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Патент USA US2409677

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Patented Oct. 22, 1946
‘ . ‘I
William Franklin Gresham, Wilmington, Del., as
signor to E. I. du Pont de Nemours ‘8r Company,
Wilmington, Del., a corporation of'Delaware
No Drawing.‘ Original application February 14,.
1942, Serial No. 430,945. Divided and this ap
plication’Decemb'er 26, 1944, Serial No. 569,915
. 5‘Claims.
(01. 260-584)
Genen'cally the reaction may be illustrated as
This invention relates to polyaminoacetals, to
processes for their preparation, and especially
to their preparation from ‘acetals and cyanohy
proceeding in accord with the equations,
drins and more particularly from formals and
cyanohydrins. The applicationis a division of
in which R is an alkyl or substituted ‘alkyl group,
R’ is hydrogen, an alkyl or substituted‘ alkyl
group, and Y is a single bond or. analkyl group;
The over-all process of the invention includes
the alcohol being removed by distillation as
three steps. ‘ In the ?rst step, cyanoacetals are
prepared by the reaction of an acetal of an alde 10 formed. More speci?cally the reaction may be
illustrated by the preparation of (methoxymeth
hyde and/or a ketone with a ‘cyanohydrin of an
my copending application S‘. N. 430,945 ?led Feb
ruary 14-, 1942.
oxy) acetonitrile in accord'with‘the equation:
aldehyde‘and/or a ketone in ‘the presence of a
suitable acidic type catalyst.- In the second step,
the cyanoacetal of the ?rst step is hydrogenated
to give the corresponding aminoacetal and. in 15
While the reaction proceeds primarily‘ between
the third step of the process the, aminoacetal is
one mole of the ‘acetal and one mole of the cyano
converted to a salt and the resulting salttreated
-‘hydrin, nevertheless, a reaction likewisetakes
to liberate the polyaminoacetal by‘ disproportion
place between one mole of the acetal and two
An object of. the invention is to provide new v20 moles of the cyanohydrin to give two moles of al
cohol and one mole of a dinitrile.
The invention provides a method for the prepa
chemical compounds, viz.-di(aminoalkyl) acetals.
Another object of the invention is to provide a
ration of cyanoacetals by the interaction of the
cyanohydrins and their equivalents listed in the
step process ‘for the preparation'of di(aminoal .125 following paragraph. with the acetals and their
equivalents listed herewith. As examples of suit
kyl), acetals and ketals together with reaction
‘process for the preparation of .di(aminoalkyl)
acetals.v Still another object is to provide a three
conditions‘therefor. Other objects and advan
tages of the invention will hereinafter appear.
In the ?rst step of the process acetals of alde
hydes‘or ketones are reacted with
reaction is
of aldehydes and ketones.
eifected by mixing the acetal and cyanohydrin
able acetals, may be designated the symmetrical
acetals which may be prepared by reacting form
aldehyde or a higher aldehyde such as acetalde
propionaldehyde, normal and isobutyralde
30 hyde,
hyde with an alcohol, such, for example, as meth
anol, ethanol, normal and isopropanol, normal
in the presence, of a suitable acidic type catalyst
and isobutanol and the higher alcohols ‘such as
mately 300° C. ‘ In many instances, however,
no heating is necessary as the reaction proceeds
at room temperatures down to in the neighbor
methyl propyl formal, ethyl‘propyl formal,‘ methyl '
hood of 0° C. Pressures‘ may be employedif
desired ranging from'atmospheric to 100: atmos
pheres or more, although for normal operation
ketals,‘ may likewise be used and as examples of
these compounds which may be employed are
pressures above atmospheric are not necessary. , .
those prepared by the interaction of ketones such
In order to force the reaction to completiomit
as acetone, methyl ethyl ketone, diethylketone,
and ‘the higher symmetrical and unsymmetrical
ketoneswith the alcohols designated‘ above,‘ the
cyclic formals and- their poly'mers‘likewise may
nonyl, decyl, cyclohexyl and like straight and
such, for example, as sulfuric acid, hydrochloric
chained alcohols.‘ The above acetals
acid, phosphoric acid, boron ?uoride (or its addi .35
are primarily of the symmetrical‘ type, unsym
tion products), paratoluene sulfonic acid or the
metrical acetals, however, ‘may. likewise be em
like and heating the resulting mixture to a tem
ployed, such,_,fcr example, as methyl ethyl formal,
perature from room ‘ temperature ,to approxl- '
is preferable to remove from the reaction zone
the alcohol ‘producedJ v'I‘his‘may be done con
tinuously or intermittently as desired.
quent to the reaction the catalyst is preferably
neutralized with a base either organic or inor
ganic such as, for example, sodium hydroxide,
sodium carbonate, sodium methoxide, pyridine, or
the like and the products distilled for the recov-,
ery of thecyanonitrile produced.
(methoxymethoxyl ethanol, methyl ethyl acetal,
propyl acetal, and the like. lAcetals of the'type
made from ketones and: alcohols, sometimes called
belused such,-for example, as 1,3-dioxolane, poly-.
so meric
1,3-dioxolane, glycol formals, 1,3-dioxane
andltheir substitution products.
‘ .
The above designated. acetals may be reacted
with such cyanohydrins and their equivalents,
as, for. example, those prepared ‘by the interac
tion of hydrocyanic acid with the aldehydes gen
erally, such as formaldehyde, acetaldehyde, pro
ethanol stopped distilling from the mixture. After
neutralizing the mixture, as described above,
pionaldehyde, normal and isobutyraldehyde and
the higher aldehydes. Ketone cyanohydrins are
fractionation was continued.
likewise suitable and as examples of these com
in 67% yield, boiled at 70° at 3 mm.
pounds-may be designated those‘pre'pared by the
interaction of hydrocyanic acid “with acetone,
Example 7.-—'A mixture of diisobutyl formal (1
'mol), acetaldehyde cyanohydrin (1 mol), and
methyl ethyl ketone, diethyl ketone, cyclohexan
sulfuric acid (2 cc.) was heated on an oil bath
rI‘he (methoxy
ethoxymethoxy) acetonitrile fraction, obtained
one, and the higher symmetrical and unsym
and the isobutanol formed in the reaction was
metrical ketones. Hydroxy acid nitriles ‘which 10 ‘tilled from the mixture at reduced pressure (55
may be called glycol cyanohydrins may also be
mm.) during the reaction. After a 6 hour reac
tion period the product, alpha (isobutoxymeth
used such, for example, as ethylenefg‘lycol'cyano
hydrin, HOCHzCHzCN, propylene ‘glycol cyano
"oxy) propionitrile, was washed with water and
distilled at 3 mm.
hydrin, HOCHzCI-IzCI-IzCN, and’so forth.
The more detailed practice of this step ‘of the 15 Example 8.——Acetaldehyde cyanohydrin was
invention is illustrated by the following exam
‘heated to a temperature between 60 and 90° C.
ples in which parts are by weight unless other
with excess'methylal and sulfuric acid catalyst
in a pressure still operating under 30# gauge
wise stated.
Example 1.—A mixture consisting of 228 parts
pressure. Methylal and methanol were distilled
of formaldehyde cyanohydrin, 1648 parts of 20 from the reaction mixture during the reaction
‘methylal (as a methanol‘azeotrope containing 8%
at 77° C. atthis pressure. The pressure was re
methanol and 92% methylal) and 10 parts of
leased and the mixture neutralized as described
sulfuric acid was boiled ?ve hours, Catalyst was
'above'and after distillation a conversion of 45%
to 'methoxymethoXy-propionitrile was realized.
The above valuable nitriles can be readily con
tilled. 110 parts of the product (methoxy-meth
verted to amines by hydrogenation. This may be
effected preferably in the liquid phase employing
oxy) acetonitrile CHsOCHzOCHaCN, a colorless,
'm'obile liquid with a B. P.‘ 66° C./23 mm. was ob
a ‘suitable active hydrogenation catalyst such, for
example, as a nickel, cobalt, fused copper-cobalt,
Example 2.——Two moles of isobutyraldehyde 30 "copper chromite catalyst or the like. The hy
cyanohydrin was reacted with 3 moles of isobutyl
drogenation can be conducted in the liquid or
vapor phase at temperatures ranging'between 25
‘formal in the presence ‘of 0.1‘mole of sulfuric acid.
and 200° C. and at pressures between 1 and 1000
The resulting mixturewas’heated'to ‘a tempera
atmospheres although it is preferred to conduct
ture in'the'neighborho‘od‘of 100° C. for ?ve hours,
the hydrogenation \of‘these nitriles at tempera
subsequent to which sodium methoxide was added
tures'between 75 and 150° C. and under pressures
‘to neutralize the catalyst‘an'd until the solution
neutralized, as indicated by phenolphthalein, by
the addition of NaOHCa and the product was dis
was neutral as indicated by phenolphthalein.
between v200 and 700 atmospheres.
An 81.4% ‘conversion of valpha (isobutoxymeth
'It 'has ‘likewise been found that polyamine
formation during hydrogenation is inhibited,
oxy) isovaleronitrile
Yo oHl'o oil-19
was ‘obtained. It ‘is a white, Water-immiscible
oil, boiling point 67° C. at 2 mm.
Example 3.—A reaction mixture ‘consisting of
114 parts of formaldehyde cyanohydrin, 320 parts
of diisobutyl'formaland 2 parts of sulfuric acid
was fractionated until no more isobutanol dis
40 yieldsare increased, and the reaction goes more
smoothly if ‘there be present durin'g'the reaction
from v1 to 20 moles of ammonia per ‘mole of the
nitrile. If ‘desired, the nitrile'to be hydrogenated
‘may-be dissolved in aqueous ammonia or the
‘nitrile may be'dis'solved in a ‘suitable solvent such,
for example, as methanol, 'di(isopropyl) ether,
vdioxarie, or 1,3-dioxolane, which is not decom
p'o's'ed or hydrogenated during the reaction or de
tilled 'from'the mixture. ‘After neutralizing’the
composed by‘the ammonia added to the solution.
mixture with sodium hydroxide, using litmus as 50 vThis step 'of the process may be illustrated by
th‘ejindicator, fractionation was continued. The
(isobutoxymethoxy) 'acetonitrile fraction, ob
.tained in 83.3% yield, boiled'at 50° at 3 mm.
Example 4.——A reaction mixture'consisting ‘of
114‘pa'rts of formaldehyde cyanohydrin, 320 parts 55 which illustrates the hydrogenation of an (al
koxymethoxy) acetonitrile to an (alkoxymeth
oxy) ethyl amine. In accord with this process
the other nitriles described and illustrated'under
tilled from the mixture. After neutralizing the
step 1 ‘of the process may be ‘similarly converted
mixture with sodium hydroxide, using litmus as
the indicator, ‘fractionation was continued. The 60 ‘to the'corresponding amine,
In order to illustrate this step of the process,
(cyanomethoxymethoxy) acetonitrile fraction
sever'al'speci?c embodiments of the invention are
'ob'ta'ined‘in 10% yield, boiled at'1l0° at 2 mm.
described herewith by way of example.
_ Example 5.-—A reaction "mixture consisting of
Example 9.——~A reaction mixture consisting of
228 parts'of formaldehyde cyanohydrin, 541 parts
78.3 parts of (isobutoxymethoxy) 'acetonitrile,
of diethyl formal'and 2 ‘parts‘of sulfuric acid was
l'00sparts of ammonia, and 20 parts of an active
fractionated until ‘the binary of diethyl formal
nickel hydrogenation catalyst supported on
and ethanol stopped distilling from the mixture.
kieselguhr was subjected to the action of hydro
After ‘neutralizing the mixture, as described
gen at 100°C. and 700 atmospheres pressure for
above, fractionation ‘was continued. The ethoxy
methoxy a'cetonitrile fraction, obtained in 57.0% 70 '1i5'hours. After removing catalyst the product
was distilled. Isobutyl aminoethyl formal,
yield,'boiled at 45° at 1 mm.
of diisobutyl formal ‘and 2 ‘parts of sulfuric acid
was fractionated until no more ‘isobutanol dis
Example 6.-—A reaction mixture consisting ‘of
142 parts of formaldehyde cyanohydrin, 277'parts
'of‘di(methoxyethyl) formal and 2 parts vof sul
‘(135R some/4 mm.) was ‘obtained in 9115 %_- yield.
furic acid was ‘fractionated until “methox'y 75
Example 10.-A reaction mixture‘con-sistmgrbr
50 parts of (isobutoxymethoxy) acetonitrile, 100
parts of diisopropyl ether, 20 parts of an active
methanol, ethanol, or 1,4-dioxane, with ammonia
to precipitate the ammonium salt with liberation
nickel‘ hydrogenation catalyst (prepared as in
Example 9) andv 50 parts of ammonia was sub
of the. amine acetal. In' a similar manner the
other products of steps 1 and 2 as well as other
aminoacetals may be converted to diamines.
In order to illustrate .the third step of the
process several specific embodiments of the in
jected to the action of hydrogen at 100° C. and .
.700 atmospheres pressure for one hour. After
removing the catalyst the product was distilled.
Isobutyl aminoethyl formal was obtained in
‘79.9% yield.
vention are given.
The invention, however, is
not to be restricted by these or the other exam
Erample 11.-—-One mole of (methoxymethoxy) 10 ples given.
Example 12.—To 73.5 parts of isobutyl amino
acetonitrile dissolved in. 12' moles of ammonium
hydroxide containing 10% nickel catalyst was
ethyl formal, C4H9OCH2OCH2CH2NH2, was added
subjected to the action of hydrogen at 100° C.
20 parts of dry HCl gas with cooling by means of
and ‘700 atmospheres pressure until the reaction
an external ice bath. After the addition the mix
was complete.‘ The catalyst was removed and 15 ture consisted of a white solid suspended in a
the product distilled. Methyl aminoethyl for
mobile liquid. Di-isobutyl formal was removed
mal, CHsOCI-IzOCHzC‘HzNI-Iz was obtained in a
from the reaction mixture at 2 mm. pressure. To
practically quantitative yield as a colorless, mo
the solid remaining ‘110 parts of 29.6% NaOCHs
bile liquid (B. P. 56-57" C‘./30 mm).
in CHsOH was added and NaCl then ?ltered off.
Similarly, methoxyethyl aminoethyl formal 20 The product was distilled and di(aminoethyl)
‘ can be made from (methoxyethoxymethoxy) ace
tonitrile; isobutyl 1-amino-3-methyl-2-butyl for
mal from (isobutoxymethoxy) isovaleronitrile;
and methyl l-amino-2-methyl-ethyl formal from
(methoxymethoxy) propionitrile.
It has likewise been found that the amines,
formal (NH2CH2CH2O)2CH2, B.IP. 70° C./2 mm.
obtained in a yield of 90% or better.
Example 13.—58.8 parts of isobutyl aminoethyl
formal was placed in a suitable container, cooled,
agitated and 20 parts of anhydrous hydrochloric
prepared in accord with step 2 by hydrogenation
acid was introduced. As a result of this reaction
diisobutyl i. formal was produced and withdrawn
in the presence of ammonia of the nitriles pre
pared in accord with the process of step 1, can be
by distillation under reduced pressure leaving the
or inorganic acid, the addition preferably being
repeated using 212 parts of ethyl aminoethyl
formal, C2H5OCH2OCH2CH2NH2, and 65 parts of
hydrochloric acid. Di(aminoethyl) formal was
salt of the diamine as a white solid. The salt
converted into salts and by disproportionation 30 was converted to the free base by neutralization
these salts converted to polyarninoacetals.
to phenolphthalein by the addition of sodium
The salts may be prepared, for example, by
methoxide. The precipitated sodium chloride
adding to the aminoacetals an organic or inor
was ?ltered off and the ?ltrate fractionally. dis
ganic acid such, for example, as hydrochloric
tilled to give di(aminoethyl) formal, obtained in
acid, sulfuric acid, phosphoric acid, acetic acid, 35 a 90% yield.
glycolic acid, oxalic acid or other suitable organic .
Example 14.-—The process of Example 13 was
carried out at a temperature between 0 and 100°
C. The salt thus prepared is then reacted with
a suitable base such as the alkali metal or alka
obtained in a yield of substantially 90%.
Example'15.-20 parts of di(aminoethyl) for
mal hydrochloride dissolved in 60 parts of iso
?ltering off the precipitated salt, if present, the
butanol is saturated with anhydrous ammonia
aminoacetal is distilled from the ?ltrate.
and the ammonium chloride formed rapidly pre
This step of the process may be illustrated by 45 cipitates. The solution was ?ltered and the 1di
line earth metal hydroxide, carbonate, or alkox
ide or an organic base such as pyridine, and after
the following equations;
(ethylamino) formal separated by distillation,
Similarly di(aminoethyl)formal can be ob
tained from methyl aminoethyl formal,
methoxyethyl aminoethyl formal,
in which R. is an alkyl or substituted alkyl group,
R’ is hydrogen, an alkyl or substituted alkyl
and from like products. Those skilled in the art
group, Yis a single bond or an alkyl group and
55 will appreciate that other aminoalkyl formals
X is the anion of a mineral acid.
and acetals can be obtained from corresponding
More speci?cally this step of the process may
monoamine alkyl formals and acetals to give
be illustrated by the equations:
products having the formula:
in which R’ is hydrogen, an alkyl or substituted
alkyl group.
The products of the invention have a wide va
riety of uses. The diamines may be reacted with
(alkoxy-methoxy) ethyl amine to its hydrochlo 65 dibasic acids, such as adipic acid, to form salts
from which linear polymers of great utility may
ride and Equation 8 illustrates the disproportion
ation of the hydrochloride to a poly salt. The
be produced and in addition to being useful in the
disproportionation results when excess acid over
preparation of the diamines the intermediates are
that used to make the salt is added. Subsequent
useful as plasticizers, softeners, thickeners, non
treatment of the polyhydrochloride by an equiv
polar detergents, softeners, and plasticizers for
alent quantity of a base, ?ltering to remove the
regenerated cellulose, cellulose ethers, esters, and
chloride salt and fractionally distilling the fil
the like.
trate will give the corresponding di(ethylamine)
I claim:
1. A process for the preparation of a di(amino
formal, CH2(OCH2CH2NH2) 2. If desired, the
salts may be treated in a suitable solvent, such as
alkyl) acetal which comprises heating an acetal
Equation "1 illustrates the conversion of an
with aldehyde cyanohydrin whereby an unsym
fine‘t'riéal cyanoalkyl acetal is obtained, heating
the resulting cyanoalkyl acetal with hydrogen in
thelpresence of ammonia and a hydrogenation
catalyst to form an unsymmetrical aminoalkyl
with formaldehyde cyanohydrin, producing
“methyl aminoethyl formal by subjecting (meth
‘o'xymethoxyl acetonitrile to a reaction with hy
drogen at a temperature between 25° and 200° C.
in the presence of ammonia and a hydrogenation
‘acetal, separating the unsymmetrical aminoalkyl
catalyst, separating the methyl aminoethyl for
acetal from the hydrogenated reaction mixture,
subjecting the separated unsymmetrical amino
mal from the hydrogenation mixture, subjecting
the methyl aminoethyl formal to a reaction with
an excess of an inorganic acid, neutralizing the
inorganic acid, neutralizing the salt obtained with 10 resulting salt with a base and after ?ltering, and
recovering di(aminoethyl) formal from the reac
'a base, and ‘subsequently removing from the re
alkyl acetal to a reaction with an excess of an
sulting mixture after ?ltration the di(amino
tion mixture by distillation.
4. In a process for the preparation of di(ami
n'oethyl) formal the steps which comprise sub
'alk'yl) formal which comprises heating a formal T15 jecting isobutyl aminoethyl formal to a reaction
-2. A process for the preparation of a di(amino
withforr'naldehyde cyanohydrin whereby an un
symmetrical cyanoalkyl formal is obtained, heat
ing the resulting cyanoalkyl formal with hydro
with an inorganic acid and thereby forming a
mono salt of the formal, subjecting said mono
salt to a reaction With an additional quantity of
a mineral acid to form a di(aminoethyl) formal
g‘enin the presence of ammonia and. a hydrogena
‘tion‘c'atalyst to form an unsymmetrical amino 20 salt, neutralizing the’ latter salt with a base and
alkyl formal, with hydrogen in the presence of
recovering the di(aminoethyl) formal from the
ammonia and a hydrogenation catalyst to form
reaction mixture by distillation.
an unsymmetrical aminoalkyl formal, separating
5. In a process for the preparation of di(ami
the unsymmetrical aminoalkyl acetal from the
noethyl) formal the steps which comprise adding
hydrogenated reaction mixture, subjecting the 25 ‘approximately 20 parts of dry hydrochloric acid
separated unsymmetrical aminoalkyl formal to a
gas with cooling to approximately 731/2 parts of
reaction with an excess of an inorganic acid, neu
isobutyl aminoethyl formal, separating the pre
tr'a'lizing the salt obtained with a base, and sub
cipitated salt by ?ltration, adding approximately
sequently'rem'oving from ‘the resulting mixture
110 parts of a 29.6% sodium methoxide solution
after ?ltration the di(aminoalkyl) formal.
in methanol, ?ltering o? the sodium chloride and
13. A process for the preparation of di(amino
recovering the di(aminoethyl) formal.
ethyl) vformal which comprises producing meth
oxymethoxy) 'ac‘etonitrile by heating methylal
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