An improved method for efficient and convenient synthesis of dioctanoyl peroxide

Article abstract of DOI:10.1081/SCC-120002516

Octanoyl chloride in methylene dichloride was added to the hydrogen peroxide solution containing 5mol.1^-1 NaOH in water-cooled flask, the reaction was carried out with high yields in ten or more minutes under vigorous stirring. The product was characterized by elemental analysis, molecular weight and spectral (IR, ¹H NMR) analysis. Furthermore, the method proposed has the advantages of operation at room temperature with safety, reliability and short time consuming.

Full text of DOI:10.1081/SCC-120002516

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AN IMPROVED METHOD FOR EFFICIENT AND
CONVENIENT SYNTHESIS OF DIOCTANOYL PEROXIDE
Guangshun Yi a , Baoquan Sun a , Run Li a , Depu Chen a , Yuxiang Zhou b & Jing Cheng b
a Department of Chemistry , Tsinghua University , Beijing, 100084, P.R. China
b Beijing National Biochip Research & Engineering Center , Beijing, 100084, P.R. China
Published online: 16 Aug 2006.
To cite this article: Guangshun Yi , Baoquan Sun , Run Li , Depu Chen , Yuxiang Zhou & Jing Cheng (2002) AN
IMPROVED METHOD FOR EFFICIENT AND CONVENIENT SYNTHESIS OF DIOCTANOYL PEROXIDE, Synthetic Communications:
An International Journal for Rapid Communication of Synthetic Organic Chemistry, 32:5, 759-762, DOI: 10.1081/
SCC-120002516
To link to this article: http://dx.doi.org/10.1081/SCC-120002516
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SYNTHETIC COMMUNICATIONS, 32(5), 759–762 (2002)
AN IMPROVED METHOD FOR EFFICIENT
AND CONVENIENT SYNTHESIS OF
DIOCTANOYL PEROXIDE
Guangshun Yi,1 Baoquan Sun,1 Run Li,1 Depu Chen,1,
*
Yuxiang Zhou,2 and Jing Cheng2
1Department of Chemistry, Tsinghua University,
Beijing 100084, P.R. China
2Beijing National Biochip Research & Engineering
Center, Beijing 100084, P.R. China
ABSTRACT
Octanoyl chloride in methylene dichloride was added to the
hydrogen peroxide solution containing 5 mol.lꢀ1 NaOH in
water-cooled flask, the reaction was carried out with high
yields in ten or more minutes under vigorous stirring. The pro-
duct was characterized by elemental analysis, molecular weight
and spectral (IR, 1H NMR) analysis. Furthermore, the method
proposed has the advantages of operation at room temperature
with safety, reliability and short time consuming.
In recent years, micron-sized mono-dispersed polymer particles
have been extensively used in biomedicine, chromatography, immunoassay,
etc. Dioctanoyl peroxide (DOP) was acted as an initiator, at the same time,
it acted as an excellent swelling agent in the preparation of mono-dispersed
*Corresponding author. Fax: (86) 10-62781690; E-mail: chendp@chem.tsinghua.edu.cn
759
Copyright & 2002 by Marcel Dekker, Inc.
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polymer beads of large size (1–100 mm) by means of two-step seed-swelling
polymerization.1 Due to the special properties of DOP, the seed could
absorb 50–500 times of its own volume monomer, which makes it possible
to prepare large monodisperse polymer particles. Today, more attentions
have been paid to its dynamic properties.2–5
The preparations of diacyl peroxides reported in literatures include the
reaction between acyl chloride or acid anhydride and hydrogen peroxide in
the presence of alkali.6–9 However, most of the methods offered in literatures
suffer the limitations of poor yields and vigorous reaction conditions. For
example, we tried to prepare dioctanoyl peroxide according to the methods
for the synthesis of benzoyl peroxide (BPO),6–8 but no target product was
obtained. Although dioctanoyl peroxide was obtained according to the
method for the preparation of dodecanoyl peroxide,9 yields were very
poor (no more than 30%) even in vigorous reaction conditions such as
low temperature, low H2O2 concentration and careful operation.
Organic solvents take an important part in the synthesis of diacyl
peroxides. Petroleum ether had been added to the reaction mixture in the
preparation of dodecanoyl peroxide.9 In this paper, the effects of several
organic solvents including petroleum ether, ethyl acetate, toluene, methylene
dichloride, chloroform and some surfactants such as sodium dodecylbenzene-
sulfonate, sodium lauryl sulfate on the synthesis of dioctanoyl peroxide were
examined. Among them, methylene dichloride was the best.
The principles of main reaction and by-reaction of the synthesis
process are shown in Scheme 1.
Scheme 1. Main reaction and by-reaction.
High concentration of NaOH is necessary to produce [O–O]2ꢀ because
H2O2 is a very weak acid. However, high concentration NaOH leads to

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761
by-reaction with both reactant and product. When organic solvents
immiscible with water are added to reaction system, two phases are
composed, acyl chloride and dioctanoyl peroxide distribute to organic
phase so that they are protected against the attack from NaOH. Once dioc-
tanoyl peroxide forms under serious stirring, it comes back to organic phase,
and did not get in touch with high concentration of NaOH. Methylene dichlo-
ride is better than that of petroleum ether, possibly it is because the polarity of
methylene dichloride is more analogous to that of acyl chloride and DOP.
Analytical data of dioctanoyl peroxide are as follows.
1H NMR (200 MHz, (CD3)2SO), d 0.83–0.89 (t, 6H, –CH3), d 1.25
(s, 16H, (–CH2)4), d 1.56–1.62(m, 4H, –CH 2), d 2.44–2.51 (t, 4H, –CO-CH2).
IR spectra: 2956 cmꢀ1, 2870 cmꢀ1, 1460 cmꢀ1, 1377 cmꢀ1, (–CH3);
2929 cmꢀ1, 2857 cmꢀ1, 1465 cmꢀ1, (–CH2); 1784 cmꢀ1, 1811 cmꢀ1, (C¼O).
The IR spectrum obtained was nearly the same as the standard spectrum of
dodecanoyl peroxide.10
Elemental analysis: Calcd for C16H30O4: C, 67.10; H, 10.56; O, 22.34.
Found: C, 67.21; H, 10.41; O, 22.34.
Melting point: 19.5ꢁC.
Molecular weight: Calcd: 286.41; Found: 286.21.
In conclusion, the present procedures for the preparation of diocta-
noyl peroxide are simple and convenient with high yields. Furthermore,
the method proposed has the advantages of operation at room temperature
with safety, reliability and short time consuming.
EXPERIMENTAL
All of the reagents used in this study were purchased from Beijing
1
Chemical Plant and were of analytical grade. H NMR was taken on a
Bruker-200 NMR spectrometer using (CD3)2SO as solvent and TMS as
internal standard; IR spectrum was recorded on a Perkin-Elmer spectro-
meter. Elemental analyses for C, H, O were performed by service from
Chemical Institute of Chinese Academy of Science. Melting point was
determined in open capillary and was uncorrected, n-octanoyl chloride
was prepared according to literature,11 molecular weight was measured by
reported volumetric analysis method.12
General Procedure for Preparation of Dioctanoyl Peroxide
Twenty grams NaOH was slowly dissolved in 100 ml deionized water
in 1000 ml water-cooled three necked round flask fitted with a condenser and

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was cooled to room temperature, 75 ml (0.63 mol) 30% H2O2 was
slowly added under moderate stirring. 47.2g (0.29 mol) n-octanoyl chloride
was dissolved in 100 ml methylene dichloride in a 250 ml dropping funnel,
and was then dropped into the flask. Reaction was carried out in ten or
more minutes under vigorous stirring. Organic phase in the reaction mixture
was separated with a separating funnel and then washed 3 times with deio-
nized water. The methylene dichloride and unreacted n-octanoyl chloride in
the residue were removed under reduced pressure. The product obtained
weighs 41 g (0.143 mol), percentage yield is 98.6% (according to n-octanoyl
chloride).
ACKNOWLEDGMENT
We are grateful for the financial support of National Joint Opening
Laboratory of Chemical Engineering of China.
REFERENCES
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M.D.; Dianoux, A.J.; Jonsen, P. Physica B 1997, 112, 234.
3. Buback, M.; Hinton, C.Z. Phys. Chem. 1997, 199(2), 229.
4. Girard, P.; Aliev, A.E.; Guillaume, F.; Harris, K.D.M.; Hollingsworth,
M.D.; Dianoux, A.J.; Jonsen, P. J. Chem. Phys. 1998, 109(10), 4078.
5. Buback, M.; Hinton, C.Z. Phys. Chem. 1996, 193(1/2), 61.
6. Caclogen, Z.I. Chem. Soc. 1959, 2844.
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12. Kolthoff, I.M.; Belcher, R. Volumetric Analysis, Vol. III, Interscience
Publishers, Inc.: New York, 1957; 367–368.
Received in the UK January 12, 2001

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