RE: ORGLIST: eugenol derivatives

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From: Ismail, Fyaz (F.M.Ismail$##$livjm.ac.uk)
Date: Thu Apr 21 2005 - 10:49:32 EDT


Eugenol was nitrated using fuming nitric acid (in diethyl ether) by =
Weselsky and Benedikat as early as 1882 [1] and a similar preparation =
was reported by Lewin and Lowy half a century later [2]. The reaction is =
not regioselective and the para- isomer is a common contaminant. In my =
opinion, unless you take special precautions, nitration in diethyl ether =
is not advisable since if it is contaminated with peroxides (due to =
auto-oxidation) it may lead to an explosion [3]; Eugenol itself is prone =
to autooxidation. During an examination of the selective nitration of =
phenols using lanthanum (III) nitrate, Ouertani et al. [4] have improved =
the regioselectivity of the reaction (ortho:para; 92:8); [sodium =
nitrate/conc. Hydrochloric acid in diethyl ether/water (3-8hrs) with =
catalytic quantities of lanthanum nitrate].

As regards esterification of this naturally occurring lignan, Indium =
(III) chloride atom-efficiently catalyses eugenol (15 min, 25 C, 95% =
yield) and is generally useful for the acylation of structurally diverse =
phenols, alcohols, thiols, and amines under solvent free conditions [5]. =
This procedure efficiently acylates acid sensitive alcohols, avoiding =
competitive side reactions (such as the Fries rearrangements) associated =
with previous methodology. Older procedure could be used for acylation =
but lack regioselectivity [7-10].

To my knowledge, I am unaware of a modern, comprehensive, review on =
reactions of eugenol. However, you could consult reactions of its =
individual functional groups by checking chemical Abstracts (e.g. the =
styrene moiety, [10]). The extensive series on functional groups edited =
by S. Patai (born 1918 - died1998) is especially useful [11]. =
Alternatively, perform a structure based reaction search on eugenol =
using Beilstein- Crossfire to retrieve a range of useful articles, =
currently numbering just over two hundred [12].

 

References

[1] Weselsky; Benedikat; MOCMB7; Monatsh. Chem. 1882 3; 87.

[2] Levin; Lowy; JACSAT; J. Am. Chem. Soc. 1933; 55, 1995.

[4] Ouertani, M.; Girard, P.; Kagan, H.B.; Tetrahedron Lett. 1982; 4315.

[3] http://www.orcbs.msu.edu/office/newsletters/September93.pdf

[5] Chakraborti, Asit K.; Gulhane, Rajesh; Tetrahedron Lett. 2003; 6749.

[6] Thoms, Arch.Pharm. 1903; 241,592.

[7] Tiemann; Nagai; Chem. Ber.; 1877; 10, 202.

[8] Erdmann; JPCEAO; J. Prakt. Chem. 1897; 56,146.

[9] Paersch bei Hillmer; Schorning; Z.Phys.Chem. 1934; 168, 81, 105.

[10] Everson, W. S. Chem. Rev.; 1949; 45, 183.

[11] http://eu.wiley.com/WileyCDA/Section/id-11128.html

[12] http://www.mimas.ac.uk/crossfire/

 

 

Fyaz M. D. Ismail

Medicinal Chemistry Research Group,

Liverpool, U.K.


________________________________

From: everybody-bounces$##$orglist.net on behalf of diogo$##$unilavras.edu.br
Sent: Wed 20/04/2005 02:10
To: everybody$##$orglist.net
Subject: ORGLIST: eugenol derivatives



Hi, everybody!
Iīm lookinf for works on eugenol reactions and similar reactions. I =
donīt
know if the reagent Iīm using isnīt pure enough but many =
difficulties are
coming up: I canīt effetuate esterifications or nitration on its
structure, besides others reactions simple at first glance.
Could anyone help me with something? Some papers? Some ideas?
Thanks in advance,
Diogo
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