A novel synthetic route to synthesize 2,4,8, 10-tetraoxaspiro[5.5]-undecane from formaldehyde under hydrothermal conditions

Article abstract of DOI:10.1002/jhet.348

(Chemical Equation Presented) We report here the hydrothermal synthesis of 2,4,8,10-tetraoxaspiro[5.5]-undecane by using formaldehyde, the only precursor, in the presence of kaolin clay and boric acid. The reported method is the simplest one to synthesize the aforementioned product.

Full text of DOI:10.1002/jhet.348

March 2010
A Novel Synthetic Route to Synthesize 2,4,8,
0-Tetraoxaspiro[5.5]-Undecane from Formaldehyde
under Hydrothermal Conditions
483
1
Gull Maheen, Ge Tian, Zhiguang Song, Chao He, Zhan Shi, Ziwei Liu,
Hongming Yuan, and Shouhua Feng*
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry,
Jilin University, Changchun 130012, People’s Republic of China
*
E-mail: shfeng@mail.jlu.edu.cn
Received July 24, 2009
DOI 10.1002/jhet.348
Published online 2 March 2010 in Wiley InterScience (www.interscience.wiley.com).
We report here the hydrothermal synthesis of 2,4,8,10-tetraoxaspiro[5.5]-undecane by using formalde-
hyde, the only precursor, in the presence of kaolin clay and boric acid. The reported method is the sim-
plest one to synthesize the aforementioned product.
J. Heterocyclic Chem., 47, 483 (2010).
INTRODUCTION
izers for polyolefins and other polymers [5]. Similarly
the binary blends of the acrylate rubber and chlorinated
polypropylene give dynamic mechanical properties
with 3,9-bis[1,1-dimethyl-2{b-(3-tert-butyl-4-hydroxy-5-
methylphenyl)-propionyloxy}ethyl]-1 [6] and 3,9-di-2-
furyl-1 type compounds serve as important intermediates
in the synthesis of pesticides [7]. Moreover, its deriva-
tives serve as prominent parts of many patents, i.e., 3,9-
bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl) propio-
nyloxy}-1,1-dimethylethyl]-1 is used in the synthesis of
high quality antioxidants for many polymers [8,9], 3,9-
bis [1,1-dimethyl-2-{b-(3-tert-butyl-4-hydroxy-5-methyl-
phenyl)propionyl-oxy}ethyl]-1 serves as an oxidant in
the synthesis of molding materials with excellent proper-
ties [10], while its many derivatives serve as essential
components to bestow excellent chemical makeup for
decorating ceramics [11]. Its derivatives enjoy a special
place in the field of medicine and surgery, e.g., -1-3,9-
The spectacular nature of the hydrothermal systems
provides a great deal of new synthetic routes in innova-
tive, unconventional, as well as safest ways. This is
exemplified by a number of novel synthetic discoveries
in the realm of hydrothermal synthesis [1,2]. Also, a
novel method for the translation of sodium hydrogen
carbonate into phenol depicts that hydrothermal reaction
routes have diverse applications [2]. Not only this but
the hydrothermal synthesis also provides intriguing clues
to the origin of life [1,3]. Furthermore, such kind of syn-
thetic routes occupy a special place because of their pol-
lution free nature. Also, the reactions take place safely
within closed systems and do not need expensive mate-
rials as used in normal organic synthesis. Here, we pres-
ent a simplest route to synthesize 2,4,8,10-tetraoxas-
piro[5.5]-undecane (1) under the simplest hydrothermal
conditions and demonstrate the versatility of the hydro-
thermal techniques.
0
dipropamine(11 ) is used in the synthesis of anti-inflam-
Compound 1 is a very important synthetic precursor
of many organic compounds. It has multifarious applica-
tions, from simple organic synthesis to medicines. One
derivative, like 3,9-bis(2-hydrazidoethyl)-1, is used as a
curing agent to produce a sufficient amount of cured ep-
oxy resin [4]. Many derivatives of 1 are used as stabil-
matory drug derivatives like pyrimidine and bispyrimi-
dine [12] derivatives, 3,9-diethylidene-1 has potential
applications in dental surgery [13], 3,9-dimethylene-1, is
used in the synthesis of biodegradable polymers for the
controlled release of paracetamol [14]. 1 has been syn-
thesized in many ways, but the most remarkable
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G. Maheen, G. Tian, Z. Song, C. He, Z. Shi, Z. Liu, H. Yuan, and S. Feng
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synthetic routes are achieved by the transacetalization of
triols [15]. Here, we report the hydrothermal synthesis
of 1 by using formaldehyde as the only starting reagent,
by using a mixture of boric acid and kaolin as catalyst,
hence it presents the simplest route to synthesize the
intended product.
that with any change in anyone of the above described
parameters, the reaction fails to occur. Moreover, all of
these parameters facilitate the synthesis of 1. We were
interested to know the effect of temperature on our path-
ꢀ
way. Hence, we performed the reaction below 100 C.
Most interestingly, we found that temperature window
ꢀ
of 80–90 C gives a series of small open chained oxy-
genated products like carbon dioxide, formic acid etc.
ꢀ
RESULTS AND DISCUSSION
Also, temperature exceeding 100 C, causes degradation
and decomposition of the product, implying that the
Compound 1 was successfully synthesized. The yield
of the reaction was 0.4%. The proposed mechanism for
the reaction is described in the Scheme 1.
above described method to synthesize 1 is only feasible
ꢀ
at 100 C. The presence of catalyst mixture (boric acid
and kaolin) is also essential, which is mainly responsible
for the condensation, cyclization and stabilization of the
formaldehyde units. Similarly, the reaction time and pH
are also critical factors for the reaction.
In the first step (Step 1) of Scheme 1, boric acid
hydrolyzes and reacts with formaldehyde which results
in the protonation of formaldehyde and another mole-
cule of formaldehyde to form acetaldehyde through a
cyclic transition state. In the second step (Step2), this
acetaldehyde molecule further undergoes a series of
mechanistic steps, to form the product.
EXPERIMENTAL
In our synthesis, 2 mL formaldehyde and 12 mL doubly dis-
tilled water [16] were added into each steel alloy (Fe-Cr-Ni,
alloy GB1220-92) autoclaves with a filling capacity of 90%
and recrystallized boric acid and kaolin clay (0.1 g each) were
also added into the reaction mixture of each of the autoclaves.
The final pH of the reaction mixture was nearly 3. The auto-
claves were then sealed tightly and placed in the ovens at a
Many parameters influence this reaction pathway, i.e.,
temperature, pH, presence of catalysts. We have found
Scheme 1. Mechanism of reaction.
ꢀ
temperature range from 100–200 C for 3 days. However, the
ꢀ
reaction was successful at 100 C. After 3 days the autoclaves
were taken out and analyzed.
The reaction can be written as follows:
CHARACTERIZATION BY GC-MS
The product was identified and characterized by the
GC-MS (Thermo Co.). Figure 1 shows the GC-MS of
product as well as that of standard.
CONCLUSIONS
As discussed above, in our synthesis, the presence of
boric acid and kaolin was essential. Our experiment
clearly proves that hydrothermal synthesis provides
unique reaction pathways, which in other ways are very
difficult to obtain [1,2]. Moreover, in similar ways,
many other polymerization reactions can be obtained by
utilizing simple precursors [2]. Also, we synthesized our
product without using any harmful or expensive reagent.
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

March 2010
A Novel Synthetic Route to Synthesize 2,4,8,10-Tetraoxaspiro[5.5]-undecane from
Formaldehyde under Hydrothermal Conditions
485
important position in the field of synthetic chemistry
and a very likely candidate for recycling of waste and
conversion of industrial waste (like formaldehyde, car-
bon monoxide, carbon dioxide, etc.) into useful products
and the most likely candidate to promote ‘‘Green
Chemistry’’.
Acknowledgment. This work was supported by the National
Nature Science Foundation of China (No. 20631010 and
9
0922034) and Jilin University Basic Scientific Research Opera-
tion Cost (200810023). Gull Maheen sincerely thanks the Chi-
nese scholarship Council and the Ministry of Education,
Government of Pakistan for awarding PHD scholarship. She also
thanks Nasim, Rahat, Zaryab, Mariam and Shani for support. She
also acknowledges the helpful discussions with Sait and Irfan.
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[
16] Before further proceeding, GC-MS of the HCHO was taken
and it indicated no organic contamination. Water was also doubly dis-
tilled and boric acid was recrystallized twice. Kaolin clay was also
free of any organic contamination.
Finally, our synthetic route to synthesize 1 clearly
proves that hydrothermal routes of synthesis enjoy an
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet