Reaction of dibromoadamantanes with glycols in the presence of sodium glycolate

Article abstract of DOI:10.1134/S1070428011120062

1,3-Dibromoadamantanes reacted with glycols in the presence of sodium glycolate to give novel unsaturated bicyclo[3.3.1]nonane derivatives and 1,3-disubstituted adamantanes.

Full text of DOI:10.1134/S1070428011120062

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2011, Vol. 47, No. 12, pp. 1811–1816. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © M.Yu. Skomorokhov, Yu.N. Klimochkin, 2011, published in Zhurnal Organicheskoi Khimii, 2011, Vol. 47, No. 12, pp. 1775–1779.
Reaction of Dibromoadamantanes with Glycols
in the Presence of Sodium Glycolate
M. Yu. Skomorokhov and Yu. N. Klimochkin
Samara State Technical University, ul. Molodogvardeiskaya 244, Samara, 443010 Russia
e-mail: orgchem@samgtu.ru
Received November 30, 2010
Abstract—1,3-Dibromoadamantanes reacted with glycols in the presence of sodium glycolate to give novel
unsaturated bicyclo[3.3.1]nonane derivatives and 1,3-disubstituted adamantanes.
DOI: 10.1134/S1070428011120062
Fragmentation of some 1,3-disubstituted adaman-
tanes through intermediate formation of stabilized
3-substituted 7-methylidenebicyclo[3.3.1]non-3-yl
cations was reported in [1–7]; in the presence of water
the latter were converted into 7-methylidenebicyclo-
[3.3.1]non-3-one (Scheme 1). Presumably, in strongly
basic medium such carbenium ions can be stabilized
via elimination of proton with formation of double
C=C bond.
We previously found [8] that 1,3-dibromoadaman-
tane (I) in ethylene glycol at 200°C in the presence of
a strong base is converted into a mixture of 2-(7-meth-
ylidenebicyclo[3.3.1]non-2-en-3-yloxy)ethanol (II)
and 7-methylidenespiro[bicyclo[3.3.1]nonane-3,2′-
[1,3]dioxolane] (III). More detailed analysis of the
product mixture allowed us to reveal 10–12% of
2,2′-(adamantane-1,3-diybisoxy)diethanol (IV).
1,3-Dibromo-5,7-dimethyladamantane (VI) reacted in
a similar way (Scheme 2).
As might be expected [9], vinyl ether II upon
distillation or heating to 100°C, as well as during
chromatography on silica gel, is quantitatively con-
verted into spiro dioxolane III. Protection of the
hydroxy group by esterification made it possible to
isolate by vacuum distillation 2-(7-methylidenebicyclo-
[3.3.1]non-2-en-3-yloxy)ethyl acetate (Va); the corre-
sponding p-nitrobenzoate Vb was isolated by frac-
tional recrystallization from methanol. Compounds
IVa and IXa were isolated and characterized as p-ni-
trobenzoates IVb and IXb (Scheme 2).
The structure of the products obtained by reactions
of 1,3-dibromoadamantanes I and VI with ethylene
glycol suggests the following reaction mechanism.
1,3-Dibromoadamantane I or VI in polar medium
gives rise to 3-bromoadamantan-1-yl cation which
takes up ethylene glycol molecule to produce inter-
mediate A. Heterolytic dissociation of the C–Br bond
in A generates cation B which undergoes Grob frag-
mentation with formation of carbenium ion C. The
latter can be stabilized according to two pathways.
Intramolecular proton abstraction from the α-carbon
The products were isolated from the reaction mix-
ture by selective extraction and subsequent vacuum dis-
tillation or recrystallization from appropriate solvent.
Scheme 1.
CH2
H2O
O
Br
CH2
CH2
··
X
X
–Br–
CH2
X
Base
X
X = Cl, Br, MeO, MeS, H2N, MeNH, Me2N.
1811

SKOMOROKHOV, KLIMOCHKIN
1812
Scheme 2.
OH
Br
O
CH2
CH2
O
HOCH2CH2OH, Na
OH
O
+
+
OH
R1
R1
R1
R1
O
Br
O
R1
R1
R1
R1
I, VI
II, VII
III, VIII
IVa, IXa
O
CH2
R2
R2COCl, Et3N
O
II, VII
O
R1
R1
Va, Vb, Xb
O
R2
O
O
O
R2COCl, Et3N
IVa, IXa
R2
R1
O
R1
O
IVb, IXb
I–V, R1 = H; VI–X, R1 = Me; R2 = Me (a), 4-O2NC6H4 (b).
atom by the action of sodium alkoxide leads to vinyl
ether II or VII (pathway a); attack by the cationic
center on the lone electron pair of the oxygen atom in
the hydroxy group yields spiro dioxolane III or VIII
(Scheme 3). A concurrent process is classical solvol-
ysis of cation B with formation of 1,3-dialkoxyada-
mantane IV or IX.
With a view to elucidate solvent effect on the frag-
mentation of 1,3-dibromoadamantane (I) we selected
the following diols: propane-1,2-diol, propane-1,3-
diol, butane-1,2-diol, butane-2,3-diol, butane-1,3-diol,
butane-1,4-diol, and diethylene glycol. Reactions of
dibromide I with primary diols under analogous condi-
tions afforded mixtures of vinyl ether XI or XV, spiro-
Scheme 3.
Br
Br
HOCH2CH2OH
–HBr
HOCH2CH2OH
IV, IX
–Br–
OH
OH
R
R
R
Br
O
O
R
R
R
I, VI
A
B
CH2
HOCH2CH2ONa
II, VII
O–
a
CH2
R
O
R
H
CH2
O
B
OH
R
O
R
H
C
–H+
b
O
R
R
III, VIII
R = H, Me.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 12 2011

REACTION OF DIBROMOADAMANTANES WITH GLYCOLS
1813
Scheme 4.
X
Br
O
OH
O
CH2
CH2
O
HO–X–OH, RONa
X
O
+
+
X
X
O
Br
OH
OH
I
XI, XV
XII, XVI
XIII, XVII
CH2
O
Me
O
X
XI, XV
O
XIV, XVIII
XI–XIV, X = CH2CH2CH2CH2; XV–XVIII, X = CH2CH2OCH2CH2.
cyclic compound XII or XVI, and 1,3-disubstituted
adamantane XIII or XVII (Scheme 4). The products
were isolated and purified as in the reaction of di-
bromide I with ethylene glycol. Compounds XI and
XV were isolated as characterized as acetic acid esters
XIV and XVIII. As the length of the carbon skeleton
in the glycol increased, the fraction of cyclic products
XII and XVI in the reaction mixture decreased to 0.5–
1%, and we failed to isolate them.
Dibromide I did not react with 1,3-glycols
(propane-1,3-diol and butane-1,3-diol) in the presence
of sodium alkoxide; in these cases, decomposition
products of the corresponding glycol were formed
exclusively.
We can conclude that fragmentation of 1,3-di-
bromoadamantane in glycols in the presence of sodium
glycolate leads to the formation of novel 3,7-disub-
stituted bicyclo[3.3.1]nonane derivatives.
1,3-Dibromoadamantane (I) reacted with secondary
diols under analogous conditions to give only substi-
tuted 7-methylidenespiro[bicyclo[3.3.1]nonane-3,2′-
[1,3]dioxolanes] XIX–XXI (Scheme 5). From com-
pound I and butane-2,3-diol we obtained 4′,5′-di-
methyl-7-methylidenespiro[bicyclo[3.3.1]nonane-3,2′-
[1,3]dioxolane] (XXI), while the reaction of I with
propane-1,2-diol afforded a mixture of stereoisomeric
4′-methyl-7-methylidenespiro[bicyclo[3.3.1]nonane-
3,2′-[1,3]dioxolanes] XIX and XX at a ratio of 1:1
(according to the 1H NMR and GLC data). Compounds
XIX–XXI were isolated and purified by column chro-
matography on silica gel.
EXPERIMENTAL
The IR spectra were recorded on an IKS-22 spec-
trometer from samples prepared as KBr pellets or
1
dispersed in mineral oil. The H NMR spectra were
measured on a Bruker AC-200 instrument at 200 MHz
using CDCl3 as solvent and hexamethyldisiloxane as
internal reference. The 13C NMR spectra were
recorded on a Bruker AM-300 spectrometer at 75 MHz
(CDCl3, HMDS) with complete decoupling from
protons, as well as using DEPT pulse sequence. The
mass spectra (electron impact, 70 eV) were obtained
Scheme 5.
Br
Me
CH2
O
CH2
O
Me
Na
+
+
OH
Me
HO
O
O
Br
I
XIX
XX
Br
Me
CH2
O
Me
Na
OH
+
HO
Me
O
Br
Me
I
XXI
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 12 2011

SKOMOROKHOV, KLIMOCHKIN
1814
on a Finnigan MAT INCOS 50 mass spectrometer. The
elemental compositions were determined on a Euro
Vector EA 3000 analyzer. GLC analysis was performed
on a Tsvet-100 chromatograph equipped with a flame-
ionization detector and a 25-m SE-30 quartz capillary
column (carrier gas helium). Silufol UV-254 plates
were used for thin-layer chromatography; spots were
developed by treatment with iodine vapor.
(1H each, =CH2), 8.19 d (2H, Harom, J = 9 Hz), 8.36 d
(2H, Harom, J = 9 Hz). 13C NMR spectrum, δC, ppm:
26.35 (C9), 28.54 (C5), 29.23 (C4), 31.06 (C6), 33.79
(C8), 42.12 (C1), 63.97 (C12), 64.09 (C11), 98.03 (C2),
111.26 (C10), 144.96 (C7), 154.04 (C3), 164.31 (C15);
123.98, 130.72, 135.01, 150.32 (Carom). Mass spec-
trum, m/z (Irel, %): 343 (15.4) [M]+, 288 (14.4), 194
(100), 150 (70.6), 104 (54). Found, %: C 66.09;
H 6.19; N 3.98. C19H21NO5. Calculated, %: C 66.46;
H 6.16; N 4.08.
Reaction of 1,3-dibromoadamantane with ethyl-
ene glycol. 1,3-Dibromoadamantane, 70 g (0.238 mol),
was added to a solution of 25 g (1.09 mol) of metallic
sodium in 500 ml of ethylene glycol. The mixture was
heated for 3 h under reflux, poured into water, and
extracted with benzene. The extract was washed with
water and dried over anhydrous sodium sulfate, the
solvent was distilled off, the residue was dissolved in
100 ml of toluene, 22 ml (0.165 mol) of triethylamine
and 14 ml (0.137 mol) of acetic anhydride were added,
and the mixture was heated for 1 h under reflux. The
mixture was then washed with a 5% solution of sodi-
um carbonate and with water, the solvent was distilled
off, and the residue was distilled under reduced pres-
sure to isolate two fractions.
After extraction with benzene (see above), the
aqueous layer was repeatedly treated with chloroform,
the extract was dried over anhydrous sodium sulfate,
8.7 ml (0.06 mol) of triethylamine and 11.1 g
(0.06 mol) of 4-nitrobenzoyl chloride were added, and
the mixture was heated for 1 h under reflux. It was
then poured into 100 ml of a saturated solution of
sodium carbonate, the organic layer was separated,
washed with water, and evaporated, and the residue
was recrystallized from toluene. We thus isolated
11.9 g (9%) of adamantane-1,3-diylbis(oxyethane-2,1-
diyl) bis(4-nitrobenzoate) (IVb), mp 115–117°C. IR
spectrum, ν, cm–1: 1735, 1600, 1520, 1240, 1135,
1
7-Methylidenespiro[bicyclo[3.3.1]nonane-3,2′-
[1,3]dioxolane] (III). First fraction; yield 5 g (11%),
bp 99–100°C (1 mm), nD20 = 1.5071. IR spectrum, ν,
1050, 895. H NMR spectrum, δ, ppm: 1.52–1.59 m
(2H, Ad), 1.65–1.78 m (8H, Ad), 1.81–1.85 m (2H,
Ad), 2.38 s (2H, Ad), 3.78–3.81 m (4H, AdOCH2),
4.48–4.51 m (4H, CH2O), 8.21 d (2H, Harom, J = 9 Hz),
8.38 d (2H, Harom, J = 9 Hz). Found, %: C 60.31;
H 5.39; N 5.05. C28H30N2O10. Calculated, %: C 60.64;
H 5.45; N 5.05.
1
cm–1: 1660, 1110, 890. H NMR spectrum, δ, ppm:
1.25–2.35 m (12H), 3.77 m (4H, OCH2CH2O), 4.66 s
(2H, =CH2). Mass spectrum, m/z (Irel, %): 194 (17)
[M]+, 139 (100), 106 (41), 92 (33). Found, %: C 79.11;
H 9.40. C12H18O2. Calculated, %: C 79.19; H 9.34.
1,3-Dibromo-5,7-dimethyladamantane (VI) reacted
with ethylene glycol in a similar way.
2-(7-Methylidenebicyclo[3.3.1]non-2-en-3-yloxy)-
ethyl acetate (Va). Second fraction; Yield 7.5 g (14%),
bp 135–136°C (1 mm), nD20 = 1.5028. IR spectrum, ν,
1,5-Dimethyl-7-methylidenespiro[bicyclo[3.3.1]-
nonane-3,2′-[1,3]dioxolane] (VIII). Yield 13%,
bp 110–113°C (1 mm), nD20 = 1.5009. IR spectrum, ν,
1
cm–1: 1750, 1660, 1050, 895. H NMR spectrum, δ,
ppm: 1.60–2.50 m (10H), 1.98 s (3H, COCH3), 3.73–
3.76 m (2H, OCH2, J = 4.5 Hz), 4.17–4.20 m (2H,
CH2OAc), 4.43 s and 4.62 s (1H each, =CH2), 4.46 d
(1H, 2-H, J = 6 Hz). Mass spectrum, m/z (Irel, %): 236
(3) [M]+, 87 (100), 43 (47). Found, %: C 71.10;
H 8.47. C14H20O3. Calculated, %: C 71.16; H 8.53.
1
cm–1: 2950, 1660, 1110, 890. H NMR spectrum, δ,
ppm: 0.95 s (3H, CH3), 1.32–2.3 m (10H), 3.84–
3.88 m (4H, OCH2CH2O), 4.69 s (2H, =CH2). Mass
spectrum, m/z (Irel, %): 222 (14) [M]+, 207 (25), 167
(84), 120 (100), 105 (45), 79 (26). Found, %: C 75.73;
H 10.02. C14H22O2. Calculated, %: C 75.63; H 9.97.
2-(7-Methylidenebicyclo[3.3.1]non-2-en-3-yloxy)-
ethyl 4-nitrobenzoate (Vb) was synthesized in a simi-
lar way by acylation with 4-nitrobenzoyl chloride; the
product was isolated by recrystallization from hexane.
Yield 12.25 g (15%), mp 114–116°C. IR spectrum, ν,
cm–1: 1735, 1660, 1600, 1520, 1240, 1050, 895.
1H NMR spectrum, δ, ppm: 1.51–2.55 m (10H), 4.03 t
(2H, COCH2, J = 4 Hz), 4.53 d (1H, 2-H, J = 6 Hz),
4.61 t [2H, CH2OC(O), J = 4 Hz], 4.64 s and 4.72 s
5,7-Dimethyladamantane-1,3-diylbis(oxyethane-
2,1-diyl) bis(4-nitrobenzoate) (IXb). Yield 12%,
mp 125–128°C. IR spectrum, ν, cm–1: 1735, 1600,
1
1520, 1240, 1140, 1050, 895. H NMR spectrum, δ,
ppm: 0.95 s (3H, CH3), 1.12–1.14 m (2H, Ad), 1.41–
1.67 m (8H, Ad), 1.72–1.74 m (2H, Ad), 3.76–3.82 m
(4H, AdOCH2), 4.45–4.47 m (4H, CHO), 8.21 d (2H,
Harom, J = 9 Hz), 8.38 d (2H, Harom, J = 9 Hz). Found,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 12 2011

REACTION OF DIBROMOADAMANTANES WITH GLYCOLS
1815
form, the extract was dried over anhydrous sodium
sulfate, the solvent was distilled off, and the residue
was subjected to chromatography on silica gel using
chloroform–methanol (15:1) as eluent.
%: C 61.92; H 5.94; N 4.88. C30H34N2O10. Calculated,
%: C 61.85; H 5.88; N 4.81.
2-(1,5-Dimethyl-7-methylidenebicyclo[3.3.1]non-
2-en-3-yloxy)ethyl 4-nitrobenzoate (Xb). Yield 17%,
mp 66–68°C. IR spectrum, ν, cm–1: 1735, 1660, 1600,
2,2′-[Adamantane-1,3-diylbis(oxyethane-2,1-di-
yloxy)]diethanol (XVII). Yield 9%, n2D0 = 1.5029. IR
1
1520, 1240, 1050, 895. H NMR spectrum, δ, ppm:
1
spectrum, ν, cm–1: 3510, 1150, 1050, 895. H NMR
1.02 s (3H, CH3), 1.1 s (3H, CH3), 1.2–2.1 m (8H),
3.95 t (2H, COCH2, J = 4 Hz), 4.34 s (1H, 2-H) 4.62 t
[2H, CH2OC(O), J = 4 Hz], 4.49 s and 4.69 s (1H each,
=CH2). 13C NMR spectrum, δC, ppm: 29.75 (CH3),
31.43 (CH3), 33.27 (C5), 34.65 (C1), 40.76 (C4), 47.27
(C9), 47.54 (C6), 49.52 (C8), 64.32 (C11, C12), 103.08
(C10), 110.19 (C2), 146.54 (C7), 154.50 (C3), 164.74
(C15); 123.61, 130.95, 135.56, 150.67 (Carom). Mass
spectrum, m/z (Irel, %): 371 (3.4) [M]+, 316 (6), 194
(100), 150 (32.4), 104 (21), 40 (51). Found, %:
C 68.07; H 6.72; N 3.69. C21H25NO5. Calculated, %:
C 67.91; H 6.78; N 3.77.
spectrum, δ, ppm: 1.5–1.58 m (2H, Ad), 1.66–1.77 m
(8H, Ad), 1.81–1.87 m (2H, Ad), 2.37 s (2H, Ad),
3.49–3.53 m (12H, OCH2), 3.70–3.74 m (4H,
CH2OH). Found, %: C 62.98; H 9.27. C18H32O6. Cal-
culated, %: C 62.77; H 9.36.
2-[2-(7-Methylidenebicyclo[3.3.1]non-2-en-3-yl-
oxy)ethoxy]ethyl acetate (XVIII). Yield 16%,
bp 161–164°C (1 mm), nD20 = 1.4989. IR spectrum, ν,
cm–1: 1750, 1660, 1100, 1050, 895. 1H NMR spectrum,
δ, ppm: 1.6–2.5 m (10H), 2.05 s (3H, COCH3), 3.72–
3.76 m (2H, OCH2), 4.20–4.24 m (2H, CH2OAc),
4.51 s and 4.72 s (1H each, =CH2), 4.51 d (1H, 2-H,
J = 6 Hz). Found, %: C 58.59; H 8.59. C16H24O4. Cal-
culated, %: C 68.55; H 8.63.
Likewise, compounds XIII, XIV were synthesized
by reaction of 1,3-dibromoadamantane with butane-
1,4-diol, followed by acylation and distillation. After
extraction with benzene (see above), the aqueous phase
was repeatedly extracted with chloroform, the extract
was dried over anhydrous sodium sulfate, the solvent
was distilled off, and the residue was subjected to
chromatography on silica gel using chloroform–
methanol (20:1) as eluent.
Reaction of 1,3-dibromoadamantane with pro-
pane-1,2-diol. 1,3-Dibromoadamantane, 7 g
(0.0238 mol), was added to a solution of 2.5 g
(0.1 mol) of metallic sodium in 60 ml of propane-1,2-
diol. The mixture was heated for 3 h under reflux,
poured into water, and extracted with chloroform. The
organic phase was washed with water and dried over
anhydrous sodium sulfate, the solvent was distilled off,
and the residue was subjected to chromatography on
silica gel using benzene as eluent to isolate a mixture
of stereoisomeric 4′-methyl-7-methylidenespiro[bicy-
clo[3.3.1]nonane-3,2′-[1,3]dioxolanes] XIX and XX.
Overall yield 0.55 g (11%), nD20 = 1.5038. IR spectrum,
4,4′-(Adamantane-1,3-diylbisoxy)dibutan-1-ol
(XIII). Yield 12%, nD20 = 1.5011. IR spectrum, ν, cm–1:
1
3510, 1140, 1050, 895. H NMR spectrum, δ, ppm:
1.42–1.47 m (8H, CH2), 1.49–1.57 m (2H, Ad), 1.63–
1.78 m (8H, Ad), 1.84–1.89 m (2H, Ad), 2.40–2.44 m
(2H, Ad), 3.36–3.40 m (4H, AdOCH2), 3.56–3.60 m
(4H, CH2O), 4.43 s (2H, OH). Found, %: C 69.01;
H 10.23. C18H32O4. Calculated, %: C 69.20; H 10.32.
1
ν, cm–1: 2950, 1660, 1070, 1050, 890. H NMR spec-
trum, δ, ppm: 1.21–1.26 d (3H, CH3, J = 5.7 Hz),
1.28–1.33 d (3H, CH3, J = 5.7 Hz), 1.35–2.30 m
(24H), 3.35–3.37 m (1H, CH), 3.45–3.47 m (1H, CH),
4.03–4.05 m (1H, CH2), 4.18 m (1H, CH2), 4.74 s and
4.76 s (1H each, =CH2). Mass spectrum, m/z (Irel, %):
208 [M]+ (8), 153 (100), 106 (38), 95 (65), 79 (31), 67
(20). Found, %: C 75.09; H 9.72. C13H20O2. Calculat-
ed, %: C 74.96; H 9.68.
4-(7-Methylidenebicyclo[3.3.1]non-2-en-3-yloxy)-
butyl acetate (XIV). Yield 16%, bp 148–149°C
(1 mm), nD20 = 1.4933. IR spectrum, ν, cm–1: 1750,
1
1660, 1050, 895. H NMR spectrum, δ, ppm: 1.60–
2.50 m (14H), 1.98 s (3H, COCH3), 3.61–3.63 m (2H,
OCH2), 4.05–4.07 m (2H, CH2OAc), 4.46 s and 4.67 s
(1H each, =CH2), 4.47 d (1H, 2-H, J = 6 Hz). Mass
spectrum, m/z (Irel, %): 264 (7) [M]+, 149 (76), 107
(58), 43 (100). Found, %: C 72.71; H 9.20. C16H24O3.
Calculated, %: C 72.69; H 9.15.
4′,5′-Dimethyl-7-methylidenespiro[bicyclo[3.3.1]-
nonane-3,2′-[1,3]dioxolane] (XXI) was synthesized
in a similar way by reaction of 1,3-dibromoadaman-
tane with butane-2,3-diol. Yield 10%, nD20 = 1.5021. IR
Compounds XVII and XVIII were synthesized in
a similar way by reaction of 1,3-dibromoadamantane
with diethylene glycol, followed by acylation and dis-
tillation. After extraction with benzene (see above), the
aqueous phase was repeatedly extracted with chloro-
1
spectrum, ν, cm–1: 2950, 1660, 1080, 890. H NMR
spectrum, δ, ppm: 1.08–1.10 d (3H, CH3, J = 5.8 Hz),
1.20–1.22 d (3H, CH3, J = 5.8 Hz), 1.30–2.30 m
(12H), 3.64–3.66 m (1H, CH), 4.15–4.17 m (1H, CH),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 12 2011

SKOMOROKHOV, KLIMOCHKIN
1816
2. Bagrii, E.I., Adamantany (Adamantanes), Moscow:
4.75 s (2H, =CH2). Mass spectrum, m/z (Irel, %): 222
(25) [M]+, 207 (20), 140 (78), 107 (55), 93 (100).
Found, %: C 75.51; H 9.94. C14H22O2. Calculated, %:
C 75.63; H 9.97.
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This study was performed with the use of equip-
ment at a collective use center under financial support
by the program “Studies on Physicochemical Prop-
erties of Substances and Materials” and by the Federal
Special-Purpose Program “Scientific and Scientific–
Pedagogical Staff of Innovation Russia 2006–2012.”
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