Process for preparation of aminocarboxylic acids

Details Process for preparation of aminocarboxylic acids Process for preparation of aminocarboxylic acids

2001-06-01

2003-04-01

Barts, Samuel (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Carboxylic acids and salts thereof

C562S552000, C502S202000, C502S208000, C502S224000, C502S232000, C502S301000

Reexamination Certificate

active

06541663

ABSTRACT:

The present invention relates to a process for the production of amine-group-containing carboxylic acid salts by oxidation of corresponding primary alcohols in an aqueous alkaline medium at an elevated temperature in the presence of a modified Raney copper catalyst.
In WO 92/06069, O. Gomez et al. describe the oxidation of ethanol amines to carboxylic acids, whereby the reaction is carried out in an aqueous-alkaline medium in the presence of Raney copper as the oxidation catalyst. In order to be able to reuse the catalyst in further reaction cycles, it must be reactivated, in this case by treatment with formic acid and then thorough washing with demineralised water and sodium hydroxide solution. Nevertheless, repeated usage is restricted because the catalyst has too short a service life and deactivates continuously.
In WO 94/24091, it is proposed that these disadvantages are remedied by doping (promoting) Raney copper with 10 to 50,000 ppm of an element or a metal, for example titanium, niobium, vanadium, molybdenum, manganese, nickel, lead and in particular chromium. The activity of the catalyst is only reduced thereby to a negligible extent. However, catalyst deactivation can be substantially improved. Of course, there is nothing to prevent the doping (promoting) metals, which are recognised as toxic, from reaching the reaction product, and after lengthy usage, the catalyst can no longer be reused. Simple reactivation is likewise impossible owing to the presence of doping (promoting) metals.
It has now surprisingly been found that the catalyst activity can be increased, the selectivity is maintained, the deactivation is only slight and, if necessary, can be eliminated by simple treatment with the doping (promoting) agent, and in this way multiple reusage in further reaction cycles is possible, and increased activity is observed in part during reusage, if the doping (promoting) agent employed is an ecologically acceptable agent, for example boric acid, onium fluorides or salts with fluorine complex anions, or heteropoly acids.
It was also surprisingly found that by adding adjuvants which contain carbaldehyde groups to the aqueous alkaline reaction medium, the catalyst activity and thus the reaction rate can be increased.
A first object of the invention is Raney copper, which is doped (promoted) with an effective quantity of a doping (promoting) agent selected from the group boric acid, onium fluorides, salts of fluorine complex anions, and heteropoly acids.
Effective quantity means that a minimum quantity is used and the effects are generally not further improved beyond the upper limit of a preferred quantity range. The minimum quantity, based on Raney copper, is preferably 10 ppm, more preferably 20 ppm and most preferably 50 ppm, and the maximum quantity is preferably 10,000 ppm, more preferably 8000 ppm and most preferably 5000 ppm.
Boric acid H
3
BO
3
can be used as such in the treatment of Raney copper, or can be produced in the reaction medium from boric acid esters.
The onium fluorides in question may be, for example, unsubstituted or substituted phosphonium fluorides and more preferably ammonium fluorides. They may correspond to formula I,
R
3
XH
+
—F
−
  (I)
wherein X is N or P and the symbols R are identical or different and signify H, C
1
-C
20
-alkyl, C
2
-C
20
-hydroxyalkyl, C
1
-C
4
-alkoxy-C
2
-C
12
-alkyl, C
2
-C
8
-cycloalkyl, C
6
-C
10
-aryl, C
7
-C
12
-aralkyl or C
8
-C
12
-alkaralkyl.
R may be linear or branched alkyl, which preferably contains 1 to 12, more preferably 1 to 8, most preferably 1 to 4 carbon atoms. Examples are methyl, ethyl, and the isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl and eicosyl. Alkyl is preferably linear and preferably denotes methyl, ethyl, n-propyl and n-butyl.
R may be linear or branched hydroxyalkyl, which preferably contains 2 to 12, more preferably 2 to 8, most preferably 2 to 4 carbon atoms. Examples are hydroxyethyl, hydroxypropyl and hydroxybutyl.
R as alkoxyalkyl preferably signifies C
1
-C
4
-alkoxy-C
2
-C
4
-alkyl, whereby alkoxy is most preferably methoxy or ethoxy. Preferred examples are methoxyethyl and ethoxyethyl.
R as cycloalkyl preferably contains 4 to 7, most preferably 5 or 6 ring carbon atoms. Examples of cycloalkyl are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. Cyclohexyl is especially preferred.
R as aryl may be naphthyl and preferably phenyl.
R as aralkyl is preferably phenylalkyl. Examples are benzyl and &bgr;-phenylethyl.
R as alkaralkyl preferably signifies alkylbenzyl, examples being methylbenzyl, dimethyl-benzyl, trimethylbenzyl and ethylbenzyl.
X in formula I preferably signifies N.
One preferred group of compounds of formula I is that in which the symbols R are identical and are selected from the group H and C
1
-C
4
-alkyl. The compound of formula I in question is most preferably NH
4
F.
Of the salts of fluorine complex anions, the alkali metal salts and onium salts are preferred in particular. Alkali metal salts are preferably, for example, lithium, sodium and potassium salts. Onium cations have already been described for the fluorides. The alkali metal salts may correspond to formula II,
Me
+
Y
−
  (II),
wherein Me
+
is NH
4
+
or an alkali metal cation, preferably Li
+
, Na
+
und K
+
, and Y
−
signifies a perfluorine complex anion from the group BF
4
−
, AlF
4
−
, PF
6
−
, AsF
6
−
, SbF
6
−
or BiF
6
−
. Preferred compounds are NaBF
4
, KBF
4
, NaPF
6
, KPF
6
and especially NH
4
BF
4
and NH
4
PF
6
.
The heteropoly acids are preferably derived from the poly-acid-forming elements W, Mo and V, whereby the polyanions contain elements from the groups P, B, Si and Ge. Heteropoly acids are known and are described for example by I. V. Kozhevnikov in Uspekhi Khimii Volume 56, pages 1417 to 1443 (1987). Preferred heteropoly acids correspond to formula III,
H
n
(ZM
12
O
40
)  (III),
wherein Z is P, B, Si or Ge, M is a metal from the group W, Mo and V, and n is an integer from 3 to 6. Preferred examples are H
3
[P(W
12
O
40
)], H
4
[P(W
12
O
40
)] and H
5
[B(W
12
O
40
)].
The carbaldehyde-group-containing adjuvants are derived e.g. from formaldehyde, paraformaldehyde, the aliphatic C
1
-C
12
-alkylcarbaldeydes, aromatic carbaldehydes and the corresponding dicarbaldehydes, whereby the aromatic rings may be substituted by C
1
-C
6
-alkyl or by OH. Of these, C
1
-C
8
-alkylcarbaldehydes, benzaldehyde, cuminaldehyde and 4-hydroxybenzaldehyde are preferred for example.
These carbaldehyde-group-containing adjuvants are conveniently employed in an amount ranging from 0.1 mol % to 50 mol %, preferably 1 mol % to 20 mol %, most preferably 2 mol % to 10 mol %, based on the primary amino alcohols of formula IV.
Production of the catalysts may take place in known manner, whereby an aqueous suspension of Raney copper is mixed with an aqueous solution of the modifying agent, the mixture is stirred or left to stand for a while, and then the impregnated Raney copper is filtered off or decanted and dried. The catalyst may also be produced and used in situ, whereby the aqueous mixture comprising catalyst and modifying agent is used directly after impregnation for the oxidation of primary alcohols. The catalyst may be used repeatedly. What is particularly advantageous here is that, when a loss of activity is first observed, further modifying agent is dispensed into the reaction mixture, and the loss of activity can be significantly to totally eliminated. In general, activated Raney copper is used for the modification. This is available commercially. Activation of Raney copper may be carried out whereby commercial Raney copper is treated for ca. 2 hours at a temperature of for example 200° C. with a mixture of nitrogen and hydrogen (volume ratio for example 4:1), and is then cooled under a protecting gas (for example argon).
A further object of the invention is a process for

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