 pages).
Документ
Категория
Без категории
Просмотров
0
Размер файла
959 Кб
Теги
1/--страниц
Пожаловаться на содержимое документа