Morpholine N-methyl

Polymere Ketone [z.B. Poly-(methyl-vinyl-keton), Styrol/Methyl-vinyl-keton-Copolymere] werden durch Natriumboranat in Bis-[2-methoxy-athyl]-ather bei 60-90° nur zu 40-60%, in N-Methyl-morpholin bei 115° durch Lithiumalanat dagegen vdllig reduziert5 und Poly-(chalkone) mit Natriumboranat in Bis-[2-methoxy-athylj-ather ebenfalls quantitativ6. Die Reduktion von Poly-acrolein zum Poly-allylalkohol gelingt mit Kalium-boranat in Wasser7. 

Mixture of 62.82% dipropylene glycol, 21.18% mercaptoacetic acid, 6% n-hexanoic acid, 6% N-methyl morpholine, 2.18% p-cresyl isovalerate, 0.91% 2-naphthalenethiol, and 0.91% skatole. 

Lyocell A papermaking process, based on dissolving wood pulp in N-methyl morpholine. Developed by Courtaulds, but the subject of a patent dispute with Lenzing, Austria, since 1993. Courtaulds has a plant in Mobile, AL, and Lenzing has one in Heiligenkreuz, Austria. 

Newcell A process for making reconstituted cellulose fibers by dissolving cellulose in N-methyl morpholine N-oxide and injecting the solution into water. Invented in 1977 by Akzona, NC. 

Acyl nitroso compounds react with 1, 3-dienes as N-O heterodienophiles to produce cycloadducts, which have found use in the total synthesis of a number of nitrogen-containing natural products [21]. The cycloadducts of acyl nitroso compounds and 9,10-dimethylanthracene (4, Scheme 7.3) undergo thermal decomposition through retro-Diels-Alder reactions to produce acyl nitroso compounds under non-oxidative conditions and at relatively mild temperatures (40-100°C) [11-14]. Decomposition of these compounds provides a particularly clean method for the formation of acyl nitroso compounds. Photolysis or thermolysis of 3, 5-diphenyl-l, 2, 4-oxadiazole-4-oxide (5) generates the aromatic acyl nitroso compound (6) and ben-zonitrile (Scheme 7.3) [22, 23]. Other reactions that generate acyl nitroso compounds include the treatment of 5 with a nitrile oxide [24], the addition of N-methyl morpholine N-oxide to nitrile oxides and the decomposition of N, O-diacylated or alkylated N-hydroxyarylsulfonamides [25-29]. 

The oxidation of alcohols to carbonyl compounds has been studied by several authors and a variety of methods have been used. Papers concerned vith such oxidations are illustrated (Scheme 3.26). Good results have been obtained using pyridinium chlor-ochromate (PCC) adsorbed onto silica gel for the selective oxidation of unsaturated substrates e.g. terpene [135] and furanyl derivatives [136]. Steroidal homoallylic alcohols can be converted to the corresponding 4-ene-3,6-diones using tetrapropylammo-nium per-ruthenate (TPAP) in catalytic amounts [137]. In this case, the oxidising agent is N-methyl morpholine N-oxide (NMO). 

Chanzy and Peguy (13) were the first to report that cellulose forms a lyotropic mesophase. They used a mixture of N-methyl-morpholine-N-oxide (MMNO) and water as the solvent. Solution birefringence occurred at concentrations greater than 20% (w/w) cellulose. The concentration at which an ordered phase formed increased as the cellulose D.P. decreased. The persistence length of cellulose in MMNO-H2O is not known but presumably it has an extended chain configuration in this solvent. Again the question arises as to what is the relevant axial ratio to be used for cellulose. This will be discussed further below. 

The very sensitive ether peroxide test strips (Merckoquant, Art. No. 10011), available from E. Merck, Darmstadt, are used. If the test is still positive at this point, an additional 0.2 ml. of N-methyl morpholine is added. Stirring and heating at 75° are continued for another 5 hours. Remaining peroxide renders the work-up and drying of the product potentially hazardous. N-Methylmorpholine N-oxide (1) and hydrogen peroxide form a strong 1 1 complex. In the reaction with osmium tetroxide, this complex produces conditions similar to those of the Milas reaction,7 and some ketol formation may result. 

Osmium tetroxide-N-Methyl-morpholine N-oxide, 222 Osmium tetroxide-Trimethylamine N-oxide-Pyridine, 223 Palladium Compounds Benzylchlorobis(triphenylphosphine)-palladium(II), 30 Bis (ace tonitrile) chloronitropalla-dium(II)-Copper(II) chloride, 33 Bis(acetonitrile)dichloropalladium(II), 33, 211, 236... 

The Upjohn Dihydroxylation allows the sy/i-selective preparation of 1,2-diols from alkenes by the use of 0s04 as a catalyst and a stoichiometric amount of an oxidant such as NMO (N-methyl morpholine- JV-Oxide). 

Oxidation of alcohols. Griffith and Ley1 report various improvements for use of this reagent for catalytic oxidation of alcohols in combination with N-methyl-morpholine N-oxide as reoxidant. In general, the yields with this oxidant are higher than those obtained by the Swern reagent. 

TPAP = Tetrapropylammonium perruthenate DMAP = 4-dimethylaminopyridine. NHO = N-methyl morpholine N-oxide ... 

Marsano, E., Corsini, P., Arosio, C., Boschi, A., Mormino, M., and Freddi, G. "Wet spinning of Bombyx mori silk fibroin dissolved in N-methyl morpholine N-oxide and properties of regenerated fibres". Int. J. Biol. Macromol. 37(4), 179-188 (2005). 

Metal complexes combined with a suitable oxygen atom donor can often act as versatile and selective oxidation catalysts. The oxygen atom donors commonly used are N-methyl morpholine oxide 8.27 (see reaction 8.30), organic hydroperoxides, sodium hypochlorite, hydrogen peroxide, etc. Three such reactions of industrial relevance are shown by 8.30, 8.31, and 8.32. Obviously these reactions are catalytic with respect to the metal complex but stoichiometric with respect to the oxygen atom donor. 

Alceru [Alternative cellulose Rudolstadt] A process for making cellulosic filaments and staple fibers. The cellulose is first dissolved in an aqueous solution of N-methyl morpholine N-oxide (NMMNO) and then spun. Developed by the Thiiringische Institut fur Textil- and Kunstoff-Forschung e.V. Rudolstadt, Germany, and Zimmer (Frankfurt) from 1987. A pilot plant was built in April, 1998 and a commercial plant was planned for installation in Baoding, China in 2005. A superabsorbent version of the fiber has been developed by Stockhausen. The fiber is now made commercially by Sea Cell GmbH, a subsidiary of Zimmer. See also Lyocell. 

A mixture of N-(benzyloxycarbonyl-a-phosphonoglycine trimethyl ester (014.7 mmol) and 10% Pd/C (2g) in 60 ml methyl alcohol was stirred under a hydrogenated atmosphere balloon for 4 hours, filtered through celite, and solvent removed under vacuum. 2-Chloronicotinyl chloride (14.7 mmol), N-methyl-morpholine (15 mmol) dissolved in 75 ml CH2CI2 were added and the mixture stirred overnight at ambient temperature. The mixture was diluted with 30 ml CH2CI2, washed with 50 ml apiece with dilute HCl and saturated NaHC03, and the product isolated as a colorless gum in 91% yield. H-NMR data supplied. 

METHYL MONOBROMOACETATE see MHR250 METHYL MONOCHLOR. CETATE see i nF775 METHYL MONOCHLOROACETATE see MIF775 4-METHYLMORPHOUXE see MAL 250 N-METHYL MORPHOLINE see MMA250 METHYLMORPHOLINE (DOT see MMA250 METHYL 10-(3-... 

---