Synthesis of gem-dichlorocyclopropane and 1,3-dioxane derivatives from divinylbenzene

Article abstract of DOI:10.1007/s11172-019-2671-4

The Prins reaction and cyclopropanation of the light fraction obtained by distillation of the technical grade divinylbenzene and consisting of a mixture of 1,3- and 1,4-divinylbenzenes with admixture of 3- and 4-ethylstyrenes were studied. These reactions

Full text of DOI:10.1007/s11172-019-2671-4

Russian Chemical Bulletin, International Edition, Vol. 68, No. 11, pp. 2092—2097, November, 2019
2092
Synthesis of gem-dichlorocyclopropane and 1,3-dioxane derivatives
from divinylbenzene
G. Z. Raskil´dina,a Yu. G. Borisova,a L. V. Spirikhin,b and S. S. Zlotskiia
aUfa State Petroleum Technological University,
1 ul. Kosmonavtov, 450062 Ufa, Russian Federation.
E-mail: graskildina444@mail.ru
bUfa Federal Research Centre of the Russian Academy of Sciences,
71 prosp. Oktyabrya, 450054 Ufa, Bashkortostan, Russian Federation.
E-mail: spectr@anrb.ru
The Prins reaction and cyclopropanation of the light fraction obtained by distillation of the
technical grade divinylbenzene and consisting of a mixture of 1,3- and 1,4-divinylbenzenes with
admixture of 3- and 4-ethylstyrenes were studied. These reactions quantitatively give the corres-
ponding gem-dichlorocyclopropane and 1,3-dioxane benzene derivatives. The structures of the
synthesized compounds were confirmed by NMR spectroscopy and mass spectrometry.
Key words: divinylbenzene, gem-dichlorocyclopropanes, 1,3-dioxanes, Prins reaction.
1,4-Divinylbenzene and its isomers are widely used for
being 3a : 4a = 2 : 1. When the reaction time was prolonged
to 2 h, quantitative conversion of the starting divinyl-
benzenes 1a and 2a into the corresponding tetrachloro
derivatives 5 and 6 was observed. It is worthy to note that
under the reaction conditions used the minor components
of the staring mixture, ethylstyrenes 1b and 2b, are com-
pletely converted into the corresponding 1,1-dichloro-2-
(ethylphenyl)cyclopropanes 3b and 4b (1H NMR spectro-
scopy and capillary GC data). Hydrogenation of the
mixture 3a,b + 4a,b following the known procedure10 gives
a product with enhanced content of ethylbenzene deriva-
tives 3b and 4b (GC data).
Acid catalyzed condensation (Scheme 2) of a 3 : 1
mixture of isomers 1a and 2a with formaldehyde (the Prins
reaction) gives 4-(vinylphenyl)-1,3-dioxanes 7a and 8a
and polycyclic products 9 and 10. The minor components,
ethyl derivatives 1b and 2b, also react under these condi-
tions to afford 4-(ethylphenyl)-1,3-dioxanes 7b and 8b,
respectively. Expectedly, hydrogenation of vinyl-substi-
tuted derivatives 7a and 8a results in a mixture of ethyl
derivatives 7b and 8b. Taking into account a ratio of the
isomers formed (7a : 8a = 1.5 : 1), reactivities of 1,3-(1a)
and 1,4-divinylbenzenes (2a) in the Prins reaction differ
more substantially than in the reaction with dichloro-
carbene. A mixture of isomers 7a and 8a reacts with
formaldehyde under the Prins conditions to give bis-di-
oxane derivatives 9 and 10 in a 1.5 : 1 ratio (1H NMR
spectroscopy data; see Scheme 2).
the production of cross-liked polymers and synthetic
resins.1,2 Separation of highly pure 1,4-divinylbenzene
from technical grade product gives the light fraction con-
taining a 3 : 1 mixture of 1,3- and 1,4-divinylbenzenes and
up to 10% of 3- and 4-ethylstyrenes.3 Therefore, it is of
practical interest to study the possibilities of utilization of
the components of this fraction mainly through the
carbon—carbon double bond functionalization. The simple
and efficient approaches to functionalization of the olefins
are dichlorocyclopropanation and the Prins reaction. For
instance, Kagabu and Mizogushi have reported an efficient
synthesis of 1,4-bis(2,2-dichloro-1-formylcyclopropyl)-
benzene from 1,4-bis(2,2-dichlorocyclopropyl)benzene.4
Effenberger and Kurtz have described the synthesis of
mono- and bis-gem-dichlorocyclopropylbenzenens from
1,3- and 1,4-divinylbenzenes.5
Earlier,6—8 we have demonstrated a great potential of
2-aryl-1,1-dichlorocyclopropanes and 4-aryl-1,3-dioxa-
cycloalkanes as the building blocks in organic synthesis.
Hence, we were interested in the synthesis of related
compounds from aromatic olefins that are produced in
large industrial scale and, especially, from the mentioned
above technical grade divinylbenzenes.
We found that dichlorocyclopropanation of a 3 : 1
mixture of 1,3- (1a) and 1,4-divinylbenzenes (2a) (Scheme 1)
carried out by known procedure9 initially gives the cor-
responding 3- and 1-(2,2-dichlorocyclopropyl)-4-vinyl-
benzenes 3a and 4a. Note that the fraction of 1,4-isomers
in the product of dichlorocyclopropanation of a mixture
of 1a and 2a was larger than that in the starting mixture
A search for a convenient route to transform vinyl
derivatives 3a, 4a and 7a, 8a into compounds 11 and 12
bearing gem-dichlorocyclopropyl and cycloacetal moieties
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2092—2097, November, 2019.
1066-5285/19/6811-2092 © 2019 Springer Science+Business Media, Inc.

Reactions of divinylbenzene
Russ. Chem. Bull., Int. Ed., Vol. 68, No. 11, November, 2019
2093
Scheme 1
R = CH=CH2 (a), Et (b)
Conditions: CHCl3, 50% NaOH, AlkMe2BnNCl (cat.), 0—3 C, 0.5 h (for 3a,b and 4a,b) or 2 h (for 5 and 6).
Scheme 2
R = CH=CH2 (a), Et (b)
Conditions: i. (CH2O)x, zeolite H-beta (cat., 10 wt.%), PhCl, Pri2O, 40 C; ii. (CH2O)x.
Scheme 3
(Scheme 3) is of considerable interest. Addition of di-
chlorocarbene to the double bond of styryldioxanes 7a + 8a
results in compounds 11 and 12 in the total yield of 35%.
Apparently, dichlorocarbenes not only add to the double
bond but also undergo insertion into a C—H bond of
1,3-dioxane moiety (cf. with the data given in Ref. 11)
thus lowering the yield of the target products (Table 1).
Note that products 11 and 12 were synthesized in 75%
total yield by condensation of a mixture of styrylcyclo-
propanes 3a and 4a with formaldehyde (see Scheme 3).
The structures of the synthesized compounds 3—12
1
were established by H and 13C NMR spectroscopy and
gas chromatography/mass spectrometry analysis.
The 1H NMR signals of compounds 3—6, 11, and 12
were attributed taking into account the chemical shifts

2094 Russ. Chem. Bull., Int. Ed., Vol. 68, No. 11, November, 2019
Raskil´dina et al.
Table 1. Synthesis of compounds 3—12
protons at δH 5.20 for 7a and 8a, δH 5.29 for 4a, δH 5.33
for 3a and δH 5.80 for 4a, 7a, and 8a, δH 5.82 for 3a
(3J  10.3 Hz, J  17.5 Hz). H NMR spectra of com-
pounds 3b, 4b, 7b, 8b show the signals of the CH2 ethyl
group protons at δH 2.94 for 3b, 4b and δH 2.66 for 7b, 8b
as the quartets with 3J  7.2 Hz and CH3 ethyl group
protons at stronger field at δH 1.30 for 3b, 4b and δH 1.20
for 7b and 8b with 3J equal to 7.0 Hz for 3b, 7.3 Hz for 4b,
and 7.1 for 7b and 8b.
3
1
Reactants Method* Reaction products Total yield (%)
1a + 2a
1a + 2a
1b + 2b
1b + 2b
3a + 4a
3a + 4a
7a + 8a
7a + 8a
A
B
A
B
A
B
B
A
3a + 4a
7a + 8a
3b + 4b
7b + 8b
5 + 6
11 + 12
9 + 10
11 + 12
65
50
25
20
35
75
30
35
13C NMR spectra of monocyclopropane derivatives 3,
4, 11, and 12 contain the following characteristic signals
of the carbon atoms of gem-dichlorocyclopropane ring:
the quaternary carbon atoms at δC 61, the methylene
carbon atoms at δC 25—26, and the methine carbon atoms
at δC 35.
* Method A: CHCl3, 50% NaOH, AlkMe2BnNCl or Et3BnNCl
(cat., 10 wt.%). Method B: (CH2O)x, zeolite H-beta (cat.,
10 wt.%), PhCl, Pri2O (see Experimental).
The presence of the vinyl group in the structure of
isomers 3a, 4a and 7a, 8a is confirmed by the carbon atom
signals at the low field at δC 114 and 136 and the presence
of the ethyl group in compounds 3b, 4b, 7b, and 8b is sup-
ported by the high field signals at δC 15 and ~25—29.
The 13C NMR signals in the spectra of compounds 3—6,
11, and 12 were assigned from the analysis of the chemi-
cal shifts and spin-spin coupling constants of gem-di-
chlorocyclopropane moiety and 13C NMR signals of
compounds 7—12 were attributed considering the chem-
ical shifts of 1,3-dioxane ring.
Mass spectra (EI) of compounds 3, 4, 11, and 12 reveal
the molecular ion peaks with the intensities up to 20%. In
the mass spectra of compounds 5 and 6, no molecular ion
peaks are observed. The most abundant ions in the mass
spectra of the synthesized compounds are the ions with
m/z 115 [M – Cl – HCl – C2H4]+ (compounds 3—6, 11,
and 12) and m/z 141 [M – Cl – HCl]+ (compounds 3a
and 4a). For the chloro-containing fragment ions, the
ratios of the peaks differing by two units are 9 : 6 : 1,
6 : 9 : 7 : 2, and 3 : 1 that reflected the natural abundance
of the isotopes 35Cl and 37Cl. For the substituted phenyl-
cyclopropanes 3—6, 11, and 12, the main fragmentation
route is the loss of radical Cl• and/or molecule HCl to give
aromatic cations with m/z 91 and 77 (Irel from 3 to 60%).
Mass spectra (EI) of compounds 7—10 exhibit the
molecular ion peaks with the intensities from 1 to 14%.
In mass spectra of compounds 9 and 10, the peaks of
cations [M – H]+ with m/z 249 are observed. Mass spectra
of compounds 7—10 reveal also the peaks of aromatic
cations with m/z 91 and 77 and the intensities from
~22 to 90%.
and spin-spin coupling constants of the protons of gem-di-
chlorocyclopropane fragment; for compounds 7—10 the
proton chemical shifts of the 1,3-dioxane moiety were
considered. For instance, in 1H NMR spectra of com-
pounds 3—6, 11, and 12 the signals of the CH cyclo-
propane ring protons are observed at δH 2.67—2.73 as the
multiplets and the C(2)H2 cyclopropane ring protons
resonate at δH 1.75—1.93 (Ha) and 1.97—2.15 (Hb). The
signals of the aromatic H(2) protons of 1,3-isomers 3a,
4a, and 11 are shifted downfield (δH 7.18—7.45) as com-
pared with the H(4), H(5), and H(6) aromatic protons
1
(δH 7.14—7.26). In the H NMR spectra of compounds
7, 8, 11, and 12, the characteristic signals are the signals
of 1,3-dioxane moiety. The methylene C(2)H2 protons of
the dioxane ring appear at the δH 4.69—5.25 range as two
doublets with spin-spin coupling constants of 3.0 Hz, the
other CH2 dioxane ring protons are observed at the stron-
ger field at δH 1.71—2.10 and 3.90—4.27 and the CH group
protons resonate at δH 4.31—4.68 as the multiplets. The
1H NMR spectra of bis-dioxane derivatives 9 and 10
contain two sets of the signals for heterocyclic fragments.
The aromatic proton signals for all compounds 3—10
are observed at the δH 7.14—7.52 as the multiplets. Analysis
of 1H NMR spectra of 1,3- (3a,b) and 1,4-isomers (4a,b)
indicates that the vinyl and ethyl substituents practically
have no effect on the positions of the CH aromatic protons
(δ 0.04—0.1 ppm). In contrast, the aromatic ring affects
the chemical shift of the CH proton of the cyclopropane ring:
these signals are shifted downfield by δ 0.40—0.65 ppm
with respect to the analogous signals of vinyl-gem-di-
chlorocyclopropanes.12 The signals of the methine group
protons of 1,3-dioxane moiety are shifted downfield by
δ 0.30—0.60 ppm as compared with the analogous signal
of 4-chloromethyl-1,3-dioxane.13
Experimental
1H NMR spectra of compounds 3a, 4a and 7a, 8a
exhibit signals characteristic of the vinyl group, namely,
the doublet of doublet of the CH group proton at the δH
6.64—6.76 range (3J  10.4 Hz for 3a and 4a; 3J  17.5 Hz
for 3a, 4a, 7a, and 8a) and two doublets of the CH2 group
The reaction products were analyzed on a Carlo Erba HR
5300 Mega Series gas chromatograph equipped with a flame
ionization detector and a 25-m column (column temperature of
50—280 C, heating rate of 8 deg min–1); the carrier gas was
helium (flow rate of 30 mL min–1). Gas-chromatography/elec-

Reactions of divinylbenzene
Russ. Chem. Bull., Int. Ed., Vol. 68, No. 11, November, 2019
2095
tron impact mass spectrometry was performed with a Chomatec
instrument (Russia) comprising a Kristall-5000 M gas chromato-
graph (30-m capillary column, column temperature 80—280 C,
transfer line temperature 300 C, ion source temperature 300 C,
heating rate 20 deg min–1, helium as a carrier gas). 1H and 13C NMR
spectra were run on a Bruker Avance-500 spectrometer (working
frequencies of 500.13 (1H) and 125.7 MHz (13C)) in CDCl3.
Technical grade divinylbenzene (a mixture of compounds
1a,b and 2a,b) was used.
1.86—1.93 (m, 1 H, C(2)Ha, cyclopropane); 1.97—2.04 (m, 1 H,
C(2)Hb, cyclopropane); 2.67—2.73 (m, 1 H, C(3)H, cyclo-
propane); 2.94 (q, 2 H, CH2, J = 7.3 Hz); 7.14—7.26 (m, 2 H,
C(2)H, C(6)H, arom.); 7.32—7.39 (m, 2 H, C(3)H, C(5)H,
arom.). 13C NMR, : 15.33 (CH3), 25.84 (C(2), cyclopropane),
28.58 (CH2), 35.32 (C(3), cyclopropane), 60.89 (CCl2), 125.48
(C(2), C(6)), 129.08 (C(3), C(5)), 134.20 (C(1)), 143.68 (C(4)).
MS, m/z (Irel (%)): 214/216/218 [M]+• (20/12/5), 179/181
[M – Cl]+ (70/26), 143 [M – Cl – HCl]+ (50), 115 [M – Cl –
– HCl – C2H4]+ (100), 91 [C6H5CH2]+ (60), 77 [Ph]+ (28),
51/53 [CH2Cl]+ (8/4), 39 [C3H3]+ (6).
Partial dichlorocyclopropanation of a mixture of 1,3- and
1,4-divinylbenzenes (general procedure). A stirred mixture of
technical grade divinylbenzene (1.3 g), chloroform (30 mL,
0.375 mol), and 10 wt.% of catamine AB as a catalyst was cooled
to 0 C and treated dropwise with a 50% aqueous solution of
NaOH (32 g) over 30 min. Then the reaction mixture was stirred
at 0—3 C for 1 h and washed with water until neutral. The or-
ganic layer was dried with freshly calcined CaCl2, the drying
agent was filtered off, and the unreacted chloroform was removed
in vacuo. The products were isolated by vacuum distillation.
1-(2,2-Dichlorocyclopropyl)-3-vinylbenzene (3a). Yield 50%,
b.p. 120 C (4 Torr). 1H NMR, : 1.86—1.93 (m, 1 H, C(2)Ha,
cyclopropane); 1.97—2.04 (m, 1 H, C(2)Hb, cyclopropane);
2.67—2.73 (m, 1 H, C(3), cyclopropane); 5.33 (d, 1 H, Ha of
=CH2, J = 10.7 Hz); 5.82 (d, 1 H, Hb of =CH2, J = 17.5 Hz);
6.76 (dd, 1 H, =CH, J = 10.7 Hz, J = 17.5 Hz); 7.14—7.26
(m, 3 H, CH, arom.); 7.45 (s, 1 H, C(2)H, arom.). 13C NMR, :
25.74 (C(2), cyclopropane); 35.27 (C(3), cyclopropane), 60.76
(CCl2), 114.48 (=CH2), 125.48 (C(2)), 125.48 (C(4), 126.74
(C(5), 129.08 (C(6)), 134.96 (C(3)), 136.37 (C(1)), 136.57 (=CH,
vinyl). MS, m/z (Irel (%)): 212/214/216 [M]+• (15/8/2), 177/179
[M – Cl]+ (70/25), 141 [M – Cl – HCl]+ (100), 115 [M – Cl –
– HCl – C2H2]+ (90), 77 [Ph]+ (10), 51/53 [CH2Cl]+ (10/3),
39 [C3H3]+.
Exhaustive dichlorocyclopropanation of 1,3- and 1,4-divinyl-
benzenes (general procedure). A stirred mixture of technical grade
divinylbenzene (2.10 g), chloroform (30 mL, 0.375 mol), and
10 wt.% (210 mg) of catamine AB as a catalyst was cooled to 0 C
and treated dropwise with a 50% aqueous NaOH (32 g) over
30 min. The reaction mixture was stirred at 5—7 C for 2 h,
washed with water until neutral, dried with freshly calcined CaCl2,
the drying agent was filtered off, and the solvent was removed
in vacuo. Products 5 and 6 were isolated by vacuum distillation.
1,3-Bis(2,2-dichlorocyclopropyl)benzene (5). Yield 25%, b.p.
161 C (1 Torr). 1H NMR, : 1.86—1.93 (m, 2 H, 2 C(2)Ha,
cyclopropane); 1.97—2.04 (m, 2 H, 2 C(2)Hb, cyclopropane);
2.67—2.73 (m, 2 H, 2 C(3)H, cyclopropane); 7.18 (s, 1 H, C(2)H,
arom.); 7.23 (t, 2 H, C(4)H, C(6)H, arom., J = 7.6 Hz); 7.38
(t, 1 H, C(5)H, arom., J = 7.6 Hz). 13C NMR, : 25.85 (2 C(2),
cyclopropane), 35.36 (2 C(3), cyclopropane), 60.78 (2 CCl2),
125.48 (C(2)), 129.08 (C(4), C(5), C(6)), 134.86 (C(1)),
134.90 (C(3)). MS, m/z (Irel (%)): 296/298/300/302 [M]+• (0),
259/261/263 [M – Cl]+ (10/7/2), 185/187/189 [M – Cl – HCl –
– C3H2]+ (76/50/24), 149/151 [M – 2 Cl – HCl – C3H2]+
(70/32), 115 [M – 2 Cl – 2 HCl – C3H2]+ (100), 91 [C6H5CH2]+
(15), 77 [Ph]+ (32), 51/53 [CH2Cl]+ (10/4).
1-(2,2-Dichlorocyclopropyl)-4-vinylbenzene (4a). Yield 15%,
b.p. 120 C (4 Torr). 1H NMR, : 1.86—1.93 (m, 1 H, C(2)Ha,
cyclopropane); 1.97—2.04 (m, 1 H, C(2)Hb, cyclopropane);
2.67—2.73 (m, 1 H, C(3)H, cyclopropane); 5.29 (d, 1 H, Ha of
=CH2, J = 10.0 Hz); 5.80 (d, 1 H, Hb of =CH2, J = 17.6 Hz);
6.74 (dd, 1 H, H of =CH, J = 10.0 Hz, J = 17.6 Hz); 7.14—7.26
(m, 2 H, C(2)H, C(6)H, arom.); 7.32—7.39 (m, 2 H, C(3)H,
C(5)H, arom.). 13C NMR, : 25.75 (C(2), cyclopropane), 35.27
(C(3), cyclopropane), 60.76 (CCl2), 114.23 (=CH2), 125.48
(C(3), C(5)), 129.08 (C(2), C(6)), 134.14 (C(1), C(4)), 136.57
(=CH). MS, m/z (Irel (%)): 212/214/216 [M]+• (15/8/2),
177/179 [M – Cl]+ (70/25), 141 [M – Cl – HCl]+ (100), 115
[M – Cl – HCl – C2H2]+ (90), 77 [Ph]+ (10), 51/53 [CH2Cl]+
(10/3), 39 [C3H3]+ (12).
1-(2,2-Dichlorocyclopropyl)-3-ethylbenzene (3b). Yield 12%,
b.p. 125 C (4 Torr). 1H NMR, : 1.30 (t, 3 H, CH3, J = 7.0 Hz);
1.86—1.93 (m, 1 H, C(2)Ha, cyclopropane); 1.97—2.04 (m, 1 H,
C(2)Hb, cyclopropane); 2.67—2.73 (m, 1 H, C(3)H, cyclopro-
pane); 2.94 (q, 2 H, CH2, J = 7.2 Hz); 7.14—7.26 (m, 3 H, C(4),
C(5), C(6)H, arom.); 7.40—7.45 (m, 1 H, C(2)H, arom.).
13C NMR, : 15.33 (CH3), 25.84 (C(2), cyclopropane), 28.58
(CH2), 35.32 (C(3), cyclopropane), 60.89 (CCl2), 125.48 (C(2)),
129.08 (C(4), C(5), C(6)), 134.20 (C(1)), 144.37 (C(3)). MS,
m/z (Irel (%)): 214/216/218 [M]+• (20/12/5), 179/181 [M – Cl]+
(70/30), 143 [M – Cl – HCl]+ (30), 115 [M – Cl – HCl – C2H4]+
(100), 77 [Ph]+ (28), 51/53 [CH2Cl]+ (15/4), 39 [C3H3]+ (12).
1-(2,2-Dichlorocyclopropyl)-4-ethylbenzene (4b). Yield 13%,
b.p. 125 C (2 Torr). 1H NMR, : 1.30 (t, 3 H, CH3, J = 7.3 Hz);
1,4-Bis(2,2-dichlorocyclopropyl)benzene (6). Yield 10%, b.p.
161 C (1 Torr). 1H NMR, : 1.86—1.93 (m, 2 H, 2 C(2)Ha,
cyclopropane); 1.97—2.04 (m, 1 H, C(2)Hb, cyclopropane);
2.67—2.73 (m, 2 H, C(3)H, cyclopropane); 7.28 (s, 4 H, C(2)H,
C(3)H, C(5)H, C6)H, arom.). 13C NMR, : 25.88 (2 C(2),
cyclopropane), 35.37 (2 C(3), cyclopropane), 60.86 (CCl2),
128.15 (C(2), C(6)), 128.25 (C(3), C(5)), 134.10 (C(1), C(4)).
MS, m/z (Irel (%)): 296/298/300/302 [M]+• (<1), 259/261/263
[M – Cl]+ (10/7/2), 185/187/189 [M – Cl – HCl – C3H2]+
(40/18/3), 149/151 [M – 2 Cl – HCl – C3H2]+ (40/12), 115
[M – 2 Cl – 2 HCl – C3H2]+ (100), 77 [Ph]+ (60), 51/53
[CH2Cl]+ (15/7).
Partial condensation of divinylbenzene with paraformaldehyde
(general procedure). A mixture of paraformaldehyde (7.8 g,
0.26 mol), chlorobenzene (30 mL), diisopropyl ether (20 mL),
and 10 wt.% (780 mg) of zeolite H-beta (M = 18) was stirred at
40 C. Then technical grade divinylbenzene (13 g) was added
and stirring was continued until complete conversion of olefin.
After completion of the reaction, the organic layer was sepa-
rated and the solvent was removed in vacuo. Products 7a,b and
8a,b were isolated by column chromatography (elution with
hexane—ethyl acetate).
4-(3-Vinylphenyl)-1,3-dioxane (7a). Yield 30%, b.p. 101 C
(1 Torr). 1H NMR, : 1.71 (dq, 2 H, C(5)Ha, dioxane, J = 12.0 Hz,
J = 4.0 Hz); 2.10 (dq, 2 H, C(5)Hb, dioxane, J = 12.0 Hz,
J = 4.0 Hz); 3.90 (dt, 2 H, C(6)Ha, dioxane, J = 12.0 Hz,
J = 4.0 Hz); 4.24 (dt, 2 H, C(6)Hb, dioxane, J = 12.0 Hz,
J = 4.0 Hz); 4.65 (dd, 1 H, C(4)H, dioxane, J = 12.0 Hz,

2096 Russ. Chem. Bull., Int. Ed., Vol. 68, No. 11, November, 2019
J = 4.0 Hz); 4.91 (d, 1 H, C(2)Ha, dioxane, J = 3.0 Hz); 5.23
Raskil´dina et al.
Exhaustive condensation of compounds 7a and 8a with para-
(d, 1 H, C(2)Hb, dioxane, J = 3.0 Hz); 5.20 (d, 1 H, C(2)Ha,
=CH2, J = 10.0 Hz); 5.80 (d, 1 H, C(2)Hb, =CH2, J = 17.6 Hz);
6.64 (dd, 1 H, C(1)H, =CH, J = 17.6 Hz, J = 10.7 Hz); 7.20—7.26
(m, C(4)H, C(5)H, C(6)H, arom.); 7.52 (s, 1 H, C(2)H, arom.).
13C NMR, : 33.98 (C(5), dioxane), 66.90 (C(6), dioxane), 78.69
(C(4), dioxane), 94.14 (OCH2O), 123.13 (C(2)), 125.18 (C(4),
C(6)), 128.66 (C(5)), 136.01 (=CH), 141.06 (C(1), C(3)).
114.23 (=CH2, vinyl). MS, m/z (Irel (%)): 190 [M]+• (8), 163
[M – C2H3]+ (6), 146 [M – CO2]+ (84), 130 [M – 2 CH2O]+
(100), 92 [C6H5CH3]+ (14), 91 [C6H5CH2]+ (90), 77 [C6H5]+
(22), 30 [CH2O]+ (12).
formaldehyde (general procedure). A mixture of paraformaldehyde
(7.8 g, 0.26 mol), chlorobenzene (30 mL), diisopropyl ether
(20 mL), and 20 wt.% (1.56 g) of zeolite H-beta (M = 18) was
stirred at 50 C. Then a mixture of compounds 7a and 8a (1.9 g,
0.1 mol) was added dropwise and the resulting mixture was stirred
until complete consumption of olefin. After completion of the
reaction, the organic layer was separated, dried with magnesium
sulfate, and concentrated in vacuo. Products 9 and 10 were iso-
lated by column chromatography (elution with hexane—ethyl
acetate).
4,4´-(1,3-Phenylene)bis-1,3-dioxane (9). Yield 18%, b.p.
181 C (2 Torr). 1H NMR, : 1.71 (dq, 2 H, 2 C(5)Ha, dioxane,
J = 12.0 Hz, J = 4.0 Hz); 2.10 (dq, 2 H, 2 C(5)Hb, dioxane,
J = 12.0 Hz, J = 4.0 Hz); 3.90 (dt, 2 H, 2 C(6)Ha, dioxane,
J = 12.0 Hz, J = 4.0 Hz); 4.24 (dt, 2 H, 2 C(6)Hb, dioxane,
J = 12.0 Hz, J = 4.0 Hz); 4.65 (dd, 2 H, 2 C(4)H, dioxane,
J = 12.0 Hz, J = 4.0 Hz); 4.90 (d, 2 H, 2 C(2)Ha, dioxane,
J = 3.0 Hz); 5.24 (d, 2 H, 2 C(2)Hb, dioxane, J = 3.0 Hz);
7.21—7.28 (m, C(4)H, C(5)H, C(6)H, arom.); 7.35 (s, 1 H,
C(2)H, arom.). 13C NMR, : 33.97 (C(5), dioxane), 66.90 (C(6),
dioxane), 78.69 (C(4), dioxane), 94.14 (C(2), dioxane), 123.13
(C(2)), 125.18 (C(5)), 128.66 (C(4), C(6)), 141.06 (C(1), C(3)).
MS, m/z (Irel (%)): 250 [M]+• (1), 249 [M – H]+ (10), 220
[M – CH2O]+ (4), 190 [M – 2 CH2O]+ (20), 146 [M – 2 CH2O –
– CO2]+ (64), 131 [M – 2 CH2O – CO2 – CH3]+ (100), 77
[C6H5]+ (34), 45 [C2H5O]+ (16), 30 [CH2O]+ (16).
4,4´-(1,4-Phenylene)bis-1,3-dioxane (10). Yield 12%, b.p.
181 C (2 Torr). 1H NMR, : 1.71 (dq, 2 H, 2 C(5)Ha, dioxane,
J = 12.0 Hz, J = 4.0 Hz), 2.10 (dq, 2 H, 2 C(5)Hb, dioxane,
J = 12.0 Hz, J = 4.0 Hz); 3.90 (dt, 2 H, 2 C(6)Ha, dioxane,
J = 12.0 Hz, J = 4.0 Hz); 4.25 (dt, 2 H, 2 C(6)Hb, dioxane,
J = 12.0 Hz, J = 4.0 Hz); 4.65 (d, 2 H, 2 C(4)H, dioxane,
J = 5.0 Hz); 4.90 (d, 2 H, C(2)Ha, dioxane, J = 3.0 Hz); 5.24
(d, 2 H, 2 C(2)Hb, dioxane, J = 3.0 Hz); 7.20—7.50 (m, 4 H,
C(2)H, C(3)H, C(5)H, C(6)H, arom.). 13C NMR, : 33.97 (C(5),
dioxane), 66.90 (C(6), dioxane), 78.48 (C(4), dioxane), 94.14
(OCH2O), 125.91 (C(2), C(3), C(5), C(6)), 139.01 (C(1), C(4)).
MS, m/z (Irel (%)): 250 [M]+• (1), 249 [M – H]+ (5), 220
[M – CH2O]+ (2), 190 [M – 2 CH2O]+ (6), 146 [M – 2 CH2O –
– CO2]+ (40), 131 [M – 2 CH2O – CO2 – CH3]+ (100), 77
[C6H5]+ (22), 45 [C2H5O]+ (6), 30 [CH2O]+ (16).
Synthesis of compounds 11 and 12. Method A: dichlorocyclo-
propanation of a mixture of isomers 7a and 8a. A stirred mixture
of compounds 7a and 8a (1.9 g, 0.01 mol), chloroform (30 mL,
0.375 mol), and 10 wt.% (190 mg) of triethylbenzylammonium
chloride as a catalyst was cooled to 0 C. The resulting mixture
was treated dropwise with 50% aqueous NaOH (32 g) over 40 min
and then stirred at 0—3 C for 2 h. After completion of the reac-
tion, the mixture was washed with water until neutral, the or-
ganic layer was dried with freshly calcined CaCl2, the drying
agent was filtered off, and the unreacted chloroform was removed
in vacuo. The products were isolated by vacuum distillation.
Method B: condensation of isomers 3a and 4a with paraform-
aldehyde. A mixture of paraformaldehyde (7.8 g, 0.26 mol),
chlorobenzene (30 mL), diisopropyl ether (20 mL), and 20 wt.%.
(1.56 g) of zeolite H-beta (M = 18) was stirred at 60 C. Then
a mixture of compounds 3a and 4a (21 g, 0.1 mol) was added
dropwise and stirring was continued until complete consumption
of olefin. After completion of the reaction, the organic layer was
separated, dried with magnesium sulfate, and concentrated
4-(4-Vinylphenyl)-1,3-dioxane (8a). Yield 20%, b.p. 101 C
(1 Torr). 1H NMR, : 1.71 (dq, 2 H, C(5)Ha, dioxane, J = 12.0 Hz,
J = 4.0 Hz); 2.10 (dq, 2 H, C(5)Hb, dioxane, J = 12.0 Hz,
J = 4.0 Hz); 3.90 (dt, 2 H, C(6)Ha, dioxane, J = 12.0 Hz,
J = 4.0 Hz); 4.24 (dt, 2 H, C(6)Hb, dioxane, J = 12.0 Hz,
J = 4.0 Hz); 4.65 (dd, 1 H, C(4)H, dioxane, J = 12.0 Hz,
J = 4.0 Hz); 4.91 (d, 1 H, C(2)Ha, dioxane, J = 3.0 Hz); 5.23
(d, 1 H, C(2)Hb, dioxane, J = 3.0 Hz); 5.20 (d, 1 H, C(2)Ha,
=CH2, J = 10.0 Hz); 5.80 (d, 1 H, C(2)Hb, =CH2, J = 17.6 Hz);
6.64 (dd, 1 H, C(1)H, =CH, J = 17.6 Hz, J = 10.7 Hz); 7.20—7.26
(m, C(2)H, C(3)H, C(5)H, C(6)H, arom.). 13C NMR, : 33.98
(C(5), dioxane), 66.90 (C(6), dioxane), 78.69 (C(4), dioxane),
94.14 (C(2), dioxane), 124.14 (C(3), C(5)), 127.13 (C(2), C(6)),
114.23 (=CH2, vinyl), 136.01 (=CH, vinyl), 141.06 (C(1), C(4)).
MS, m/z (Irel (%)): 190 [M]+ (14), 163 [M – C2H3]+ (6), 146
[M – CO2]+ (84), 130 [M – 2 CH2O]+ (100), 92 [C6H5CH3]+
(14), 91 [C6H5CH2]+ (90), 77 [C6H5]+ (36), 30 [CH2O]+ (12).
4-(3-Ethylphenyl)-1,3-dioxane (7b). Yield 10%, b.p. 108 C
(1 Torr). 1H NMR, : 1.20 (t, 3 H, CH3, J = 7.1 Hz); 2.66 (q, 2 H,
CH2CH3, J = 7.2 Hz); 1.71 (dq, 2 H, C(5)Ha, dioxane, J = 12.0 Hz,
J = 4.0 Hz); 2.10 (dq, 2 H, C(5)Hb, dioxane, J = 12.0 Hz,
J = 4.0 Hz); 3.90 (dt, 2 H, C(6)Ha, dioxane, J = 12.0 Hz,
J = 4.0 Hz); 4.24 (dt, 2 H, C(6)Hb, dioxane, J = 12.0 Hz,
J = 4.0 Hz); 4.65 (dd, 1 H, C(4)H, dioxane, J = 12.0 Hz,
J = 4.0 Hz); 4.91 (d, 1 H, C(2)Ha, dioxane, J = 3.0 Hz); 5.23
(d, 1 H, C(2)Hb, dioxane, J = 3.0 Hz); 7.20—7.26 (m, C(10)H,
C(11)H, C(12)H, arom.); 7.55 (s, 1 H, C(8)H, arom.). 13C NMR,
: 16.23 (CH3), 29.01 (CH2CH3), 33.98 (C(5), dioxane), 66.90
(C(6), dioxane), 78.69 (C(4), dioxane), 94.14 (OCH2O), 123.13
(C(2)), 125.18 (C(5), arom.),128.66 (C(4), C(6)), 140.06 (C(1),
C(3)). MS, m/z (Irel (%)): 192 [M]+• (1), 149 [M – CH3CO]+
(33), 87 [C4H7O2]+ (95), 77 [C6H5]+ (33), 69 [C5H9]+ (100),
41 [C3H5]+ (12).
4-(4-Ethylphenyl)-1,3-dioxane (8b). Yield 10%, b.p. 108 C
(1 Torr). 1H NMR, : 1.20 (t, 3 H, CH3, J = 7.1 Hz); 2.66 (q, 2 H,
CH2CH3, J = 7.2 Hz); 1.71 (dq, 1 H, C(5)Ha, dioxane, J = 12.0 Hz,
J = 4.0 Hz); 2.10 (dq, 1 H, C(5)Hb, dioxane, J = 12.0 Hz,
J = 4.0 Hz); 3.90 (dt, 1 H, C(6)Ha, dioxane, J = 12.0 Hz,
J = 4.0 Hz); 4.24 (dt, 1 H, C(6)Hb, dioxane, J = 12.0 Hz,
J = 4.0 Hz); 4.65 (dd, 1 H, C(4)H, dioxane, J = 12.0 Hz,
J = 4.0 Hz); 4.91 (d, 1 H, C(2)Ha, dioxane, J = 3.0 Hz); 5.23
(d, 1 H, C(2)Hb, dioxane, J = 3.0 Hz); 7.31—7.38 (m, 2 H, C(2)H,
C(6)H, arom.); 7.52 (s, 2 H, C(3)H, C(5)H, arom.). 13C NMR,
: 16.23 (CH3), 29.01 (CH2CH3), 33.98 (C(5), dioxane), 66.90
(C(6), dioxane), 78.69 (C(4), dioxane), 94.14 (OCH2O), 123.13
(C(2)), 127.18 (C(2), C(3)), 128.66 (C(5), C(6)), 139.06 (C(1),
C(4)). MS, m/z (Irel (%)): 192 [M]+• (6), 149 [M – CH3CO]+
(30), 87 [C4H7O2]+ (55), 77 [C6H5]+ (59), 69 [C5H9]+ (100),
41 [C3H5]+ (29).

Reactions of divinylbenzene
Russ. Chem. Bull., Int. Ed., Vol. 68, No. 11, November, 2019
2097
in vacuo. Products 11 and 12 were isolated by column chroma-
tography (elution with hexane—ethyl acetate).
(1 Torr)), and 8b (yield 9%, b.p. 108 C (1 Torr)). Spectral
properties of the synthesized compounds are in agreement with
those given above.
4-[3-(2,2-Dichlorocyclopropyl)phenyl]-1,3-dioxane (11).
Yield 19% by method A and 50% by method B. B.p. 170 C
(1 Torr). 1H NMR, : 1.75—1.93 (m, 1 H, C(2)Ha, cyclopropane);
1.86—1.93 (m, 1 H, C(2)Hb, cyclopropane); 1.97—2.04 (m, 1 H,
C(5)Ha, dioxane); 2.67—2.73 (m, 1 H, C(3)H, cyclopropane);
2.05—2.15 (m, 1 H, C(5)Hb, dioxane); 3.90 (t, 1 H, C(6)Ha,
dioxane, J = 6.0 Hz); 4.22 (dd, 1 H, C(6)Hb, dioxane, J = 6.0 Hz);
4.68 (m, 1 H, C(4)H, dioxane); 4.91 (d, 1 H, C(2)Ha, dioxane,
J = 3.0 Hz); 5.25 (d, 1 H, C(2)Hb, dioxane, J = 3.0 Hz);
7.21—7.24 (m, 3 H, C(4)H, C(5)H, C(6)H, arom.); 7.28 (s, 1 H,
C(2)H, arom.). 13C NMR, : 25.79 (C(2), cyclopropane), 34.05
(C(5), dioxane), 35.44 (C(3), cyclopropane), 60.74 (CCl2), 66.89
(C(6), dioxane), 76.76 (C(4), dioxane), 94.18 (OCH2O), 124.99
(C(5)), 127.13 (C(2)), 141.68 (C(4), C(6)) 134.96 (C(1), C(3)).
MS, m/z (Irel (%)): 273/275/277 [M]+• (8/5/2), 229/231/233
[M – CO2]+ (58/12/2), 195/193 [M – CO2 – HCl]+ (5/17/21),
115 [M – C4H7O2 – Cl – HCl]+ (100), 77 [C6H5]+ (10),
30 [CH2O]+ (12).
This work was financially supported by the Russian
Foundation for Basic Research (competition mol_ev_a
(Eureka! Idea), Project No. 19-33-80002\19 from
07.12.2018).
References
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Received Apryl 22, 2019;
in revised form August 15, 2019;
accepted August 22, 2019