Improvement of the phase-transfer catalysis method for synthesis of glycidyl ether

Article abstract of DOI:10.1007/s11746-001-0279-y

A convenient procedure for the synthesis of aliphatic alkylglycidyl ether has been studied. It has been found that the improved preparation of the alkylglycidyl ether can be achieved by using fatty alcohol such as octanol and octadecanol with epichlorohydrin in the presence of phase-transfer catalyst (PTC) such as 1-alkyloxypropan-2-ol-3-trimethyl ammonium methylsulfate, 1-alkyloxypropan-2-ol-3-methyldiethanolammonium methylsulfate, alkyloxy-2-hydroxypropyldimethylamine and alkyloxy-2-hydroxypropyldiethanolamine, tetrabutylammonium bromide, etc. without water and other organic solvents. This method, carried out in solid phase/organic phase (reactants and product themselves), has the following merits: (i) producing the solid by-products such as sodium chloride and sodium hydroxide which are easily removed by simple filtration, (ii) saving the amount of reactants used such as sodium chloride and phase-transfer catalyst, and (iii) increasing the yields of glycidyl ethers. The yields of octylglycidyl ether and octadecylglycidyl ether are 92.0 and 91.7%, respectively. The amount of sodium hydroxide used can be saved by from 1.5 to 0.7 molar ratio with respect to octanol in comparison with those in the conventional method using PTC.

Full text of DOI:10.1007/s11746-001-0279-y

Improvement of the Phase-Transfer Catalysis Method
for Synthesis of Glycidyl Ether
Ho-Cheol Kang,a,b Byung Min Lee,a,* Jungho Yoona, and Minjoong Yoonb,*
aApplied and Engineering Chemistry Division, Korea Research Institute of Chemical Technology, Yusung
Taejon 305-600, Korea, and bDepartment of Chemistry, Chungnam National University, Yusung, Taejon 305-764, Korea
ABSTRACT: A convenient procedure for the synthesis of ported the yield of 72–86% for various glycidyl ethers in the
aliphatic alkylglycidyl ether has been studied. It has been found
that the improved preparation of the alkylglycidyl ether can be
achieved by using fatty alcohol such as octanol and octadec-
anol with epichlorohydrin in the presence of phase-transfer
catalyst (PTC) such as 1-alkyloxypropan-2-ol-3-trimethyl am-
monium methylsulfate, 1-alkyloxypropan-2-ol-3-methyldi-
ethanolammonium methylsulfate, alkyloxy-2-hydroxypropyl-
dimethylamine and alkyloxy-2-hydroxypropyldiethanolamine,
tetrabutylammonium bromide, etc. without water and other or-
ganic solvents. This method, carried out in solid phase/organic
phase (reactants and product themselves), has the following
presence of phase-transfer catalyst (PTC). Also, the method
of Najem and Borred on (10), using epibromohydrin instead
of epichlorohydrin, has been reported to have yields of
40–90% for various glycidyl ethers (10).
However, the conventional PTC method generates some
by-product solution that consists of sodium hydroxide and
sodium chloride. It needs an additional special device for the
solidification process of the aqueous mixture solution for
reuse or disposal of these chemicals. Even though the method
is generally useful in small-scale synthesis, it is inconvenient
merits: (i) producing the solid by-products such as sodium chlo- in large-scale preparation because of heavy consumption of
ride and sodium hydroxide which are easily removed by simple
filtration, (ii) saving the amount of reactants used such as
sodium chloride and phase-transfer catalyst, and (iii) increasing
the yields of glycidyl ethers. The yields of octylglycidyl ether
and octadecylglycidyl ether are 92.0 and 91.7%, respectively.
The amount of sodium hydroxide used can be saved by from
1.5 to 0.7 molar ratio with respect to octanol in comparison
with those in the conventional method using PTC.
time and expenses. Therefore, a new synthetic attempt has
been made to improve the yield of glycidyl ether and the fea-
sibility of its commercial production by avoiding the use of
the aqueous sodium hydroxide solution. The new synthesis of
the glycidyl ethers has been achieved by using just epichloro-
hydrin and octanol or octadecanol as starting materials with-
out water and other (organic) solvents.
Paper no. J9599 in JAOCS 78, 423–429 (April 2001).
EXPERIMENTAL PROCEDURES
KEY WORDS: Alkylglycidyl ether, epichlorohydrin, glycerol de-
rivatives, non-solvent, phase-transfer catalyst, surface-modify- Materials. Epichlorohydrin (99%), hexanol (99%), octanol
ing, surfactants, two phase reaction.
(99%), dodecanol (98%), tetradecanol (97%), octadecanol
(99%), sodium hydroxide (97%, 20–40 mesh beads), di-
methylamine (40% solution), diethanolamine (99%), di-
The derivatives of alkylglycidyl ether with a long alkyl chain methyl sulfate (99%), tetrabutylammonium bromide (99%)
are very important intermediates in physical and pharmaceu- (TBAB), and tetrabutylammonium hydrogensulfate (97%)
tical applications such as manufacturing softeners, antistatic (TBAH) were purchased from Aldrich Chemical Co. (Mil-
agents, emulsifiers (1), drugs (2), plastic additives (3), cos- waukee, WI). Cetyltrimethylammonium chloride (98%)
metics, pseudoceramides (4), surface-modifying agents (5), (CETAC) and lauryldimethylbenzylammonium chloride
gemini-type surfactants (6), and ether lipids (7). Generally, (98%) (LMBAC) were obtained from Il-Chil Chemical Co.
two methods for the syntheses of glycidyl ethers are well (Yeochun, Korea). All these chemicals were used without fur-
known: (i) Lewis acid method and (ii) phase-transfer catalyst ther purification.
(PTC) method. The Lewis acid method consists of the halo-
Gas chromatography (GC). The GC analyses were per-
hydrin intermediate process and the dehydrochlorination formed on an HP 5890 gas chromatograph (Hewlett-Packard,
process, and it has two major disadvantages, i.e., halohydrin Wilmington, DE) equipped with flame-ionization detector
ether formation and polymerization (8). For these reasons, the (FID) and DB-1HT column (0.32 mm i.d. × 30 m) (J&W Sci-
PTC method using the reaction of alcohol with epichlorohy- entific, Folsom, CA). The yields of the product and by-prod-
drin in aqueous sodium hydroxide solution and n-hexane is ucts for the synthesis of glycidyl ether were quantified by GC
known to be more useful than the Lewis acid method for the with naphthalene as an internal standard. The experimental
preparation of glycidyl ether. Recently, Urata et al. (9) has re- conditions for GC are as follows: carrier gas, nitrogen; col-
umn pressure, 55 kPa; carrier gas flow rate, 2.2 mL/min; split
ratio, 20:1; initial oven temperature, 60°C; initial time, 3 min;
*To whom correspondence should be addressed.
ramp, 12°C/min; final time, 360°C; final time, 30 min.
E-mail: bmlee@pado.krict.re.kr
Copyright © 2001 by AOCS Press
423
JAOCS, Vol. 78, no. 4 (2000)

424
H.-C. KANG ET AL.
TABLE 1
Analytical and Nuclear Magnetic Resonance (NMR) Spectral Data for GE-8 and GE-18a
1H NMR (CDCl3)
13C NMR (CDCl3)
HRMS
Mode : El (M)
186.1620
GE-8
3.71 (dd, J = 11.6 and 3.1 Hz, H-1), 3.49 (m, H-1′),
3.38 (dd, J = 11.6 and 5.8 Hz, H-1), 3.15
71.78 (C-1), 71.52 (C-1′), 50.93 (C-2),
44.33 (C-3), 31.89 (C-6′), 29.77
(C-2′), 29.50 (C-4′), 29.32 (C-5′),
26.15 (C-3′), 22.72 (C-7′), 14.12
(m, H-2), 2.80 (dd, J = 4.9 and 4.3 Hz, H-3), 2.61
(dd, J = 4.9 and 2.9 Hz, H-3), 1.58 (p, H-2′), 1.26
(calcd.: 186.1620)
(m, H-3′ – H-7′), 0.88 (t, J = 6.6 Hz, H-8′)
(C-8′)
GE-18
3.70 (dd, J = 11.5 and 3.2 Hz, H-1), 3.48 (m, H-1′),
3.38 (dd, J = 11.5 and 5.7 Hz, H-1), 3.14 (m,
H-2), 2.79 (dd, J = 5.0 and 4.3 Hz, H-3), 2.60 (dd,
J = 5.0 and 2.7 Hz, H-3), 1.58 (p, H-2′), 1.26 (m,
H-3′ – H-17′), 0.88 (t, J = 6.6 Hz, H-18′)
71.76 (C-1), 71.49 (C-1′), 50.92 (C-2),
44.32 (C-3), 31.98 (C-16′), 29.75
(C-5′ – C-14′), 29.66 (C-2′), 29.53
(C-4′), 29.42 (C-15′), 26.13 (C-3′),
22.74 (C-17′), 14.14 (C-18′)
Mode : Cl (M + 1)
327.3259
(calcd.: 327.3263)
aGE = alkylglycidyl ether. The numbers (8 and 18) refer to the chain length at the alkyl groups. See Scheme 1. EI, electron impact; HRMS, high-resolution
mass spectra. CI, chemical ionization.
Nuclear magnetic resonance (NMR) spectrometer. 1H (300
The other catalysts (0.015 mol) (TBAH, CETAC, LMBAC,
MHz) and 13C (75 MHz) NMR spectra of the synthetic prod- QM, QEA, GM, and GEA; see below for definitions not al-
ucts were recorded on a Bruker AMX 300 NMR spectrometer ready given) instead of TBAB were used to test the catalytic
(Karlsruhe, Germany). The chemical shifts are reported in δ effects of the reaction.
units (ppm) with tetramethylsilane (TMS) as internal standard.
Synthesis of octadecylglycidyl ether (GE-18). Octadecyl-
Mass spectrometer. High-resolution mass spectra (HRMS) glycidyl ether was prepared by the same method as described
were obtained on a Micromass Autospec mass spectrometer for the preparation of octylglycidyl ether. The reaction sys-
(Manchester, United Kingdom). The HRMS spectrum for tem consisted of octadecanol (163.9 g, 0.60 mol), sodium hy-
octylglycidyl ether was obtained by electron impact (EI) droxide (56.9 g, 1.38 mol), TBAB (1.20 g, 3.75 mmol), and
method (40 eV) and that for octadecylglycidyl ether was ob- epichlorohydrin (112.2 g, 1.20 mol) at 60°C. After the reac-
tained by chemical ionization (CI) method (methane, M + 1, tion was completed, octadecylglycidyl ether was extracted
40 eV).
twice with 250 mL of n-hexane and was purified by distilla-
Synthesis of octylglycidyl ether (GE-8). Octanol (132 g, tion (134–136°C at 0.054 mm Hg). Table 1 shows analytical
1.0 mol) was heated in the reaction vessel to 40°C. Sodium and NMR data for GE-18 (Scheme 1) (10).
hydroxide (61.9 g, 1.5 mol) and TBAB (2.00 g, 6.25 mmol)
Synthesis of catalysts: Alkylglycidyl ether (GE). Alkyl
were added, and the mixture was stirred for 30 min at the groups are hexyl, octyl, dodecyl, and octadecyl, and their de-
same temperature. Epichlorohydrin (187 g, 2.0 mol) was rivatives are GE-6, GE-8, GE-12, and GE-18, respectively. The
added, and the temperature was kept between 38 and 42°C. synthesis of GE-8 and GE-18 was mentioned above. GE-6 and
The reaction was completed when the yield of the octylgly- GE-12 were synthesized by the method of Urata et al. (9). GE-
cidyl ether (monitored by GC) did not increase any more with 6 and GE-12 were purified by distillation (40°C at 0.102 mm
the increase of reaction time. The product was extracted twice Hg for GE-6, and 97–98°C at 0.060 mm Hg for GE-12).
with 250 mL of n-hexane and was purified by distillation
Alkyloxy-2-hydroxypropyldimethylamine (GM). Alkyl
1
(50–51°C at 0.041 mmHg). The H and 13C NMR data for groups are hexyl, octyl, dodecyl, and octadecyl, and their de-
GE-8 were collected with the correlated data and are summa- rivatives are GM-6, GM-8, GM-12, and GM-18, respectively
rized in Table 1 (Scheme 1) (10).
(Scheme 2). All the GM were synthesized by the general syn-
The variables for the optimal reaction condition are as fol- thetic method (11). All of them were purified by distillation
lows: the amount of sodium hydroxide, from 1.0 to 2.0 mol; at their boiling points, respectively (GM-6, 54.5°C at 0.067
the amount of epichlorohydrin, from 1.2 to 3.0 mol; the mm Hg; GM-8, 75–77°C at 0.041 mm Hg; GM-12, 123–125°C
amount of catalyst (TBAB), from 0.00625 to 0.05 mol; reac- at 0.031 mm Hg; GM-18, 181–184°C at 0.035 mm Hg). The
tion temperature, from 20 to 70°C.
SCHEME 2
SCHEME 1
JAOCS, Vol. 78, no. 4 (2001)

AN IMPROVED METHOD FOR SYNTHESIS OF GLYCIDYL ETHER
425
TABLE 2
Analytical and NMR Spectral Data for GMa, GEAb, QMc and QEAd
1H NMR (CDCl3)
3.84 (m, H-2), 3.46 (t, J = 6.6 Hz, H-1′), 3.42 (m, H-1), 2.43 (dd, J = 12.1 and 9.8 Hz, H-3), 2.28 (s, N-CH3), 2.24 (dd,
Purity (%)
99.7
GM-6
J = 12.1 and 3.9 Hz, H-3), 1.58 (p, H-2′), 1.26 (m, H-3′ – H-5′), 0.89 (t, J = 6.7 Hz, H-6′)
GM-8
3.75 (m, H-2), 3.36 (t, J = 6.8 Hz, H-1′), 3.34 (m, H-1), 2.33 (dd, J = 12.4 and 9.4 Hz, H-3), 2.18 (s, N-CH3), 2.16
(dd, J = 12.4 and 3.8 Hz, H-3), 1.49 (p, H-2′), 1.18 (m, H-3′ – H-7′), 0.79 (t, J = 6.8 Hz, H-8′)
3.74 (m, H-2), 3.36 (t, J = 6.6 Hz, H-1′), 3.32 (m, H-1), 2.33 (dd, J = 12.3 and 9.8 Hz, H-3), 2.18 (s, N-CH3), 2.16 (dd,
J = 12.3 and 3.8 Hz, H-3), 1.49 (p, H-2′), 1.17 (m, H-3′ – H-11′), 0.76 (t, J = 7.2 Hz, H-12′)
3.77 (m, H-2), 3.38 (t, J = 6.5 Hz, H-1′), 3.34 (m, H-1), 2.35 (dd, J = 12.3 and 9.7 Hz, H-3), 2.18 (s, N-CH3), 2.17
(dd, J = 12.3 and 3.8 Hz, H-3), 1.51(p, H-2′), 1.18 (m, H-3′ – H-17′), 0.76 (t, J = 6.8 Hz, H-18′)
4.10 (bs, OH), 3.91 (m, H-2), 3.71 (m, J = 11.8 and 9.1 Hz, N-CH2CH2), 3.54 (m, J = 11.8 Hz, N-CH2CH2), 3.45 (t, J =
6.7 Hz, H-1′), 3.41 (d, J = 1.4 Hz, H-1), 3.39 (d, J = 2.3 Hz, H-1), 2.76 (m, J = 13.5 and 9.1 Hz, N-CH2CH2), 2.59 (dd,
J = 13.2 and 9.5 Hz, H-3), 2.49–2.40 (m, H-3 and N-CH2CH2), 1.57 (p, H-2′), 1.30 (m, H-3′ – H-5′), 0.89 (t, J = 6.7 Hz,
H-6′)
99.7
99.8
99.8
99.3
GM-12
GM-18
GEA-6
GEA-8
4.71 (s, OH), 3.84 (m, H-2), 3.63 (m, J = 11.6 and 9.1 Hz, N-CH2CH2), 3.46 (m, J = 11.6 Hz, N-CH2CH2), 3.37 (t, J = 6.7
Hz, H-1′), 3.33 (d, J = 5.3 Hz, H-1), 2.68 (m, J = 12.9 and 9.1 Hz, N-CH2CH2), 2.49 (dd, J = 13.3 and 9.6 Hz, H-3),
2.40–2.33 (m, H-3 and N-CH2CH2), 1.49 (p, H-2′), 1.21 (m, H-3′ – H-7′), 0.81 (t, J = 6.7 Hz, H-8′)
99.1
99.6
99.2
GEA-12 4.81 (bs, OH), 3.88 (m, H-2), 3.67 (m, J = 11.6 and 9.3 Hz, N-CH2CH2), 3.49 (m, J = 11.6 Hz, N-CH2CH2), 3.40 (t, J =
6.7 Hz, H-1′), 3.36 (d, J = 5.3 Hz, H-1), 2.72 (m, J = 13.4 and 9.2 Hz, N-CH2CH2), 2.54 (dd, J = 13.3 and 9.7 Hz, H-3),
2.43–2.35 (m, H-3 and N-CH2CH2), 1.53 (p, H-2′), 1.22 (m, H-3′ – H-11′), 0.81 (t, J = 6.7 Hz, H-12′)
GEA-18 4.86 (bs, OH), 3.92 (m, H-2), 3.71 (m, J = 11.6 and 9.0 Hz, N-CH2CH2), 3.54 (m, J = 11.8 Hz, N-CH2CH2), 3.41 (d, J =
2.5 Hz, H-1′), 3.39 (t, J = 3.5 Hz, H-1′), 3.36 (d, J = 5.3 Hz, H-1), 2.76 (m, J = 13.5 and 9.0 Hz, N-CH2CH2), 2.59 (dd, J =
13.4 and 9.7 Hz, H-3), 2.51–2.40 (m, H-3 and N-CH2CH2), 1.57 (p, H-2′), 1.22 (m, H-3′ – H-17′), 0.88 (t, J = 6.7 Hz,
H 18′)
QM-6
4.36 (m, H-2), 3.71 (s, CH3OSO3−), 3.55–3.36 (m, H-1′, H-1, and H-3), 3.32 (s, N-CH3), 2.55 (bs, OH), 1.59 (p, H-2′),
1.28 (m, H-3′ – H-5′), 0.89 (t, J = 6.7 Hz, H-6′)
99.5
98.7
QM-8
4.97 (bs, OH), 4.37 (m, H-2), 3.71 (s, CH3OSO3−), 3.56–3.38 (m, H-1′, H-1, and H-3), 3.33 (s, N-CH3), 1.54 (p, H-2′),
1.27 (m, H-3′ – H-7′), 0.88 (t, J = 6.6 Hz, H-8′)
QM-12
QM-18
QEA-6
QEA-8
5.78 (s, OH), 4.29 (m, H-2), 3.90 (s, CH3OSO3−), 3.47–3.29 (m, H-1′, H-1, and H-3), 3.25 (s, N-CH3), 1.47 (p, H-2′), 1.19 99.2
(m, H-3′ – H-11′), 0.81 (t, J = 6.6 Hz, H-12′)
4.80 (bs, OH), 4.30 (m, H-2), 3.65 (s, CH3OSO3−), 3.49–3.32 (m, H-1′, H-1, and H-3), 3.27 (s, N-CH3), 1.46 (p, H-2′),
1.19 (m, H-3′ – H-17′), 0.81 (t, J = 6.2 Hz, H-18′)
99.5
99.0
99.4
98.7
99.0
4.70 (bs, OH), 4.36 (m, H-2), 4.06 (m, N-CH2CH2), 3.71 (m, CH3OSO3 and N-CH2CH2), 3.57 (m, H-1), 3.49 – 3.30 (m,
H-1′, H-3), 3.31 (s, N-CH3), 1.48 (p, H-2′), 1.28 (m, H-3′ – H-5′), 0.81 (t, J = 6.4 Hz, H-6′)
4.60 (s, OH), 4.28 (m, H-2), 3.99 (m, N-CH2CH2), 3.64 (m, CH3OSO3 and N-CH2CH2), 3.50 (m, H-1), 3.50 – 3.29 (m,
H-1′, H-3), 3.24 (s, N-CH3), 1.48 (p, H-2′), 1.20 (m, H-3′ – H-7′), 0.81 (t, J = 6.4 Hz, H-8′)
QEA-12 4.76 (s, OH), 4.36 (m, H-2), 4.06 (m, N-CH2CH2), 3.71 (m, CH3OSO3 and N-CH2CH2), 3.56 (m, H-1), 3.46 – 3.38 (m,
H-1′, H-3), 3.31 (s, N-CH3), 1.54 (p, H-2′), 1.26 (m, H-3′ – H-11′), 0.88 (t, J = 6.7 Hz, H-12′)
QEA-18 4.73 (s, OH), 4.35 (m, H-2), 4.06 (m, N-CH2CH2), 3.71 (m, CH3OSO3 and N-CH2CH2), 3.56 (m, H-1), 3.46 – 3.36 (m,
H-1′, H-3), 3.31 (s, N-CH3), 1.54 (p, H-2′), 1.25 (m, H-3′ – H-17′), 0.88 (t, J = 6.7 Hz, H-18′)
aSee Scheme 2; GM, alkyloxy-2-hydroxypropyldimethylamine.
bSee Scheme 3;GEA, alkyloxy-2-hydroxypropyldiethanolamine.
cSee Scheme 4; QM, 1-alkyloxypropan-2-ol-3-trimethylammoniium methylsulfate.
dSee Scheme 5; QEA, 1-alkyloxypropan-2-ol-3-methyldiethanolammonium methylsulfate. See Table 1 for abbreviation.
purity of GM series was determined by amine value (12). The QM-18, respectively (Scheme 4). All the QM were synthe-
1H NMR data for GM series were collected with the corre- sized by the general synthetic method (11). The purity of QM
lated data and are summarized in Table 2 (Scheme 2).
series was determined by 1H NMR, i.e., the integration ratio
Alkyloxy-2-hydroxypropyldiethanolamine (GEA). Alkyl of the separated peaks of GM (2.43–2.24 ppm) against the
groups are hexyl, octyl, dodecyl, and octadecyl, and their de- overlapped peaks of GM and QM (3.55–3.32 ppm). The ana-
rivatives are GEA-6, GEA-8, GEA-12, and GM-18, respec- lytical results and the 1H NMR data for QM series are sum-
tively (Scheme 3). All the GEA were synthesized by the gen- marized in Table 2 (Scheme 4).
eral synthetic method (11) except using excess 0.05 molar ra-
1-Alkyloxypropan-2-ol-3-methyldiethanolammonium
tios of GE to diethanolamine. By removing the unreacted GE methylsulfate (QEA). Alkyl groups are hexyl, octyl, dodecyl,
at the boiling point of GE, all GEA were purified, respec- and octadecyl, and their derivatives are QEA-6, QEA-8,
tively. The purity of GEA series was determined by amine QEA-12, and QEA-18, respectively (Scheme 5). All the QEA
value (12). Table 2 shows the analytical and 1H NMR data for were synthesized by the general synthetic method (11). The
GEA series (Scheme 3).
purity of QEA series was determined by 1H NMR, i.e., the in-
1-Alkyloxypropan-2-ol-3-trimethylammonium methylsul- tegration ratio of the separated peaks of GEA (2.76–2.40
fate (QM). Alkyl groups are hexyl, octyl, dodecyl, and oc- ppm) against the overlapped peaks of GEA and QEA
tadecyl, and their derivatives are QM-6, QM -8, QM-12, and (3.71–3.31 ppm). The 1H NMR data for QEA series were col-
JAOCS, Vol. 78, no. 4 (2001)

426
H.-C. KANG ET AL.
(i) Solvent effects. The effect of water on the formation of
glycidyl ether was investigated in the binary phase system of
water/n-hexane. In the experiments on the effect of water, we
employed the optimal condition of Urata et al. (9). Various
mixed solvents of water (0–7.2 mol) and n-hexane (11.6 mol)
were added to the mixture of octanol (1 mol), sodium hydrox-
ide (3 mol) (20–40 mesh beads), and TBAB (0.05 mol) at
40°C before adding epichlorohydrin (2 mol). The reaction
was completed when the yield of the octylglycidyl ether did
not increase any more with the reaction time. The final prod-
uct components were analyzed by GC, and their GC retention
times are as follows: unreacted octanol (6.87 min), 3-chloro-
prop-2-enylglycidyl ether (7.31 min), octylglycidyl ether
(11.39 min), 1,3-dioctyloxy-2-propanol (18.88 min), and 1,3-
dioctyloxy-2-propylglycidyl ether (21.04 min). The effects of
mixed solvents on the yields of final product components are
shown in Table 3. It is interesting to note that the yields of
octylglycidyl ether showed the similar value of 84.5–85.5%
regardless of the amount of the water in the mixed solvents
(Table 3). By decreasing the amount of the water from 7.2 to
0 mol, the reaction time is reduced from 6 to 3.5 h, with the
amount of the unreacted octanol decreased from 7.9 to 1.4%.
However, the amount of 3-chloroprop-2-enylglycidyl ether
was increased from 0.8 to 8.9%. This is the only disadvan-
tage accompanied by an increase in the amount of 3-chloro-
prop-2-enylglycidyl ether generated from epichlorohydrin by
hydrogen elimination under excess base condition (13).
Therefore, the introduction of some other conditions should
be considered for the formation of octylglycidyl ether with-
out using water (see below).
SCHEME 3
SCHEME 4
SCHEME 5
lected with the correlated data and are summarized in Table 2
(Scheme 5).
On the other hand, when using the various amounts of n-
hexane (2.9–11.6 mol) with the fixed 7.2 mol of water, each
reaction time was about 6 h. The amounts of unreacted oc-
tanol (7.9–7.6%), 3-chloroprop-2-enylglycidyl ether (0.8–1.0
%), and octylglycidyl ether (84.2–84.5%) were almost con-
stant regardless of the amount of the added n-hexane (Table
3). These results indicate that the change in the amount of the
n-hexane added does not affect the formation of octylglycidyl
ether. The removal of the n-hexane in the reaction system for
the preparation could be considered. Therefore, the method
for the synthesis of the glycidyl ethers was investigated in the
reaction condition without water and other organic solvents
RESULTS AND DISCUSSION
The formation of octylglycidyl ether: In order to develop the
improved synthetic method, the effects of the following fac-
tors on the glycidyl ether formation have been considered: (i)
solvent, (ii) the concentration of reactants (epichlorohydrin
and sodium hydroxide), (iii) various catalysts such as amine
derivatives and ammonium derivatives, and (iv) reaction tem-
perature.
TABLE 3
Solvent Effects on the Formation of Octylglycidyl Ethera
Glycidyl ethers (%)
1,3-
3-Chloroprop-2-
1,3-Dioctyloxy-2- Dioctyloxy-
Solvents (mol)
n-Hexane
Reaction time
(h)
Octanol
(%)
enylglycidyl ether
(%)
Octylglycidyl
ether
propylglycidyl
ether
2-propanol
(%)
Water
11.6
11.6
11.6
5.8
7.2
1.8
0
7.2
7.2
6
7.9
2
1.4
7.9
7.6
0.8
6.9
8.9
0.9
1.0
84.5
85.5
84.6
84.5
84.2
2.2
0.8
0.8
1.8
1.3
1.5
1.5
3.3
1.7
3.6
3.5
3.5
6
2.9
6
aThe reaction condition: octanol (1 mol), epichlorohydrin (2 mol), sodium hydroxide (3 mol), and tetrabutylammonium bromide (TBAB) (0.05
mol) at reaction temperature of 40°C.
JAOCS, Vol. 78, no. 4 (2001)

AN IMPROVED METHOD FOR SYNTHESIS OF GLYCIDYL ETHER
427
TABLE 4
The Effect of the Reactants and Temperature Factors on the Formation of Octylglycidyl Ethera
Amount of reactants (mol)
Reaction
time
3-Chloroprop-2-
enylglycidyl
ether (%)
Glycidyl ethers (%)
Octylglycidyl 1,3-Dioctyloxy-2-
propylglycidyl ether propanol (%)
1,3-
Dioctyloxy-2-
Sodium
Epichloro-
hydrin
PTC
Temperature
(°C)
Octanol
(%)
hydroxide
(TBAB)
(h)
ether
1.0
1.2
1.5
1.6
1.7
1.8
2.0
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
2.0
2.0
2.0
2.0
2.0
2.0
2.0
1.2
1.4
1.6
1.8
2.0
3.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
0.00625
0.00625
0.00625
0.00625
0.00625
0.00625
0.00625
0.00625
0.00625
0.00625
0.00625
0.00625
0.00625
0.0015
0.00625
0.0500
0.00625
0.00625
0.00625
0.00625
40
40
40
40
40
40
40
40
40
40
40
40
40
40
40
40
20
40
60
70
3
3
17.4
10.9
1.5
1.7
1.6
1.2
2
1.6
1.3
1.6
1.4
1.5
3.4
3.1
1.5
1.7
1.9
1.5
3.5
10.5
<0.2
<0.2
<0.2
1.1
1.1
2.4
78.1
84.8
92.0
92.0
92.3
91.0
86.0
81.0
85.3
87.2
89.2
92.0
89.0
90.2
92.0
90.2
91.6
92.0
90.1
80.0
1.7
2.3
4.8
5.4
5
2.7
2
3.5
3.5
3.5
3.5
3.5
3.5
3.5
3.5
3.5
3.5
3.5
11.5
3.5
3
0.8
0.4
<0.2
<0.2
1.2
11.2
6.0
1.0
0.7
0.8
0.9
1.3
0.8
0.7
0.6
0.8
1.4
3.0
5.6
3
7.9
<0.2
<0.2
<0.2
<0.2
<0.2
1.0
0.9
<0.2
1.3
1.8
8.4
7.4
6.3
4.8
5.8
4.5
4.8
5.1
5.2
4.8
4.3
2.0
12
0.6
<0.2
0.7
3.5
3.5
3.5
1.9
aPTC, phase transfer catalyst. See Table 3 for other abbreviation.
by preventing the formation of 3-chloroprop-2-enylglycidyl the amount of the epichlorohydrin added. The amount of the
ether with using the optimal reaction conditions, i.e., reaction undesired 1,3-dioctyloxy-2-propanol increased proportion-
mole ratio (epichlorohydrin, sodium hydroxide, and TBAB), ally from 1.0 to 11.2% with decreasing the amount of the
temperature and catalyst, especially, the optimal amount of added epichlorohydrin from 1.6 to 1.2 mol. Accordingly, in
sodium hydroxide.
order to prevent the formation of the undesired 1,3-dioctyl-
(ii) The effects of reactants (sodium hydroxide and oxy-2-propanol and/or polymerization, the amount of
epichlorohydrin) concentration. In the reaction condition epichlorohydrin more than 1.6 mol was used in the reaction
without water and other organic solvents at 40°C, the reac- for octylglycidyl ether. The yield of octylglycidyl ether in-
tants used and their amounts are octanol (1 mol), epichloro- creased gradually from 81.0 to 92.0% with increasing amount
hydrin (2 mol), solid sodium hydroxide (20–40 mesh beads), of the added epichlorohydrin from 1.2 to 2.0 mol. The use of
and TBAB (0.00625 mol). The amount of sodium hydroxide excess epichlorohydrin (3 mol) did not increase the yield of
used varied from 1.0 to 2.0 mol. Table 4 represents the yields glycidyl ether, but did increase the amount of the unreacted
of octylglycidyl ether, unreacted octanol, and by-products in octanol and 3-chloroprop-2-enylglycidyl ether. Therefore,
the reaction mixture after the reaction was completed. The these results indicate that the optimal amount of epichlorohy-
unreacted octanol remained more than 10% when the amount drin is 2.0 mol for the efficient formation of the octylglycidyl
of the solid sodium hydroxide added was less than 1.2 mol. ether.
When the amount of sodium hydroxide added was between
(iii) The catalyst effects. Generally, PTC is used in a binary
1.5 and 1.7 mol, the yield of octylglycidyl ether reached solvent system due to its solubility in both solvents. The con-
92.0–92.3%. The amount of 3-chloroprop-2-enylglycidyl ventional PTC methods to obtain glycidyl ether or glycidyl
ether increased gradually from 1.1 to 7.9% with increasing ester are the reaction in aqueous phase/organic phase (n-
the amount of sodium hydroxide from 1.6 to 2.0 mol. There- hexane) (9) or solid phase/organic phase (toluene) (14). How-
fore, a waste of the reactant such as epichlorohydrin increases ever, our reaction system contains neither aqueous phase nor
gradually with increasing the amount of the undesired 3- organic phase (n-hexane or toluene). For this reason, the sol-
chloroprop-2-enylglycidyl ether derived from epichlorohy- ubility reaction of TBAB to the reactants and octylglycidyl
drin in excess sodium hydroxide. These results indicate that ether was tested. TBAB (0.001 mol) is dissolved clearly in
the optimal quantity of sodium hydroxide is 1.5 mol.
octanol (0.1 mol), epichlorohydrin (0.1 mol), and octylgly-
The concentration of epichlorohydrin also has the impor- cidyl ether (0.1 mol) at 40°C, respectively. Therefore, the re-
tant effect on the formation of glycidyl ether. The various actants and products themselves play the role of solvent, re-
amount of epichlorohydrin (1.2–3.0 mol) was added to the re- placing other organic solvents. Thus, our reaction system con-
action mixture solution with 1.5 mol of sodium hydroxide op- sists of solid phase/organic phase (reactants and product).
timized as mentioned above. Table 4 shows the yields of
As mentioned above, the various amounts of TBAB
octylglycidyl ether, octanol, and by-product as a function of (0.0015–0.05 mol) were added to the reactant mixture with
JAOCS, Vol. 78, no. 4 (2001)

428
H.-C. KANG ET AL.
TABLE 5
Test of Various Catalysts for the Formation of Octylglycidyl Ethera
Reaction
time
3-Chloroprop-2-
enylglycidyl ether
(%)
Glycidyl ethers (%)
1,3-Dioctyloxy-
propan-2-ol
(%)
Octanol
(%)
Octylglycidyl
1,3-Dioctyloxy-2-
Catalyst
(h)
ether
propylglycidyl ether
QM-6
QM-8
4
5
9
8
5
9
9
9
3
4
12
4
5
5
5
3
24
24
24
1.6
0.9
2.2
0.9
1.3
2.9
2.2
1.7
0.8
0.6
<0.2
<0.2
1.3
1.4
1.2
1.1
1.8
2.3
1.9
<0.2
<0.2
<0.2
<0.2
0.3
<0.2
<0.2
<0.2
0.6
90.4
89.4
89.6
88.9
91.4
89.3
88.1
91.1
92.4
89.3
92.0
93.2
90.9
91.9
89.6
92.9
92.7
91.9
93.0
6.0
7.5
6.8
7.7
4.5
5.9
8.0
6.1
5.7
6.0
6.0
4.8
6.2
6.2
6.4
5.1
4.3
4.1
3.8
1.0
0.4
1.5
0.4
0.8
1.4
1.8
1.1
0.6
0.5
<0.2
<0.2
0.5
0.5
0.5
0.8
0.6
0.8
0.5
QM-12
QM-18
QEA-6
QEA-8
QEA-12
QEA-18
CETAC
LMBAC
TBAH
1.6
<0.2
<0.2
0.4
<0.2
0.6
<0.2
<0.2
<0.2
<0.2
GM-6
GM-8
GM-12
GM-18
GEA-6
GEA-8
GEA-12
GEA-18
aThe reaction condition: octanol (1 mol), epichlorohydrin (2 mol), sodium hydroxide (1.5 mol), and catalyst (0.015 mol) at reation temperature of 40°C.
CETAC, cetyltrimethylammonium chloride; LMBAC, lauryldimethylbenzylammonium chloride; TBAH, tetrabutylammonium hydrogensulfate. See Table 2
for other abbreviations.
the optimized amounts of the sodium hydroxide and uct themselves play the role of solvent to replace other organic
epichlorohydrin. After the reaction was completed, the yields solvents. The QM, QEA, GM, GEA series can be easily syn-
of octylglycidyl ether, octanol, and by-products were quanti- thesized as represented in the Experimental Procedures section
fied by GC, and their results are shown in Table 4. When the (Tables 2 and 5). The above optimized reaction system using
amount of the added TBAB was 0.0015 mol, the amount of the catalysts instead of TBAB produced octylglycidyl ether
unreacted octanol was 3.1%. When the amount of the TBAB with the yield of 88.1–93.2% (Table 5). The reaction time in-
added was 0.0016, 0.00625, and 0.05 mol, respectively, the creased by increasing the alkyl chain length of our synthesized
yields of octylglycidyl ether were almost the same (90.2–92.0%) catalysts (QM, QEA, GM, and GEA series).
regardless of the amount of the TBAB added. The reaction
(iv) The temperature effects. Under the optimized molar
time increased gradually from 3.0 to 11.5 h with decreasing ratio of reactants as mentioned above, the reaction tempera-
amount of added TBAB, from 0.05 to 0.0015 mol. However, ture was varied from 20 to 70°C. Table 4 represents the
variation of the amount of TBAB (0.00625–0.05 mol) used amount of the components in product mixture as a function
did not affect the reaction time very significantly (3.0–3.5 h). of the temperature. In the reaction at 20 and 40°C, the yields
In order to determine the optimal amount of the added TBAB of the octylglycidyl are the high value of 91.6 and 92.0%, re-
for the preparation of the octylglycidyl ether, we chose the spectively. The reaction time at 20 and 40°C was about 12 and
amount of the catalyst to derive the short reaction time 3.5 h, respectively. As the reaction temperature rose from 40
(0.00625 and 0.05 mol) and then minimize the amount of the to 70°C, the yield of octylglycidyl ether was decreased from
catalyst used (0.0015 and 0.00625 mol). These results indi- 92.0 to 80.0%, and the amount of unreacted octanol increased
cate that the optimal quantity of TBAB for its preparation is from 1.5 to 10.5%. The reaction at high temperature drops the
0.00625 mol.
yield of octylglycidyl ether because of the exothermic reac-
To investigate the effect of various PTC on the glycidyl tion. It was supposed the reverse reaction, which progresses
ether formation, TBAB (0.00625 mol) was replaced by the fol- from octylglycidyl ether to octanol at high temperature (60
lowing catalysts (0.015 mol). The tested catalysts were the de- and 70°C), caused these phenomena, as shown by the de-
rivatives of alkylamines and alkylammonium salts, i.e., TBAH, creasing yield of octylglycidyl ether with rising reaction tem-
CETAC, LMBAC, QM-6, QM-8, QM-12, QM-18, QEA-6, perature. At the reaction temperature of 70°C, the formation
QEA-8, QEA-12, QEA-18, GM-6, GM-8, GM-12, GM-18, of a tiny amount of octanol (about 1% for 1 h) was confirmed
GEA-6, GEA-8, GEA-12, and GEA-18. The solubilities of the by GC from the reaction system using reactants of octylgly-
catalysts in the reactants and octylglycidyl ether were tested. cidyl ether (0.20 mol), sodium hydroxide (0.10 mol), sodium
All of them (0.002 mol) are dissolved clearly in octanol (0.1 chloride (0.20 mol), and TBAB (0.0013 mol). This is the
mol), epichlorohydrin (0.1 mol), and octylglycidyl ether (0.1 probe of reverse reaction occurring at high temperature.
mol) at 40°C, respectively. Therefore, the reactants and prod- Therefore, the optimized temperature for the formation of
JAOCS, Vol. 78, no. 4 (2001)

AN IMPROVED METHOD FOR SYNTHESIS OF GLYCIDYL ETHER
429
TABLE 6
The Standard Deviation for the Formation of Octylglycidyl Ethera
3-Chloroprop-2-
enylglycidyl ether
(%)
Glycidyl ethers (%)
1,3-Dioctyloxy-2-
propanol
Octanol
(%)
Octylglycidyl
ether
1,3-Dioctyloxy-2-
propylglycidyl ether
Order
(%)
1
2
3
4
1.5
1.9
1.5
1.6
1.2
1.5
0.4
<0.2
<0.2
<0.2
<0.2
<0.2
92.0
92.0
91.7
92.3
91.2
91.8
0.4
4.8
4.3
4.6
4.9
6.0
4.9
0.7
0.8
0.6
0.6
0.8
0.7
0.7
0.1
5
b
Average value
Standard
deviation
—
b
—
aThe reaction condition: octanol (1.0 mol), epichlorhydrin (2.0 mol), sodium hydroxide (1.5 mol), and TBAB
(0.00625 mol), temperature 40°C. See Table 3 for abbreviation.
bNot determined.
2. Barlow, J.J., and L.H. Smith, Alkanolamine Derivatives, U.S.
Patent 4,550,111 (1985).
3. Saito, N., S. Kanagawa, and H. Sakamoto, Glycidyl Ethers of
Phenolic Compounds and Process for Producing the Same, U.S.
Patent 5,008,350 (1991).
4. Suzuki, T., G. Imokawa, and A. Kawamata, Development of
Synthetic Ceramide-Based Biomimetic Skin-Care Products,
Nippon Kagaku Kaishi:1107–1117 (1993).
5. Chang, W.-H., R. Piccirilli, and D.A. Diehl, Coating Composi-
tions Formulated from Polyols Modified by Reaction with Gly-
cidyl Ether, U.S. Patent 4,314,923 (1982).
6. Kim, T.-S., T. Hirao, and I. Ikeda, Preparation of bis-quaternary
Ammonium Salts from Epichlorohydrin, J. Am. Oil. Chem. Soc.
73:67–71 (1996).
7. Urata, K., and N. Takaishi, Ether Lipids Based on the Glyceryl
Ether Skeleton: Present State, Future Potential, Ibid.
73:819–830 (1996).
8. Andrew, C.M., W.M. Rolfe, and M.R. Thoseby, Glycidyl Ether
from Alcohol and Epichlorohydrin, U.S. Patent 5,420,312
(1995).
9. Urata, K., S. Yano, A. Kawamata, N. Takaishi, and Y. Inamoto,
A Convenient Synthesis of Long-Chain 1-O-Alkyl Glyceryl
Ethers, J. Am. Oil. Chem. Soc. 65:1299–1302 (1988).
10. Najem, L., and M.E. Borredon, Single-Step Etherification of
Fatty Alcohols by an Epihalohydrin, Syn. Comm. 24:3021–3030
(1994).
11. Kalopissis, G., and G. Vanlerberghe, Cationic Surface-Active
Agents, U.S. Patent 3,879,464 (1975).
12. Official Methods and Recommended Practices of the American
Oil Chemists’ Society, edited by D. Firestone, American Oil
Chemists’ Society, Champaign, 1989, Official Methods Tf 1b-
64 and 2b-64.
13. Bartók, M., and K.L. Láng, Oxiranes, in The Chemistry of
Ethers, Crown Ethers, Hydroxyl Groups and Their Sulphur Ana-
logues, edited by S. Patai, Wiley, New York, 1980, pp. 609–681.
14. Serin, A., N. Gartl, and Y. Sasson, Preparation of Monoglyc-
erides of Fatty Acids from Epichlorohydrin by Phase-Transfer
Catalysis. Glycidyl Esters, Ind. Eng. Chem. Prod. Res. Dev. 23:
452–454 (1984).
octylglycidyl ether is 40°C in the reaction condition using re-
actants of octanol (1.0 mol), epichlorohydrin (2.0 mol),
sodium hydroxide (1.5 mol), and TBAB (0.00625 mol). To
provide the estimate of the standard deviation, five repetitive
experiments were carried out in the optimized reaction condi-
tion. The average value and standard deviation of octylgly-
cidyl ether yield are 91.8 and 0.42%, respectively (Table 6).
II. The formation of octadecylglycidyl ether. As mentioned
above, glycidyl ether has been conventionally synthesized by
the Lewis acid method or the PTC method in the water/
n-hexane system. However, especially, these methods do not
give rise to the high yield of the alkylglycidyl ether having
long-chain alcohol such as an octadecanol. Then the present
reaction system using the PTC method without water and
other organic solvents was applied to the synthesis of octade-
cylglycidyl ether. The reaction temperature of 60°C was used
to liquify octadecanol (melting point: 60°C). The effects of
sodium hydroxide and epichlorohydrin for the formation of
octadecylglycidyl ether were similar to those of previous
octylglycidyl ether except the added amount of sodium hy-
droxide. In the optimal reaction condition using reactants of
octadecanol (0.60 mol), epichlorohydrin (1.2 mol), sodium
hydroxide (1.4 mol), and TBAB (0.0038 mol) at 60°C, the
yields of the components and the retention time in the prod-
uct mixture are as follows: 3-chloroprop-2-enylglycidyl ether
(1.5%, 7.31 min), unreacted octadecanol (0.7%, 18.21 min),
octadecylglycidyl ether (91.7%, 20.85 min), 1,3-dioctadecyl-
oxy-2-propylglycidyl ether (3.8%, 33.68 min) (the molar ratio
of octadecanol/epichlorohydrin/sodium hydroxide/TBAB =
1:2.3:2:0.00625).
ACKNOWLEDGMENT
This work has been supported by the Ministry of Science and Tech-
nology.
REFERENCES
1. Reinehr, D., and R. Töpfl, Phenylalkyl Glycidyl Ether Addition
Products, U.S. Patent 5,250,202 (1993).
[Received April 24, 2000; accepted September 28, 2000]
JAOCS, Vol. 78, no. 4 (2001)