Process for the preparation of N-methylmorpholine oxide

Abstract: N-methylmorpholine oxide with a very low level of contamination by nitrosamine impurities, e.g. below 25 parts per billion, can be obtained by oxidizing N-methylmorpholine with a solution of hydrogen peroxide in water and/or methanol, under an atmosphere of carbon dioxide at a temperature of 50 to 100°C and a pressure of 0.1 to 0.8 MPa (0 to 100 psig).

Description: This invention relates to a method for the production of N-methylmorpholine oxide. More particularly, this invention relates to a method wherein N-methylmorpholine is reacted with aqueous hydrogen peroxide in an atmosphere of carbon dioxide in order to provide N-methylmorpholine oxide contaminated with less than 25 parts per billion of nitrosamine impurities. EP-A-0307184 discloses a method for the preparation of tertiary amine oxides substantially free from nitrosamine by-products wherein a tertiary amine is reacted with aqueous hydrogen peroxide in the presence of carbon dioxide at a temperature of 45°C or less. EP-A-0307184 is insistent upon the use of temperatures below 45°C, more preferably 40°C or less and most preferably below 30°C, in order to inhibit the formation of nitrosamines. The preferred amine starting materials are alkyl amines. N-methyl morpholine is mentioned, but there is no mention of the discovery that leads to the present invention, that N-methyl morpholine is a unique feedstock, in that N-methyl morpholine oxide, substantially free from nitrosamine by-products, can be prepared by reacting N-methyl morpholine with hydrogen peroxide, in the presence of carbon dioxide at a reaction temperature of 50 to 100°C. US-A-4247480 is directed to a method for the preparation of amine oxides wherein a tertiary amine is oxidized with hydrogen peroxide in the presence of carbon dioxide and a promotor, such as ethylenediaminetetraacetic acid, stannates, or polyphosphates. US-A-4994614 is also directed to the preparation of tertiary amine oxides, by reaction of a tertiary amine with hydrogen peroxide in the presence of carbon dioxide and ascorbic acid. The stated advantage of the process is the provision of tertiary amine oxides that are substantially free from nitrosamine by-products. It is stated that the results were unexpected because, under the same reaction conditions, amine oxides made in the presence of either carbon dioxide or ascorbic acid individually contain significant quantities of nitrosamines. A wide variety of tertiary amines are mentioned as feedstocks including dialkyl amines, triaryl amines, mixed alkyl aryl, alkyl-arylalkyl, aryl-arylalkyl or alkyl-aryl-arylalkylamines including using heterocyclic amines such as N-methyl piperidine, N,N'-dimethyl piperazine, pyridine, 2-methyl pyridine, N-methyl pyrrolidine, N-methyl pyrrolidone, N-methyl morpholine and N-ethyl morpholine. EP-A-0356918 discloses a process for preparing amine oxides having decreased levels of nitrosamine contamination, by reacting a tertiary amine with hydrogen peroxide, in the presence of titanium alone or in the combined presence of titanium and carbon dioxide. EP-A-0409043 discloses a process for the preparation of amine oxides having reduced nitrosamine contamination by the reaction of a tertiary amine with hydrogen peroxide in the presence of an alkyleneaminopoly(methylene-phosphonic acid). It has been surprisingly discovered, in accordance with the present invention, that when N-methylmorpholine is reacted with aqueous hydrogen peroxide in an atmosphere of carbon dioxide in the absence of other additive materials, there is a substantially quantitative conversion of the N-methylmorpholine into N-methylmorpholine oxide, and the product will contain less than 25 parts per billion of nitrosamine contaminants. The results are particularly surprising because the prior art, as exemplified by the references cited above, teaches that it is necessary to use a second catalytic material, such as titanium or ascorbic acid, in order to obtain a significant reduction in nitrosamine by-product formation, even when the reaction is conducted in an atmosphere of carbon dioxide. Amine oxides are useful in the preparation of shampoos, hair conditioners, dish and laundry detergents, and fabric softeners. However, nitrosamines are suspected carcinogens and mutagens, and also can contribute a yellow colour to the amine oxide product. It has surprisingly been discovered, in accordance with the present invention, that when N-methylmorpholine is reacted with aqueous hydrogen peroxide in a carbon dioxide atmosphere, the resultant product, N-methylmorpholine oxide will have a very low nitrosamine contamination level, which may be less than 10 parts per billion. The starting materials for the preferred embodiment of the present invention are N-methylmorpholine, an aqueous solution of hydrogen peroxide, such as an aqueous solution containing from 10 to 55 wt.% of hydrogen peroxide and carbon dioxide. If desired, the hydrogen peroxide can be stabilized with a stabilizer of the type disclosed in EP-A-0409043, namely, an alkyleneaminopoly(methylenephosphonic acid). Good results may, however, be obtained when using hydrogen peroxide without such a stabilizer, e.g. technical grade hydrogen peroxide - see Example III. The amount of hydrogen peroxide to be used should be less than the equivalent amount of N-methylmorpholine to be oxidized and, preferably, an excess of N-methyl morpholine is employed. Preferably, from 0.80 to 0.99 moles of hydrogen peroxide are used per mole of N-methylmorpholine. The reaction is suitably conducted at a temperature of 50 to 100°C and at a pressure of 0.1 to 0.8 MPa (0 to 100 psig). EXAMPLES In the following Examples, a 2 litre flask, equipped with an addition funnel, mechanical stirrer, thermometer and gas sweep, was charged with 484.8g of N-methylmorpholine and 22.5g of water. To this were added 423.3g of a 35% aqueous solution of hydrogen peroxide. The reactants were digested to a hydrogen peroxide content of 0.01 wt. %, and then about 60g of material (N-methylmorpholine and water) were removed under vacuum. The product was then analyzed. Example I II III Gas used (70 cm 3 /min) N 2 CO 2 CO 2 Hydrogen Peroxide 1 1 2 Maximum Temperature 84°C 85°C 58°C Digestion Temperature 65°C 65°C 53°C Nitroso Morpholine Content 4 ppm <30 PPB Non Detected Comparing Examples I and II, a 100 fold decrease in nitrosamine is seen. This very large change is not expected. Also, in Example III, where technical grade hydrogen peroxide was used, no nitrosamine could be detected.

Claims: A method for the preparation of N-methylmorpholine oxide which comprises oxidizing N-methylmorpholine with a solution of hydrogen peroxide in water, under an atmosphere of carbon dioxide at a temperature of 50 to 100°C and a pressure of 0.1 to 0.8 MPa (0 to 100 psig). A method according to Claim 1 characterized in that the hydrogen peroxide solution is an aqueous solution containing 10 to 55 wt.% of hydrogen peroxide. A method according to Claim 2 or 3 characterized in that from 0.80 to 0.99 moles of hydrogen peroxide are used per mole of N-methylmorpholine.

Inventors: ZIMMERMAN ROBERT LEROY, ZIMMERMAN, ROBERT LEROY
Applicants: HUNTSMAN CORP, HUNTSMAN CORPORATION
Application year: 1992
Main classification: C07D295
IPC codes: C07D295