Note: Descriptions are shown in the official language in which they were submitted.
I
-- 1 --
This invention relates to aliphatic diisocyanates.
specifically it relates to alkyl-substituted isocyanato-
isocyanatomethylcyclohexanes.
Description of the Prior Art
Both aromatic and aliphatic isocyanates are known
to the art. Aromatic diisocyanates such as 2,4- and 2,6-
Tulane diisocyanate, 1,5-naphthylene diisocyanate, 4,4'-
diphenylmethane diisocyanate, and mixtures of 4,4i-, 2,4'-,
and 2,2'-diphenylmethane diisocyanates and polyphenyl-
polyethylene polyisocyanates, aliphatic diisocyanates such
as 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate
are known commercial products which are preferably used to
prepare polyurethane plastics. The polyisocyanates are
generally prepared from their corresponding amino compounds
through phosgenation and subsequent thermal cleavage of the
intermediately formed carbamic chlorides. Numerous organic
moo- and polyisocyanates are described, for example, in
the Aniline don Chemise 562 (1949), p. 75 if.
The objective of the invention at hand was to
develop cycloaliphatic diisocyana-tes with the isocyanate
groups having different reactivity.
Summary ox like Invention
The objective of -the invention is achieved with
diisocyanates of formulae:
R R
2 NO
(I) (II)
NO CHINOOK
or mixtures thereof, in which R is an alkyd group having
from 1 to 12 carbon atoms.
~23~4~i
Preferred are diisocyanates of formulae:
R R
2 NO
(III) (IV)
NO H2NCO
or mixtures thereof, in which the isocyanatomethyl group is
bonded in the 2- or 4-position and the isocyanate group is
in the 4- or 2-position.
The invention also relates to a process for the
preparation of the above diisocyanates using dominoes of
; formulae:
SHEEHAN
No SHEEHAN
Descr~ltion of the Preferred Embodiments
In formulae (I) through (VI), R is an alkyd radical
having from l -to 12 carbon atoms, preferably from 1 to 4
carbon atoms, which may be branched, however, is preferably
linear. Typical examples of such alkyd radicals are n-
ponytail-, n-hexyl, Natalie, n-octyl, 2-ethyl-n-hexyl, n-
nonyl, n-decyl, n-undecyl, n-dodecyl radicals, preferably
the ethyl, n- and isopropyl, and n- and sec.-butyl radicals,
and more preferably the methyl radical.
The following are typical examples of the dozes-
antes of the invention:
1-methyl-2-isocyanatomethyl-3-isocyanato-, 1-
methyl-2-isocyanatomethyl-5-isocyanato-, 1-methyl-2-isocyana-
tomethyl-6-isocyanato-, 1 methyl-4-isocyanatomethyl-3-
isocyanato-cyclohexane; 1-ethyl-2-isocyanatomethyl-3-
:~;
I
isn't-, 1 ethy}-2-isocyanatomethyl-5-isocyanato-,
l-ethyl-2-isocyanatomethyl-6-i~ocyanato-, ethyls-
nato~ethyl-3-isocyanato-cyclohexane; 1-n--propyl-2-i ooze-
natomethyl-3-i~ocyana~o-, 1-n-propyl-2-i~ocyanatomethyl-5-
isocyanato-, l-n-propyl-2-i~ocyanatomethyl-6-isocyanato , 1-
n-propyl-4-isocyanatomethyl-3-isocyanato-cyclohexaanew 1-
isopropyl-2-iqocyanatomethyl-3-i~ocyanato-, 1-i~opropyl-2-
i~ocyanatomethyl-4-isocyanato-, 1-isopropyl-2-isocyanato-
methyl-5-isocyanato-, 1-isopropyl-2-isocyanatomethyl-6-
isocyanato-, 1-i~opropyl-4-isocyanatomethyl-2-isocyanato-,
~opropyl-4-isocyanatome~hyl-3-isocyanato-cyclohexanno; 1-
n-butyl-2-i~ocyanatomethyl-3-i~ocyanato-, l-n-butyl-2-
isocyanatomethyl-4-isocyanato-, 1-n-butyl-2-isocyanato-
methyl-5-isocyanato-, 1-n-butyl-2-i~ocyana~omethyl-6-
isocyanato-, l-n-butyl-4-isocyanatomethyl-2-i~ocyanato-, 1-
n-butyl-4-isocyanatomethyl-3-isocyanato-cyclohexanno, l-n-
pentyl-2-isocyanatomethyl-4 isocyanato-, 1-n-pentyl-2
i30cyanatomethyl-6-isocyanato-, 1 n-pentyl-4-isocyanato-
methyl-2-i ocyana~o-cyclohexane, 1-n-hexyl-2-i~ocyanato-
methyl-4-isocyanato-, l-n-hexyl-2-i30cyanatomethyl-6-
isocyanato-, l-n-hexyl-4 isocyanatomethyl-2-isocyanato-
cyclohexane, l-n-heptyl-2-i~ocyanatomethyl-4-i~ocyanato-, 1-
n-h~ptyl-2-isocyanatome~hyl-6-i~ocyanato-, Natalie-
isocyanatomethyl~2-isocyanato-cyclohexane, 1-~-octyl-2-
isocyanatom~thyl-4-isocyanato-, 1-n-octyl-2-isocyanato-
S
methyl-6-i~ocyanato-, l n-octyl-4~isocyanatomethyl-2-
isocyanato-cyclohexane; l-n-nonyl-2-i~ocyanatomethyl-4-
iqocyanato~ n-nonyl-2-isocyanatome~hyl-6-i~ocyanato~
n-nonyl-A-i~ocyanatomethyl-2~ ocyanato-cyclohexane, l-n-
dozily i~ocyanatomethyl-4-i30cyanato-, l-n-decyl-2-isocya-
natomethyl-6 isocyana~o-, l-n-decyl-4-i~ocyanatomethyl-2-
i~ocyanato-cyclohexane, l-n-undecyl-2-isocyana~omethyl-4-
isocyanato~ n-undecyl-2-isocyanatomethyl-6-isocyanato-,
l-n-undecyl-~-isocyanatomethyl-2-i30cyanato-cyclohhexane, l-
n~dodecyl-2-isocyanatomethyl-4~isocyanato-, l-n-dodecyl-2-
isocyanatomethyl-6-iqocyanato- and l-n-dodecyl~-4-isocyanato-
methyl-2-i~ocyanato-cyclohexane.
Preferred are: l-ethyl-2-i~ocyanatomethyl-4-
isn't-, 1-2thyl-4-isocyanatomethyl-2-i~ocyanato-cyclo-
hexane, l-n-propyl-2-isocyanatomethyl-4-isocyanato- and l-n-
propyl-4-i~ocyanatomethyl-2-i~ocyanato-cyclohexanee and more
preferably l-methyl-2-i~ocyanatomethyl-4-isocyanato-, l-
methyl-2-inocyanatomethyl-6-i~ocyanato-cyclohexanee as well
a their ire mixture and l~methyl-4-isocyanatomethyl-2-
i~ocyana~o-cyclohexa~e.
Demurrals corresponding to the dozes-
notes cited above are used as the starting components for
the preparation of the dli~ocyanate~ of the invention.
Here the following compound have proved to be
particularly successful and are, therefore, preferably
-- 4
I
used: l-ethyl-2-a~inomethyl-4-amino-, 1-ethyl~4-amino-
methyl-2~amino-cyclohexane, 1-n~propyl-2-aminomethyl-2-
amino cyclohexane, l-n propyl-2-aminomethyl-4-amino- and 1-
n-propyl-4 aminomethyl-2-amino-cyclohexane, and more
preferably l-methyl-2-aminomethyl-4-amino-, 1-methyl-2-
aminomethyl-6-amino-cyclohexane a well as their isomer
mixer and l-methyl-4-aminomethyl-2-amino cyclohexane.
The dll~ocyanate3 and dominoes for these compound
can be prevent in the form of isomer mixtures, mixtures of
the tame immure but with different alkyd radical, or a
mixture ox both types of mixture
The preparation ox the novel dozes-
antes can hollow the hollowing sequence, for example:
R R
: ON SHEEHAN
N02 I
SIX) (Xj (XIj
Pi
ago I, C~2~H2
ICKY NH;2
(I) MY)
Jo
..~
~3~5
The l-alkyl-2-cyanonitrobenzene~ (X) or the 1-
alkyl-4-cyanonitrobenzene~ can Allah be prepared in even-
tidally known procedures through the nitration of the
corresponding l-~lkyl-2-cyanob2nzene~ (IX) or l-alkyl-4-
cyanobenzenes, for example, in the manner described in thy
(1~98),
p. 2880 if. or in the Journal of American Chemical So
99 (1977), p. 6721 or suitable variant of these method.
Another method for the preparation of the alkyd-
cyanonitrobenzenes cited a an example lie in the known
process for exchanging the amino group in the alkyl-amino
nitrobenzenes for a neural group, corresponding to Journal
I (1979), p. 4003.
Thy l-alkyl-cyanonitrobenzene~ obtained in the
nitration or their Homer mixtures can be reduced directly,
i.e., without further purification, to l-alkyl-aminomethyl-
aminobenzene~ or their isomer mixture. Similar, for
example, to the process described for 2-cyanonitrotoluene in
Formic peeve), Edit. Sat. 25 (1970), p. 163 (C. A. 72,
~21 101 d, 1970). The reduction of the vitro and the cyan
group can be completed here in one or two ~equen',ial
reaction Taipei. It it not always necessary to add ammonia.
The aromatic ring reduction of the alkali-
aminomethyl-aminobenzenes I or the l-alkyl-4-aminomethyl-
aminob~n Noah follows known prowesses, for example, those
G
-or -
I
cited in Hobnail, Methadone don organlsch~n Comma, Thea
Ed., solo XI/l, (Stuttgart: Gorge Thyme Verlag, 1957~,
p. 678 if., I Ferry Reaktionen don orqa~ en Saab
(George Thyme V~rlag: Stuttgart, 19783, pp. 83, 90 of.;
A. E. ark doll et at, J. Amen Comma. Sock 75 (1953~,
p. 1156, ye lo Lookers. (1982), pp. 603~606, Us S.
Patent 2,494,563 or German laid-open Application 21 32 547.
In order to prepare the l~alkyl-2-aminomethyl~
aminocyclohexane (~) or the l-alkyl-4-aminom~thyl amino-
cyclohexane, one can alto tart directly with alkali-
cyanonitrobenzenes (X).
The resulting l-alkyl aminomethyl-aminocyclo
hexanes can be phosgenated in solvents either directly or as
salts, preferably hydrogen chlorides. Suitable solvent
are, for example: Tulane, zillion, chlorobenzene, or
dichlorobenzene. A 301ution of the l-alXyl-aminomethyl-
aminocyclohexane~ or a suspension of the corresponding salts
is reacted accordingly at temperature of approximately 0C
to 100C, preferably from 10C to SKYE, with 1 to 6 moles
pho~gene per NH2-HCl, preferably from 1 to 2.5 moles
phosgene, and the intermediately formed carbamic chloride
can by cleaved at temperature from 80C to 180C, prefer-
ably from 120 to 160C in the l-alkyl-i30cyanato~eehyl-
iRocyanatocyclohexane. The gaseous or liquid pho3g~ne is
charged directly into the reaction mixture at such a rate
it
"
~23~
that the emerging gases primarily are composed of hydrogen
chloride.
After completion of pho~genation and cleavage, the
solvent it distilled off at reduced pressure, for example,
from lo to lo mar. However, it may Allah be Advents
to trip the hydrogen chloride or any excel phosgene which
may be present Prom the doesn't solution with the aid
of nitrogen or another inert gee before the solvent it
distilled off.
The resulting crude l-alkyl-2- or 4-isocyanato-
methyl-lsocyanatocyclohexane~ or isomer mixtures can by
separated and purified by distillation at reduced prowar.
The disunites of the invention can also be
Jo prepared through the thermal cleavage of the corresponding
diurethane~ in the guy or liquid phase, if Nasser in
the prank of c~ta.ly~t3, whereby the diurethane~ are
obtained in an efficacious manner according to the process
described in European Patent published application 18 583
(U. S. Patent 4, 278, 805) through the reaction of carbamate
I with the l-alkyl-aminocyclohexane~ in the presence of
alcohols and, if necessary, urea.
The l-alkyl-2- or 4-aminomethyl-aminocyclohexane~
and alkali- or 4-i~ocyanatomethyl-i30cyanatocylohexane~
are valuable intermediate and eed~tock~ for crop protect
lion agent and plastic
~23~ 5
The dominoes are preferably converted into
diisocyanat~s. Such diisocyanates are particularly well
suited for the preparation of polyurethane foam, adhesives,
paints, coatings, and sealants.
The following examples art intended to further
explain the invention without necessarily limiting it
scope.
' J
I
eye
a) Preparation of an isomer mixture of l-methyl-2-cyano~4-
nitrobsnzene and 1-methyl-2-cyano-6-nitrobenzene
Twelve hundred part by weight concentrated sulfuric
acid were cooled to -5C in a reaction flask equipped
with an addition funnel, a stirrer, and a thermometer.
While stirring well, 200 weight part 2-cyanotoluene
followed by 151 weight parts concentrated nitric acid
between -5~C and ~5C were added drops within one
hour. In order to complete the nitration, stirring
continued for an additional 1.5 hour at 0C, whereupon
the reaction mixture was poured onto 2000 weight part
ice The precipitate way filtered off, the filtered
solid was thoroughly washed with water and dried on
clay.
Two hundred and eighty-two weight part of a crude
isomer mixture of l-methyl-2-cyano-4- and 6-nitrobenzene
were obtained at a weigh ratio of approximately 87:13
and having a melting point ox from glC to 92~C.
0 by Preparation of an isomer mixture of l-methyl-2-amino-
methyl-4- and 6-aminobenzene
JO
r-
One hundred weigh parts of the isomer mixture of 1-
methyl-2-cyano-4- and 6-nitroben~ene obtained it
accordance with a) were dissolved in 800 weight part
ethanol and hydrogenated at 50 bar and 80C after adding
25 weigh part Rangy nickel. Thy catalyst way filtered
off after cooling to room temperature, the filtrate was
concentrated at reduced pressure, and the residue way
dwelled. One then obtained 76 weight parts of a
mixture of l-methyl-2-aminomethyl-4- and 6-aminob~nzene
in the form of an oil which qolidifiad quickly. This
mixture distilled at 135C to 180C ~0.3 mar).
;
C8H12N2 (Molecular weight 136, ma spectrometer)
c) Preparation of an isomer mixture of 1 methyl-2-a~ino-
methyl-4- and 6-aminocyclohexane
Fifty weight part of the l-methyl~2-aminomethyl-4- and
6-aminobenzene obtained in accordance with b) wore
hydrogenated in 400 volume parts Dixon in thy presence
of 1.5 weight parts ruthenium oxide hydrate (prepared in
accordance with German Patent 2132547~ at 150C and
250 bar. After cooling to room temperature, the
catalyst was filtered off, the filtrate way concentrated
at a reduced prowar and the residue way detailed
I 1/
I, Jo
Thirty two weight part of a mixture of l-methyl-2-
aminome~hyl 4 and 6-aminocyclohexane were obtained.
This mixture distilled at 83C to 85C (0.4 mar).
Analy8iq: C8H18~2 (Molecular weight: 142, Miss
spectrum try
C El N
Calculated, % by wt. 67.55 12.75 19.69
Found, % by weight 67. 30 12 . 70 19. 60
d) Preparation of an isomer mixture of l-methyl-2-i~o-
cyanatomethyl-4- and 6-isocyanatocyclohexane
301ution of 14.2 weight part of the isomer mixture of
l-methyl~2-aminomethyl--4 and 6-aminocyclohexane
obtained in accordance with c) in 100 weight part
o-dichlorobenzQne were added drops while stirring to
a mixture of 260 weight part o-dichlorobenzene and 80
weight parts phosgene cooled to 0C. Aster completion
of the addition, the mixture way heated slowly to 130C
and phosgene way directed through the reaction mixture
: a this temperature for 1.5 hour. Then the reaction
mixture was cooled to room temperature and excess
phosgene was removed by purging nitrogen into thy
mixture. Then the solvent way first distilled off at 10
to 20 mar and thereupon the residue way distilled under
high vacuum. Ten and one-half weight part ox a mixture
of l-methyl-2-i3Oeyanatomethyl-4- and 6-i~ocyanatocyclo-
hexane having a distillation range of 110C to 112C
(cay. 0.1 bar) were obtained.
Analog: Clue (Molecular weight: 194, Moe
spectrometer )
C H N 0
Calculated, % by wt. 61.83 7.2614.42 16.47
Found, % by White 7.5014.40 16.00
Example 2
a) Preparation of l-methyl-4-cyano-2-nitrobenzene
Two hundred and forty weight parts of concentrated
sulfuric acid were cooled to -5C in a reaction flask
equipped with an addition funnel, stirrer, and thermos-
eater. While stirring well, 40 weight parts Sweeney-
Tulane way added in portions and then 25 volume parts
concentrated nitric acid between -5C and ~5~C was added
drops. In order to complete the nitration, eke
mixture was stirred for an additional two hours a 09C
/3
I
and the reaction Myra way then poured onto 400 weight
part ice. The precipitate way filtered off, the
filtered material way thoroughly washed with water and
air-dried.
The product (50.9 weight parts) way 1-methyl-4-cyano-2-
nitrobenzene having a melting point ox from 105C to
106C.
Preparation of l-methyl 4-aminomethyl-2-aminobenzene
Sixty weigh part of the l-methyl-4-cyano-2-~itro-
Bunsen obtained in accordance with a) were dissolved in
~00 weigh part ethanol and, after adding 20 weight
part Rangy nickel, hydrogenated at 10 bar and 60~C
until no further hydrogen way consumed After adding 8
volume parts 3 percent ammonia solution, the hydrogen
lion way again undertaken at 10 bar and 60C. After
cooling to room temperature, the catalyst was filtered
off and the filtrate way concentrated at reduced`
pressure. The residue was distilled under a high
vacuum. Thirty-two and one-tenth weight part l-methyl-
4-aminom~thyl-2-aminobenzene wore obtained, having a
distillation range of from 130C Jo 135C (0.3 mar).
,
C H N
Calculated, % by we. OWE 8.88 20.57
Found, % by wt. 70.80 9..00 19.90
I Preparation of l-methyl-4~aminomethyl-2-aminocyclohexane
Twenty weight part of the l-methyl-4-aminomethyl~2-
aminobenzene obtained in accordance with b) were
hydrogenated in 150 volume part Dixon in the presence
of 0.5 weight part ruthenium oxide hydrate (prepared in
accordance with German Patent 2132547~ at 150C and 250
bar. After cooling to room temperature, the catalyst
way filtered off, the filtrate way concentrated at
reduced prowar, and the rudely way distilled.
Fourteen and four-tenths weight part methyl
aminomethyl-2-aminocyclohexane were obtained having a
boiling point of from 60C to 63C (0~04 mar).
Annul C8H18N2 (molecular weight: 142~ mast
Jo ~pec~rometry)
.
C H
Jo Calculated, % by wt. 67.55 12.75 19.69
I-: 20 Found, % by White 12.60 lg~.90
I
d) Preparation of l-methyl-4-i~ocyanatomeehyl-2-isocyanato-
eyclohexane
A solution of 9.1 weight part of the 1-methyl-4-a~ino-
methyl-~-aminocyclohexan0 obtained in accordance with c)
in 75 weight parts o~dichlorobenzene were added drops
while mixing to a mixture of 150 weight parts ode-
chlorobenzene and 55 weight part pho~gene cooled to
0C. After completion ox this addition, the mixture way
Wylie heated to 130C and phosgene way directed into
Jo 10 the reaction mixture at this temperature for 15 hour.
I;
I: Then the reaction mixture way cooled to room tempera-
lure, and the excel phosgene was separated by using
nitrogen. Thereupon, the solvent way distilled off at
from 10 to 20 mar and the residue way distilled under
high vacuum. Two and four tenth weight parts l-methyl-
4-isocyanatomethyl-2-i~ocyanatocyclohexane having a
boiling point of 9BC Jo 102~C (0.4 mar) were obtained.
Analysis Clown molecular weight: 194~ maws
Bp~c~ome~cry )
Jo
ï . ~,~ Us
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