Methylation of mono- and dicarboxylic acids with dimethyl carbonate catalyzed with binder-free zeolite NaY

Article abstract of DOI:10.1134/S107042801702004X

Synthesis of methyl mono- and dicarboxylates was developed consisting in treating the corresponding acids with dimethyl carbonate in the presence of a heterogenic catalyst, crystalline aluminosilicate whose mechanically strong granules to 90–95% were built of crystal aggregates of zeolite Y with modulus of about 5.0 in the Na-form. Optimum catalyst and reagents ratio and the reaction conditions were found for the preparation in high yields of methyl esters of mono- and dicarboxylic acids.

Full text of DOI:10.1134/S107042801702004X

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2017, Vol. 53, No. 2, pp. 163–168. © Pleiades Publishing, Ltd., 2017.
Original Russian Text © R.I. Khusnutdinov, N.A Shchadneva, Yu.Yu. Mayakova, Yu.S. Konovalova, A.N. Khazipova, B.I. Kutepov, 2017, published in
Zhurnal Organicheskoi Khimii, 2017, Vol. 53, No. 2, pp. 177–181.
Methylation of Mono- and Dicarboxylic Acids with Dimethyl
Carbonate Catalyzed with Binder-Free Zeolite NaY
R. I. Khusnutdinov, N. A Shchadneva, Yu. Yu. Mayakova, Yu. S. Konovalova,
A. N. Khazipova, and B. I. Kutepov*
Institute of Petrochemistry and Catalysis, Russian Academy of Sciences, pr. Oktyabrya 141, Ufa, 450075 Russia
*
e-mail: inklab4@gmail.com
Received September 14, 2016
Abstract—Synthesis of methyl mono- and dicarboxylates was developed consisting in treating the
corresponding acids with dimethyl carbonate in the presence of a heterogenic catalyst, crystalline
aluminosilicate whose mechanically strong granules to 90–95% were built of crystal aggregates of zeolite Y
with modulus of about 5.0 in the Na-form. Optimum catalyst and reagents ratio and the reaction conditions
were found for the preparation in high yields of methyl esters of mono- and dicarboxylic acids.
DOI: 10.1134/S107042801702004X
Methyl esters of carboxylic acids are among the
most important oxygen-containing organic compounds.
They are widely used in diverse fields of human
practice. For instance, methyl benzoate, methyl salicylate,
methyl anthranilate, and methyl abietate possessing a
nice smell are utilized in perfumery and food industry
as aromatizers [1]. Methyl acetate and methyl butyrate
are universal solvents for cellulose ethers and esters,
for poly(vinyl acetate, and many synthetic resins.
Methyl esters of higher saturated and unsaturated fatty
acids are standard substances for the chromatographic
analysis of foodstuff [2]. A mixture consisting of
methyl oleate, methyl linoleate, and methyl linolenate
is the major part of the biofuel for engines used in
European Union [3].
of carboxylic acids of diverse nature. The reaction is
catalyzed with bases K СО , KНСО [6], and also by
2
3
3
zeolite NaY of the faujasite type taken in a triple
excess with respect to the acid (165°С, 24 h) [7].
It was established in the present study that the
methylation of carboxylic acids with dimethyl carbonate
was effectively catalyzed by crystalline aluminosilicate
1
(
NaY-Bf ), whose mechanically strong granules to
9
0–95% were built of crystal aggregates of zeolite Y
with modulus (SiO /Al O molar ratio) of about 5.0 in
2
2
3
the Na-form [8]. The catalyst is characterized by the
presence of basic sites, and its porous structure
contains micro, meso, and macro pores [9]. The
presence of meso and macro pores ensures an efficient
diffusion of reactant molecules to the catalytic active
sites and back to the granule surface. For instance, the
reaction of benzoic acid 1а with dimethyl carbonate in
the presence of 5 wt % of NaY-Bf (molar ratio 1а–
The classic procedure for the preparation of
methyl esters of carboxylic acids is the direct
esterification of RCOOH with methanol catalyzed
with strong acids: H SO , HCl (anhydrous), and
Me OCO 1 : 10) led to the formation of methyl benzoate
2
2
2
4
1
b in 98% yield. The reaction at 200°С was completed
RSO H. As efficient methylating agent for carboxylic
3
in 5 h. In all experiments dimethyl carbonate was used
in excess since it served both as reagent and solvent
simultaneously (Scheme 1).
acids diazomethane can be applied yet due to its
toxicity and explosiveness its application is limited to
analytic uses [4].
о-Anisic acid 2а reacted with dimethyl carbonate
under similar conditions affording methyl 2-methoxy-
benzoate 2b in 98% yield (Scheme 2).
According to published information a very
promising and general methylating reagent for alcohols,
diols, phenols, and acids is a known “green chemistry”
reagent dimethyl carbonate. It was shown in [5] that
dimethyl carbonate can be applied for the methylation
1
Bf means binder-free.
1
63

1
64
KHUSNUTDINOV et al.
Dimethyl carbonate reacted with 1- and 2-
Scheme 1.
COOH
CO
2
Me
naphthoic acids 6a and 7a at 200°С for 5 h only in the
presence of 25 wt % of NaY-Bf to give methyl
esters 6b and 7b respectively in a quantitative yield
(Scheme 6).
5
wt % NaY-Bf
+
MeOCO Me
2
_
_
MeOH, CO ,
2
o
2
00 C, 5 h
1
a
1b
The methylation of thiophene-2-carboxylic acid 8a
with dimethyl carbonate in the presence of 5 wt % of
NaY-Bf at 180°С occurred without complications
within 5 h. At the activation of the catalyst with
triethylamine (0.1 mol per 100 mol of carboxylic acid)
the reaction temperature decreased to 160°С (3 h), the
yield of methyl thiophene-2-carboxylate 8b was
quantitative (Scheme 7).
Scheme 2.
COOH
CO Me
2
MeO
MeO
5
wt % NaY-Bf
+
MeOCO Me
2
_
_
MeOH, CO ,
2
o
2
00 C, 5 h
2
a
2b
4
-tert-Butylbenzoic acid 3a in the reaction with
Despite the large volume of the adamantyl radical
adamantane-1-carboxylic acid 9a was methylated with
dimethyl carbonate under the catalysis of zeolite NaY-
dimethyl carbonate formed within 5 h methyl 4-tert-
butyl benzoate 3b in 58% yield. At reaction duration
increased to 10 h the yield of the target product 3b
became quantitative (Scheme 3).
Bf activated with Et N at 160°С for 5 h giving methyl
3
ester 9b in a high yield (Scheme 8).
Phthalic acid 4 reacting with dimethyl carbonate for
h (180°C) gave quantitatively a product of monomer-
thylation, monomethyl phthalate 4b, after 15 h a
mixture of reaction products 4b and 4c formed in a
ratio 2 : 1, at the reaction time increased up to 20 h the
only reaction product was dimethyl phthalate 4c
Highly active in the methylation with dimethyl
5
carbonate under the catalysis with NaY-Bf–Et N
3
turned out to be aliphatic carboxylic acids (acetic 10a,
propionic 11a, butyric 12a, valeric 13a, hexanoic 14a,
undecanoic 15a, dodecanoic 16a and behenic 17a)
which regardless of the length of the alkyl radical were
converted in high yields to the corresponding esters:
methyl acetate 10b, methyl propionate 11b, methyl n-
butyrate 12b, methyl n-valerate 13b, methyl n-
hexanoate 14b, methyl undecanoate 15b, methyl
(
Scheme 4).
Terephthalic acid 5 furnished a single product,
dimethyl terephthalate 5b, in a quantitative yield
Scheme 5).
(
Scheme 3.
COOH
CO Me
2
5
wt % NaY-Bf
+
MeOCO Me
2
_
_
MeOH, CO ,
t-Bu
2
t-Bu
o
2
00 C, 10 h
3
a
3b
Scheme 4.
COOH
5
h
COOH
CO Me
2
5
wt % NaY-Bf
+
MeOCO Me
4b
2
_MeOH, _CO2,
COOH
o
1
80 C
CO Me
2
4
a
20 h
CO Me
2
4
c
Scheme 5.
COOH
CO Me
2
5
wt % NaY-Bf
+
MeOCO Me
2
_
_
MeOH, CO ,
2
HOOC
MeO C
2
o
1
80 C, 5 h
5
a
5b
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 53 No. 2 2017

METHYLATION OF MONO- AND DICARBOXYLIC ACIDS WITH DIMETHYL CARBONATE
165
Scheme 6.
COOH
CO Me
2
6
a
2
5 wt % NaY-Bf
6b
MeOCO Me
2
COOH
_
MeOH, _CO2,
o
2
00 C, 5 h
CO Me
2
7
a
7
b
Scheme 7.
5
0
wt % NaY-Bf,
.1 mmol Et N
3
+
MeOCO Me
2
COOH
_
_
CO Me
S
MeOH, CO ,
S
2
2
o
1
60 C, 3 h
8
a
8b
Scheme 8.
5
0
wt % NaY-Bf,
.1 mmol Et N
3
+
MeOCO Me
2
COOH
_
_
CO Me
2
MeOH, CO ,
2
o
1
60 C, 5 h
9
a
9b
Scheme 9.
5
0
wt % NaY-Bf,
.1 mmol Et N
3
CH (CH ) COOH
+ MeOCO Me
2
3
2 n
CH (CH ) COOMe
3 2 n
_
_
MeOH, CO ,
_
2
_
1
0a 17a
10b 17b
o
1
60 C, 5 h
n = 0 (10), 1 (11), 2 (12), 3 (13), 4 (14), 9 (15), 10 (16), 20 (17).
Scheme 10.
5
0
wt % NaY-Bf,
.1 mmol Et N
3
HOOC(CH ) COOH
+
MeOCO Me
MeOOC(CH ) COOMe
2 n
2
n
2
_
_
MeOH, CO ,
2
_
o
_
1
8a 23a
160 C, 5 h
18b 23b
n = 2 (18), 3 (19), 4 (20), 5 (21), 6 (22), 8 (23).
dodecanoate 16b, methyl behenate 17b respectively
EXPERIMENTAL
С NMR spectra were registered on a spectrometer
(
Scheme 9).
1
3
High activity in the methylation with dimethyl
Bruker Avance-400 (400.13 and 100.62 МHz) from
carbonate under the catalysis with NaY-Bf–Et N
3
solutions in CDCl . Mass spectra were taken on an
3
was demonstrated as well by aliphatic dicarboxylic
acids (succinic 18a, glutaric 19a, adipic 20a, pimelic
instrument Shimadzu GCMS-QP2010Plus [capillary
column SPB-5 30 m × 0.25 mm, carrier gas helium,
ramp from 40 to 300°С (heating rate 8 deg/min),
vaporizer temperature 280°С, ion source temperature
00°С, energy of ionizing electrons 70 eV]. Elemental
composition of samples was measured on an analyzer
Carlo Erba 1106.
2
1a, suberic 22a, and decanedioic 23a) that
notwithstanding the length of the alkyl radical reacted
simultaneously at both СООН groups to afford in high
yields the corresponding dimethyl esters: dimethyl
succinate 18b, dimethyl glutarate 19b, dimethyl
adipate 20b, dimethyl heptanedioate 21b, dimethyl
octanedioate 22b, and dimethyl decanedioate 23b
2
The reaction progress and the purity of obtained
compounds were monitored by GLC on a chromato-
(
Scheme 10).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 53 No. 2 2017

1
66
KHUSNUTDINOV et al.
graph Shimadzu GC-9A, GC-2014 [column 2 m × 3 mm,
stationary phase silicone SE-30 (5%) on a carrier
Chromaton N-AW-HMDS, ramp from 50 to 270°С
Dimethyl phthalate (4c). Yield 95%, bp 120–121°С
1
3
(3 mmHg) (bp 283°С [10]). С NMR spectrum, δ,
3
,6
4,5
ppm: 52.36 (2 ОСН ), 128.83 (С ), 130.15 (С ),
3
1
,2
(
heating rate 8 deg/min), carrier gas helium (flow rate
133.99 (С ), 167.06 (2 С=О). Found, %: С 61.69; Н
5.11. C H O . Calculated, %: С 61.85; Н 5.19.
4
7 mL/min)].
1
0
10
4
Yields are reported for the practically isolated
Dimethyl terephthalate (5b). Yield 99%, mp 138–
1
3
reaction product. The structures of compounds
obtained were established by spectral methods and by
comparison with authentic samples.
139.5°С (ethanol) (mp 141–142°С [10]). С NMR
2
,3,5,6
spectrum, δ, ppm: 52.72 (2 ОСН ), 129.50 (С
),
135.89 (С ), 165.53 (2 С=О). Found, %: С 61.70; Н
.08. C H O . Calculated, %: С 61.85; Н 5.19.
3
1
,4
5
1
0
10
4
Methylation of carboxylic acids with dimethyl
carbonate. General procedure. Into a stainless steel
pressure microreactor of capacity 17 mL was charged
Methyl 1-naphthoate (6b). Yield 99%, mp 51–52°С
1
3
(ethanol) (mp 59.5°C [13]). С NMR spectrum, δ,
3
6
5
wt % of zeolite NaY-Bf, 100 mmol of carboxylic
ppm: 51.86 (ОСН ), 125.32 (С ), 126.25 (С ), 126.32
3
7
8
5
1
acid, and 300–400 mmol of dimethyl carbonate, the
reactor was hermetically closed, and the reaction
mixture was heated at 180–200°С for 5 h. On
completion of the reaction the reactor was cooled to
room temperature, opened, the reaction mixture was
filtered through a bed of Al O . Unreacted dimethyl
(С ), 127.22 (С ), 128.27 (С ), 128.96 (С ), 130.14
(С ), 132.08 (С ), 132.71 (С ), 133.99 (С ), 169.37
(С=О). Found, %: С 77.22; Н 5.27. С Н О .
2
9
4
10
1
2
10
2
Calculated, %: С 77.40; Н 5.41.
Methyl 2-naphthoate (7b). Yield 98%, mp 75–76°С
2
3
13
(
ethanol) (mp 77°С [13]). С NMR spectrum, δ, ppm:
carbonate was distilled off, the residue was distilled at
atmospheric pressure or in a vacuum, or it was
crystallized from ethanol.
6
3
10
5
1
1
2.05 (ОСН ), 125. 01 (С ), 125.37 (С ), 126.84 (С ),
3
4
7
5
1
27.11 (С ), 127.82 (С ), 128.42 (С ), 128.90 (С ),
31.12 (С ), 131.91 (С ), 134.38 (С ), 166.05 (С=О).
8
9
2
Methyl benzoate (1b). Yield 98%, bp 76.5–77°С
Found, %: С 77.28; Н 5.32. С Н О . Calculated, %:
С 77.4; Н 5.41.
12 10 2
1
3
(
9 mmHg) (bp 198°С [10]). С NMR spectrum, δ,
3
2
ppm: 51.28 (СН ), 128.40 (С ), 129.67 (С ), 130.45
3
Methyl thiophene-2-carboxylate (8b). Yield 95%, bp
1
4
(
С ), 132.83 (С ), 166.38 (С=О). Found, %: С 70.25;
1
20.5–121°С (10 mmHg) {bp 120–121°С (10 mmHg)
Н 5.79. С Н О . Calculated, %: С 70.57; Н 5.92.
13
8
8
2
[14]}. С NMR spectrum, δ, ppm: 51.22 (ОСН ),
3
2
4
5
3
Methyl 2-methoxybenzoate (2b). Yield 98%, bp
9–100°С (5 mmHg) {bp 127–127.5°С (11 mmHg)
127.11 (С ), 131.86 (С ), 132.72 (С ), 133.70 (С ),
161.64 (С=О). Mass spectrum, m/z (I , %): 142 [M]
+
9
[
5
1
rel
1
3
11]}. С NMR spectrum, δ, ppm: 51.15 (ОСН ),
(35), 141 (24), 113 (7), 112 (10), 111 (100), 110 (39),
38 (12). Found, %: С 50.44; Н 4.13; S 22.43.
С Н О S. Calculated, %: С 50.69; Н 4.25; S 22.55. М
3
1
5
5
5.80 (ОСН ), 112.30 (С ), 119.82 (С ), 120.09 (С ),
30.61 (С ), 133.18 (С ), 158.17 (С ), 166.39 (С=О).
3
6
4
2
6
6
2
Found, %: С 64.88; Н 6.02. С Н О . Calculated, %: С
142.1756.
Methyl adamantane-1-carboxylate (9b). Yield
97%, bp 99–100°С (10 mmHg) {bp 77–79°С (1 mmHg)
9
10
3
6
5.05; Н 6.07.
Methyl 4-tert-butylbenzoate (3b). Yield 58%, bp
22–124°С (9 mmHg) {bp 121–122°С (9 mmHg) [12]}.
С NMR spectrum, δ, ppm: 28.80[(ССН ) ], 31.91
1
3
3,5,7
1
[15]}. С NMR spectrum, δ, ppm: 28.18 (С ), 36.67
1
3
4,6,9
2,8,10
1
(C ), 39.14 (С
), 39.34 (С ), 51.51 (ОСН ),
3
3
3
3
,5
2,6
+
[
(ССН ) ], 52.15 (ОСН ), 123.17 (С ), 128.82 (С ),
178.52 (С=О). Mass spectrum, m/z (I , %): 194 [M]
3
3
3
4
rel
1
1
7
29.09 (С ), 156.61 (С ), 166.39 (С=О). Found, %: С
4.87; Н 8.02. C H O . Calculated, %: С 74.97; Н 8.39.
(14), 136 (10), 135 (100), 107 (8), 93 (22), 91 (20), 79
(28), 77 (10), 67 (12), 55 (8), 53 (7). Found, %: С
12
18
2
7
4.08; Н 9.16. С Н О . Calculated, %: С 74.19; Н
12 18 2
2
-(Methoxycarbonyl)benzoic acid (4b). Yield
1
3
9.34. М 194.2701.
9
9%, mp 84–86°С (ethanol) (mp 82–84°С [10]).
NMR spectrum, δ, ppm: 52.85 (ОСН ), 128.17 (С ),
29.82 (С ), 129.99 (С ), 130.61 (С ), 132.21 (С ),
33.61 (С ), 168.39 (СООСН ), 172.59 (СООН).
С
6
Methyl acetate (10b). Yield 98%, bp 56.5–57°С
3
4
3
1
5
13
1
1
(bp 57°C [10]). С NMR spectrum, δ, ppm: 20.63
(СН ), 51.25 (СН ), 171.37 (С=О). Found, %: С
2
3
3
3
Found, %: С 61.07; Н 5.02. C Н О . Calculated, %: С
48.51; Н 8.04. С Н О . Calculated, %: С 48.64; Н
9
8
4
3 6 2
6
0.00; Н 4.48.
8.16.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 53 No. 2 2017

METHYLATION OF MONO- AND DICARBOXYLIC ACIDS WITH DIMETHYL CARBONATE
167
Methyl propionate (11b). Yield 98%, bp 77.5–78°С
Dimethyl glutarate (19b). Yield 99%, bp 97–98°С
1
3
13
(
(
bp 80°C [10]). С NMR spectrum, δ, ppm: 9.18
СН ), 27.32 (СН ), 51.38 (ОСН ), 173.93 (С=О).
(15 mmHg) (bp 214°C [10]). С NMR spectrum, δ,
3
2,4
ppm: 29.10 (С ), 33.21 (C ), 51.44 (ОСН ), 173.90
3
2
3
3
Found, %: С 54.49; Н 9.13. С Н О . Calculated, %: С
(С=О). Found, %: С 52.40; Н 7.15. С Н О .
4
8
2
7
12
4
5
4.34; Н 9.02.
Calculated, %: С 52.49; Н 7.55.
Methyl n-butyrate (12b). Yield 97%, bp 102.6–
Dimethyl adipate (20b). Yield 73%, bp 105–106°С
1
3
13
1
1
1
03°С (bp 102°C [10]). С NMR spectrum, δ, ppm:
3.87 (СН ), 19.03 (СН ), 35.69 (СН ), 52.08 (ОСН ),
(12 mmHg) {bp 109°C (14 mmHg) [19]}. С NMR
3
,4
2,5
spectrum, δ, ppm: 24.02 (С ), 33.47 (С ), 51.48 (o-
3
2
2
3
1
,6
72.25 (С=О). Found, %: С 58.54; Н 9.47. С Н О .
СН ), 173.82 (С ).
5
10
2
3
Calculated, %: С 58.80; Н 9.87.
Dimethyl heptanedioate (21b). Yield 98%, bp 130–
131°С (9 mmHg) {bp 121–122°C (14 mmHg) [20]}.
Methyl n-valerate (13b). Yield 97%, bp 129–130°С
1
3
13
3,5
4
(
(
(
bp 130°C [10]). С NMR spectrum, δ, ppm: 13.85
СН ), 22.03 (СН ), 27.41 (СН ), 34.19 (СН ), 52.08
С NMR spectrum, δ, ppm: 24.39 (C ), 28.42 (С ),
2
,6
1,7
3
2
2
2
33.67 (С ), 51.35 (o-СН ), 173.90 (С ).
3
ОСН ), 174.25 (С=О). Found, %: С 61.93; Н 10.31.
3
Dimethyl octanedioate (22b). Yield 99%, bp 120–
С Н О . Calculated, %: С 62.04; Н 10.41.
13
6
12
2
1
21°C (8 mmHg) (263–265°С [21]). С NMR
3
,6
4,5
Methyl n-hexanoate (14b). Yield 98%, bp 72°С
spectrum, δ, ppm: 24.39 (C ), 28.41 (С ), 33.61
1
3
2,7
1,8
(
1
(
50 mmHg) (bp 150°C [10]). С NMR spectrum, δ, ppm:
(С ), 51.11 (o-СН ), 173.79 (С ).
3
2
4
3
4.08 (СН ), 23.06 (С ), 25.27 (С ), 32.13 (С ), 34.28
С ), 51.02 (ОСН ), 173.13 (С=О). Found, %: С 64.42;
3
Dimethyl decanedioate (23b). Yield 99%, bp 158–
5
3
13
1
59°С (7 mmHg) {bp 186°C (10 mmHg) [22]}.
С
Н 10.59. С Н О . Calculated, %: С 64.58; Н 10.84.
3,8
4,7
7
14
2
NMR spectrum, δ, ppm: 25.23 (C ), 28.98 (C ),
5
,6
2,9
1,10
Methyl undecanoate (15b). Yield 99%, bp 112–
29.38 (С ), 34.38 (С ), 51.76 (o-СН ), 174.63(С ).
3
1
3
1
13°C (10 mmHg) (bp 246–248°С [16]). С NMR
1
1
10
3
spectrum, δ, ppm: 14.06 (С ), 22.65 (C ), 24.93 (C ),
2
ACKNOWLEDGMENTS
4
6
7
5
9.13 (С ), 29.24 (С ), 29.28 (С ), 29.43 (С ), 29.53
8
9
2
(
(
С ), 31.87 (С ), 34.09 (С ), 51.41 (o-СН ), 174.39
С ).
3
Study of compounds structures were performed in the
Center of joint usage “Agidel” at the Institute of Petro-
chemistry and Catalysis, Russian Academy of Sciences.
1
Methyl dodecanoate (methyl laurate) (16b).
Yield 95%, bp 114–114.5°С (5 mmHg) (bp 262–268°C
1
3
1
REFERENCES
[
(
2
(
17]). С NMR spectrum, δ, ppm: 14.10 (С ), 22.72
2
10
9
4
7
С ), 24.95 (С ), 29.11 (С ), 29.36 (С ), 29.41 (С ),
6
5
8
3
1
. Khimicheskaya entsiklopedia (Chemical Encyclopedia),
Zefirov, N.S., Ed., Moscow: Bol’shaya Rossiiskaya
entsiklopedia, 1999, vol. 5.
. D’Oca, C.D.R.M., Coelho, T., Marinho, T.G.,
Hack, C.R.L., Duarte, R.C., Silva, P.A., and
D’Oca, M.G.M., Bioorg. Med. Chem. Lett., 2010,
vol. 20, p. 5255. doi 10.1016/j.bmcl.2010.06.149
3. Mitusova, T.N., Polina, E.V., and Kalinina, M.V.,
Sovremennye dizel’nye topliva i prisadki k nim (Modern
Diesel Fuel and an Additive Thereto), Moscow: Izd.
Tekhnika, 2002.
9.48 (С ), 29.54 (С ), 29.70 (С ), 31.98 (С ), 34.12
1
1
С ), 51.39 (ОСН ), 174.02 (С=О). Found, %: С
3
7
1
2.71; Н 12.02. С Н О . Calculated, %: С 72.84; Н
13 26 2
2.23.
2
Methyl behenate (17b). Yield 95%, mp 53–54.5°С
1
3
(
ethanol) (mp 54–55°C [18]). С NMR spectrum, δ,
1
2
20
19
ppm: 14.14 (С ), 22.60 (С ), 25.04 (С ), 29.16 (С ),
9.26 (С ), 29.41 (С ), 29.45 (С ), 29.53 (С ),
9.58 (С ), 29.59 (С ), 29.76 (С ), 32.02 (С ), 34.12
С ), 51.39 (ОСН ), 174.02 (С=О), Found, %: С
1
8
4
17
7-15
2
2
(
6
16
5
3
2
1
3
4
. Reutov, O.A., Kurts, A.L., and Butin, K.P.,
Organicheskaya khimiya tomakh (Organic
7
1
7.72; Н 12.95. С Н О . Calculated, %: С 77.90; Н
23 46 2
3.07.
v
4
Chemistry in 4 vol.), Moscow: Izd. MGU, 1999, vol. 3.
Dimethyl succinate (18b). Yield 99%, bp 94–95°С
5
. Arikò, F. and Tundo, P., Russ. Chem. Rev., 2010, vol. 79,
p. 479. doi 10.1070/RC2010v079n06ABEH004113
1
3
(
30 mmHg) (bp 196°С [10]) С NMR spectrum, δ,
2
,3
ppm: 29.10 (С ), 51.19 (ОСН ), 172.90 (С=О),
3
6. Chau, K.D.N., Duus, F., and Le, T.N., Green Chem.
Lett. Rev., 2013, vol. 6, p. 89. doi 10.1080/
17518253.2012.706647
Found, %: С 49.00; Н 7.15. С Н О . Calculated, %: С
6
10
4
4
9.31; Н 6.90.
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