Highly selective zeolite-catalysed mono-N-alkylation of arylenediamines by dialkyl carbonates

Tetrahedron Letters

Volumn 48, Issue 9, 2007, Pages 1641-1643

  Ebenezer, Warren J ^a   Hutchings, Michael G ^a   Jones, Ken ^a   Lambert, David A ^a   Watt, Ian ^a  

^a UNIVERSITY OF MANCHESTER   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

ALKYL GROUP; CARBONIC ACID DERIVATIVE; DIAMINE DERIVATIVE; POLYCYCLIC AROMATIC HYDROCARBON DERIVATIVE; SODIUM; YTTRIUM; ZEOLITE;

ALKYLATION; ARTICLE; CATALYSIS; CATALYST; CHEMICAL REACTION; CHEMICAL STRUCTURE; REACTION ANALYSIS; STRUCTURE ANALYSIS;

EID: 33846568468     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tetlet.2006.12.131     Document Type: Article

References (19)

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2. See also a statistical analysis of scaled reactions used in a Pfizer facility:. Dugger R.W., Ragan J.A., and Ripin D.H.B. Org. Proc. Res. Dev. 9 (2005) 253
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10. The zeolite is currently available for $4/kg and the carbonates for less than $1.9/kg.
11. 3c and we have also observed that the carbonate can be decreased substantially on scale-up
12. Demonstration of catalyst reuse: OPD was methylated with DMC using the general procedure described above. On completion of the reaction, the zeolite catalyst was recovered by suction filtration and washed with methanol. The recovered zeolite was reused, following the same protocol with fresh OPD and DMC, with identical results. In three successive cycles of catalyst recovery and reuse in methylations of OPD there was no measurable loss of activity or selectivity.
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15. A formal process to mono-N-alkylated MPD based on the new procedure would likely comprise benzene dinitration, reduction and N-alkylation. This may be compared with the conventional alternative starting from N-alkylaniline (derived formally from benzene by halogenation and displacement by primary alkylamine, or by nitration, reduction, alkylation), involving nitration and isomer separation (implying a possible discard of the p-isomer) and finally reduction. It is not our intention to provide environmental audits for these various processes, but nevertheless a simple unit operation count suggests potential environmental and economic benefits would derive from the new, more direct reaction.
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19. The material described in this Letter is the subject of DyStar Patent Application WO2006/013164, priority date July 29th, 2004.