Synthesis of unsaturated dibasic acid esters from five-, six-, and seven-membered cycloalkanones

Article abstract of DOI:10.1007/s11172-006-0545-z

A new route to diesters of symmetrical octene-, decene-, and dodecenedioic acids was proposed. The ratio of the cis/trans-isomers was 1:4. The synthesis involved oxidative splitting of five-, six-, and seven-membered cycloalkanones with hydrogen peroxide into the corresponding ω-alkenoic acids followed by esterification and metathesis over Re₂O₇/B ₂O₃-Al₂O₃-SnMe₄.

Full text of DOI:10.1007/s11172-006-0545-z

Russian Chemical Bulletin, International Edition, Vol. 55, No. 11, pp. 2016—2019, November, 2006
2016
Synthesis of unsaturated dibasic acid esters
from fiveꢀ, sixꢀ, and sevenꢀmembered cycloalkanones*
E. K. Starostin,ꢀ D. B. Furman, A. V. Ignatenko, A. P. Barkova, and G. I. Nikishin
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences,
47 Leninsky prosp., 119991 Moscow, Russian Federation.
Fax: +7 (495) 135 5328. Eꢀmail: nika@ioc.ac.ru
A new route to diesters of symmetrical octeneꢀ, deceneꢀ, and dodecenedioic acids
was proposed. The ratio of the cis/transꢀisomers was 1 : 4. The synthesis involved oxidative
splitting of fiveꢀ, sixꢀ, and sevenꢀmembered cycloalkanones with hydrogen peroxide into
the corresponding ωꢀalkenoic acids followed by esterification and metathesis over
Re2O7/B2O3—Al2O3—SnMe4.
Key words: cycloalkanones, ωꢀalkenoic acids and esters, diesters of alkenedioic acids,
metathesis reaction, catalyst for the metathesis, rhenium.
Organic peroxides are widely used to initiate free radiꢀ
cal processes for production of polymeric materials but
much more rarely employed as reagents in organic synꢀ
thesis. Among peroxides that function as building blocks
in organic chemistry, cycloalkanone peroxides are of priꢀ
mary importance; they are easily derived from cyclic keꢀ
tones and H2O2 (see Refs 1 and 2).
Straightforward schemes for the synthesis of oxo carꢀ
boxylic,3 ωꢀalkenoic,3 and ωꢀhaloalkanoic acids4 involve
reactions of cycloalkanone peroxides with methyl vinyl
ketone and FeII sulfate, with the FeSO4—CuSO4 or
FeSO4—CuX2—MX2 system (M = Na and K; X = Cl,
Br, and I).
At the same time, ωꢀalkenoic acids are employed
as starting materials for the synthesis of ωꢀ and
(ω – 1)ꢀalkynoic acids5 used to obtain natural compounds.
Previous investigations of oxidative decyclization of
cycloalkanones in the presence of H2O2 have been aimed
at obtaining functionalized aliphatic compounds.3—5 Here
we report on the results of stepwise transformation of
cyclic ketones into symmetrical alkenedioic acid esters.
The proposed method involves three successive steps, viz.,
oxidation of cycloalkanones (1a—e) into ωꢀalkenoic
acids (2a—e), their transformation into esters (3a—f), and
metathesis leading to alkenedioic acid esters (4a,b,e,f).
ωꢀAlkenoic acids 2a—e were synthesized according to
a known procedure.2,4 Reactions of cycloalkanones 1a—c
with 30% H2O2 gave 1ꢀhydroperoxyꢀ1ꢀhydroxycycloꢀ
alkanes, which decomposed under the action of
i. 1) 30% H2O2, 2) FeSO4—CuSO4. ii. H2SO4.
iii. Re2O7—B2O3/Al2O3—SnMe4 or Re2O7/Al2O3—SnMe4.
Compound
n
R
R´
1a—4a
1b—4b
1c—4c
1d—4d
1e—4e
3f, 4f
1
2
2
2
3
2
H
H
Me
But
H
Me
Me
Me
Me
Me
Et
H
FeSO4—CuSO4 to acids 2a—e. The yields of acids 2b—d
were 60—65% and the yields of acids 2a and 2e were 20
and 40%, respectively (calculated to the starting cycloꢀ
alkanone). The nonconsumed ketone can be recycled.
Esterification of acids 2a—e with methanol and ethanol
was carried out under classic conditions of sulfuric acid
catalysis. The resulting esters 3a,b,e,f were used in the
* Dedicated to Academician O. M. Nefedov on the occasion of
his 75th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1942—1944, November, 2006.
1066ꢀ5285/06/5511ꢀ2016 © 2006 Springer Science+Business Media, Inc.

Symmetrical unsaturated dibasic acid esters
Russ.Chem.Bull., Int.Ed., Vol. 55, No. 11, November, 2006 2017
Table 1. Metathesis reaction of alkyl ωꢀalkenoates 3a—f
not optimized). The αꢀmethyl group with respect to
the double bond in ester 3c strongly hinders the metaꢀ
thesis reaction; ester 3d containing the tertꢀbutyl group
does not undergo metathesis at all. The alkoxy group
of the ester fragment also affects the metathesis: the conꢀ
version of methyl hexꢀ5ꢀenoate 3b is appreciably higher
than that of ethyl ester 3f. A variation in the rhenium
content from 9 to 12% virtually does not affect the activꢀ
ity of the catalyst; the B2O3ꢀfree catalyst is less effective
(see Table 1).
According to NMR and GLC data, dialkyl alkeneꢀ
dioates 4a,b,e,f are mixtures of the cisꢀ and transꢀisomers
in the ratio ~1 : 4. This ratio was confirmed by calculaꢀ
tions performed with the Panic program for the sixꢀspin
system CH2CH=CHCH2 in ester 4a. A satisfactory agreeꢀ
ment of experimental and theoretical spectra was obtained
for the transꢀisomer with the characteristic coupling conꢀ
stant Jtrans = 15.16 Hz.
Entry Reꢀ
[Re] Sn/Re Product Conversion Yield of
of esters (%) ethene
agent (%)*
3a—f
(%)
1
2
3
4
5
6
7
8
3a
3a
3a
3a
3b
3b
3b
3f
19
9
9
12
12
12
9
9
9
12
12
9
1 : 1
1 : 1
1 : 2
1 : 2
1 : 0.5
1 : 1
1 : 1
1 : 1
1 : 1
1 : 1
1 : 1
1 : 1
4a
4a
4a
4a
4b
4b
4b
4f
34
50
64
67
59
92
91
64
52
8
32
48
66
64
54
90
89
62
50
10
0
9
3f
4f
10
11
12
3c
3d
3e
4c
4d
4e
0
79
81
* The rhenium content of the catalyst (Re2O7—B2O3/Al2O3 in
entries 2—8 and 10—12 and Re2O7/Al2O3 in entries 1 and 9).
The B2O3 content of the catalyst was 5%.
Experimental
metathesis reaction over a Re catalyst to give dialkyl
alkenedioates 4a,b,e,f (Table 1).
GLCꢀanalysis was carried out on an LKhMꢀ80 chromatoꢀ
graph (flame ionization detector, column 3000×3 mm, 6% SEꢀ30
on Chromosorb´e W (60—80 mesh)). 1H and 13C NMR spectra
were recorded on a Bruker ACꢀ200 instrument (200.13 and
50.32 MHz, respectively).
Commercial starting ketones 1a—e (97—98% purity; Across,
Lancaster) were used as purchased. ωꢀAlkenoic acids 2a—e
were synthesized by oxidation of ketones 1a—e with 30%
H2O2—FeSO4 according to a known procedure;3 2a: b.p.
86—87 °C (15 Torr); 2b: b.p. 93—95 °C (14 Torr); 2c: b.p.
102—104 °C (15 Torr); 2d: b.p. 141—143 °C (14 Torr); 2e: b.p.
116—117 °C (15 Torr). Esters 3a—f were obtained by esterificaꢀ
tion of acids 2a—e with methanol or ethanol in the presence of
98% H2SO4.
When preparing the catalysts Re2O7—B2O3/Al2O3 and
Re2O7/Al2O3 containing 9 or 12% Re and 5% B2O3, NH4ReO4
(Aldrich) was used as a precursor of the active phase.12
The carrier B2O3/Al2O3 was prepared by impregnation of
γꢀAl2O3 (Ssp = 196 m2 g–1, grain size 0.3—0.6 mm, d =
0.56 g cm–3) with aqueous H3BO3 followed by drying in a drying
box at 150 °C. The activator SnMe4 was synthesized as described
earlier12 and stored over molecular sieves in argon.
Metathesis reaction. Hexane (5 mL) distilled over sodium in
an argon atmosphere and Re2O7—B2O3/Al2O3 or Re2O7/Al2O3
(0.47 g (9% Re) or 0.35 g (12% Re), which corresponds to
2.4•10–3 mol of rhenium (see Table 1), were placed in a flask
connected to a gas burette. Then a required amount of SnMe4
(2.4•10–3 or 4.8•10–3 mol, depending on the given Re : Sn
ratio) in hexane (1.0 mL) was added and the mixture was stirred
with a magnetic stirring bar at 20 °C for 1 h. Ester 3 (12•10–2 mol;
Re : 3 = 1 : 50) in hexane (5 mL) was added and the volume of
evolved ethene was measured. After the evolution of ethene
ceased, the reaction mixture was filtered, the solid phase
was washed with hexane, and the hexane and nonconsumed
ester 3 were removed. The residue was diester 4 (GLC and
NMR data).
Similar diesters and the corresponding dibasic acids
are used in organic synthesis, e.g., in the synthesis of
pheromones.6 Symmetrical (with respect to the position
of the double bond) alkenedioic acid esters can be obꢀ
tained in several ways: (1) catalytic decomposition of
not easily accessible diazo esters,7 (2) multistep syntheꢀ
sis from ωꢀchloroalkynes and ωꢀbromoꢀαꢀchloroalkaꢀ
nes (the synthesis includes replacement of the Cl atoms
by cyano groups, their hydrolysis, and hydrogenation
of the triple bond),8 (3) electrolysis of alkanoic acid
esters with participation of butadiene (isomeric alkeneꢀ
dioic and alkadienedioic acids are byꢀproducts),9 and
(4) oxidative dehydrodimerization of cycloalkanones
into bicycloalkaneꢀ2,2´ꢀdiones followed by their reaction
with H2O2 and thermolysis of the resulting peroxides.
The last method10 also gives rise to isomeric alkenedioic
acids.
Among the existing approaches to the synthesis of
esters 4, metathesis has been employed in the template
intramolecular cyclization of dihexenoyl derivatives of
diamines and diglycols and the resulting macrocycles
have been converted into the target compound 4b (see
Ref. 11).
The route to diesters 4 we propose is experimentally
simple and the starting reagents are accessible. The metaꢀ
thesis of esters 3a—f is the most important step of the
synthesis. Reactions were carried out over Re2O7/Al2O3
and Re2O7—B2O3/Al2O3 in combination with SnMe4 as
an activator. The results obtained are summarized in
Table 1. The conversions of esters 3a,b,e containing no
alkyl substituents in the side chain into the target prodꢀ
ucts 4a,b,e were 65—90% (reaction conditions were

2018
Russ.Chem.Bull., Int.Ed., Vol. 55, No. 11, November, 2006
Starostin et al.
4ꢀMethylhexꢀ5ꢀenoic acid (2c) (see Ref. 13). 1H NMR
(CDCl3), δ: 1.02 (d, 3 H, Me, J = 6.70 Hz); 1.64 (m, 2 H,
CH2CH2CO); 2.17 (m, 1 H, CHMe); 2.34 (t, 2 H, CH2COO,
J = 7.72 Hz); 5.02 (m, 2 H, CH=CH2); 5.64 (m, 1 H, CH=CH2);
10.60 (br.s, 1 H). 13C NMR (CDCl3), δ: 20.12 (CMe), 31.01,
31.93 (CH2CH2), 37.39 (CHMe), 113.84 (CH=CH2), 143.20
(CH=CH2), 180.50 (C=O).
4ꢀtertꢀButylhexꢀ5ꢀenoic acid (2d) (see Ref. 14). 1H NMR
(CDCl3), δ: 0.88 (s, 9 H, CMe3); 1.30—1.70 (wm, 2 H,
CH2CH2CO); 1.92 (m, 1 H, CH); 2.1—2.50 (wm, 2 H, CH2CO);
5.00 (m, 2 H, CH=CH2); 5.53 (m, 1 H, CH=CH2); 11.30 (br.s,
1 H). 13C NMR (CDCl3), δ: 27.63 (Me3), 32.57 (CMe3),
32.86 (CH2CO), 54.75 (CHCMe3), 117.15 (CH=CH2), 139.05
(CH=CH2), 180.85 (C=O).
Methyl pentꢀ4ꢀenoate (3a) (see Ref. 15). 1H NMR (CDCl3),
δ: 2.44 (m, 4 H, CH2CH2); 3.67 (s, 3 H, OMe); 5.0 (m, 2 H,
CH=CH2); 5.8 (wm, 1 H, CH=CH2). 13C NMR (CDCl3), δ:
27.31 (CH2CH=); 32.92 (CH2C=O); 51.42 (OMe); 115.34
(CH=CH2); 135.92 (CH=CH2); 173.41 (C=O).
Methyl hexꢀ5ꢀenoate (3b) (see Ref. 16). 1H NMR (CDCl3),
δ: 1.8 (m, 2 H, CCH2C, J = 7.3 Hz); 2.10 (quint, 2 H, CH2C=,
J = 7.3 Hz); 2.31 (t, 2 H, O=CCH2, J = 7.2 Hz); 3.66 (s, 3 H,
OMe). 13C NMR (CDCl3), δ: 24.1 (CCH2C); 32.44 (CH2CH=);
33.64 (CH2C=O), 50.95 (OMe), 115.41 (CH=CH2), 136.61
(CH=CH2), 173.32 (C=O).
2 H, CH2CH=); 2.30 (t, 2 H, O=CCH2, J = 7.46 Hz); 3.67
(s, 3 H, OMe); 5.38 (m, 1 H, CH=C). 13C NMR (CDCl3),
δ: 24.62 (CCH2C); 31.84 (CH2CH=); 34.01 (CH2C=O);
51.46 (OMe); 129.50 (cisꢀCH=CH); 130.00 (transꢀCH=CH);
174.50 (C=O).
Dimethyl Z,Eꢀdodecꢀ6ꢀenedioate (4e) (see Ref. 10). 1H NMR
(CDCl3), δ: 1.35 and 1.58 (m, 4 H, CCH2CH2C); 1.98 (m, 2 H,
CH2CH=); 2.30 (t, 2 H, O=CCH2, J = 7.2 Hz); 3.63 (s, 3 H,
OMe); 5.37 (m, 1 H, CH=C). 13C NMR (CDCl3), δ: 24.33,
28.75, 31.79 (3 CH2); 33.50 (CH2C=O); 51.00 (OMe), 129.28
(cisꢀCH=CH), 129.79 (transꢀCH=CH), 173.68 (C=O).
Diethyl Z,Eꢀdecꢀ5ꢀenedioate (4f) (see Ref. 23). 1H NMR
(CDCl3), δ: 1.20 (m, 3 H, CH2CH3); 1.70 (q, 2 H, CCH2C, J =
7.3 Hz); 2.04 (q, 2 H, CH2CH=CH, J = 7.2 Hz); 2.30 (t, 2 H,
O=CCH2, J = 7.2 Hz); 4.10 (q, 2 H, OCH2Me, J = 7.1 Hz);
5.29 (m, 1 H, CH=C).
We are grateful to Yu. A. Strelenko for calculations
with the Panic program.
This work was financially supported by the Council on
Grants of the President of the Russian Federation (State
Program for Support of Russian Leading Scientific
Schools, Grant NShꢀ5022.2006.3).
Methyl 4ꢀmethylhexꢀ5ꢀenoate (3c) (see Ref. 17). 1H NMR
(CDCl3), δ: 0.95 (d, 3 H, Me, J = 6.72 Hz); 1.58 (m, 2 H,
CH2CH2CO); 2.09 (m, 1 H, CHMe); 2.25 (t, 2 H, CH2CO, J =
7.74 Hz); 3.61 (s, 3 H, OMe); 4.93 (m, 2 H, CH=CH2); 5.58
(m, 1 H, CH=CH2). 13C NMR (CDCl3), δ: 19.96 (CCH3);
31.23, 31.77 (CH2CH2); 37.36 (CHMe); 51.30 (OMe); 113.47
(CH=CH2); 143.24 (CH=CH2); 174.30 (C=O).
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Symmetrical unsaturated dibasic acid esters
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Received June 20, 2006