PREPARATION OF UNSATURATED AMINES

PREPARATION D'AMINES INSATUREES

English Abstract

Abstract of the disclosure: a process for preparing
unsaturated amines of the general formula I

Image (I),


where

R1,R2,R3,R4,R5 are hydrogen, C1- to C20-alkyl, C2- to
C20-a1kenY1, C3- to C8-cycloalkyl, C3- to
C8-cycloalkenyl, phe~nyl, C7- to C20-phenyl-
alkyl, C1- to C20-alkoxy, phenoxy, C7- to
C20-phenoxyalkyl, C1- to C20-alkylamino,
phenylamino, C7- to C20-phenylalkylamino,
pyridyl or imidazolyl, or R1 and R2 or R1
and R3 or R2 and R3 together are a C2- to
C8-alkylene which is unsubtituted or
monosubstituted to pentasubstituted by C1-
to C4-alkyl or unsubstituted or monosub-
stituted to tetrasubstituted by amino,
N-C1- to C8-alkylamino, N,N-C1- to C8-di-
alkylamino, hydroxyl, O-C1- to C8-alkyl-
amino and/or C1- to C8-alkoxycarbonyl, and

X is =C-N(R4R5) or -C=N-R4,
by reacting 2-alkenals of the general formula II

Image (II),

where R1, R2 and R3 have the abovementioned meanings,
with primary or secondary amines of the general formula
III


- 2 -

Image ( III ),

where R4 and R5 have the abovementioned meanings, at from
(-20) to 70°C and pressures from 0.01 to 100 bar, by
carrying out the reaction without removing the water of
reaction and transaminating the product to give the
compounds I' and hydrogenating the latter to give novel
1,3-diamines of the general formula IV

(IV),
Image

where

R1,R2,R3,R4,R5,R6,R7 are
hydrogen, C1- to C20-alkyl, C2- to C20-alkenyl, C3- to
C8-cycloalkyl, C3- to C8-cycloalkenyl, phenyl, C7- to
C20-phenylalkyl, C1- to C20-alkoxy, phenoxy, C7- to
C20-phenoxyalkyl, C1- to C20-alkylamino, phenylamino,
C7- to C20-phenylalkylamino, pyridyl or imidazolyl, or R1
and R2 or R1 and R3 or R2 and R3 together are a C2- to
C8-alkylene which is unsubtituted or monosubstituted to
pentasubstituted by C1- to C4-alkyl or unsubstituted or
monosubstituted to tetrasubstituted by amino, N-C1- to
C8-alkylamino, N,N-C1- to C8-dialkylamino, hydroxyl,
O-C1- to C8-alkylamino and/or C1- to C8-alkoxycarbonyl,
with the proviso that R1 and R2 are not hydrogen if R3 is
methyl and R4 and R5, R6 and R7 are in each case hydrogen
or methyl, R4 and R6 are hydrogen and R5 and R7 are ethyl
and also R4 and R5, R6 and R7 are in each case together
(CH2)5 or (CH2)2-O-(CH2)2, is disclosed.

Claims

- 19 -
We claim.
1. A process for preparing unsaturated amines of the
general formula I

Image (I),

where
R1,R2,R3,R4,R5 are hydrogen, C1- to C20-alkyl, C2- to
C20-alkenyl, C3- to C8-cycloalkyl, C3- to
C8-cycloalkenyl, phenyl, C7- to C20-phenyl-
alkyl, C1- to C20-alkoxy, phenoxy, C7- to
C20-phenoxyalkyl, C1- to C20-alkylamino,
phenylamino, C7- to C20-phenylalkylamino,
pyridyl or imidazolyl, or R1 and R2 or R1
and R3 or R2 and R3 together are a C2- to
C8-alkylene which is unsubtituted or
monosubstituted to pentasubstituted by C1-
to C4-alkyl or unsubstituted or monosub-
tituted to tetrasubstituted by amino,
N-C1- to C8-alkylaminol N,N-C1- to C8-di-
alkylamino, hydroxyl, O-C1- to C8-alkyl-
amino and/or C1- to C8-alkoxycarboxyl, and

X is =C-N(R4R5) or -C=N-R4,

by reacting 2-alkenals of the genhral formula II

Image (II),

wherw R1, R2 and R3 have the abovementioned meanings,
with ammonia or primary or secondary amines of the
general formula III

- 20 -

Image (III),

where R4 and R5 have the abovementioned meanings, at from
(-20) to 70°C and pressures from 0.01 to 100 bar, which
comprises carrying out the reaction without removing the
water of reaction.
2. A process for reacting unsaturated amines I as
claimed in claim 1 to give the unsaturated amines I'

Image (I '),

where R1, R2, R3, R4 and R5 have the abovementioned mean
ings and X' is =C-N(R6R7) or -C=N-R6 and R6 and R7 have the
meanings given for R1 to R5, which comprises reacting the
unsaturated amines I with primary or secondary amines of
the general formula III'

Image (III'),

where R6 and R7 have the meanings given for R1 to R5, at
from 20 to 150°C.
3. A process for hydrogenating unsaturated aminee I
or I' as claimed in claim 1 or 2, which comprises hydro-
genating the unsaturated amines I or I' under a hydrogen
pressure from 1 to 350 bar at from 0 to 150°C.
4. A 1,3-diamine of the general formula IV

Image (IV),

- 21 -
where
R1,R2,R3,R4,R5,R6,R7 are
hydrogen, C1- to C20-alkyl, C2- to C20-alkenyl, C3 to
C8-cycloalkyl, C3- to C8-cycloalkenyl, phenyl, C7- to
C20-phenylalkyl, C1- to C20-alkoxy, phenoxy, C7- to
C20-phenoxyalkyl, C1- to C20-alkylamino, phenylamino,
C7- to C20-phenylalkylamino, pyridyl or imidazolyl, or
and R2 or R1 and R3 or R2 and R3 together are a C2- to
C8-alkylene which is unsubtituted or monosubstituted to
pentasubstituted by C1- to C4-alkyl or unsubstituted or
monosubstitutad to tetrasubstituted by amino, N-C1- to
C8-alkylamino, N,N-C1- to C8-dialkylamino, hydroxyl,
O-C1- to C8-alkylamino and/or C1- to C8-alkoxycarbonyl,

with the proviso that R1 and R2 are not hydrogen if R3 is
methyl and R4 and R5, R6 and R7 are in each case hydrogen
or methyl, R4 and R5 are hydrogen and R5 and R7 are ethyl
and also R4 and R5, R6 and R7 are in each case together
(CH2)5 or (CH2)2 O-(CH2)2.

Description

3 ~
O.Z. 0050/43579
Pre~aration o~ unsaturated amines
The present inven~ion relates to a novel procea~
for preparing 1,3 diaminopropene~ by reacting 2-alkenal~
with primary and secondary amines without removing the
water of reaction.
Acrolein, Wiley & Sons, N.Y., Chaper 6, (1975)
page~ 96 to 109 disclo~es reaction~ o~ primary and
secondary aliphatic amines with acrolein to give alkyl-
~ub~tituted 1-propens-1,3-diamines. According to thi
process, N,N'-dialkyl-l-propene-1,3-diamines are formed
~rom 2 mol of amine with 1 mol of acrolein with removal
of water in the pre ence of a dehydrating a~ent or of a
water-immi~cible 301vent-
US-A-2 565 488 disclose~ ~,N~-dialkyl 1-propene-
1,3-diamlne~ and their preparation from 2 alkenals and
prLma~y amines under dehydrating ~ondition~ in the
pre~ence of dehydrating agent~ ~uch a~ potassium car-
bonate.
The addition of di-n-propylamlne to acrolein i9
known from EP-A-424 171. The water of rea~tion must al~o
be removed in thi~ proce~s either by usiny a drying agent
or alternativ~ly by using a wat~r-immi~cible ~olvent and
removing the aqueou~ pha~e.
Th~ proces~e~ known o date ~or preparing alkyl-
substituted 1-propene-1,3-diamlne~ ~rom 2-alkenal using
primary and econdary aliphati~ amlnes ha~e the di~ad-
vantage that they mu~t be carried out with the addition
of a dehydrating agent or of a water-immiscible so1vent
and removal of an aqueous phase and only modarat~ yield~
are achieved.
: It i~ an object of the pre~e~t invention to
remedy tho abovementioned disadvantages.
We have found that this object is aahieved by a
novel a~d improved proce~s ~or preparing un~aturated
amines o~ the general formula I




' ~ ' ' ' , , ' , ' , , ! ., ' , ' . . ' .' . .

o~o~
- 2 - O.Z. 0050/43579
Ri R2
R4 - N ~ x ~I),
¦ R3
R5




where
R1,R2,R3,R4,Rs are hydrogen, Cl- to C20 alkyl, C2- to
C20-alkenyl, C3- to C9-cycloalkyl, C3- to Ca-cycloalkenyl,
phenyl, C7~ to C20-phenylalkyl, C, to C20-alkoxy, phenoxy,
C7- to C20-phenoxyalkyl, C~- to C20-alkylamino,
phenylamino, C,- to C20-phenylalkylamlno, pyridyl or
imidazolyl, or R1 and R2 or R1 and R3 or R2 and R3 toyether
are a C2- to Ca-alkylene which is un~ubtituted or
monosub~tituted to penta3ubstituted by C~ to C4-alkyl or
unsub~tituted or mo~o~ubstituted to tetra~ub~tituted by
amino, ~-C,- to C~-alkylamlno, ~,N-C,- to Ca-dialk~lamino,
hydroxyl, O-C,- to C~-alkylamino and/or C,- to C8-
alkoxycarbonyl, and
X is -C-N~RqR5~ or -C=N-R4,
by reacti~g 2-alkenaIs of the general formula II
Rl CE30
~ (II),
\
R2 R3

where Rl, R2 ànd R3 have the abovementioned meanings,
with ammonia or pximary or ~econdary amines o~ the
: g~neral formula III
: R4
: N - B IIII)~
R5




: where R4 and Rs have the aboveM~ntioned meaning~, at from
~(~20) ko 70C and pres~ures from 0.01 ko 100 bar, which
compri~e~ carrying out khe reaction without removing the
water o~ reaction and kransamlnating the produ~k ko give
th- oompound~ I' and hydrogenating the latter to give

; ~
,
~.
.




: , ., , , ~, . ~ .: . , : . ..

2 ~ 0 ~
- 3 - O. Z . 0050/43579
1, 3-diamine~ and novel 1, 3-diamine~ of the yeneral
formula IV
Rl R2
R4--N~ N--R6 (IVj,
RS R7
where
Rl R2 R3 R4 Rs R6 R7
,,,,,, are
5hydrogen~ C1- to C20-alkyl, C2- to C20-alkenyl ~ C3- to
C8-cycloallcyl, C3- to C8-cycloalkenyl, phenyl, C7- to
C20-phenylalkyl, C~- to C20-alko3~y, phenoxy, C7- t;o
C:20-phenoxyalkyl, Cl- to C20-alkylamino, phenylamino,
C7- to C20-phenylallylamino, pyridyl or imidazolyl, or
and R2 or R1 and R3 or R2 and R3 together are a C2- to
Ca-alkylene whit:h i~ unqub~i~uted or mono3ub~tituted ts~
penta~ubqtituted by Cl- to C4~ or un-qub~tituted or
mono8ub~tltuted to tetxa~ub~tituted by amino, N~ to
C8-alkyl~mino, N,N-Cl- to C8-dialkylamino, hydroxyl,
O-C~- to C,~-alkylamino and~or Cl- to C~-alkoxycarbonyl,
with the provi~o that R1 and R2 are not hydrogen if R3 is
methyl and R~ and Rs, R6 and R7 are in each ca ~ hydrogen
or methyl, R4 and R6 are hydrogen and Rs and R7 are eth~ l
and al~o R4 and Rs, R6 alld R7 are in each case together
(CH2)s or (CH2)2-O~(CH2~2-
The process according ~o ~e: in~ention can ~e
caxried out a~ $0110w8:
- ~Preparatîon of unsaturated amines I
he 2-alkenal II ~an bs reacted wi~h ammonia or
:~ 25 a pr~ary or secondary amine III ei ther batchwi~e or
continuou~ly at from (-20) to 70C, preferably 20 to 50C
and :from ~.1 to 10 bar, preferably 1 to 5 bar,
partic:ularly preferably atmospheric presx3ure. It may only
be neces~ary to u8e preqsures frt)m 2 to 300 bar,
:~ 30 preerabl3~ 5 to 200 bar, with gas~ouB amines III. If a
primary amine III or III ' is ucied, un~atuxa~ed amine~
or I' ar~ obtained in which X is C=N-R4 or X' i~ C=~-R6.


:




, . , .. , ~ , . . . . .

2 ~
_ 4 _ o.z. 0050/43579
When using a secondary amine III or III', unsaturated
amine-~ I or I' are obtained in which X is =C-N(R4Rs) or X'
is =C-N-(R ,R ).
The molar ~atio of the prLmary or secondary amine
III to the 2-alke~al III should be at lea~t 2 : 1, as a
rule from 2 : 1 to 50 : 1, prQferably 2: 1 to 10:
particularly preferably 3 : 1 to 5 : 1.
2-AlkQnals of the general formula II are, for
example:
acrolein, methacrolein, crotonaldehyde, 2-methylcroton-
aldehyde, 3~methylcrotonaldehyde, 2-ethylacrolein, 2-
propylacrolein, 2 isopropylacrolein, 2-nonylacrolein,
2-ethylhe~anal,2-propylheptenal,l-cyclopentenecarboxal-
dehyde, l-cyclohexenecarboxaldehyde and cinnamaldehyde.
- Txansamina~ion of the un~aturated amines I
Th~ unsaturated amines I obtained from ammonia or
primary or 3econdary amines III with 2-alkenal~ II can ba
employed with primary or ~econdary amines III~ to give
un~aturated amines I' directly and without removing the
water of reaction or excess amine III. However, the
un~aturated amine I can also be u~ed as a pure product.
The exchango can be acc31srated and completed by
heating the raaction solution to 20 to 150C, pre~erably
30 to 120C, particularly prefsrably 45 to gOC. In this
proce0s the nitrogen which i8 next to the double bond i~
preferably 0xchanged. Exchange ~or a primary or secondary
amin~ III', who~e boiling point i~ higher than that of
the amine of the ~eneral formula I to be removed, i3
particularly preferred. The reaction i~ preferably
carried out under a pressure at which the boiling point
of ~he amine to be removed i~ from 50 to 80C, iOe. at
pre~sures from 0.01 to 3 bar, pre~erably O.OS to 1.5 bar,
:~ particularly preferably 0.1 to 0.7 bar.
Ammonia or primary or secondary amine~ III and
III' can be employed for preparing un~a~urated amines I
and for preparing un~aturated am~ne3 I' by
tran~amination. The most importan~ are li~ted balow:
.

- 5 - O.z. 0050/43579
Ammonia.
Primary amine~ III and III~ are, for examples
Primary amine~ without further heteroatoms are, for
example: methylamine, ethylamine, n-propylamine,
S isopropylamine, n-butylamine, 2-methylpropylamine, tert-
butylamine, n-pentylamine, 2-methylbutylamine, 3-methyl-
butylamlne, 2,2-dimethylpropylamine, 3,3-dimethylpropyl-
amine, n-hexylamine, n-octylamine, 2-ethylhexylamine,
tridecylamine, allylamlne, crotylamine, methallylamine,
cyclopropylamin~, cyclopentylamlne, cyclohexylamine,
be~zylamine and aniline.
Polyfunctionalized amine~ III and III' containing
at least one primary amino radical are, for example:
Ethylenediamine, 1,3-propyle~ediamine, 1,4 butylene-
diamine, 1,5-pentamethylenediamine, 1,6-hexamethylene-
diamin~ ophoronediamine, 2-butyl-2-ethyl-1,5-penta
diamine, 1~2-propylenediamine, 2,2-dimet~yl-1,3-propyl-
enediamine, ~4,4'-diaminodicyclohexylmethane, 3,3'-di-
methyl-4,4'diaminodicyclohexylmethane, 4,4'-diaminodi-
phenylmethane, N-methylethyle~ediamine, N,N-dimethyl-
ethylenediamine, N,N-diethylethylenediamine, N-methyl-
1,3-propylenediamine, N,N-dLmethyl-1,3-propylenediamin~,
N,N-diethyl-1,3-propylenediamine, N-cy~lohexyl-1,3-
propylenediamine~ 1-diethylamino-4-aminopentane,
diethylenetriamine, N,N-dLmethylethylenetriamine,
dimethylpropylenetriamin~, N-(2-amino~thyl)-1,3-
propanediamine, N,N'-bi~(3-aminopropyl)-ethylenediamine
a~d ~ dimethyl-1,6-hexamethylenediamine.
Primary amine~ III and III' containing further
: 30 heteroatom ~ubstituents are, ~or example:
2-Aminoethanol, 1-amino-2-propanol, 2-(2-amlnoethoxy)-
: ethanol, 3-aminopropanol, 2-amino-1-butanol, 4,9-dioxado-
decan 1,12-diamine, 4,7,10-trioxatridecan-1,13-diamine,
2-methoxyethylamine,2-ethoxyethylamine,3-meth3xypropyl-
amlne,3-ethoxypropylamlne,3-~2-ethylhexoxy)propylamine,
3-(2-methoxyethoxy)propylamine, 2-methoxyphenylethyl-
amlne, 4-methoxyphenylethyl d ne and homoveratrylamine.

- 6 - O.Z. 0050/43579
Secondary amines III and III' are, for example:
Secondary amines without ~urther heteroatoms are, for
example: dLmethylamine, diethylamine, di-n~propylamine,
di-isopropylamine, di-n-butylamine, di-(2-methylpropyl)-
S amine, di-tert-butylamine, di-n-pentylamine, di-
(2-methylbutyl)amin~, di-(3-methylbutyl)amine, di-
(2,2-dLmethylpropyl)amine, di-(3,3 dimethylpropyl)amine,
di-n-hexylamine, di-2-ethylhexylamine, di-tridecylamine,
N-methylbutylamine, N-ethylbutylamine, diallylamine,
dicrotylamine, dLmethallylamine, dicyclopropylamine,
dicyclopentylamine, ~-methylcyclohexylamine, N-ethyl-
cyclohexylamine, dicyclohe~ylamine, N-methylaniline,
N-ethylaniline and diphenylamine.
Secondary amine~ III and I}I' containing further
heteroa~om sub~tituent~ ar~, for example:
Diethanolamina, di-isopropanolamine, methylethanolamine,
ethylethanolamine, butylethanolamine, cyclohe~yl-
ethanolamine, hydroxyothylaniline and di-2-methoxyethyl-
amine.
- Hydrogenation of unsaturated amine~ :
~he unsaturated amine~ I obtained from reacting - -
ammonia or primary or ~econdary amine~ III and 2-alkenal~
II can be hydrogenated on customsry hydrogenation
catalysts æuch as palladium, platinum, ruthenium,
2~ rhodium, cobalt, nickel and copper as a metal or metal
mixtura or o~ a support material such a~ alumina,-silica,
activ~ carbon, zirconium o~ide or titanium dioxide, in
particular on palladium as metal or on a support
material ~uch a3 alumina, silica or ac~ive carbon,
without working up and in the presence of the water of
reaction, preferably without working up and without
remoYing ~he water o~ reactionp to give tho corre~pond~ng
~aturated 1,3-diami~e~ IV. The u~saturated amine~ I'
prepared by amine exchange reaction can equally be
hydrogenated, pre~erably withou~ working up ~he crude
: produc~. -
The hydrogenation can be carried out in the

,.


_ 7 _ O.Z. 0050/43579
pre~ence or ab ence of inert ~olvent~ such as ether~, for
example methyl tert~butyl ether, tetrahydrofuran and
dioxane~ or esters, for example methyl acetate and ethyl
acetate, at from 0 to 150C, preferably 10 to 80C,
particularly preferably 30 to ~0C. The hydrogen pre~ure
is from 1 to 350 bar, preferably from 1 to 100 bar.
The ~ub~tituent~ Rl, R2, R3, R~, Rg, R6 and R7 in
the compounds of the general formulae I, I~, II, III,
III' and IV have the following meanings:
n 1 ~2 R3 R4 Rs R6 R7 e
R ,~ , , , , , ar
- hydrogen,
- Cl- to C20-alkyl, preferably Cl- to Cl2-alkyl such as
methyl, ethyl, n-propyl, isopropyl, n-butyl, i~obutyl,
sec-bu~yl, tert-kutyl, n-pentyl, isopentyl, sec-pentyl,
neo-penty~, 1,2-dimethylpropyl, n-hexyl, isohexyl, sec-
hexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, n-nonyl,
isononyl, n-decyl, isodecyl, n-undecyl, isoundecyl, n-
dodecyl and i~ododecyl particularly prefsrably Cl- to C~-
alkyl such as methyl, ethyl, n-propyl, i opropyl, n-
butyl, isobutyl, sac-butyl and tert-butyl,
- C2- to C20-alkenyl, preferably C2- to Cl2-alkenyl such as
ethenyl, n-propenyl, isopropenyl, n-butenyl, isobutenyl,
~ec-butenyl, tert-but2nyl, n-pen~enyl, isopenten~l, sec-
pentenyl, neo-pentenyl, 1,2-dimethenylpropenyl, n-
hexenyl, isnhexenyl, sec-hexenyl, n-heptenyl,
isoheptenyl, n-octenyl, i~ooctenyl, n-nonenyl,
isononenyl, n-decsnyl, isodecenyl, n-undecenyl,
isoundecen~l, n-dodecenyl and isodcdecanyl, particularly
preferabl~ C~- to C4-alkenyl ~uch as e~henyl, n-propenyl,
: 30 isopropenyl, n-butenyl, i obutanyl, sec-butenyl and ter~-
butenyl,
: - C3- to C8-cycloalkyl such a~ cyclopropyl, cyclobutyl,
cy¢lopentyl, cyclohexyl, cycloheptyl and cyclooctyl, :
preferably cyclopentyl, cyclohexyl and cyclooctyl,
particularly preferably cyclopentyl and cyclohe~yl,
- C3- to C8-cyeloalkenyl i~iuch as cyelopropenyl, cyclo-
butenyl, cyelopentenyl, cyclohexenyl, cyclohept~nyl and
,




' :', ,: ': ', '' ' ' ' ' ' '.' ;' ' ' , : ' ' , ' ~.:, '

' ' '. '': , ~' :', - ' ' " '' ', .' ";' ' ' . ' ' '' ' "" '. ' . ' ~ ': '' ' : ' '
, ' ' , . ' :' ~ ' , ', : . : ' ' , . i' , , ' . " . " : '
',, , . ~' .' ', ' , ~' " ~ ,,'' ' '' , " ' ' ' ' ' ' '

2 ~
- 8 - O.z. 0050/~3579
cyclooctentyl, preferably cyclopentenyl, cyclohexenyl and
cyclooctenyl,
- phenyl,
- C7- to C20-phenylalkyl~ preferably C7- to C~2-phenylalkyl
such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenylpropyl,
2-phenylpropyl, 3-phenylpropyl, 1-phenylbutyl, 2
phenylbutyl, 3-phenylbutyl and 4-phenylbutyl,
particularly preferably benzyl, 1-phenethyl and 2-
phenethyl,
- C1- to C20 alkoxy, preferably C,- to C12-alkoxy ~uch a~
methoxy, ethoxy, n-propoxy, i opropoxy, n-butoxy,
i~obutoxy, sec-butoxy, tert-butoxy, n-pentoxy,
isopentoxy, sec-pentoxy, neo-pentoxy, 1,2 dimethyl-
propoxy, n-hexoxy, isohexoxy, cec-he~oxy, n heptoxy,
i~oheptoxy, n-octoxy, i900CtoXy~ n-nonoxy, isononoxy~ n-
decoxy, isodecoxy, n-undecoxy, i~oundecoxy, n-dodecoxy
and isododecoxy, particularly preferably C1- to ~4-alkoxy
such as methoxy, ethoxy, n-propoxy, isopropcxy, n-butoxy,
isobutoxy, sec-butoxy and tert-butoxy~
- phenoxy,
- C7- to C20-phenoxyalkyl, preferably C7- to C12-
phenoxyalkyl such as benzoxy, l-phenoxyethyl,
2-phenoxyethyl, 1-phenoxypxopyl, 2-phenoxypropyl,
3-phenoxypropyl, 1-phenoxybutyl, 2-phenoxybutyl,
3 phenoxybutyl and 4-phenoxybutyl, particularly
preferably benzoxy, 1 phenoxysthyl and 2-phenoxy~thyl,
- C~- to C20-alkylamirlo, preferably Cl- to Cl2-alkylamino
such a~ methylamino, ethylamlno, n-propylamino,
i~opropylamlno, n-butylamino, isobutylamino, sec-
butqlamino, ter~-butylsmino, n-pentylamino,
isopentylamino, sec pentylamino, n~o pentylamino,
1,2-dimethylpropylamino, n-hexylamino, i~ohexylamino,
sec-hexylamino, n-heptylamino, isoheptylamino, n-
octylamino~ isooctylamino, n-nonylamino~ isononylamino,
n-decylamino, isodecylamino, n-undecylamino,
isoundecylæmino, n-dodecylamlno and i~ododecylamino,
particularly preferably Cl- to C4-alkylamino such a~




- , . ,.. , ., . , ~ . . , . , .. ,: : : , : ; ; ;

-` 2~1Q~
_ g _ o.z. 0050/43579
methylamino, ethylamino, n-propylamino t isopropylamino,
n-butylamino, isobutylamino, sec-butylamino and tert-
butylamino,
- phenylamino,
- C7- to CzO-phenylalkylamino, preferably C7- to
Cl2-phenylalkylamino ~uch as benzylamino, l-phen
ethylamino, 2-phenethylamino, l-phenylpropylamino,
2-phenylpropylamino, 3-phenylpropylamino, l-phenyl-
butylamino, 2-phenylbutylamino, 3-phenylbutylamino and 4-
phenylbutylamino, particularly preferably benzylamino, 1-
phenethylamino and 2-phenethylamino,
- pyridyl,
- imidazolyl or R~ and R2 or Rl and R3 or R2 and R3
together are a C2- to C8-alkylene which ~ 8 unsub~tituted
or mono- to pentasubstituted by Cl- to C4-alkyl or
un ub~ti~uted or mono~ub~tituted to tetra~ub~tituted by
amino, N-Cl- to C3-alkylamino, N,N-Cl- to C~-dialkylamino,
hydroxyl, O-C1- to C~-alkylamino and/or Cl- to
C8-alkoxycarbonyl, such as aminoalkyl, N-methyl-
aminoalk~ ,N-dLmethylamino-alkyl, N-ethylaminoalkyl,
N,N-diethylaminoalkyl, methoxyal~yl and ethoxyalkyl,
preferably aminoethyl, N-methylaminoethyl, N,N-
dimethylaminoethyl, aminopropyl, N-methylaminopropyl,
N,N~dimethylaminopropyl, h~dro~yethyl, methoxyethyl,
ethoxyethyl, hydroxypropyl, methoxypropyl and
ethoxypropyl.
~ he ~ollowing may be men~ioned a~ novel 1,3-
diamines IV-
N,N~-2-trima~hyl 1,3-propanediamine, N,N,~,N~-~etra-
ethyl-2 methyl-1,3-propanediamine, N,~-di-n-propyl-
2-methyl-1,3-propanediamine, N t N,N~,N~-tetra-n-propyl-
2-methyl-1,3-propanediamine, N,N'-di-i-propyl-2-methyl-
1,3-propanediamine, N,N'-di-n-butyl-2-me~hyl-1/3-propane-
diamine, N,N,N~,N'-tetra-n-butyl-2-methyl-1,3-propane~
diamine, N,N'-dicyclohexyl-2-methyl-1,3-propanediamin0,
N,N'-di~2-ethylhaxyl)-2-methyl-1,3-propanediamine,
N,N,~'/N'-tetra(2-ethylhexyl)-2-methyl-1,3-propanedi-




....... . . .

.. ! , " . , ' . , ~ : " . ~ , .. , ., . ,~

- 10 - O.Z. 0050/43579
amine, N,N~-di(2-hydroxyethyl) 2-methyl-1,3-propanedi-
amine, N,N'-di(3 hydroxypropyl)-2-methyl-1,3-propanedi ~
amine, N,N'-di(3-methoxypropyl)-2-methyl-1,3-propanedi-
amine, N,N'-di(N,N-dimethyl-2-aminoethyl)-2-methyl
1,3-propanediamine, N,N'-di(N,N-dimethyl-3-am~nopropyl)-
2~methyl-1,3-propanediamine, N,N'-diphenyl -2-methylo
1,3-propanediamine, N,N~-dibenzyl-2-methyl-1,3-propane-
diamine, di(N-i-propylamino-2-methylpropyl)-1,6-hexarldi-
arnLne,
N-cyclohexyl-N'-i-propyl-2-methylpropane-1,3-diamine,
N,N~-di-n-propyl-N'-i-propyl-2-methylpropane-1,3-diam~ne,
N-i-pxopyl-N'-phenyl-2-methylpropane-1,3-diamine,
propyl-N~-(2-hydroxyethyl)-2-methylpropane-1,3-diamine,
N-i-propyl-N '-(3-hydroxypropyl)-2-methylpropane-
1, 3-diamine, N-i-propyl-N' (3 mathoxypropyl)-2-methyl-
propane-1,3-diamine, N-i-propyl-N'-(3-methylam~nopropyl)-
2-methylpropane-1,3-diamine, N-i-propyl~ 3-dimethyl-
am~nopropyl)-2-methylpropane-1,3-diam~ne, 11,14-dimethyl-
1,5,9,13-tetraazapentadecan, 1-cyclohexylamino-2-methyl-
3 piperidylpropane, 2-methyl-1-piperidyl 3-i-propylamino-
propane, 2-methyl-1-morpholino-3-i-propylaminopropane, 2-
methyl- 1-morpholino-3-piperidylpropane,
2,5,12,15-tetramethyl-3,7,10,14 tetraazahexadecan,
2,5,16, 19-tetramethyl-3,7, 14y 18-tetraa~aeicosan,
2,5,17,20-tetramethyl-3,7,11,15,19-pentaazaheneicosan,
N,~'-di-t-butyl-l,3-propanediamine, ~,N'-di-t-butyl-
2-ethyl-1,3-propanediamine, N,~ di-t-butyl-2-n-nonyl-
1,3-propanediamine, N,N'~di-i-propyl~l,3-butanediamine,
M,N'-di-n-butyl-1,3-butanediamirle, N,N '-di-n-butyl-2-n-
propyl-1,3-pentanedia~Line, 1~,N'-di-i-propyl-1,3-butanedi-
am~ne.
N,N' -alkyl-~ub tituted 1,3-propanediamine~ are u~ed, for
example, in the preparation of CFC-free polymer~, ae
catalyst~ for polyurethanes and curing ;~gen~s, e.g~ for
epoxy resin3, a~ components or additive~ in the prepara-
tion o c:ertain types o~ nylon, as ~tarting materials for
polyurea~ or in the preparation of iEinishing agents for

2'~
- 11 - o.z. oOsO/43579
textile fibers and for adhesives.
EXAMPLES
- Preparation of unsaturated amine~ I and subsequent
hydrogena~ion
EXAMPLE 1
26.3 g (0.375 mol) of methacrolein were added
dropwise over an hour to 88.5 g (1.5 mol) of
isopropylamine such that the temperature does not rise
above 35C. qlhe mixture i~ stirred at 40C for an hour
and the crude isopropylaminQ~methacrol~in condansation
product is hydrogenated over 3 g of palladium on active
carbon ~10% Pd) at 50C and 100 bar of hydrogen until
ab~orption of hydrosen i~ complete. Fractional
di ~illation (b.p.- 100C/25 mbar) yielded 52 g ~81 %3 of
N,~'-dii~opropyl-2-methyl 1,3-propanediamine.
EXAMPLE 2
26.3 g (0.375 mol) of methacrolein were added
dropwise over an hour to 88.5 g (1.5 mol) of
isopropylamine such that the temperature doe~ not rise
above 45~C. The mixture i~ ~tirre~ at 40C for an hour
and the crude isopropylamine!methacrolein condensation
product i8 hydrogenated over 0.5 g o~ palladium on active
carbon (10 % Pd) at 50C and a hydrogen pre~surs of 100
bar until absorption of hydrogen i~ complete. Fractional
distillation (b.p.: 100C/25 mbar) yialded 52 g (81 ~) of
N,N~-diisopropyl-2-methyl-1~3-propanediamine.
EXA~P~ 3
61.3 g (0.875 mol3 of methacrolein were added
dropwi~e over an hour ~o 2Q6.5 g (3.5 mol~ of
isopropylamine ~uch ~hat the ~mperature does not ri~e
above 35C. The mixture is stirred at 40C for an hour
and the crude isopropylamine/methacrolein condena~ion
product i~ hydrogenated over 5 g of palladium on active
: carbon (10~ Pd) at 25C an~ atmo3pheric pre~ure until
ah80rption of hy~ro~en i~ complete. ~ractional
distillation (b.p.: 98C/20 ~bar) yieldad 118 g (79%) of
N,N'-diisopropyl-2-mothyl-1,3-propanediami~e.



.


. : . , . .. : . ,

21~ j~OO
- 12 - O. Z . ~050/43579
EXA~LE 4
105 ~ (1.5 mol) o~ methacrolein were added
dropwise over an hour to 3.54 g (~ mol) of isopropylamine
such that the temperature does not ri~e above 45C. The
mixture is 3tirred at 40C for an hour and thP crude
i~opropylamine/methacrolein condensation product i~
hydrogenated, after diluting with 400 ml of
tetrahydxofuran, over 15 g of palladium on active carbon
(10 ~ Pd) at 50C and 100 bar of hydrogen until absorp-
t~on of hydrogen is complete. Fractional distillation(b.p.: 98C/20 mbar) yielded 212 g ~83%) of N,N'-diiso-
propyl-2-methyl-1,3-propanediamine.
EXANPLE ~
By a method 3imilar to Example l, 310 g (83 %) of
N,N~-di-n-bu~yl-2-m~thyl-1,3-propanedia~ine (b.p.:
97C/1 mbar) were obtained from 140 g (2 mol) of
methacrolein and 672 g (8 mol) of n-bu~ylamine (molar
ratio 1 : 4) ovar 15 g of palladium on active carbon (10%
Pd)- . .
EXAMPLE 6
By a mathod similar to Example 4, 346 g (87 %) of
N,~'-di-tert-butyl-2-methyl-1,3-propanediamine (m.p.:
58C; b.p.s 106C/lS mbar) were obtained from 140 ~ (2
mol) o~ methacrolein and 504 g (6 mol) o~ tert-butylamine
(molar ratio 1 : 3) over lS g of palladium on active
carbon (10 % Pd~.
. EXA~PL~ 7
B~ a method ~imilar to Example 1, 459 g (83 %) of
N,N'-dicyclohexyl-2-methyl-1,3-propanediamine (b.p.: 150
to 160~C/1 mbar) were obtained fro~ 153.5 g (2.2 mol~ of
met~acrolein and 870 g (8.8 mol) o~ cyclohe~ylamine
(molar ratio 1 : 4 ) over 15 g of palladium on active
carbon (10 ~ Pd~.
EXAMPLE 8
By a method ~imilar to Example 1~ 398 g (87 ~) of
N,N'-di-t2~ethylhexyl)-2-methyl-1,3-propanediamine
(b.p.: 170C/1 mbar) were obtained from 100 g (1.5 mol)




:, ... ,:: , , .. , :, :: . . . . .......................... .. . - .~:


., .. . , ,. .................. ,, ,,.. .. . . : ... : .,

: : . . . . . - . . .. . , . , ., , ~ . ,.. . : . , : .. .: . .. ..

` - 13 - O.z. OOS0/43579
of me~hacrolein and 754 g (5.8 mol) of 2-ethylhexylamine
(molar ratio 4 : 1) over 15 g of palladium on active
carbon (10 ~ Pd).
E~AMPLE 9
By a method ~ ~ilar to Example 1, 76 g (20 %) of
N,N'-dibenzyl-2~methyl-1,3 propanediamine (b.p.: 59C/1
mbar) were obtained from 112 g (1.6 mol) of methacrolein
and 686 g (6.4 mol) of benzylamine (molar ratio 4 : 1)
over 10 g of palladium on astive carbon (10 ~ Pd).
EXAMPLE 10
By a method ~imilar to Example 1, 376 g (73 %) of
N,N'-di-(N,N-dimethyl-3~aminopropyl)-2-methyl-1,3-
propanediamine ~b.p.: 159C/5 ~bar) were obtained from
140 g (2 mol) of methacrolein and 816 g (8 mol) of N!N-
dimethylprop~lenediamin2 (molar ratio 4 : 1) over 15 g o~
palladium on active carbon (10 % Pd~.
EXA~PLE 11
By a method ~imilar to Ex~mple 1, 167 g (64 ~) of
N,N'-di-(2-aminoethyl~-2-methyl-1~3-diaminopropane
(b.p.: 118 to 130Ctl mbar) were obtained from 102 g
(1.5 mol) of methacr~lein and 901.5 g (15 mol) of ethyl-
enediamine (molar ratio 1 : 10~ over 15 g of palladium on
active carbon (10 ~ Pd).
EXAMPLE 12
By a m~thod ~imilar to Ex~mple 1, 310 g (59 %) of
N,N'-di-(2~hydroxyethylj-2-methyl-1,3-propanadiamine
(b.p.: 162 to 172C/1 mbar).were obta~ned from 140 g
(3 mol) of methacrolein and 488 g (8 mol3 o~ ethanolamine
(molar ratio 1 : 4) over 15 g of palladium on active
3Q carbon (10 % Pdj.
.'
~XANPL~ 13
By a method similar to Example 1, 350 g (69 %) of
N,~'-di (2-methoxyethyl)-2~methyl 1,3-propaned~amine
(b.p.~ 96C/1 mbar) were obtained from 17S g (2.5 mol) of
methacrolein and 750 q (10 mol) of me~hoxyethylamine
(molar ratio 1 : 4) over 15 g of palladium on active




- ,, ~ , :,, - -. , .,: ,. . . . ..



, , ,:::, ~. . . . . . .

~1~5~
- 14 - O.Z. 0050/43579
carbon (10 % Pd).
EXAMPLE 14
By a method sLmilar to Example 1, 150 g (60 %) of
N,N'-dii~opropyl-1,3~butanediamine (b.p.: 43C) were
5obtained from 102 g (1.5 mol) of crotonaldehyde and 344 g
(5.8 mol) of isopropylamine (molar ratio 1 : 4) over 10 g
of palladium on active carbon (10 ~ Pd).
EXAMPLE 15
By a method ~imilar to Example 1, 162 g (81 ~) of
10N,N'-di-n-butyl-1,3-butanediamine (b.p.: 120C/18 mbar)
were obtained from 70 g (1 mol3 of crotonaldehyde and
584 g (8 mol) of N-butylamine (molar ratio 1 : 8) over
15 g of palladium on active carbon (10 ~ Pd).
EXAMPLE 16
15By a method ~Lmilar to ExEmple l, 440 g (67 %) of
N,N'-di-tert-~u~yl-2-nonyl-1,3-propanediami~e
(b.p.: 150C/1 mbar) w~r~ obta$ned from 546 g (2.1 mol3
of 2-nonylacrolein (a~ a 70 % strength ~olu~ion in
decane) a~d 444 g (6 mol~ of tert-butylamine ~molar ratio
201 : 3) over 15 g of palladium on active carbon (10 % Pd).
EXAMPL~ 17
By a method similar to Example 1, 395 g (84 %) of
N,N'~di-tert-butyl-1,3-propanediamine (b.p. 5 132C/
100 mbar) ware obtained from 140 g (2.5 mol) of acrolein
25and 732 g (10 mol) of tert-butylamine (molar ratio 1 : 4)
over I5 g of palladium on active carbon (10 ~ Pd).
. E~AMPL~ 18
: ~By a~method ~imilar to ~ample 1, 29 g ~80 ~) of
1,3-dipiperidyl-2-methylpropane (b.p.: 90 ~o
30: 100C/l mbar) were obtained from 10 g (0.14 mol) of
mathacrolein and 50 g (0.6 mol) of piperidine (molar
:~ ratio 1 s 4.2) over 2 g of Pd on active carbon (10 % Pd3.
EXANP~ I9
By a method ~imilar to Example 1, 250 g (40 %) of
35N~N~N',N'-tetra-n-butyl-2-methyl-1,3-propa~ediamine
(~.p.: 125C/1 mbar) were obtained from 140 g (2 mol) of
methacrolein and 155 g (12 mol) o~ di n-butylamine (molar


'' ~
' " ,.

- 15 - O.~. 0050/43579
ratio 1 : 6) over 15 g of Pd on active carbon (10 % Pd).
EXAMPLE 20
By a method similar ~o Example 1, 149 g (50 %) of
N,N,N',N'-tetra-n-propyl-1,3-propanediamine (b.p.: 137C~
5were obtained from 68 g (1.2 mol) of acrolein and 740 g
(7.3 mol) o~ di-n-propylamine (molar ratio 1 : 6) ovar
15 g of Pd on active carbon (10 % Pd).
COMP MISON EXAMPLE
According to J. Am. Chem. Soc. 74, tl952) 2016 to
102018 Table 1, 10th example
35 g (0.5 mol) of methacrolein were added
dropwise over an hour to a solution of 25 g of anhydrou~
pota~sium carbonate in 147.5 g (2.5 mol) of
isopropylamine and from 5 to 10QC.-After filtering off
15the pota~sium carbonate, the crude isopropylamine/-
methacrolein conden~ation product wa~ hydroge~ated over
5 g of Raney ~ickel freed from water at 105C and 70 bar
of hydrogen over 6 h. Fractional distillation (b.p.: 80-
100C/35 mbar) yielded 47 g ~50 ~i) of N,~'-diisopropyl-2-
2~methyl-1,3-diamlne. The literature yield is 58 %.
Examples of the continuoue hydrogenation of the
Schiff ~ 9 base~:
EXAMPL~ 21
A vertically arranged tubular reactor ~diameter:
2514 mm, packing height: 50 cm, oil-heated double jaak~t)
wa~ packed with 75 ml (47.6 g~ of a catalyst containing
O.5 % Pd on y-alumina in the form of 4 mm strands
(preparation of cataly~t by pora LmmersiOn of yoalumina
using aqueou~ palladium nitrate ~olution and drying at
30120~C). The catalyst i9 reduced ln situ.
20 g of a ~olution of 155 g (2.6 mol) of
iscpropylamine and 61 g (0.88 mol) of methacrolein in
-200 g of t~trahydrofuran are pa~ed through the reactor
hourly from the bottom upward~. 10 (s~t~pO) of hydrogen
35are pa~sed through th~ reactor hourly at a pre~ure of 80
bar. The temperature i8 70C. The: di~charged reactio~
produat i8 decompreY~ed to atmospheric pre3sur~. The
.




,

- 16 - O.Z. 0050/43579
yield of N,N' diisopropyl-2-methyl-1,3-diaminipropane i~
80 %.
EXAMP~E 22
N,N,N',N',2-pentamethyl-1,3-diamlnopropane
A vertically arranged tu~ular reactor (diameter:
14 mm, packing height: 50 cm, oil-heated double jacket)
wa~ packed with 75 ml (47.6 g) of a cataly~t containing
O.5 ~ Pd on y-alumina in the form of 4 mm ~trands
(preparation of catalyst by pore imm~r~ion of ~-alumina
. using aqueous palladium nitrate ~olution and drying at
120C). The cat~ly~t i~ reduced in ~itu.
lOQ ml of a 20% strength ~olution of methacrolein
in tetrahydro~uran and 60 ml of dimethylamine are pa~ ed
through the reactor hourly from the bottom upward~. 10
(~.t.p.) of hydrogen are pa~ed through the reactor
hourly at a pre ~ur~ of 75 bar. The temperature is 70C.
The discharged reaction product is decompressed to
atmo~pheric pressure, fr2ed from dL~ethylamlne and
distiIled. Tha di~charged reaction product collected over
the course of an hour yield~, after distillation at
70C/100 mbar, 28 g of N,N,N~ 2-pe~tamethyl-1,3-
diaminopropane. Ths yield iB 85 96.
- Transam~nation of the unsaturated amines I and
ubsequent hydrogenation
EXA~hl~ 23
168 g t 2, 4 mol ) of methacrolein were added
dropwi~e in th~ course of an hour to 354 g l6 mol3 of
i~opropylamine uch that the temperature doe~ not exc:eed
35C~ Ths mixtur~ i~ stirred at 40C for an hour. This
crude i~opropylamine/methacrol~i~ conden~ation product i~
treated at 40C with 287 g (2.9 mol) of cyclohexylamine
and i~opropylamlne i~ sLmultaneou~ly di~tilled o~f. The
un~ymmetrically ~ubst~tuted diamine precursor thus
o~tained i~ diluted with 400 ml o~ tetrahydrofuran and
hydrogenated over 15 g of Pd on active carbon (10 % Pdj
at 50C and 100 bar until absorption o~ hydro~en i~
completo. Practional di tillation (b-p-. 99 to


,
.




. : , -,, ~

. ~

- 17 - O.Z. OOS0/43579
106C/1 mbar) yielded 311 g (73 ~) of N-iRopropyl-N'-
cyclohexyl-2-methyl-1,3-propanediamine.
EX~MPLE 24
By a method ~imilar to Example 23, 191 g (52 %)
of 11,14-dimethyl-1,5,9,13-tetrsa2apentadecan (b.p.: 188
to l90~C/5 mbar) were obtained from 105 g (1.5 mol) of
methacrolein, 267 g (4.5 mol) of isopropylamine and
196.5 g (1.5 mol) of dipropylenetriamine (molar ratio
1 : 3 : 3) over 15 g of active carbon (10 % Pd) and in
400 ml of tetrahydrofuran.
~XAMPLE 25
By a method similar to Example 23, S3 g (52 %) of
dl~ isopropylamino-2-methylpropyl)-1,6 hexanediamine
(~.p.s 170C/1 mbar) wsre obtained from 50 g (Q.71 mol)
of methacrolein, 176 g ~2098 mol) of isopropylaminQ and
41.5 g (0.35 mol) o~ hexamethylsnediamine (molar ratio
2 : 8 : 1) over 5 g of palladium on active carbon
(10 % Pd) and in 50 ml of tetrahydrofuran.
EXAMPLE 26
By a method sLmilar to Ex2mpla 23, 171 g (51 %)
of N-isopropyl-N'-(N-methyl-3-aminopropyl)-2-methyl-1,3-
propanediamine (B.P.: 90 to 96C/l mbar) were obtained
from 116 g (1.7 mol) of methacrolein~ 245 g (4.2 mol) of
isopropylamine and 176 g (2 mol) of N-methylpropylenedi-
amino (molar ratio 1 : 2.5 ~ ) over 10 g of palladium
on acti~e carbon (10 ~ Pd ) a~ in 40Q ml of tetrahydro-
furan.
: EXANPLE 27
By a method similar to exampl~ 23, 61 g (47 %) o~
1-i~opropylamino-2-me~hyl-3-morpholinspropane
(b.p.s 75~C) wers obtained from 61.3 g (0.78 mol) o
methacrolein, 206 g (3.5 mol) of i~opropylamine and 76 g
(0.8~ mol) of morpholin~ (mol~r ratio 1 : 4 ~ 1) over
10 g of palladium on active carbon (10 ~ Pd).
3S E~ 28
By amethodsimilar to E~cample 23, 56 g (50 %) of
l-cyclohexylamino-2-methyl-3-piperidylpropane




, ' :. ' ' . ' ' ' . . .'. ' .

- c2~J ~
`18 - O.Z. 0050/43579
(b.p.. 120C/1 mbar) were obtained from 35 g (0.5 mol) o
me~hacrolein, 170 g (2 mol) of piperidine and 43.5 g
(0.5 mol~ of cyclohexylamine (molar ratio 1 : 4 : 1) over
3 g of Pd on active carbon (10 ~ Pd) and in 50 ml of
S tetrahydrofuran.
EXAMPLE 29
By a method ~imilar t~ Example 23, 17 g (16 %) of
l-morpholino-2-methyl-3-piperidylpropane (b.p.~ 110C/
1 mbar) were obtained from 35 g (0.5 mol) of
10methacrolein, 170 g (2 mol) of piperidine and 43.5 g
(O.S mol) of morpholine (molar ratio 1 : 4 : 1~ over 3 g
of Pd on ac~ive carbon (10 % Pd).




'


,

'
.. ... .




- , ., . . ., , . . ~..... .. ", . , : . , . .. ; . ...
.. ,: ., . . ~. . , .. . . . : , . . ,, :. ~, :.. 1 ., .. , . , . .,; . , .. :