Studies into reactions of N-methylmorpholine-N-oxide (NMMO) and its hydrates with cyanuric chloride

Tetrahedron

Volumn 58, Issue 49, 2002, Pages 9809-9815

  Rosenau, Thomas ^a   Potthast, Antje ^a   Kosma, Paul ^a  

^a UNIVERSITY OF NATURAL RESOURCES AND LIFE SCIENCES   (Austria)

Author keywords

Cyanuric chloride; Isotopic labeling; NMMO; Reaction mechanism; Tertiary amine N oxides; Trapping reactions

Indexed keywords

4 METHYLMORPHOLINE N OXIDE; AMINE OXIDE; CHLOROHYDRIN DERIVATIVE; CYANURIC ACID; CYANURIC CHLORIDE; FORMALDEHYDE; HYPOCHLOROUS ACID; MORPHOLINE; MORPHOLINE DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; DEMETHYLATION; PRIORITY JOURNAL; QUANTITATIVE ANALYSIS; SOLID; WATER CONTENT;

EID: 0037010837     PISSN: 00404020     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4020(02)01291-7     Document Type: Article

References (26)

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2. See for instance: Godfrey A.G., Ganem B. Tetrahedron Lett. 31:1990;4825 Suzuki S., Onishi T., Fujita Y., Misawa H., Otera J. Bull. Chem. Soc. Jpn. 59:1986;3287.
3. . For a review see: Albini A. Synthesis. 1993;263.
4. Chanzy H. J. Polym. Sci., Polym. Phys. Ed. 1980;1137 Today, NMMO is used to generate the Lyocell fiber type.
5. Rosenau T., Potthast A., Ebner G., Kosma P. Synlett. 5:1999;623.
6. Rosenau T., Potthast A., Kosma P., Chen C.L., Gratzl J.S. J. Org. Chem. 64:1999;2166.
7. Rosenau T., Potthast A., Sixta H., Kosma P. Tetrahedron. 58:(15):2002;3073.
8. . For a review on side reactions of NMMO in the Lyocell process see: Rosenau T., Potthast A., Sixta H., Kosma P. Prog. Polym. Sci. 26:(9):2001;1763.
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12. If larger amounts of 2, up to stoichiometric amounts, are introduced, the mechanism of the reaction did not change, but the generated morpholine reacted with excess 2 to form morpholinium chloride and 4,6-dichloro-2-(morpholin-4-yl)-1,3,5-triazine. At the relatively short reaction times (15 min) used, triazines with more than one morpholine substituent were not found.
13. . Briefly, the trapping reagent 2-acetonaphthone (5% rel. to 1a) was added under stirring 1 min after addition of 2, and was converted into the trapping product, Mannich base β-(4-morpholino)-propionaphthone (82%). For experimental details see: Potthast A., Rosenau T., Kosma P., Chen C.L., Gratzl J.S. Holzforschung. 54:2000;101.
14. HCHO readily forms a 1:2 aldol product ('dimedone adduct') with 5,5-dimethyl-1,3-cyclohexanedione (dimedone) in aqueous ethanol (v/v=1:1). This reaction is widely used for HCHO quantification: cf. Hopkin A., Williams E. Organic Reagents for Organic Analysis. 2nd ed. 1950;Chadwell Heath. p 61. For analytical and NMR data of the trapping products see: Cremlyn R.J., Osborne A.G., Warmsley J.F. Spectrochim. Acta Part A. 52:1996;1433.
15. HCHO readily forms a 1:2 aldol product ('dimedone adduct') with 5,5-dimethyl-1,3-cyclohexanedione (dimedone) in aqueous ethanol (v/v=1:1). This reaction is widely used for HCHO quantification: cf. Hopkin A., Williams E. Organic Reagents for Organic Analysis. 2nd ed. 1950;Chadwell Heath. p 61. For analytical and NMR data of the trapping products see: Cremlyn R.J., Osborne A.G., Warmsley J.F. Spectrochim. Acta Part A. 52:1996;1433.
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17. 4.
18. 3 to the reaction mixture prevents the formation of 7·HCl. In this case, a mixture of 6-(N-methylmorpholin-4-yl)-2,4-dichloro-1,3,5-triazinium chloride (main product) and 6-(N-methylmorpholin-4-yl)-2-hydroxy-4-chloro-1,3,5-triazinium chloride was produced by reaction of free 7 with 2 and 5, respectively. The completely dechlorinated triazines, i.e. 2,4,6-tris(N-methylmorpholin-4-yl)-1,3,5-triazinium trichloride from 2 and 4,6-bis(N-methylmorpholin-4-yl)-2-hydroxy-1,3,5-triazinium dichloride from 5, were not found. The nucleophilic substitution of the third Cl at the triazine ring was evidently too slow under the prevailing conditions.
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23. Results will be reported elsewhere.
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