CEJC 3(3) 2005 417–431
New transformation of cycloalkanone acetals by
peracids α, ω – dicarboxylic acids synthesis
Alexander O. Terent’ev∗, Sergey V. Chodykin
N.D. Zelinsky Institute of Organic Chemistry,
Russian Academy of Sciences,
119991 Leninsky Prospect 47, Moscow, Russia
Received 24 February 2005; accepted 13 April 2005
Abstract: A new process of oxidation of cycloalkanone acetals under the action of in situ
generated performic acid has been found. The main products of the reaction are α, ωdicarboxylic acids obtained with the yield up to 77 % depending on the size of acetals ring. The
process has been explored and optimized on the example of the dodecanedioic acid synthesis (a
valuable industrial product).
c Central European Science Journals. All rights reserved.
Keywords: Cycloalkanone acetals, hydrogen peroxide, dodecanedioic acid, dicarboxylic acid,
performic acid, enol-ether, oxidation, Baeyer-Villiger rearrangement
1
Introduction
The Baeyer-Villiger reaction [1-6], known already for more than a century, has found
wide application in synthesis of lactones and ω-hydroxycarboxylic acids. The oxidation
of acetals (obtained from cyclic ketones) under action of peracids was investigated in a
small number of works [7-11]. Practically all of these works describe the reaction with
participation of MCPBA as oxidative agent. Orthocarbonates and cyclic ethers [7,8],
optically active lactones [9], and orthoesters [10] were obtained depending on conditions
of the oxidation and acetal structures. The cyclic acetals with oxygen in cycle were
transformed into lactones [11] by MCPBA in the presence of boron trifluoride.
The present paper reports a new conversion of cycloalkanone acetals using peracids.
It has been found that α,ω-dicarboxylic acids are formed upon reaction of performic acid
with cycloalkanone acetals in the presence of sulfuric acid.
∗
E-mail: alterex@yandex.ru
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This oxidative process is of interest from two standpoints: as a new reaction in acetal chemistry and as a method of α,ω-dicarboxylic acid synthesis. The method has no
analogues. It can be applied in the synthesis of dodecanedioic acid [12-19], broadly used
for lubricants, anticorrosive composition, polyester covering and polyamide filaments,
and for the synthesis of tridecanedioic (brassylic) acid [20-22], a component of perfume
compositions.
2
Results and discussion
In continuation of our studies of acid-catalyzed reaction of acetals with hydrogen peroxide
[23], it was revealed that upon reaction of performic acid (generated in situ from HCOOH
and H2 O2 ) with 1,1-dimethoxycyclododecane (1a) in the presence of sulfuric acid dodecanedioic acid (2a) is formed as a major product. The by-product of the reaction is
12-hydroxydodecanoic acid (3a) (in a mix with its formate 3a’). Scheme 1.
Scheme 1 Oxidation of 1,1-dimethoxycyclododecane 1a.
The influence of the following factors on the yield of acids 2a and 3a (3a’) was
investigated: quantity of hydrogen peroxide in relation to acetal 1a, the type of H2 O2
solution (water or ether solution), the quantity of sulfuric acid, and temperature (Table 1).
As can be seen from Table 1, the greatest yields of 2a (64-72 %) were obtained when
the quantity of sulfuric acid was 15mmol and there was eightfold excess of H2 O2 (ether
solution); using an aqueous solution of H2 O2 , the yields of 2a were 6-10 % lower, most
likely due to partial hydrolysis of 1a into cyclododecanone 4.
Considering of this fact, a number of experiments on the oxidation of 4 were performed
in the presence of methanol in twofold excess with use of both water and ether solutions
of H2 O2 and H2 SO4 (15mmol) in eightfold excess. In result, the acid 3a was obtained
as the major product with a yield of 51-53 % and 2a as by-product at 39-43 %. These
results are in good agreement with an assumption that the decrease of the yield of 2a,
with use of aqueous H2 O2 , occurs due to hydrolysis of 1a to form 4.
It is necessary to use 8 eqv of H2 O2 in relation to 1a for full conversion of 1a into
acids 2a and 3a. Using H2 O2 in twofold excess, cyclododecanone 4 was isolated with
60 % yield (Table 1, footnote e ).
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H2 O2 ,
eqv b mmol
H2 SO4 ,
Temperature upon
addition of 1aa ,
◦C
Yield 2a,
(%)
Yield 3a,
(%)
5
5
5
8
8
8
8c
8c
2c
20 c
0.45
3.5
15
4
15
15
15
15
15
15
20
20
20
20
20
0
20
0
0
0
traces
45
57
56
58
62
64
72
traces
64
70 d
35 d
32
31
29
22
16
15
(17) e
14 f
419
a
Reaction conditions: 0.5 g (2.2 mmol) acetal 1a was added for 10-20 seconds to prepared
in situ solution of HCOOOH obtained from HCOOH (7 ml), H2 O2 solution, and H2 SO4 ,
maintaining the reaction temperature. Then the mixture was refluxed for 15-20 minutes.
Acetal conversion is 100 %. Owing to the significant dependence of the ratio of 3a (R=H)
and 3a’ (HC=O) due to the conditions of the reaction and workup, yields of 3a and for other
ω-hydroxycarboxylic acids 3b-g were determined after workup of the reaction mixture by a
solution of sodium hydroxide (formate hydrolysis) and the subsequent acidification.
b 30 % Water solution of H O .
2 2
c 6 % Ether solution of H O .
2 2
d Cyclododecanone (4) 6-7 %.
e The workup procedure is described in the Experimental section. The yield of 3a’ is shown.
Cyclododecanone (4) 60 % and 2-formyloxycyclododecanone (5) 11 %.
f A significant amount of tar.
Table 1 Influence of the reaction conditions on the yields of acids 2a and 3aa .
Additional increase (4-8 %) of the yield of 2a was reached by means of temperature
modification; 1a was added to a solution of performic acid at 0 ◦ C (instead of at 20 ◦ C),
then the mixture was heated to boiling.
After refluxing for 15-20 minutes, the qualitative reaction with KI did not indicate
peroxides, therefore further heating was unnecessary.
Oxidation of 1-methoxycyclododecene (6) by in situ generated performic, peracetic
and pertrifluoroacetic acids has been carried out to establish the possibility of elimination
of methanol from 1a with formation of 1-methoxycyclododecene (6) and subsequent oxidation of 6 into acids 2a and 3a. The same peracids were used for comparative oxidation
of 1a (Table 2).
The data in Tables 1 and 2 show that upon oxidation of 1a the yields of acid 2a were
always 7-29 % higher in comparison with the yields from 6. Performic acid oxidizes 1a
more effective than peracetic and pertrifluoroacetic acids.
The homologue row of cycloalkanone acetals 1b-g with different ring sizes was used as
an object of research during the following stage of our work. Acetals 1b-g were oxidized
in the similar conditions used for oxidation of 1a (see Table 2, footnote a ) (Scheme 2,
Table 3).
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Oxidizing agent
(oxidized substances)
Yield 2a,
(%)
Yield 3a,
(%)
HCOOOH (6)
CF3 COOOH (1a)
CF3 COOOH (6)
CH3 COOOH (1a)
CH3 COOOH (6)
43 (28b )
48
41
62
51
35 (58b )
41
24
23
35
a
Reaction conditions: 1a 0. 5 g (2.2 mmol), 6 0.5 g (2.55
mmol), acid (7 ml), H2 SO4 1.5 g (15 mmol), temperature of
the reaction mixture at addition of 1a or 6 0◦ C, overall reaction time 15-20 minutes, conversion of oxidized substances
100 %. 6 % Ether solution of H2 O2 (8 eqv, 17.6-20.4 mmol)
was used for in situ peracids preparation.
b Temperature of the reaction mixture at addition of 1methoxycyclododecene (6) was 30 ◦ C.
Table 2 Oxidation of 1-methoxycyclododecene 6 and 1,1-dimethoxycyclododecane 1a by performic, peracetic and pertrifluoroacetic acids prepared with use of ether solution of H2 Oa2 .
Scheme 2 Oxidation of cycloalkanone acetals 1b-g.
Acetal
1bb
1cb
1d
1e
1f
1g
1-3
b
c
d
e
f
g
n
1
2
3
4
7
9
R
Et
Me
Me
Me
Me
Me
H2 O2 (6 % ether solution)
Yield 2, (%) Yield 3, (%)
14
6
63
77
74
72
51
68
15
16
14
19
H2 O2 (30 % water solution)
Yield 2, (%) Yield 3, (%)
11
traces
44
57
69
65
61
61
17
21
21
23
a Reaction conditions: 1b-g 0.5 g (2.07-3.47 mmol), HCOOH (7 ml), H SO 1.5 g (15
2
4
mmol), temperature of the reaction mixture at addition of 1b-g 0 ◦ C, overall reaction
time 15-20 minutes, conversion of oxidized substances 100 %. Hydrogen peroxide (8 eqv,
16.5-27.8 mmol) was used for in situ HCOOOH preparation. The yields of acids 2b-2e
and 3b-3e are dependent upon methyl ethers.
b Significant amount of by-product is formed.
Table 3 Oxidation of 1b-g by HCOOOH prepared in situ from HCOOH and H2 Oa2
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Acids 2b and 2c were obtained with low yield from five- and six-membered cycloalkanone acetals 1b and 1c. The yield of heptanedioic acid (2d) from a seven-membered
cycloalkanone (1d) was 63 % and achieved a maximum of 77 % for octanedioic acid (2e)
by oxidation of eight-membered acetal 1e. Yields of dicarboxylic acids differ insignificantly for oxidation of acetals 1f and 1g with n ≥ 7.
The fact that upon oxidation of cyclododecanone 4, yields of 2a (34-43 %) are lower in
comparison with the yields of 2a (62-72 %) upon oxidation of 1a (in identical conditions),
leads one to believe that acid 2a is formed mainly from 1a instead of cyclododecanone 4
(product of hydrolysis of 1a). This assumption is confirmed by the fact that the yields
of dicarboxylic acid upon oxidation with aqueous H2 O2 are 3-20 % lower than oxidation
with the use of ether H2 O2 solution. In the aqueous H2 O2 , acetals hydrolyze partly to
ketones. This process leads to a decrease of the dicarboxylic acids yields.
As the yields of acid 2a upon oxidation of 1a by various peracids are higher than
from enol-ether 6 (Table 2), it is possible that at the first stage of the reaction the loss
of methanol from 1a with formation of 6 is not the basic route of the reaction. Probably
perester 7 is formed alongside of 6 (Scheme 3, stages ii).
R can be = H, Me, HC=O, O=C (H) O.
Scheme 3 Proposed mechanism for the oxidation of acetal 1a.
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Assumption of the formation of compound 7 from acetals was indirectly confirmed by
the experiment in which upon oxidation of 1,1-dihydroperoxycyclododecane 7’ in conditions identical to those for 1a, acids 2a and 3a were obtained with 62 % and 28 % yields,
respectively (Scheme 4).
Scheme 4 Oxidation of 1,1-bishydroperoxycyclododecane 7’.
An appreciable difference between the yields of 2b and 2c (oxidation of five- and sixmembered cycles respectively) and 2a, 2d-2g (oxidation of cycles of greater size) does
not allow one to assign the formation of enol-ethers 6 as a general reaction route at the
initial stage of the oxidation, as formation of enol-ethers for all oxidized acetals show.
After formation of compound 7, the reaction proceeds by two routes. The first route
is the formation of epoxide 8 (Scheme 3, stages iii), the second is the Baeyer-Villiger
reaction with formation of lactone 9 and subsequent acid hydrolysis to 3a (Scheme 3,
stage v). Epoxide 8 is similar in structure to the products of oxidation of the enol-ethers
observed in other works [24-27]. These products can be transformed by hydrolysis into
2-hydroxycycloalkanones under conditions of acid catalysis.
For definition of the structures of intermediate products, the reaction of 1a oxidation
has been stopped after 2 minutes by addition of water and methylene chloride to the reaction mixture. As a result, cyclododecanone 4, 2-formyloxycyclododecanone 5, dodecanedioic acid 2a, and 12-formyloxydodecanoic 3a’ were obtained. 2-Formyloxycyclododecanone
5 has also been isolated with a yield of 11 % upon oxidation of 1a with use of 2 eqv
H2 O2 (ether solution, Table 1, footnote e ).
The isolation of 2-formyloxycyclododecanone 5 as an intermediate product in the
incomplete oxidation of 1a is possible due to the hydrolysis of intermediate ether 10
and epoxide 8. This fact confirms the possible formation at stage iii (Scheme 3) 1-Osubstituted (hydroxy-, methoxy-, formyl- and performyl-) epoxides 8.
The data from works [24-27] in which the stage of enol-ether epoxidation was studied
and the fact that 2a is formed upon oxidation of 6 (Table 2) allows one to assume that
the formation of epoxide 8 is an initial stage of oxidative transformation of 6 from 2a
(Scheme 3, stage i).
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yl-formate 11, which is oxidized (Scheme 3, stage vi) to form 2a. The similar mechanism
of 2-hydroxycycloalcanone transformation in dicarboxylic acids was discussed in the paper
[28].
The possibility of oxidative transformation of the O-CH-O fragment (11) into the
carboxylic group was proved by the oxidation of 1,1-dimethoxynonane (12). Nonanoic
acid (13) was obtained with 92 % yield.
Oxidation of 2-formyloxycyclododecanone 5 was carried out under the conditions of
the investigated reaction for confirmation of ester 10 transformation into acid 2a. As
a result, acid 2a was obtained with 91 % yield. Based on the Baeyer-Villiger oxidation mechanism [2-6] it is possible to believe that the performic acid reacts with 2formyloxycyclododecanone 5 to form ether 10 (R = H). Consequently, isolation of 2a
with high yield upon oxidation of 5 confirms the ability of ether 10 to be oxidized with
formation of acid 2a.
The enlargement of acetal ring size from 5 to 8 carbon atoms leads to a decrease in
the ω-hydroxycarboxylic acid 3 yields (products of hydrolysis of lactones - homologue
9). The Baeyer-Villiger rearrangement of perester 7 homologues is a major reaction in
the formation of thermodynamically favorable 6-,7-membered lactones. The decreasing
yield of acid 3 is due to the rearrangement of perester 7 homologues, becoming minor for
lactones with larger cycle.
Similar observations have been reported in paper [29] where, under conditions of
the Baeyer-Villiger rearrangement, the yield of lactones decreased from 84 % to 6 %
by enlargement of the ring size from 6 to 8 carbon atoms. The authors [7,8] failed to
synthesize the expected products of the Baeyer-Villiger rearrangements under action of
MCPBA on cycloalkanone acetals with the cycle size more than six carbon atoms.
Probably, the formation of epoxides (similar to 8) occurs (Scheme 3, stage iii) in the
case of larger cycles (n=3, 4, 7-9; Scheme 2) instead of the thermodynamically unfavorable
reaction of cycle expansion similar to transformation of 7 to 9.
An attempt at the oxidation of acetals containing aryl fragments (derivatives of benzaldehyde, acetophenone, a-tetralone and phenylacetaldehyde) were not successful, tar
products were formed only.
In summary, a new transformation of cycloalkanone acetals by peracids has been
revealed and investigated. The main products of this reaction are α,ω-dicarboxylic and
ω-hydroxycarboxylic acids. The greatest yield of α,ω-dicarboxylic acids (72-77 %) is
achieved upon oxidation of acetals with a ring size of more than 7 carbon atoms and using
8-fold molar excess of H2 O2 in ether solution. The assumption about of the oxidation
mechanism has been made and is based on the structure of reaction products, with
dependence of quantity of these products on the reaction conditions, size of acetals rings,
and known literary data.
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Experimental part
1
H NMR and 13 C NMR spectra were recorded on a Bruker AC-200 and a Bruker WM-250.
Analytical TLC: Silufol UV-254, Silpearl as the sorbent, starch as the binder. Column
chromatography was performed on silica gel (63-200 mesh, Merk).
Melting points were determined using a Kofler hot stage.
The GLC analysis was carried out with ”Varian-3700” (FID, a glass column 2000×3
mm, 5 % Carbowax 20M on Inerton and 5 % XE-60 on Chromaton N-AW).
Cycloalcanones, formic, acetic and trifluoroacetic acids, 30 % water solution of hydrogen peroxide (all reagent grade) were used without additional purification. Solutions of
H2 O2 in Et2 O are prepared according to [30]. Solvents: petroleum ether, diethyl ether,
methylene chloride and methanol were distilled before use.
General procedure for acetals (1a-g, 12) synthesis
Trimethyl orthoformate 31.8 g (0.3 mol) and TsOH·H2 O 50 mg (1b-d) or 150 mg
(1a, 1e-g) were added to a solution of ketone (0.1 mol) in methanol 70 ml. The mixture
was boiled for 10-30 minutes (1b-d), 1-6 h (1a, 1e-g), K2 CO3 2 g (7.2mmol) was added
and the mixture was stirred for 15 minutes. Solids were filtered. Acetals were purified by
distillation.
1,1-Diethoxycyclopentane (1b): 9.5 g (60 %); b.p. 162-165 ◦ C; 162-166 ◦ C [31]. Prepared
in a similar manner using triethyl orthoformate.
1,1-Dimethoxycyclohexane (1c): 11.5 g (80 %); b.p. 60 ◦ C (20 Torr); 67 ◦ C (27 Torr)
[32].
1,1-Dimethoxycycloheptane (1d): 13.3 g (84 %); b.p. 74-76 ◦ C (10 Torr); 73 ◦ C (10 Torr)
[33].
1,1-Dimethoxycyclooctane (1e): 14.8 g (86 %); b.p. 92-94 ◦ C (10 Torr); 88 ◦ C (7.7 Torr)
[33].
1,1-Dimethoxycycloudecane (1f): 12.5 g (58 %); b.p. 93-95 ◦ C (1 Torr); 87-88 ◦ C (0.7
Torr) [33].
1,1-Dimethoxycyclododecane (1a): 18.5 g (81 %); b.p. 56-58 ◦ C (0.1 Torr); 63-64 ◦ C (0.2
Torr) [33].
1,1-Dimethoxycyclotridecane (1g): 15.1 g (62.4 %);
NMR 1 H 250 MHz (δ, CDCl3 ): 1.17-1.62 (m, 18H, CH2 ), 3.16 (s, 6H, CH3 ).
NMR 13 C 250 MHz (δ, CDCl3 ): 24.3, 25.1, 25.9, 26.3, 26.7, 30.3 (CH2 ), 47.6 (OCH3 ),
103.8 (C).
1,1-Dimethoxynonane (12): 14.1 g (75 %); b.p. 90-92 ◦ C (20 Torr); 91-92 ◦ C (20 Torr)
[34].
1,1-Bishydroperoxycyclododecane (7’) and 1-methoxycyclododecene (6) were prepared in
accordance with [35].
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General procedure for oxidation of acetals (1a-g), 1-methoxycyclododecene
(6), 1,1-bishydroperoxycyclododecane (7’), 1,1-dimethoxynonane (12),
2-formyloxycyclododecanone (5)
0.044-1.5 g (0.45-15 mmol) H2 SO4 and 5-20 eqv 30 % water or 6 % ether solution of H2 O2
were added to 7 ml HCOOH (CH3 COOH, CF3 COOH) at 0 or 20 ◦ C. This temperature
was maintained for 10 minutes. 1 eqv Oxidized substance (0.5 g) was added for 1020 seconds with stirring. The mixture was heated to boiling. In the case of H2 O2 in
ether solution, the ether was distilled off at boiling within 2-5 minutes, at which point
the temperature has risen up to 90-95 ◦ C. Heating was continued for approximately 20
minutes, sustaining moderate boiling. After this time the qualitative test with KI to
determine the presence of peroxide compounds was negative.
For determination of 2b-e and 3b-e yields upon oxidation of 1b-e acetals, formic
acid was evaporated, methanol (100 ml) was added and the mixture was heated for 2 h
in a water bath. The mixture was neutralized by a sufficient quantity of K2 CO3 and the
residue was filtered. The composition of the mixtures was analyzed by GLC with use of
esters 2b-e and 3b-e as standards previously isolated by column chromatography.
For determination of the yields of 2a, 2f, 2g, 3a, 3f, 3g and 13, carboxylic acid
was evaporated, >20 % solution of NaOH in water was added to initiate a strongly
alkaline reaction. The mixture was heated up within 1h in a water bath, then acidified
by hydrochloric acid. Target acids were extracted by 4×(Et2 O (25 ml) + CHCl3 (25 ml)).
The yields of acids 2a, 2f, 2g, 3a, 3f, 3g, and 13 were determined after column
chromatography using petroleum ether/diethyl ether (with the portion of diethyl ether
increasing from 50 % to 85 %).
Oxidation of 1a with use of 2 eqv of H2 O2 (6 % ether solution) (Table 1)
Oxidation of 1a was performed in accordance with the general procedure. The products
were isolated as follows. After the heating was stopped, the reaction mixture was cooled
to room temperature and diluted with water (40 ml) and methylene chloride (100 ml).
The organic layer was separated, washed by water 5×10 ml, dried under MgSO4 , filtered,
and evaporated. Cyclododecanone 4 (60 %), 2-formyloxycyclododecanone 5 (11 %),
dodecanedioic acid 2a (traces), and 12-formyloxydodecanoic acid 3a’ (17 %) were isolated
by column chromatography.
Oxidation of cyclododecanone 4
A number of experiments on the oxidation of 4 were performed in a similar manner to the
general procedure for oxidation of acetals (1a-g) using a twofold molar excess of methanol.
The acids 3a and 2a were obtained with 51-53 % and 39-43 % yields, respectively.
Oxidation of 1a with isolation of intermediate products
The oxidation of 1a was carried out according to the general procedure (1.5 g (15
mmol) H2 SO4 and 8 eqv 6 % ether solution of H2 O2 ) with heating of reaction mixture for 2 minutes, then quickly cooled to room temperature and diluted with water
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(40 ml) and methylene chloride (100 ml). the organic layer was separated, washed
by water 5×10 ml, dried under MgSO4 , filtered, and evaporated. Cyclododecanone 4
(12 %), 2-formyloxycyclododecanone 5 (15 %), dodecanedioic acid 2a (39 %), and 12formyloxydodecanoic acid 3a’ (24 %) were isolated by column chromatography.
Dodecanedioic acid (2a) [36].
M.p. = 124.5-125.5 ◦ C (toluene). (m.p. = 125 ◦ C) [36].
NMR 1 H, 250 MHz (δ, DMSO) 1.17-1.62 (m, 16H, CH2 ), 2.18 (t, 4H, CH2 COOH, J=7
Hz), 11.85-12.10 (br. s., 2H, COOH).
NMR 13 C, 62.9 MHz (δ, DMSO): 24.5, 28.6, 28.7, 28.9, 33.7 (CH2 ), 174.5 (COOH).
12-Hydroxydodecanoic acid (3b) [37].
M.p. = 81.5-83.5 ◦ C (toluene). (m.p. = 82-84 ◦ C) [37].
NMR 1 H, 250 MHz (δ, DMSO): 1.18-1.61 (m, 18H, CH2 ), 2.18 (t, 2H, CH2 COOH, J=7.3
Hz), 3.37 (t, 2H, CH2 OH, J=6.3 Hz), 3.50-4.50 (br. s., 2H, OH, COOH).
NMR 13 C, 62.9 MHz (δ, DMSO): 24.1, 25.1, 28.2, 28.41, 28.49, 28.55, 28.62, 28.7, 32.1,
33.2, 60.3 (CH2OH), 174.1 (COOH).
12-Formyloxydodecanoic acid (3a’) [38].
M.p. = 59-61 ◦ C. (m.p. = 61-62 ◦ C) [38].
NMR 1 H, 250 MHz (δ, DMSO): 1.15-1.69 (m, 18H, CH2 ), 2.19 (t, 2H, CH2 COOH, J=7.3
Hz), 4.10 (t, 2H, CH2 O, J=6.5 Hz), 7.98 (s, 1H).
Dimethylpentanedioate (2b) [39].
NMR 1 H, 250 MHz (δ, CDCl3 ): 1.83 (quint, 2H, CH2 CH2 COOMe, J = 7.5 Hz), 2.27 (t,
4H, CH2 COOMe, J=7.2 Hz), 3.54 (s, 6H, OCH3 ).
Methyl 5-hydroxypentanoate (3b) [40].
NMR 1 H, 200 MHz (δ, CDCl3 ): 1.43-1.75 (m, 4H, CH2 ), 2.29 (t, 2H, CH2 COOMe, J =
7.2 Hz), 2.55-2.65 (br. s., 1H, OH), 3.64-3.71 (m, 5H, CH2 OH, CH3 ).
Dimethylhexanedioate (2c) [39].
NMR 1 H, 250 MHz (δ, CDCl3 ): 1.55-1.64 (m, 4H, CH2 CH2 COOMe), 2.23-2.31 (m, 4H,
CH2 COOMe), 3.59 (s, 6H, OCH3 ).
Methyl 6-hydroxyhexanoate (3c) [41].
NMR 1 H, 250 MHz (δ, CDCl3 ): 1.4 (m, 2H, CH2 ), 1.45-1.72 (m, 4H, CH2 ), 2.22 (t, 2H,
CH2 COOMe, J = 7.2 Hz), 2.60-2.70 (br. s., 1H, OH), 3.62 (t, 2H, CH2 OH, J = 7 Hz),
3.66 (s, 3H, CH3 ).
NMR 13 C, 62.9 MHz (δ, CDCl3 ): 24.4, 24.5, 32.2, 33.7 (CH2 ), 51.5 (OCH3 ), 62.5
(CH2 OH), 174.2 (C=O).
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Dimethylheptanedioate (2d) [39].
NMR 1 H, 250 MHz (δ, CDCl3 ): 1.32 (m, 2H, CH2 CH2 CH2 COOMe), 1.58 (m, 4H,
CH2 CH2 COOMe), 2.25 (t, 4H, CH2 COOMe, J = 7.5 Hz), 3.60 (s, 6H, OCH3 ).
Methyl 7-hydroxyheptanoate (3d) [42].
NMR 1 H, 250 MHz (δ, CDCl3 ): 1.15-1.61 (m, 8H, CH2 ), 2.20 (t, 2H, CH2 COOMe, J =
7.2 Hz), 2.45-2.55 (br. s, 1H, OH), 3.48 (t, 2H, CH2 OH, J = 7.5 Hz), 3.65 (s, 3H, CH3 ).
NMR 13 C, 62.9 MHz (δ, CDCl3 ): 24.6, 25.2, 28.5, 32.1, 33.7 (CH2 ), 51.4 (OCH3 ), 62.3
(CH2 OH), 174.6 (C=O).
Dimethyloctanedioate (2e) [39].
NMR 1 H, 250 MHz (δ, CDCl3 ): 1.25-1.34 (m, 4H, CH2 CH2 CH2 COOMe), 1.57 (m, 4H,
CH2 CH2 COOMe), 2.25 (t, 4H, CH2 COOMe, J = 7.5 Hz), 3.61 (s, 6H, OCH3 ).
Methyl 8-hydroxyoctanoate (3e) [42].
NMR 1 H, 250 MHz (δ, CDCl3 ): 1.20-1.62 (m, 10H, CH2 ), 2.26 (t, 2H, CH2 COOMe, J =
7.2 Hz), 2.42-2.57 (br. s, 1H, OH), 3.62 (t, 2H, CH2 OH, J = 6.7 Hz), 3.65 (s, 3H, OCH3 ).
Undecanedioic acid (2f) [43].
M.p. = 108-109.5 ◦ C (H2 O) (m.p. = 110 ◦ C) [43].
NMR 1 H, 250 MHz (δ, DMSO): 1.10-1.62 (m, 14H, CH2 ), 2.18 (t, 4H, CH2 COOH, J = 7
Hz), 11.80-12.15 (br.s., 2H, COOH).
11-Hydroxyundecanoic acid (3f) [44].
M.p. = 68 ◦ C (H2 O) (m.p. = 65-67 ◦ C) [44].
NMR 1 H, 250 MHz (δ, CDCl3 ): 1.12-1.69 (m, 16H, CH2 ), 2.34 (t, 2H, CH2 COOH, J =
6.9 Hz), 3.60 (t, 2H, CH2 OH, J = 6.5 Hz), 3.70-4.40 (br. s., 2H, OH).
Tridecanedioic acid (2g) [45].
M.p. = 110.5-111.5 ◦ C (toluene) (m.p. = 113.0-113.5 ◦ C) [45].
NMR 1 H, 200 MHz (δ, DMSO): 1.10-1.65 (m, 18H, CH2 ), 2.17 (t, 4H, CH2 COOH, J=7.0
Hz), 11.85-12.15 (br. s., 2H, COOH).
NMR 13 C, 50.32 MHz (δ, DMSO): 24.5, 28.5, 28.6, 28.7, 28.9, 33.6 (CH2 ), 174.4 (COOH).
13-Hydroxytridecanoic acid (3g) [46].
M.p. = 76.5-78 ◦ C (toluene) (m.p. = 77 ◦ C) [46].
NMR 1 H, 200 MHz (δ, DMSO): 1.12-1.65 (m, 20H, CH2 ), 2.17 (t, 2H, CH2 COOH, J =
7.0 Hz), 3.36 (t, 2H, CH2 OH, J=6.3 Hz), 3.10-3.60 (br.s., 2H, OH).
NMR 13 C, 50.32 MHz (δ, DMSO): 24.1, 25.3, 28.6, 28.72, 28.77, 28.85, 28.92, 28.97, 29.1,
32.5, 33.7 (CH2 ), 60.3 (CH2 OH), 174.4 (COOH).
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2-Formyloxycyclododecanone (5).
NMR 1 H, 200 MHz (δ, CDCl3 ): 1.12-2.05 (m, 18H, CH2 ), 2.38-2.47 (m, 2H, CH2 ), 5.225.25 (m, 1H, CHOC (O) H), 8.09 (s, 1H, C (O) H).
NMR 13 C, 50.32 MHz (δ, CDCl3 ): 21.0, 22.3, 22.4, 22.7, 23.8, 26.0, 26.2, 27.7, 34.8, 40.3
(CH2 ), 78.0 (CHOC (O) H), 160.0 (CHOC (O) H), 205.3 (C=O).
MS: m/z (%) = 226 (M+ , 10), 198 (11), 181 (70), 163 (62).
Found (%): 68.61; H, 9.67. C12 H24 04 . Calculated (%): 68.99; H, 9.80.
Nonanoic acid (13).
NMR 1 H, 200 MHz (δ, CDCl3 ): 0.86 (t, 3H, CH3 , J=7.2 Hz), 1.18-1.42 (m, 10H, CH2 ),
1.49-1.72 (m, 2H, CH2 CH2 COOH), 2.31 (t, 2H, CH2 COOH, J=7 Hz), 10.95-11.10 (br. s.,
1H, COOH).
NMR 13 C, 50.32MHz (δ, CDCl3 ): 13.94 (CH3 ), 22.6, 24.6, 29.0, 29.1, 29.3, 31.7, 34.0
(CH2 ), 180.4 (COOH).
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