Synthesis, structure, and transformations of cyclic glycerol formals

Article abstract of DOI:10.1007/s11172-015-1123-z

Glycerol reacts with paraformaldehyde to give a mixture of 4-hydroxymethyl-1,3-dioxolane and 5-hydroxy-1,3-dioxane. Some transformations (alkylation and replacement of the OH groups with the Cl atoms) of the synthesized compounds were performed. The differences in NMR and mass spectra of the corresponding 1,3-dioxolanes and 1,3-dioxanes were revealed and discussed.

Full text of DOI:10.1007/s11172-015-1123-z

Russian Chemical Bulletin, International Edition, Vol. 64, No. 9, pp. 2095—2099, September, 2015
2095
Synthesis, structure, and transformations of cyclic glycerol formals*
G. Z. Raskildina, V. F. Valiev, R. M. Sultanova, and S. S. Zlotsky
Ufa State Petroleum Technological University,
1
ul. Kosmonavtov, 450062 Ufa, Russian Federation.
Tel.: +7 (347) 242 0854. Eꢀmail: graskildina444@mail.ru
Glycerol reacts with paraformaldehyde to give a mixture of 4ꢀhydroxymethylꢀ1,3ꢀdioxolane
and 5ꢀhydroxyꢀ1,3ꢀdioxane. Some transformations (alkylation and replacement of the OH
groups with the Cl atoms) of the synthesized compounds were performed. The differences in
NMR and mass spectra of the corresponding 1,3ꢀdioxolanes and 1,3ꢀdioxanes were revealed
and discussed.
Key words: cyclic glycerol formals, alkylation, 1,3ꢀdioxolanes, 1,3ꢀdioxanes.
Cyclic acetals and ketals of triols, particularly glycerol,
The starting glycerol formals 1a,b (in a ratio 1a : 1b = 3 : 2)
were synthesized in 95% yield by condensation of glycerol
with paraformaldehyde in toluene at 100 C in the presꢀ
ence of ionꢀexchange resin Dowexꢀ50 as a catalyst.
Subsequent Oꢀalkylation of 1a,b with allyl chloride
and benzyl chloride (Scheme 1) afforded the correspondꢀ
ing ethers 2a,b and 3a,b in the yields of 75—80%. In
the obtained mixtures, the content of fiveꢀmembered
derivatives 2a and 3a (2a : 2b = 3a : 3b = 2 : 1) is someꢀ
what higher as compared with the starting formal mixꢀ
ture. This fact can be explained by the enhanced reacꢀ
tivity of the primary hydroxy group of formal 1a comꢀ
pared with the secondary one of incompletely reacted
isomer 1b.
1
—3
found a wide application in fine organic synthesis.
It
has been recently shown that certain compounds of this
4
,5
series can be employed as antiꢀfreeze additives for fuels,
6
7
8
as surfactants, additives in food and cosmetic indusꢀ
tries. Therefore, the studies of the structure of cyclic glycꢀ
erol formals and their derivatives are of great interest. Earꢀ
lier, we have shown that Oꢀalkylation of 4ꢀhydroxymethꢀ
ylꢀ2,2ꢀdimethylꢀ1,3ꢀdioxolane resulted in the correspondꢀ
ing derivatives in quantitative yield.9
The present work is devoted to the synthesis and strucꢀ
ture elucidation of ethers and chlorides derived from
ꢀhydroxymethylꢀ1,3ꢀdioxolane (1a) and 5ꢀhydroxyꢀ1,3ꢀ
4
dioxane (1b).
Scheme 1
R = CH —CH=CH (2a,b), Bn (3a,b)
2
2
+
–
Reagent and conditions: a. HO(CH O) H (n  8—100), toluene, 100 C, 6 h; b. RCl, 50% aqueous NaOH, Q Cl , toluene, 70 C, 1 h;
2
n
+
–
c. SOCl , pyridine, 55—60 C, 6 h; d. ROH, NaOH, Q Cl , DMSO, 90—70 C, 10 h; e. HO(CH O) H, H O, H SO , 90—100 C, 2 h.
2
2
n
2
2
4
*
Dedicated to Academician of the Russian Academy of Sciences N. S. Zefirov on the occasion of his 80th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2095—2099, September, 2015.
066ꢀ5285/15/6409ꢀ2095 © 2015 Springer Science+Business Media, Inc.
1

2
096
Russ.Chem.Bull., Int.Ed., Vol. 64, No. 9, September, 2015
Raskildina et al.
Treatment of a mixture of glycerol formals 1a,b with
thionyl chloride in pyridine (see Scheme 1) resulted in
ꢀchloromethylꢀ1,3ꢀdioxolane (4a) and 5ꢀchloroꢀ1,3ꢀdiꢀ
oxane (4b). A mixture of chloro derivatives 4a,b with an
increased content of dioxolane derivative 4a (4a : 4b = 3 : 1)
was obtained in 50% yield.
The structures of synthesized fiveꢀ and sixꢀmembered
1
13
heterocycles were confirmed by H and C NMR spectroꢀ
scopy (Table 1) and gas chromatography/mass spectroꢀ
metry. Note that the spectral data for glycerol formals
lacking substituents at the 2 position of heterocycle are
scarce.
4
Individual ethers 2a and 3a were synthesized by Oꢀalkylꢀ
ation of the corresponding alcohols with 4ꢀchloromethylꢀ
The signals of substituted 1,3ꢀdioxolanes 1a—4a and
1,3ꢀdioxanes 1b—4b are attributed taking into account the
chemical shifts and spinꢀspin coupling constant values of
the heterocyclic fragments (Fig. 1). Thus, singlet signals
1
,3ꢀdioxolane (4a) obtained from epichlorohydrin and
paraformaldehyde (see Scheme 1).
Table 1. H and 13C NMR spectra of compounds 1a,b—4a,b
1
Comꢀ
pound
X
 (J/Hz)
1H
13C
Н(2)
Н(4)
Н(5)
Н(6)
—
X
С(2) С(4) С(5) С(6)
94.76 76.97 69.65
93.62 74.50 65.04 66.18
X
1
1
а
b
CH OH
4.83 (s),
.97 (s)
4.71
3.50—4.00 3.50—3.70
(m) (m)
3.50—4.00 3.40—3.43 3.50—3.70
3.40—3.43
(m, 3 Н)
3.10
—
35.27
2
5
OH
—
(
d, J = 5.9);
.80
(m)
(m)
(m)
(br.s)
4
(
d, J = 6.0)
2
2
а
b
СН OCH CH=CH
2
4.95 (s),
4.22
(quint,
J = 6.2)
4.02
(m)
—
3.70 (m);
3.55 (m, 2 Н);
5.10
95.95 75.19 72.83
—
67.90
2
2
5
.00 (s)
(СН );
2
3
71.36;
135.74;
116.96
70.63,
135.85,
116.96
(
dd, 2 Н);
5
.90 (1 Нb)
3.55
OCH CH=CH2
4.70
3.30—3.80
3.95
3
3.30—3.80
94.14 70.35 69.62 70.35
2
(
d, J = 5.9); (m, 2 Н) (t, J = 7.4) (m, 2 Н)
.85
(m, 2 Н);
5.10
4
(
d, J = 6.0)
(dd, 2 Н)
5
.90
(
1 Нb)
3
а
СН ОCH Ph
4.90 (s),
4.25
4.05
—
3.55—3.73
(m, 4 Н);
6.90—7.30
(5 Н, Ph)
95.34 77.58 74.44
—
70.41
2
2
3
5
.04 (s)
(quint, (d, J = 3.6);
J = 6.2)
(СН );
2
3
4.08
76.73
3
(
d, J = 4.8)
(СН Ph);
2
1
1
1
37.95,
28.19,
28.53,
1
1
27.15 (Ar)
77.15
3b
4а
4b
ОCH Ph
4.71
4.54—4.62
3.96
4.54—4.62 3.55—3.73
93.61 68.94 71.28 69.49
2
3
(
d, J = 6.1); (m, 2 Н) (t, J = 7.0) (m, 2 Н)
(m, 2 Н);
6.90—7.30
(5 Н, Ph)
(СН Ph);
2
4
.87
138.04,
127.94,
(
d, J = 6.2)
1
28.80,
28.47 (Ar)
43.96
СН Сl
4.92 (s),
.07 (s)
4.26
3.84
—
3.46
(dd, J = 6.8,
J = 11.1);
95.73 74.79 71.74
—
2
3
3
5
(tdd,
J = 6.8,
J = 6.5,
(dd, J = 4.9,
3
3
3
2
3
J = 8.7);
4.00
3
3.60
3
J = 4.9) (dd, J = 6.5,
(dd, J = 4.9,
3
3
J = 8.7)
4.00—4.09
(m)
J = 10.9)
Cl
4.67
3.74
3
3.68
(d, J = 5.4);
—
93.66 71.74 48.74 68.07
—
3
(
d, J = 6.1); (d, J = 5.4);
.96 3.80
d, J = 6.2) (d, J = 5.4)
4
3.78
3
3
(
(d, J = 5.4)

Cyclic glycerol formals
Russ.Chem.Bull., Int.Ed., Vol. 64, No. 9, September, 2015 2097
1
at H 4.92 and 5.07 in H NMR spectrum of a mixture of
appears at H 3.68 as doublets with spinꢀspin coupling
4
ꢀchloromethylꢀ1,3ꢀdioxolane (4a) and 5ꢀchloroꢀ1,3ꢀdiꢀ
constant of 5.4 Hz; the H (4) and H (6) protons resoꢀ
eq
eq
oxane (4b) are attributed to the protons of the methylene
group at C(2) of dioxolane 4a, the methyne proton at C(4)
nate at H 3.74 and 3.80 as doublets with equal spinꢀspin
coupling constant value of 5.4 Hz.
of dioxolane cycle resonates at  4.26 as triplet of doublet
of doublets with spinꢀspin coupling constants J = 6.8,
Note that the chemical shifts of the C(5)H and OH
protons ( 3.40—3.43 and 3.1, respectively) in 1,3ꢀdiꢀ
oxane 1b indicate the intramolecular Hꢀbond formation
due to predominant axial orientation of the OH group.
H
3
6
.5, and 4.9 Hz. Nonꢀequivalent C(5)H protons resonate
2
at H 3.84 and 4.00 as doublet of doublets with spinꢀspin
2
3
10
coupling constants of J = 8.7 Hz and J = 4.9 and 6.5 Hz,
This is in agreement with the previous data on chemical
respectively. Chloromethyl group protons of dioxolane 4a
shifts for cisꢀ2ꢀalkylꢀ5ꢀhydroxyꢀ1,3ꢀdioxane:  3.51 of the
equatorial C(5)H proton and  2.76 of the axial OH group;
while the equatorial OH group signal of transꢀ5ꢀhydroxyꢀ
appear as two doublet of doublets at  3.46 (J = 6.8, 11.1 Hz)
H
and  3.60 (J = 4.9, 10.9 Hz).
H
1
,3ꢀdioxanes is shifted to the upper field ( 1.78) and axial
C(5)H proton resonates in the lower field ( 3.86).
13
C NMR spectra of 1,3ꢀdioxolane derivatives 1a—4a
see Table 1) show characteristic signals of the C(5) atoms
(
at C 70—75, which are shifted downfield as compared
with the C(6) atoms signals of 1,3ꢀdioxanes 1b—4b
(
C 66—70). It is also worthy to note that the signal of the
C(2) adjacent to two heteroatoms in 1,3ꢀdioxolanes 1a—
4a is in lower field ( 95—96) than the signal of the similar
methylene carbon atoms in sixꢀmembered cycles 1b—4b
( 93—94). According to Ref. 11, the C(5) atoms of
2ꢀsubstituted 5ꢀhydroxyꢀ1,3ꢀdioxanes bearing the axial OH
group resonate in the range of  64—65. This is in agreeꢀ
ment with the chemical shift of the C(5) atom of comꢀ
pound 1b and additionally confirms the predominant equaꢀ
torial orientation of the C(5)—H bond.
In the case of 1,3ꢀdioxane 4b, the proton signal at
H 4.00—4.09 corresponds to the C(5) methyne proton.
Anomeric protons at C(2) of dioxane 4b resonate at  4.67
H
and 4.96 as doublets with spinꢀspin coupling constants of
6
5
.1 and 6.2 Hz, respectively, which is characteristic of
ꢀsubstituted 1,3ꢀdioxanes. Axial and equatorial protons
of the C(4) methylene group are equivalent to the C(6)
protons. The high field shifted H (4) and H (6) signals
ax
ax
a
H (2)
H (2)
a
b
H (6)
H (6)
b
H (5) H (5)
a
a
b
H(4)
b
H (6´)
a
H (2)
a
H (6´)
b
H (6)
a
H (5)
a
H (5) H (4´)
Hb(6)
b
a
H(4)
H (4´)
b
H(5´)
H (2´)
H (2´)
a
b
5
.2
5.0
4.8
4.6
4.4
4.2
4.0
3.8
3.6
3.4

1
Fig. 1. H NMR spectra of compound 4a (a) and a mixture of 4a and 4b (b).

2
1
098
Russ.Chem.Bull., Int.Ed., Vol. 64, No. 9, September, 2015
Raskildina et al.
Mass spectra (EI) of the synthesized 4ꢀchloromethylꢀ
,3ꢀdioxolane (4a) and 5ꢀchloroꢀ1,3ꢀdioxane (4b) conꢀ
The principal difference between mass spectra (EI) of
5ꢀchloroꢀ1,3ꢀdioxane 4b and 1,3ꢀdioxolane 4a is the fragꢀ
ment ion with m/z 62/64 [C H Cl]
from ready loss of formaldehyde CH O. The fragmentaꢀ
tion pattern of dioxane 4b confirmed by metastable ion
peaks is given on Scheme 3.
Differences in NMR and mass spectra of isomers
1a,b—4a,b discussed above allow unambiguous identificaꢀ
tion of substituted 1,3ꢀdioxacycloalkanes in the complex
mixtures.
+
•
tain the molecular ion peaks with the intensity >1%, and
fragment ion peaks with m/z 92/94 and m/z 121/123. Forꢀ
mation of these fragment ions can result from various fragꢀ
mentation patterns for compounds 4a and 4b. Thus, diꢀ
oxolane 4a shows characteristic fragment ion with m/z 73
(100%) resulted
2
3
2
(
100%), which is the most abundant fragment ion for cyclic
acetals. Main fragmentation reactions of 1,3ꢀdioxolane 4a
confirmed by metastable ion peaks are shown on Scheme 2.
Experimental
Scheme 2
Gas chromatography was performed on a HRGS 5300 Megaꢀ
Series Carlo Erba chromatograph equipped with a flame ionizaꢀ
tion detector (a 25 m column), carrier gas was helium. Gas chroꢀ
matography/mass spectrometry was performed using a Fisons
instrument (DB 560 quartz capillary column) and a Focus inꢀ
strument equipped with a Finnigan DSQ II mass spectrometer
detector (a Termo TRꢀ5MS column, 50×2.5•10–4) (electron
impact, 70 eV), ionizing chamber temperature of 200 C, direct
–
1
inlet temperature of 50—270 C, heating rate of 10 deg min
,
helium flow rate of 0.7 mL min– ). H and C NMR spectra
were recorded with a Bruker AMꢀ300 instrument (working
frequencies of 300.13 and 75.47 MHz, respectively) in CDCl3
using SiMe4 as an internal standard. Glycerol, epichlorohyꢀ
drin, allyl chloride, and benzyl chloride were commercially
available.
1
1
13
1H and 13C NMR spectral data for compounds 1a,b—4a,b
are summarized in Table 1.
4
ꢀChloromethylꢀ1,3ꢀdioxolane (4a). A mixture of epichloroꢀ
hydrin (9.2 g, 0.1 mol), water (36 mL, 2 mol), and sulfuric acid
0.1 mL, d = 1.84 g mL– ) was vigorously stirred at 90—100 C
1
(
Scheme 3
for 2 h. Then, paraformaldehyde (2.7 g, 0.09 mol) was added and
heating with stirring was continued until complete dissolution.
After completion of the reaction (12 h), the mixture was cooled
to room temperature, washed with 10% aqueous Na CO and
2
3
water till neutral, and extracted with chloroform. The organic
layer was dried with magnesium sulfate, filtered, and distilled
twice to give the product 4a in the yield of 8.5 g (70%). Transparꢀ
ent liquid with a specific odor (b.p. 148 C). MS, m/z (I (%)):
rel
+
1
22/124 [M] (not detected), 121/123 (20/7), 73(100), 45 (36),
4
4 (39), 31 (15).
4
ꢀHydroxymethylꢀ1,3ꢀdioxolane (1a) and 5ꢀhydroxyꢀ1,3ꢀdiꢀ
oxane (1b) (an isomeric mixture). A 250 mL threeꢀneck flask
equipped with a stirrer, an addition funnel, and a Dean—Stark
trap was charged with glycerol (9.2 g, 0.1 mol), paraformaldeꢀ
hyde (2.7 g, 0.09 mol), activated ionꢀexchange resin Dowexꢀ50
(
10 wt.%), and anhydrous toluene (70 mL). The reaction mixꢀ
ture was refluxed until calculated amount of water was distilled
off. The mixture was cooled and filtered. The solvent was reꢀ
moved in low vacuum. Distillation of the residue afforded
a mixture of compounds 1a and 1b in the yield of 9.2 g (93%),
b.p. 190—195 C (760 Torr). An isomeric ratio was determined
1
by H NMR spectroscopy from the integrated intensity ratio of
the signals of H(4) methyne protons (H 3.5—4.0) of dioxolane 1a
and H(5) methyne proton (H 3.5—4.0) of dioxane 1b. Comꢀ
pound 1a. MS (EI, 70 eV), m/z (Irel (%)): 103 [M – H]+ (not
detected), 73 (75), 57 (15), 45 (100), 31 (15). Compound 1b. MS

Cyclic glycerol formals
Russ.Chem.Bull., Int.Ed., Vol. 64, No. 9, September, 2015 2099
+
(
7
EI, 70 eV), m/z (Irel (%)): 103 [M – H] (not detected), 87 (1),
4 (31), 45 (17), 44 (100), 31 (12).
OꢀAlkylation of a mixture of 4ꢀhydroxymethylꢀ1,3ꢀdioxolane
1a) and 5ꢀhydroxyꢀ1,3ꢀdioxane (1b) (general procedure). A fourꢀ
benzyl alcohol (10.8 g), NaOH (10 g, 0.25 mol), Katamine AB
catalyst (0.001 mol), and DMSO (100 mL). The reaction mixꢀ
ture was stirred at 70 C for 2 h until alcoholate was formed, then
4ꢀchloromethylꢀ1,3ꢀdioxolane (4a) (14.8 g, 0.12 mol) was added
over a period of 30 min and the reaction was continued for 8 h.
The mixture was cooled down, washed with water, and extracted
with diethyl ether. The organic layer was dried with calcined
magnesium sulfate. The solvent was removed in low vacuum.
The residue was distilled in vacuo to give either 4ꢀallyloxymethꢀ
ylꢀ1,3ꢀdioxolane (2a) (12 g, 87%), colorless liquid, b.p. 61 C (1 Torr)
or 4ꢀbenzyloxymethylꢀ1,3ꢀdioxolane (3a) (17 g, 90%), colorless
liquid, b.p. 151 C (2 Torr).
(
neck flask equipped with a stirrer, a condenser, and an addition
funnel was charged with an isomeric mixture of 1a and 1b (10.4 g,
0
.1 mol), 50% aqueous NaOH (80 g), Katamine AB cataꢀ
lyst (N´ꢀalkylꢀNꢀbenzylꢀN,Nꢀdimethylammonium chloride)
0.001 mol), and toluene (100 mL). The reaction mixture was
stirred at 70 C for 1 h followed by addition of allyl chloride
29 g, 0.5 mol) or allyl bromide (63 g, 0.5 mol) over a period of
0 min. Then the reaction mixture was cooled down, washed
with water, and extracted with diethyl ether. The organic layer
was dried with calcined magnesium sulfate. The solvent was
removed in low vacuum. Vacuum distillation of the residue afꢀ
forded a mixture of 4ꢀallyloxymethylꢀ1,3ꢀdioxolane (2a) and
(
(
3
Compound 2a. MS, m/z (Irel (%)): [M]+ 143 (2), 103 (5),
87 (100), 73 (23), 57 (50), 43 (53). Compound 3a. MS, m/z
+
(Irel (%)): [M] 194 (53), 135 (5), 148 (3), 121 (10), 108 (100),
91 (10), 87 (23), 77 (13), 73 (40), 57 (13).
5
ꢀallyloxyꢀ1,3ꢀdioxane (2b) in the yield of 11.5 g (80%), transꢀ
parent oil with pleasant odor, b.p. 87 C (4 Torr). An isomeric
ratio was determined by H NMR spectroscopy from the inteꢀ
grated intensity ratio of the signals of H(4) methyne proton
This work was financially supported by the Ministry of
Education and Science of the Russian Federation (Conꢀ
tract No. 2014/241, Project No. 1180) and the President
of the Russian Federation (Stipendium of the President of
RF for young scientists and PhD students SPꢀ1960.2015.4
1
(
(
(
H 4.22) of 2a and H(5) methyne proton (H 3.3—3.8) of 2b
2a : 2b = 2 : 1). Compound 2a. MS, m/z (Irel (%)): 143 [M + H]
2), 113 (15), 103 (10), 86 (15), 73 (65), 67 (15), 57 (60), 41 (100).
+
for 2015—2017, Decree No. 184 from March 10, 2015).
+
Compound 2b. MS, m/z (Irel (%)): 144 [M] (1), 114 (5),
8
4 (100), 71 (15), 55 (45), 41 (100).
A mixture of 4ꢀbenzyloxymethylꢀ1,3ꢀdioxolane (3a) and 5ꢀbenzꢀ
References
yloxyꢀ1,3ꢀdioxane (3b). Yield 14.5 g (76%), b.p. 101 C (4 Torr).
An isomeric ratio was determined by 1H NMR spectroscopy
from the integrated intensity ratio of the signals of H(4) methyne
proton (H 4.25) of 3a and H(5) methyne proton (H 4.54—4.62)
1
. N. S. Zefirov, N. M. Shekhtman, Russ. Chem. Rev., 1971,
0, 315.
4
2. A. A. Bogomazova, N. N. Mikhailova, S. S. Zlotskiy, Sovreꢀ
mennaya khimiya tsiklicheskikh atsetaley: Poluchenie. Reaktsii.
Svoystva [Modern Chemistry of Acetals. Synthesis. Reactions.
Properties], Lambert Academic Publishing, Saarbrucken,
of 3b (3a : 3b = 1.7 : 1). Compound 3a. MS, m/z (I (%)): 143
rel
+
[
4
8
M + H] (2), 113 (15), 103 (10), 86 (15), 73 (65), 67 (15), 57 (60),
+
1 (100). Compound 3b. MS, m/z (Irel (%)): 144 [M] (1), 114 (5),
4 (100), 71 (15), 55 (45), 41 (100).
2
012, 96 pp. (in Russian).
Synthesis of chloroꢀ1,3ꢀdioxacycloalkanes 4a,b (general proꢀ
3
4
. Y. Xu, Q. Lian, A. V. Pontsler, T. M. McIntyre, G. D.
Prestwich, Tetrahedron, 2004, 60, 43.
. P. H. R. Silva, V. L. C. Goncalves, C. J. A. Mota, Bioresour.
Technol. 2010, 101, 6225.
. R. S. Karinen, A. O. I. Krause, Appl. Catal., A, 2006, 306, 128.
. G. H. P. Cho, S. K. Yeong, T. L. Ooi, C. H. Chuah,
J. Surfactants Deterg., 2006, 9, 147.
cedure). To a stirred mixture of 4ꢀhydroxymethylꢀ1,3ꢀdioxolane
1a) and 5ꢀhydroxymethylꢀ1,3ꢀdioxane (1b) (10.4 g, 0.1 mol) in
pyridine (7.5 g, 0.1 mol) cooled to 0 C, thionyl chloride (17.8 g,
.15 mol) was added dropwise over a period of 15 min. Then the
(
0
5
6
stirred reaction mixture was heated at 55—60 C for 6 h until the
evolution of SO ceased. The mixture was cooled to room temꢀ
2
perature and diluted with water (25 mL), extracted with diethyl
ether (4×10 mL), and the combined organic phases were dried
with calcium chloride. The solvent was removed in low vacuum.
Distillation of the residue afforded a mixture of 4a and 4b in the
yield of 5.7 g (55%), colorless liquid, b.p. 145 C (760 Torr). An
isomeric ratio was determined by H NMR spectroscopy from
the integrated intensity ratio of the signals of H(4) methyne
proton (H 4.26) of dioxolane 4a and H(5) methyne proton
7
8
9
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2
63, 155.
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1
[
Zh. Prikl. Khim., 2015, 88, 1414].
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11. Y. Wedmid, C. A. Evans, W. J. Baumann, J. Org. Chem.,
(
H 3.74—3.80) of dioxane 4b (4a : 4b = 1.5 : 1). Compound 4a.
+
MS, m/z (Irel (%)): 122/124 (not detected), 121/123 (20/7) [M] ,
3 (100), 45 (36), 44 (39), 31 (15). Compound 4b. MS, m/z
Irel (%)): 121/123 (not detected), 87 (1), 74 (34), 45 (17), 44 (100),
1 (12).
Alkylation of alcohols with 4ꢀchloromethylꢀ1,3ꢀdioxolane (4a).
7
(
3
1
980, 45, 1582.
A threeꢀneck flask equipped with a stirrer, a condenser, and an
addition funnel was charged with allyl alcohol (5.8 g, 0.1 mol) or
Received May 27, 2015;
in revised form July 14, 2015