Europaisches Patentamt

3 0 1 42 8 6 8
European Patent Office (ii) Publication number:
B1
Office europeen des brevets

EUROPEAN PATENT SPECIFICATION

(§) Date of publication of patent specification: 01.06.88 int. ci.4: C 07 C 85/08, C 07 C 8 7 / 0 4 ,

C 07 C 8 7 / 1 4
@ Application number: 84114133.6
@ Date of filing: 22.11.84

Process for producing tertiary amines.

Priority: 22.11.83 JP 218689/83 Proprietor: NIPPON OIL AND FATS COMPANY,

19.09.84 JP 194758/84 LIMITED
10-1, Yuraku-cho 1-chome
Chiyoda-ku Tokyo (JP)
Date of publication of application:
29.05.85 Bulletin 85/22
Inventor: Koyama, Motoo
No. 7-284, Otodacho
Publication of the grant of the patent: Ikoma-shi Nara (JP)
01.06.88 Bulletin 88/22 Inventor: Takahasni, Fujio
No. 4-12-1, Oshonishimachi
Amagasaki-shi Hyogo (JP)
Designated Contracting States: Inventor: Noji, Yukihiro
BEDEFRGBITNL No. 4-12-1, Oshonishimachi
Amagasaki-shi Hyogo (JP)
Inventor: Niiyama, Kaoru
References cited: No. 2-53-1-304, Mukonosonishi
BE-A-672711 Amagasaki-shi Hyogo (JP)
FR-A-2 231663 Inventor: Miyata, Toyomi
FR-A-2 289 486 No. 2-53-1-402, Mukonosonishi
CQ FR-A-2349 565 Amagasaki-shi Hyogo (JP)
GB-A-2 025 408
00 US-A-4207 260
Representative: Hansen, Bernd, Dr.rer.nat. et al
Hoffmann, Eitle & Partner Patentanwalte
CO Arabellastrasse 4
CM D-8000 Miinchen 81 (DE)

Note: Within nine months from the publication of the mention of the grant of the European patent, any person may
give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall
Q. be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been
LJJ paid. (Art. 99(1 ) European patent convention).
Courier Press, Leamington Spa, England.
 0 142 868

Description

The present invention relates to a process for producing tertiary amines. More particularly, the
invention relates to a process for producing tertiary amines of high purity and quality in high yield by
5 reductively alkylating primary or secondary amines with hydrogen and an aldehyde in the presence of
certain hydrogenating catalysts.
Aliphatic tertiary amines are useful as corrosion inhibitors and oil additives. They are also useful as
intermediates for the production of quaternary ammonium salts and amphoteric surface active agents such
as disinfectants, fungicides, sanitary agents, retarders in dyeing, and antistatic agents. As the use of
io aliphatic tertiary amines is expanding today, the requirements for their quality as intermediates are
becoming increasingly stringent. Among other things, tertiary amines are required to have minimum levels
of impurities that may impart undesired colors or smells to the final product.
Various methods are known for methylating primary or secondary amines: (A) methylation with formic
acid and formaldehyde (Organic Syntheses, Collective Volume 4, p. 723, John Wiley & Sons, Inc. (1963)),
'5 (B) methylation with hydrogen and formaldehyde (Organic Syntheses, Vol. 4, p. 174, John Wiley & Sons,
Inc. (1963)). Higher alkyl methylamines may be produced by (C) reaction between higher alkyl halides and
methylamine (U.S. Patent 3,379,764) or (D) reductive amination between higher alcohols and methylamine
(Japanese Patent Application (OPI) No. 19604/1977, Japanese Patent Publication Nos. 849/1982 and
55704/1982) (the symbol "OPI" as used herein means an unexamined published Japanese patent
20 application).
Conventionally, the higher alkyl dimethylamines are manufactured by method (C), which involves a
reaction that entirely differs from the one used in the process of the present invention. In method (D),
higher aldehyde produced by the dehydrogenation of a higher alcohol is reacted with methylamine.
However, because of the high reaction temperatures involved and the high yield of by-products, the quality
25 of the tertiary amines produced by method (D) is very poor.
Method (A) is unable to give a sufficient conversion of formaldehyde unless formic acid is used in large
excess. Since formic acid is expensive, this method is not commercially useful except in the case of
producing special tertiary amines.
Method (B) uses the same type of reaction as is employed in the process of the present invention. This
30 method has so far been considered unsuitable for implementation on an industrial scale because the
reaction yield and the quality of .the product are much inferior to those obtained in method (C). However,
researchers have made various efforts to improve this method since it has potentially a wide scope of
applications, and an increase in the reaction yield and the product quality might render the method
cost-effective. An example of the studies made along this line is shown in Organic Reactions, Vol. 4, p. 244
35 and p. 248, John Wiley & Sons, Inc. (1948). According to this paper, yields no higher than 90% were
obtained when primary or secondary amines were reacted with hydrogen and formaldehyde in the
presence of Raney nickel or platinum catalyst. United States Patent No. 3,136,819 shows a method for
improving a yield by using an additional catalyst in the reaction such as a short chain monocarboxylic acid
or a short chain hydroxy monocarboxylic acid. However, when a primary amine having an alkyl group of 8
40 or more carbon atoms was subjected to reaction in the presence of a Raney nickel catalyst, the reaction
yield was low and the resulting product contained only about 85% of a tertiary amine.
The present inventors have made detailed studies with respect to the alkylation of primary or
secondary amines with hydrogen and an aldehyde, and obtained the following observations.
When the primary or secondary amine is reacted with an aldehyde, 1-hydroxyalkylamine
45
OH
I /
(-C-N )
50
is formed as an intermediate, and an imine (—CH=N —) is also formed as a result of intramolecular
dehydration. These are highly reactive compounds. However, if the reaction system has an insufficient
reductive action, the hydrogenation of 1-hydroxyalkylamine or imine is unlikely to occur; instead, they
react with the primary or secondary amine present in a large amount in the reaction system, thereby
55 forming an unstable polymer such as polyalkylene-polyamine which is deposited on the hydrogenation
catalyst and inhibits the diffusion of the amine into the catalyst surface. In an extreme case,
1-hydroxyalkylamine or imine may also react with the active methylene group of the resulting
polyalkylenepolyamine. The aldehyde may also react with this active methylene group. According to the
finding of the present inventors, the aldehyde reacted with 1-hydroxyalkylamine as well as the
so polyalkylenepolyamine, and the resulting complex by-products not only reduced the yield of the intended
tertiary amine, but also caused a malodor, stain, and gradual coloration in the amine.
Based on these observations, the present inventors made various studies with a view toward obtaining
a hydrogenation catalyst that satisfied the following three requirements; good dispersion in the amine
layer (reactive phase), high stability of the dispersion against moisture, and great hydrogenating ability.
65 The present invention has been accomplished as a result of these studies.
 0 142 868

The present invention provides a process for producing a tertiary amine by alkylating an amine of
formula (I)

R1R2N[(CH2)nNH]mR3 (I)
5
wherein R1 represents a linear or branched alkyl or alkenyl group having from 8 to 24 carbon atoms; R2 and
R3 each represents a hydrogen atom, or a linear or branched alkyl or alkenyl group having from 8 to 24
carbon atoms; m is 0 or an integer of 1 to 5 and n is 2 or 3, provided that when m=0, at least one of R2 and
R3 represents a hydrogen atom with an aldehyde of formula (II)
w
0
II
R4CH (II)

15 wherein R4 represents a hydrogen atom, a saturated or unsaturated, linear, branched or cyclic aliphatic
hydrocarbon group having from 1 to 24 total carbon atoms, an aromatic group-substituted aliphatic
hydrocarbon group having 24 or less total carbon atoms, or a substituted or unsubstituted aromatic
hydrocarbon group having 24 or less total carbon atoms.
According to the present invention, a hydrogenation catalyst having from 0.1 to 10 wt% of at least one
20 of Co, Ni, Ru, Rh, Pd, and Pt supported on pulverized or granular carbon is provided in a reaction zone at the
concentration of from 5 to 5,000 ppm of the catalyst metal based on the amount of the amine of formula (I),
and the reaction is performed at a temperature of from 80 to 250°C and a hydrogen pressure of at least 2
kg/cm2 (gauge) while the aldehyde is continuously supplied to the reaction zone.
Illustrative amines of formula (I) include octylamine, dodecylamine, tetradecylamine, hexadecylamine,
25 octacdecylamine, docosylamine, oleylamine, linolylamine, and erucylamine. Amine mixtures may also be
used, including cocoalkyl amine, tallowalkyl amine, hydrogenated tallowalkyl amine, rapeseed-oil-
alkylamine, dicocoalkyl amine, ditallowalkyl amine, dihydrogenated tallowalkyl amine, 2-aminoethyl
cocoalkyl amine, 2-aminoethyl tallowalkyl amine, 3-aminopropyl cocoalkyl amine, 3-aminopropyl
tallowalkyl amine, N,N'-dicocoalkyl ethylenediamine, N-cocoalkyl N'-tallowalkyl ethylenediamine, N-
30 cocoalkyl diethylenetriamine, N-tallowalkyl diethylenetriamine, N-cocoalkyl dipropylenetriamine, N-tallow-
alkyl dipropylenetriamine, N-cocoalkyl tripropylenetetramine, N-tallowalkyl tripropylenetetramine, N-coco-
alkyl tetrapropylenepentamine, N-tallowalkyl tetrapropylenepentamine, N-cocoalkyl pentapropylene-
hexamine, and N-tallowalkyl pentapropylenehexamine. These amines may be used either individually or in
combination.
35 Illustrative aldehydes of formula (II) include saturated or unsaturated, linear, branched or cyclic
aliphatic aldehydes such as formaldehyde, acetaldehyde, propanal, hexanal, 2-ethylhexanal, 2-hexenal,
2-nonenal and cyclohexylaldehyde; aromatic group-substituted aliphatic aldehydes such as phenylacet-
aldehyde and 3-phenylpropanal; aromatic aldehydes such as benzaldehyde, o-, m- or p-tolualdehyde,
p-methoxybenzaldehyde, p-chlorobenzaldehyde and 1-naphthylaldehyde. These aldehydes may be used
40 either independently or in combination. The aldehydes may be used as an aqueous solution or a
non-reactive solvent solution [examples of the solvent including an alcohol (e.g., methanol, ethanol), an
ether (e.g., tetrahydrofuran) and a hydrocarbon (e.g., hexane, cyclohexane)], if desired.
The aldehyde is used in an amount of from 1 to 1.5 mols, and preferably 1 to 1.05 mols, per mol of
active hydrogen on the amino or imino group of a primary or secondary amine. If the amount of the
45 aldehyde used is less than 1 mol per mol of the active hydrogen defined above, the primary or secondary
amine remains unreacted in the final product. If the amount of the aldehyde is more than 1.5 mols per mol
of the'active hydrogen, the process is not cost-effective and an extra and prolonged step is required for
removing the residual aldehyde by reduction.
The hydrogenation catalyst used according to the present invention comprises from 0.1 to 10 wt% of
so Ni, Co, Ru, Rh, Pd or Pt as supported on pulverized or granular carbon. Such a hydrogenation catalyst may
be prepared by any conventional method, such as the one shown in Advances in Catalysis, Vol. 20, p. 112
(1 969). The hydrogenation catalyst is used in the present invention at the concentration of 5 to 5,000 ppm of
the catalyst metal based on the amount of the starting amine. Even in a reaction system comprising both
water and amine layers, the hydrogenation catalyst shown above is dispersed predominantly into the
55 amine layer, and its dispersion into the aqueous layer is negligible.
Alumina, silica, and diatomaceous earth are not desired as supports for the hydrogenation catalyst
since they do not provide a good dispersion of the catalyst in the reaction system concerned. Metals and
metal oxides such as Raney nickel, Raney cobalt, platinum oxide, platinum black, and palladium black are
known as hydrogenation catalysts having an extremely high activity, but they do not provide good results
60 in the reaction of the present invention.
The process of the present invention uses an autoclave and performs the intended reaction at a
hydrogen pressure of at least 2 kg/cm2 (gauge), preferably from 5 to 50 kg/cm2 (gauge), and at a
temperature of from 80 to 250°C, and preferably from 100 to 250°C. If the hydrogen pressure is less than 2
kg/cm2 (gauge) or if the reaction temperature is less than 80°C, the desired hydrogenation does not proceed
65 satisfactorily, and instead, by-products such as 1-hydroxyalkylamine or its polymer and imine are formed
 0 142 868

in increasing amounts. If the reaction temperature exceeds 250°C, by-products such as a polyalkylamine
and hydrocarbon are formed in increasing amounts due to the dehydrogenation of the starting amine.
The aldehyde may be added by any method that permits its continuous or periodic addition. Usually,
the aldehyde is supplied in small portions into the reaction zone of a reactor by means of a compressor.
5 If an aqueous solution of the aldehyde is likely to cause a great accumulation of water during the
reaction, or if the reaction is expected to produce a large amount of water as a by-product, hydrogen may
be released or circulated so as to discharge water out of the system while the reaction is being carried out.
An illustrative method for implementing the present invention is shown below. An autoclave equipped
with a stirrer, a compressor, and an optional gas circulator with a cooling condenser is charged with the
'0 starting amine and a hydrogenation catalyst. The temperature in the autoclave is elevated to the desired
level under stirring, and after the atmosphere of the reactor is replaced by hydrogen, an additional amount
of hydrogen is supplied to a predetermined pressure. Subsequently, the aldehyde is fed into the autoclave
under pressure, and the amine is reductively alkylated at the predetermined hydrogen pressure. When the
removal of the accumulated water from the reaction system is desired to decrease the partial pressure of
15 the water in the reaction system and to accelerate the reaction, a hydrogen gas circulator equipped with a
cooling condenser is used to discharge the condensed water out of the system. After all of the aldehyde has
been fed into the reactor, the reaction is continued for a given period while the temperature and hydrogen
pressure are held constant.
If amine alkylation is performed by the method of the present invention, the intended reaction
20 proceeds in a substantially quantitative manner and the formation of by-products that may impair the
quality of the end compound is negligible. Therefore, a crude tertiary amine product that is substantially
colorless and odorless is obtained. The amine alkylation ratio is at least 97% irrespective of the type of the
starting primary or secondary amine. The distillation yield is 95% or more, and a tertiary amine having a
purity of 98% or higher can be obtained.
25 The tertiary amine produced by the method of the present invention is highly stable against heat and
light; it withstands a heat resistance test at 50°C and a daylight exposure test for at least 6 months without
experiencing any change in color or smell.
This tertiary amine can be used to prepare amine oxides and quaternary ammonium salts. All the
products are substantially colorless and odorless and have no problems at all in appearance or quality.
30 The advantages of the present invention will become more apparent by reading the following working
examples and comparative examples.

Examples 1 to 17
An autoclave (capacity: 2 liters) equipped with a turbine stirrer and a compressor was charged with a
35 starting primary or secondary amine (800 g in Examples 1 to 9, and 400 g in Examples 10 to 17) and a
hydrogenation catalyst (for its type, see Table 1). The temperature in the autoclave was elevated to a
predetermined level under agitation at 900 rpm with the turbine stirrer. The atmosphere of the autoclave
was replaced by hydrogen, and an additional volume of hydrogen was supplied to a predetermined level.
While an aldehyde was pumped into the autoclave over a predetermined period, the starting amine
40 was reductively alkylated at a predetermined temperature and hydrogen pressure. After the completion of
the addition of the aldehyde, the reaction was continued for 30 minutes. After completion of the reaction,
the hydrogenation catalyst was filtered off and the aqueous layer was separated to obtain a crude tertiary
amine. In some Examples, the crude tertiary amine was purified by vacuum distillation. The reaction
conditions used in the respective Examples and the analytical values for the resulting products are shown
45 in Table 1.
As is clear from Table 1, all the crude tertiary amines obtained were substantially colorless (APHAO0).
The purified tertiary amines were completely colorless and transparent. None of the purified and crude
tertiary amines had a smell other than that of amines. The crude tertiary amines had a purity of at least
98%, whereas the purified tertiary amines were at least 99% pure. The purified tertiary amines were stored
so at 50°C for 6 months. They were also subjected to a daylight exposure test outdoors for 6 months. In either
test, the amines experienced no change in appearance or smell.

55

60

65
 0 142 868

Example 18 to 40
A 50 liter autoclave equipped with a stirrer, a hydrogen circulator with a condenser and a compressor
was charged with 20 kg of a starting amine and a hydrogenation catalyst. The temperature in the autoclave
was elevated to a predetermined level under agitation. After replacing the atmosphere in the autoclave
5 with hydrogen, an additional volume of hydrogen was supplied to a predetermined level. The starting
amine was hydrogenated while an aldehyde was pumped into the autoclave over a predetermined period.
After the completion of the addition of the aldehyde, the reaction was continued for 30 minutes. The
reaction was performed at a constant temperature and pressure while hydrogen was circulated and water
that was condensed was removed from the reactor. After completion of the reaction, the hydrogenation
w catalyst was filtered off to obtain a crude tertiary amine. In some Examples, the crude amine was purified
by vacuum distillation. The reaction conditions used in the respective Examples and the analytical values
for the resulting products are shown in Table 2.
As is clear from Table 2, all the crude tertiary amines obtained were substantially colorless (APHA<30),
and so were the purified tertiary amines. Neither the crude nor purified tertiary amines had a smell other
is than that of the amines. The product tertiary amines, whether they were crude or purified, had a purity of at
least 98%.
The purified tertiary amines were stored at 50°C for 6 months. They were also subjected to a daylight
exposure test outdoors for 6 months. In neither test did the amines undergo a change in appearance or
smell.
20

25

30

35

40

45

50

55

60

65
 0 142 868

Example 41
A 2 liter conical flask was charged with 500 g of dodecylamine, which was heated to 70°C under
agitation. The flask was also charged with 219 g of 37% aqueous formaldehyde (0.5 mol per mol of the
active hydrogen in dodecylamine) that was added dropwise over a period of 30 minutes. After the addition
5 of aqueous formaldehyde, the mixture was stirred for 1 hour at 90°C, and thereafter, the aqueous layer was
separated.
An autoclave which was the same as used in Example 1 was charged with the condensation product of
dodecylamine with formaldehyde, and a hydrogenation catalyst [5% Pd-C: 0.5 g, or 0.1 wt%. for the
starting amine (i.e., 50 ppm of Pd based on the amount of starting amine)]. The mixture was heated at 160°C
to under agitation with the turbine stirrer at 900 rpm. After replacing the system atmosphere with hydrogen,
an additional volume of hydrogen was supplied until the gauge pressure in the reactor reached 10 kg/cm2.
Hydrogen absorption began immediately after the supply of hydrogen, and its pressure was held constant
throughout the reaction. Two hours later, the hydrogen absorption ceased. Thereafter, 219 g of 37%
aqueous formaldehyde (0.5 mol per mol of the active hydrogen in dodecylamine) was pumped in over a
15 period of 2 hours, while the hydrogen pressure was kept at 10 kg/cm2G (gauge). Under the same
conditions, the reaction was continued for 1 hour. After the completion of the reaction, the hydrogenation
catalyst was filtered off and the aqueous layer was separated to obtain a crude tertiary amine. This amine
was substantially colorless (APHA<30). It did not have a smell other than that of amines. The purity of the
crude product was 97.4%. The crude amine was purified by vacuum distillation. The distillation yield was
20 95.2%. The purified amine had a purity of 98.1% and was completely colorless (APHA<10).
The purified tertiary amine was stored at 50°C for 6 months. It was also subjected to a daylight
exposure test outdoors for 6 months. In either test, the amine experienced no change in appearance or
smell.
This experiment shows that a tertiary amine of good quality can be obtained in high yield even if part of
25 the formaldehyde is first added and the remainder is continuously added in the subsequent hydrogenation
reaction.

Example 42
A hydrogenation reaction was conducted as in Example 41. Dodecylamine (500 g) was used as the
30 starting amine. As an aldehyde, 60% aqueous acetaldehyde was added dropwise in an amount of 198 g (0.5
mol per mol of the active hydrogen in dodecylamine). In the subsequent reaction, the same amount of 60%
aqueous acetaldehyde was pumped into the reaction system.
The resulting crude tertiary amine was substantially colorless (APHA<30). It had no smell other than
that of amines, and its purity was 97.7%. The crude product was purified by vacuum distillation. The
35 distillation yield was 96.1 %. The purified tertiary amine had a purity of 98.4% and was completely colorless
(APHA<10) and transparent.
The purified tertiary amine was stored at 50°C for 6 months. It was also subjected to a daylight
exposure test outdoors for 6 months. In neither test did the amine undergo any change in appearance or
smell.
40 This experiment also shows that a tertiary amine of good quality can be obtained in high yield even if
part of an aldehyde is first added and the remainder is continuously added in the subsequent
hydrogenation reaction.

Comparative Examples 1 to 16
45 In Comparative Examples 1 to 9, the hydrogenation reaction was conducted as in Example 1, except
that the amount of the starting amine used was 800 g (Comparative Examples 1 to 5) or 400 g (Comparative
Examples 6 to 9), and the catalyst used was Raney nickel (Comparative Examples 1 and 6), palladium black
(Comparative Examples 2 and 7), platinum supported on silica (Comparative Examples 3 and 8), palladium
supported on diatomaceous earth (Comparative Examples 4 and 9), or platinum oxide (Comparative
so Example 5 ) . .
In Comparative Examples 10 to 14, the hydrogenation reaction was conducted as in Example 18, except
that the catalyst used was platinum oxide (Comparative Example 13) and Raney nickel (Comparative
Examples 10, 11, 12 and 14).
In Comparative Examples 15 and 16, the reaction was started with ail the necessary amount of an
55 aldehyde. The catalyst used was palladium on carbon which is included within the scope defined by the
present invention. The reductive alkylation reaction was conducted as in Example 1, but no aldehyde was
added during the reaction.
In each Comparative Example, the resulting crude tertiary amine was treated as in Examples 1 to 42:
the hydrogenation catalyst was filtered off, and after separating the aqueous layer, the product was purified
so by vacuum distillation. The reaction conditions used in the respective Comparative Examples and the
analytical values for the resulting products are shown in Table 3.

65

11
 0 142 868
As is apparent from Table 3, the distillation yields and the purities of the product tertiary amines were
lower than those obtained in Examples 1 to 42. The purified tertiary amines were colorless and transparent
just after distillation, but upon standing at room temperature for 1 month, they acquired appreciable
shades of color. This color staining proceeded further when the amines were left at 50°C or exposed to a
5 daylight exposure test. The amines produced in the Comparative Examples smelled of aldehydes or had
other unpleasant odors just after distillation. The undesired odors became intense when they were left at
50°C or subjected to a daylight exposure test.
The results of Comparative Examples 1 to 9 show that catalysts outside the scope of the present
invention do not give good results in reductive alkylation of amines. Data of Comparative Examples 10 to
to 14 show that the effectiveness of catalysts outside the scope of the present invention is not enhanced to the
desired level even if hydrogen is circulated for removing water during the reaction. Comparative Examples
15 and 16 show that the aldehyde must be continuously added throughout the reductive alkylation
reaction.

is Claims

1. A process for producing a tertiary amine by alkylating an amine of formula (I)

R1R2N[(CH2)nNH]mR3 (I)
20
wherein R1 represents a linear or branched alkyl or alkenyl group having from 8 to 24 carbon atoms; R2 and
R3 each represents a hydrogen atom, or a linear or branched alkyl or alkenyl group having from 8 to 24
carbon atoms; m is 0 or an integer of 1 to 5 and n is 2 or 3, provided that when m=0, at least one of R2 and
R3 represents a hydrogen atom with an aldehyde of formula (II)
25
0
II
R4CH • (II)

30 wherein R4 represents a hydrogen atom, a saturated or unsaturated, linear, branched or cyclic aliphatic
hydrocarbon group having from 1 to 24 total carbon atoms, an aromatic group-substituted aliphatic
hydrocarbon group having 24 or less total carbon atoms, or a substituted or unsubstituted aromatic
hydrocarbon group having 24 or less total carbon atoms, wherein a hydrogenation catalyst having from 0.1
to 10 wt% of at least one of Co, Ni, Ru, Rh, Pd, and Pt supported on pulverized or granular carbon is
35 provided in a reaction zone at the concentration of from 5 to 5,000 ppm of the catalyst metal based on the
amount of the amine of formula (I), and the reaction is performed at a temperature of from 80 to 250cC and
a hydrogen pressure of at least 2 kg/cm2 (gauge) while the aldehyde is continuously supplied to the
reaction zone.
2. A process as in claim 1, wherein the hydrogen pressure is from 5 to 50 kg/cm2 (gauge).
40 3. A process as in claim 1, wherein the reaction is performed at a temperature of from 100 to 250°C.
4. A process as in claim 2, wherein the reaction is performed at a temperature of from 100 to 250°C.
5. A process as in claim 1, wherein the aldehyde is used in an amount of from 1 to 1.5 mols per mol of
active hydrogen of the amine of the formula (I).
6. A process as in claim 5, wherein the aldehyde is used in an amount of from 1 to 1.05 mols per mol of
45 active hydrogen of the amine of the formula (I).

Patentanspriiche

1. Verfahren zur Herstellung eines tertiaren Amins durch

so — Alkylieren eines Amins der Formel (I)
R1R2N[(CH2)nNH]mR3 (I)

wobei R1 eine geradkettige oder verzweigte Alkyl- oder Alkenylgruppe mit 8 bis 24 Kohlenstoffatomen
55 darstellt; R2 und R3 stellen jeweils ein Wasserstoffatom, oder eine geradkettige oder verzweigte Alkyl- oder
Alkenylgruppe mit 8 bis 24 Kohlenstoffatomen dar; m ist 0 oder eine ganze Zahl zwischen 1 und 5 und n ist
2 oder 3, vorausgesetzt, dass, wenn m=0, zumindest eine der beiden Gruppen R2 und R3 ein
Wasserstoffatom darstellt,
— mit einer Aldehydverbindung der Formel (II)
60
O

R4CH (II)

65 wobei R4 ein Wasserstoffatom, eine gesattigte oder ungesattigte, geradkettige, verzweigte oder zyklische,

14
 0 142 868

aliphatische Kohlenwasserstoffgruppe mit insgesamt. 1 bis 24 Kohlenstoffatomen, eine mit einer

aromatischen Gruppe substituierte aliphatische Kohlenwasserstoffgruppe mit insgesamt 24 oder weniger
Kohlenstoffatomen, oder eine substituierte oder unsubstituierte aromatische Kohlenwasserstoffgruppe mit
insgesamt 24 oder weniger Kohlenstoffatomen darstellt,
5 — wobei ein Hydrierkatalysator, der zwischen 0,1 und 10 Gew.% zumindest eines Elementes aus der
Reihe Co, Ni, Ru, Rh, Pd und Pt, getragen von pulverisiertem oder gekorntem Kohlenstoff, enthalt, einer
Reaktionszone zugefuhrt wird, wobei die Konzentration des katalystisch aktiven Metalls zwischen 5 und
5.000 ppm, bezogen auf die Menge des Amins mit der Formel (I), betragt, und die Reaktion bei einer
Temperatur von 80 bis 250°C und einem Wasserstoffdruck von mindestens 2 kg/cm2 (Gauge) durchgefuhrt
w wird, wahrend die Aldehydverbindung kontinuierlich der Reaktionszone zugefuhrt wird.
2. Verfahren nach Anspruch 1, wobei der Wasserstoffdruck im Bereich zwischen 5 und 50 kg/cm2
(Gauge) liegt.
3. Verfahren nach Anspruch 1, wobei die Reaktion bei einer Temperatur zwischen 100 und 250°C
durchgefuhrt wird.
is 4. Verfahren nach Anspruch 2, wobei die Reaktion bei einer Temperature zwischen 100 und 250°C
durchgefuhrt wird.
5. Verfahren nach Anspruch 1, wobei die Aldehydverbindung in einer Menge von 1 bis 1,5 Mol pro Mol
aktiven Wasserstoffes des Amins der Formel (I) eingesetzt wird.
6. Verfahren nach Anspruch 5, wobei die Aldehydverbindung in einer Menge von 1 bis 1,05 Mol pro
20 Mol aktiven Wasserstoffes des Amins der Formel (I) eingesetzt wird.

Revendications

25 1. Un procede de production d'une amine tertiaire par alkylation d'une amine de formule (I)
R1R2N[(CH2)nNH]mR3 (I)

dans laquelle R1 represente un groupe alkyle ou alcenyle lineaire ou ramifie ayant de 8 a 24 atomes de
30 carbone; R2 et R3 represented chacun un atome d'hydrogene ou un groupe alkyle ou alcenyle lineaire ou
ramifie ayant de 8 a 24 atomes de carbone; m est 0 ou un nombre entier de 1 a 5 et n est 2 ou 3, a la
condition que lorsque m=0, I'une au moins des substituants R2 et R3 represente un atome d'hydrogene,
avec un aldehyde de formule (II)

35 O
II
R4CH (II)

dans laquelle R4 represente un atome d'hydrogene, un groupe hydrocarbone aliphatique sature ou

40 insature, lineaire, ramifie ou cyclique ayant de 1 a 24 atomes de carbone au total, un groupe hydrocarbone
aliphatique substitue par un groupe aromatique ayant 24 atomes de carbone au total ou moins ou un
groupe hydrocarbone aromatique substitue ou non substitue ayant 24 atomes de carbone au total ou
moins, procede selon lequel un catalyseur d'hydrogenation ayant de 0,1 a 10% en poids de I'un au moins
des Co, Ni, Ru, Rh, Pd et Pt sur support de charbon pulverise ou granulaire est fourni dans une zone de
45 reaction a la concentration de 5 a 5 000 ppm de metal catalytique basee sur la quantite de I'amine de
formule (I), et la reaction est conduite a une temperature de 80 a 250°C et a une pression d'hydrogene d'au
moins 2 kg/cm2 (au manometre) pendant que I'aldehyde est fourni en continu dans la zone de reaction.
2. Un Procede selon la revendication 1, selon lequel la pression d'hydrogene est de 5 a 50 kg/cm2 (au
manometre).
50 3. Un procede selon la revendication 1, selon lequel la reaction est conduite a une temperature de 100 a
250°C.
4. Un procede selon la revendication 2, selon lequel la reaction est conduite a une temperature de 100 a
250°C.
5. Un procede selon la revendication 1, selon lequel I'aldehyde est utilise en quantite de 1 a 1,5 mole
55 par mole d'hydrogene actif de I'amine de formule (I).
6. Un procede selon la revendication 5, selon lequel I'aldehyde est utilise en quantite de 1 a 1,05 mole
par mole d'hydrogene actif de I'amine de formule (I).

50

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