PHOSPHORUS, SULFUR, AND SILICON
, VOL. , NO. , –
Synthesis of the novel crown and lariat ethers with integrated ,,-triazole ring
Jarosław Roman´ski and Przemysław Jaworski
´
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Department of Organic and Applied Chemistry, Faculty of Chemistry, University of Łódz, Łódz, Poland
ABSTRACT
ARTICLE HISTORY
Received October
Accepted October
Crown ethers possessing an external chain are called lariat ethers. Huisgen cycloaddition is the 1,3-dipolar
cycloaddition occurs between a suitable azide and terminal alkyne to give a stable 1,2,3-triazole system. It
is the most common reaction of the so called philosophy of “click chemistry,” introduced by Nobel prize
laureate Sharpless.
KEYWORDS
Crown ethers; ,-dipolar
cycloaddition; click
chemistry; ,,-triazole
system
GRAPHICAL ABSTRACT
after extraction and chromatographic purification led to corre-
sponding bis-azide derivative 3 in 65%.4
Introduction
Azides are well known and highly useful compounds contain-
ing in its structure N3 group which can be applied in, e.g.,
Staudinger reaction. Recently those compounds are applied for
the [2+3] cycloaddition in “click” variant (catalyzed by Cu(I)
cations) leading to a 1,2,3-triazole (by reaction with alkynes)
and tetrazole (by reaction with nitriles).1 This approach is
commonly used in medicine and related fields: for example,
as an effective method for construction of modified peptides,
or dendrimers. They are also important substrates in the syn-
thesis of primary amines (reduction) and isocyanates (Curtius
The macrocyclic compounds obtained in this series were
prepared by usage of “click” Huisgen cycloaddition reac-
tion starting from the corresponding bis-azides and terminal
alkynes. The high dilution condition method approx. 1 mg/mL
was used, which prevents the formation of linear products.3
Synthesis of propargyl derivatives
Synthesis of bis(propargyl)dietanolamine 7 and sulfurized
propargyl derivatives 10 and 11 can be divided into two reaction
pathways. In first step of preparation of 7 the diethanolamine 1
was reacted with THP-protected bromoethanol 4 to give puri-
fied by Kugelrohr distillation product 5 in good yield. In the next
step the reaction with propargyl bromide was performed to give,
after chromatographic purification, new propargyl derivative 6.
Finally the protection of hydroxyl group was removed using 6 M
hydrochloric acid in methanol, to give expected compound 7.5
Propargyl derivatives of sulfur containing polyglycols were
synthesized under classical conditions.6 2,2’-Thiodiethanol 8
and 3,6-dithia-1,8-octanediol 9 were reacted with propargyl
bromide, using sodium hydride in THF at room temperature, to
give, after standard chromatographic purification, sulfur deriva-
Results and discussion
Synthesis of bis-azide
Synthesis of sulfur containing macrocycles via Cu(I)
catalyzed cyclization
In first step the starting materials were prepared form
diethanolamine 1 which was reacted with thionyl chloride and
after crystallization gives diethanolamine hydrochloride 2 in
quantitativeyield. Next, salt 2 wasreactedwith sodium azide and
The synthesis of new nitrogen and sulfur containing macro-
cycles was carried out using high dilution method where
CONTACT Jarosław Roman´ski
Łódz´, Poland.
Department of Organic and Applied Chemistry, Faculty of Chemistry, University of Łódz´, Tamka , -
© Taylor & Francis Group, LLC
Romański, Jaros?aw
