Synthesis of naphthalenecarboxylic and naphthalenedicarboxylic acids from naphthalene, carbon tetrachloride, and alcohols in the presence of iron catalysts

Article abstract of DOI:10.1134/S1070363217030057

Alkyl naphthalenecarboxylates and dialkyl naphthalenedicarboxylates have been synthesized by reactions of naphthalene and its derivatives with alcohols and carbon tetrachloride in the presence of iron catalysts.

Full text of DOI:10.1134/S1070363217030057

ISSN 1070-3632, Russian Journal of General Chemistry, 2017, Vol. 87, No. 3, pp. 389–395. © Pleiades Publishing, Ltd., 2017.
Original Russian Text © A.R. Baiguzina, I.S. Erokhina, R.I. Khusnutdinov, 2017, published in Zhurnal Obshchei Khimii, 2017, Vol. 87, No. 3, pp. 380–386.
Synthesis of Naphthalenecarboxylic
and Naphthalenedicarboxylic Acids from Naphthalene,
Carbon Tetrachloride, and Alcohols
in the Presence of Iron Catalysts
A. R. Baiguzinaa,b, I. S. Erokhinab, and R. I. Khusnutdinova,b*
a Institute of Petrochemistry and Catalysis, Russian Academy of Sciences,
pr. Oktyabrya 141, Ufa, 450075 Bashkortostan, Russia
*e-mail: inklab4@gmai.com
b Ufa State Petroleum Technological University, Ufa, Bashkortostan, Russia
Received October 13, 2016
Abstract—Alkyl naphthalenecarboxylates and dialkyl naphthalenedicarboxylates have been synthesized by
reactions of naphthalene and its derivatives with alcohols and carbon tetrachloride in the presence of iron
catalysts.
Keywords: naphthalene, naphthalenecarboxylic acids, esters, carbon tetrachloride, aliphatic alcohols, iron catalysts
DOI: 10.1134/S1070363217030057
Naphthalenecarboxylic acids constitute an important
class of aromatic carboxylic acids. They are widely
used in the synthesis of herbicides, phytohormones,
dyes, photographic materials, and polymers [1]. Naph-
thalenecarboxylic acid derivatives are also extensively
used in medicine and cosmetology [2]. Several
synthetic approaches to naphthalenecarboxylic acids
are known. The classical method is based on the oxida-
tion of alkylnaphthalenes with various oxidants such as
nitric acid, hydrogen peroxide, sodium bromate, etc.
[3–5]. Naphthalene-1- and 2-carboxylic acids can also
be synthesized by carbonylation of halogen-substituted
naphthalenes catalyzed by transition metal complexes
(Co, Rh, Pd, Mo, Ni) [6, 7]. However, of particular
interest is the synthesis of naphthalenecarboxylic acids
directly from cheap and readily accessible naph-
thalene. For example, a mixture of naphthalene-1- and
naphthalene-2-carboxylic acid was obtained by car-
boxylation of naphthalene with carbon dioxide in the
presence of Ph3SiCl/AlBr3 as catalytic system [8–11].
of the reactants and catalyst were optimized for the
reaction of naphthalene with CCl4 and propan-1-ol in
the presence of iron(III) acetylacetonate. The reaction
of naphthalene (1) with carbon tetrachloride and propan-
1-ol in the presence of Fe(acac)3 at 130°C [6 h; molar
ratio Fe(acac)3–1–CCl4–PrOH (5–15) : 100 : (500–
1000) : (500–1000)] gave a mixture of propyl naph-
thalene-1-carboxylate (1a), propyl naphthalene-2-car-
boxylate (1b), dipropyl naphthalene-1,5-dicarboxylate
(1c) and dipropyl naphthalene-2,6-dicarboxylate (1d)
(Scheme 1).
The product yield and ratio depended on many
factors. The yields of esters 1a–1d at different catalyst
concentrations are given in Table 1. No reaction
occurred in the absence of Fe(acac)3 (Table 1; run
no. 1). As the catalyst concentration increased from 5
to 15 mol %, the conversion of naphthalene changed
from 46 to 96%. The optimal Fe(acac)3 concentration
was 10%. Although the conversion of naphthalene
increased by 6% when the catalyst concentration was
raised to 15%, the selectivity of the reaction decreased
due to formation of dipropyl naphthalene-1,5- and -2,6-
dicarboxylates 1c and 1d.
In this article we report the synthesis of alkyl
naphthalene-1- and naphthalene-2-carboxylates by
reaction of naphthalene with carbon tetrachloride and
alcohols catalyzed by iron compounds as well as by
iron metal. The reaction conditions and concentrations
A
significant effect of carbon tetrachloride
concentration on the yield of 1a–1d was revealed
389

390
BAIGUZINA et al.
Scheme 1.
CO2Pr-n
CO2Pr-n
+
1a
1b
CCl4, n-PrOH
CO2Pr-n
[Fe], 130οC, 6 h
CO2Pr-n
1
+
n-PrO2C
CO2Pr-n
1c
1d
(Table 2). The conversion of naphthalene attained its
maximum value at a 1-to-CCl4 ratio of 1 : 10. Despite
increase of the naphthalene concentration, decrease of
the amount of CCl4 was accompanied by reduction of
the conversion of naphthalene; simultaneously, di-
propyl esters 1c and 1d were formed at a ratio of 1 : 1.
The amount of propyl alcohol was also significant
(Table 3). The maximum conversion of naphthalene
was reached when 8 equiv of propyl alcohol was used;
however, in this case dipropyl ethers 1c and 1d were
obtained at a ratio of 2 : 1. The optimal ratio of propyl
alcohol and naphthalene was 10 : 1; it favored
selective formation of monoesters 1a and 1b.
methanol, the major isomer was methyl naphthalene-2-
carboxylate (1e).
In order to improve the reaction selectivity we
examined the effect of some activating ligands. Such
classical activating ligands as triphenylphosphine,
triphenyl phosphite, triethylamine, pyridine, 1,10-
phenanthroline, N,N-dimethylaniline, and acetonitrile
insignificantly affected the chemoselectivity, reaction
rate, and product yield.
We then tried naphthalene-1- and -2-carboxylic
acids 2 and 3 as substrates in the reaction with carbon
tetrachloride and proan-1-ol in the presence of
Fe(acac)3. The major products were the corresponding
monoeesters 1a and 1b, whereas the yield of diesters
(isomer mixtures) was 26% (Scheme 2).
Table 4 summarizes the results of the reactions of
naphthalene with carbon tetrachloride and methanol,
ethanol, and butan-1-ol in the presence of Fe(acac)3
with formation of the corresponding naphthalene-1-
and -2-carboxylic esters 1e–1j. The product ratio
depended on the alcohol nature. In the reaction with
1-Methyl- and 2-methylnaphthalenes 4 and 5, as
well as 1,3-, 1,6-, 1,7-, 2,7-, and 1,8-dimethylnaph-
thalenes 6–10, reacted with carbon tetrachloride and
Table 1. Yields of propyl naphthalenecarboxylates 1a and
1b and dipropyl naphthalene dicarboxylates 1c and 1g in the
reaction of naphthalene with carbon tetrachloride and propyl
alcohol in the presence of Fe(acac)3 at different concentrationsa
Table 2. Yields of esters 1a–1d at different concentrations of
carbon tetrachloridea
Molar ratio
Fe(acac)3–
naphthalene–
CCl4–PrOH
Conversion
Yield, %
Run
no.
of
naphthalene,
%
Molar ratio
Fe(acac)3–
naphthalene–
CCl4–PrOH
Conversion
Yield, %
1a 1b 1c 1d
Run
no.
of
naphthalene,
%
1
2
3
4
10:100:0:1000
0
–
–
–
–
4
2
–
–
4
2
1a 1b 1c 1d
1
2
3
4
0:100:1000:1000
5:100:1000:1000
10:100:1000:1000
15:100:1000:1000
0
–
–
–
–
–
–
–
–
8
10:100:1000:1000
10:100:800:1000
10:100:500:1000
90
84
67
55 35
61 15
49 14
46
90
96
30 16
55 35
45 31 12
a
a
130°C, 6 h.
130°C, 6 h.
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SYNTHESIS OF NAPHTHALENECARBOXYLIC AND NAPHTHALENEDICARBOXYLIC ACIDS
391
Table 3. Yields of esters 1a–1d depending on the amount of
Table 4. Yields of esters 1a, 1b, and 1e–1j in the reaction of
propyl alcohola
naphthalene derivatives with carbon tetrachloride and
a
different alcohols in the presence of Fe(acac)3
Molar ratio
Conversion
of naphtha-
lene, %
Yield, %
Run
no.
Fe(acac)3–
naphthalene–
CCl4–PrOH
Yield, %
Run
no.
Conversion of
naphthalene, %
Alcohol
1-isomer 2-isomer
1a 1b 1c 1d
1
2
3
4
MeOH
EtOH
42
35
90
81
15 (1e)
27 (1g)
55 (1a)
63 (1i)
27 (1f)
8 (1h)
1
2
3
4
10:100:1000:0
0
–
–
–
–
–
–
7
2
10:100:1000:1000
10:100:1000:800
10:100:1000:500
90
96
89
55 35
PrOH
35 (1b)
18 (1j)
62 13 16
61 15
1-BuOH
4
a
a
130°C, 6 h.
130°C, 6 h, Fe(acac)3–naphthalene–CCl4–alcohol 10:100:1000:1000.
The structure of ester 10a was proved by one- (1H,
popan-1-ol in the presence of Fe(acac)3 to give the
corresponding mono- and diesters. The reactions with
4 and 5 were characterized by high conversion, and the
major products were monoesters 4a and 4b and 5a and
5b, respectively, as mixtures of isomers which were
difficult to separate. Apart from 4a, 4b and 5a, 5b, the
reaction mixtures contained small amounts (6–9%) of
dipropyl esters 4c, 4d and 5c, 4d (Scheme 3).
13C) and two-dimensional (COSY, HSQC, HMBC)
1
NMR data. The H NMR spectrum of 10a displayed
one triplet and four doublets in the aromatic region,
which is consistent with structure 10a with the ester
group attached to C4. Two three-proton singlets at
δ 2.96 and 2.95 ppm were assigned to protons of the
methyl groups on C1 and C8, and protons of the propyl
group resonated as upfield multiplet and triplet signals.
As follows from the COSY spectrum, the 6-H proton
Under analogous conditions, dimethylnaphthalenes
6–9 were converted into the corresponding diemthyl-
naphthalenecarboxylates 6a–6d and 7a–9c as mixtures
of isomers differing by the position of the ester group;
the conversion of initial naphthalene 6–9 was 79, 74,
73, and 82%, respectively (Scheme 4). An exception
was 1,8-dimethylnaphthalene (10) which was quanti-
tatively converted to propyl 1,8-dimethylnaphthalene-4
-carboxylate (10a) (Scheme 5).
3
(δ 7.45 ppm, t, J = 7.2 Hz) is coupled with 5-H
3
3
(δ 8.77 ppm, J = 8.4 Hz) and 7-H (7.35 ppm, J =
3
8.0 Hz). The two doublets of 3-H (δ 7.94 ppm, J =
7.2 Hz) and 2-H (δ 7.29 ppm, J = 8.0 Hz) showed
3
correlation with each other. The carbon signals in the
13C NMR spectrum of 10a were assigned on the basis
of the HSQC and HMBC spectra.
Scheme 2.
CO2H
CO2Pr-n
CO2Pr-n
CCl4, n-PrOH
+
Fe(acac)3, 130οC, 6 h
conversion 100%
n-PrO2C
26%, 3 isomers
2
1a (74%)
CO2Pr-n
CO2H
1b
(73%)
CCl4, n-PrOH
+
Fe(acac)3, 130οC, 6h
conversion 99%
CO2Pr-n
3
n-PrO2C
26%, 3 isomers
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392
BAIGUZINA et al.
Scheme 3.
CH3
CH3
CH3
CCl4, n-PrOH
+
Fe(acac)3
conversion 77%
n-PrO2C
CO2Pr-n
CO2Pr-n
4а, 4b
2 isomers, 71%
4c, 4d
2 isomers, 6%
4
CH3
CH3
CH3
CCl4, n-PrOH
+
Fe(acac)3
conversion 87%
CO2Pr-n
5c, 5d
2 isomers, 9%
n-PrO2C
CO2Pr-n
5
5а, 5b
2 isomers, 78%
Scheme 4.
CH3
CH3
CCl4, n-PrOH
Fe(acac)3
CH3
CH3
CH3
conversion 79%
n-PrO2C
6а_6d
4 иisomers
6
CH3
CCl4, n-PrOH
Fe(acac)3
H3C
H3C
H3C
H3C
conversion 74%
CO2Pr-n
7
7а_7c
3 isomers
CH3
CH3
CCl4, n-PrOH
Fe(acac)3
conversion 73%
CO2Pr-n
8а_8c
8
3 isomers
H3C
CH3
H3C
CH3
CCl4, n-PrOH
Fe(acac)3
conversion 72%
CO2Pr-n
9а_9c
9
3 isomers
Apart from Fe(acac)3, other iron compounds [FeCl3,
FeCl3·6H2O, FeBr2, Fe, Fe2(CO)9] were tried as
catalysts. However, the catalytic activity of all these
compounds was lower than that of Fe(acac)3. The
behavior of iron metal was interesting. It showed an
appreciable catalytic activity in the presence of
acetylacetone [Fe–Hacac ratio 1 : (1–10)]. The reaction
of naphthalene with carbon tetrachloride and propan-1-
ol at 130°C (6 h) in the presence of iron metal
(preliminarily activated with 5% HCl) and
acetylacetone (molar ratio Fe–Hacac–1–CCl4–PrOH
5 : 5 : 100 : 300 : 300) afforded a mixture of propyl
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SYNTHESIS OF NAPHTHALENECARBOXYLIC AND NAPHTHALENEDICARBOXYLIC ACIDS
393
Scheme 5.
CH3 CH3
CH3 CH3
CCl4, n-PrOH
Fe(acac)3
conversion 90%
CO2Pr-n
10
10a
Scheme 6.
CO2Pr-n
CO2Pr-n
CCl4, n-PrOH
+
[Fe], 130οC, 6 h
conversion 50%
1b (15%)
1
1a (35%)
Scheme 7.
CCl3
CO2R
CCl4, ROH
3 ROH
_3 HCl
_ROR
[Fe]
_HCl
1A
1
1a, 1b
naphthalene-1- and -2-carboxylates 1a and 2b in an
overall yield of 50% (Scheme 6). Iron metal gradually
dissolved during the process; presumably, the
catalytically active form was not Fe0 but iron(III)
acetylacetonate.
and 8.04 ppm (J = 8 Hz, 8-H), one multiplet at
δ 7.50 ppm (6-H, 7-H), one singlet at δ 8.60 ppm
(1-H), and upfield signals typical of propoxy group.
Thus, we have demonstrated the possibility of
synthesizing alkyl naphthalenecarboxylates and dialkyl
naphthalenedicarboxylates by multicomponent reac-
tion of naphthalene with carbon tetrachloride and
alcohols catalyzed by iron compounds.
In all cases, the reactions were accompanied by
formation of hydrogen chloride and the corresponding
ethers as by-products. Taking these data into account,
we propose the following mechanism of the formation
of ester group. The first step is alkylation of
naphthalene (1) with carbon tetrachloride, and the
resulting trichloromethyl derivative 1A undergoes
alcoholysis to give ester 1a or 1b (Scheme 7).
EXPERIMENTAL
1
The H and 13C NMR spectra were recorded on a
Bruker Avance-400 spectrometer at 400.1 and 100.6
MHz, respectively, using CDCl3 as solvent; the
chemical shifts are given relative to tetramethylsilane.
The mass spectra were obtained on a Shimadzu GCMS
-QP2010Plus (SPB-5 capillary column, 30 m × 0.25
mm; carrier gas helium; oven temperature
programming from 40 to 300°C at a rate of 8 deg/min,
injector temperature 280°C, ion source temperature
200°C; electron impact, 70 eV). The reaction mixtures
were analyzed by GLC on Shimadzu GC-9A and GC-
2014 instruments using a 2-m × 3-mm column packed
with 5% SE-30 on Chromaton N-AW-HMDS; oben
temperature programming from 50 to 270°C at a rate
of 8 deg/min; carrier gas helium, flow rate 47 mL/min.
1
The structure of 1a and 1b was confirmed by H
1
and 13C NMR spectra. Ester 1a displayed in the H
NMR spectrum five doublets corresponding to 2-H
(δ 8.98 ppm, J = 8.8 Hz), 3-H (δ 7.65 ppm, J = 7.2 Hz),
4-H (δ 8.23 ppm, J = 7.2 Hz), 5-H (δ 8.03 ppm, J =
8.4 Hz), and 8-H (δ 7.90 ppm, J = 8 Hz) and one
multiplet signal due to 6-H and 7-H (δ 7.53 ppm). In
the upfield region we observed signals of the propyl
group at δ 4.42 (J = 6.8 Hz, OCH2), 1.89 (OCH2CH2),
1
and 1.12 ppm (J = 7.6 Hz, CH3). The H NMR
spectrum of 1b contained four doublets at δ 7.68 (J =
8 Hz, 3-H), 8.20 (J = 7 Hz, 4-H), 7.80 (J = 8 Hz, 5-H),
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 3 2017

394
BAIGUZINA et al.
GLC analyses were also done on a Shimadzu GCMS-
QP2010 Ultra instrument (Supel-Q PLOT capillary
column, 30 m × 0.53 mm; oven temperature prog-
ramming from 37 to 250°C at a rate of 10 deg/min;
carrier gas helium, flow rate 3 mL/min; ion source
temperature 200°C; electron impact, 70 eV). All
reagents and solvent were of analytical grade.
Dipropyl naphthalene-1,5-dicarboxylate (1c).
Yield 16%, bp 160–162°C (0.2 mm). H NMR spec-
1
trum, δ, ppm: 1.08 t (3H, CH2CH3, J = 6.8 Hz), 1.65 m
(2H, CH2CH3), 4.23 t (2H, OCH2, J = 7.2 Hz), 8.97 d
(2H, 2-H, 6-H, J = 8.8 Hz), 7.68 m (1H, 3-H, 7-H),
8.25 d (2H, 4-H, 8-H, J = 7.2 Hz). 13C NMR spectrum,
δC, ppm: 10.58 (CH3), 22.10 (CH2CH3), 67.03 (OCH2),
125.83 (C4, C8), 126.21 (C3, C7), 132.20 (C2, C6),
133.23 (C4a, C8a), 140.26 (C1, C5), 167.62 (C=O). Mass
spectrum, m/z (Irel, %): 300 (66) [M]+, 258 (29), 241
(87), 221 (20), 216 (100), 199 (63), 150 (15), 126 (20).
Alkyl naphthalenecarboxylates and dialkyl naph-
thalenedicarboxylates (general procedure). The
reactions were carried out in a 10-mL glass ampule
placed in a 17-ml stainless steel high pressure reactor
with controlled heating. The ampule was charged
under argon with 10 mmol of Fe(acac)3, 0.1 mol of the
corresponding naphthalene derivative, 1 mol of carbon
tetrachloride, and 0.8–1.0 mol of the corresponding
alcohol. The ampule was sealed and placed in the high-
pressure reactor which was heated at 130°C for 6 h
with continuous stirring. When the reaction was
complete, the reactor was cooled to room temperature,
the ampule was opened, and the reaction mixture was
neutralized and filtered. The solvent was distilled off,
and the residue was distilled under reduced pressure or
recrystallized from ethanol.
Dipropyl naphthalene-2,6-dicarboxylate (1d).
1
Yield 7%, bp 163–165°C (0.2 mm). H NMR spec-
trum, δ, ppm: 1.13 t (3H, CH2CH3, J = 6.8 Hz), 1.75 m
(2H, CH2CH3), 4.38 t (2H, OCH2, J = 4.0 Hz), 8.76 s
(1H, 1-H, 5-H), 8.24 d (2H, 3-H, 7-H, J = 8.0 Hz),
8.17 d (2H, 4-H, 8-H, J = 7.2 Hz). 13C NMR spectrum,
δC, ppm: 10.69 (CH3), 22.19 (CH2CH3), 66.90 (OCH2),
127.65 (C3, C7), 130.51 (C4, C8), 131.72 (C1, C5),
134.06 (C4a, C8a), 140.28 (C2, C6), 167.64 (C=O). Mass
spectrum, m/z (Irel, %): 300 (45) [M]+, 281 (23), 258
(25), 241 (84), 216 (100), 207 (51), 199 (50), 171 (30),
126 (19), 115 (27).
Methyl naphthalene-1-carboxylate (1e). Yield
Propyl naphthalene-1-carboxylate (1a). Yield
74%, bp 105–107°C (0.2 mm). H NMR spectrum, δ,
1
15%, bp 155–157°C (10 mm); published data [12]: bp
1
165°C (17 mm). H NMR spectrum, δ, ppm: 3.99 s
ppm: 1.12 t (3H, CH2CH3, J = 7.6 Hz), 1.89 m (2H,
CH2CH3), 4.42 t (2H, OCH2, J = 6.8 Hz), 8.98 d (1H,
2-H, J = 8.8 Hz), 7.65 d (1H, 3-H, J = 7.2 Hz), 8.23 d
(1H, 4-H, J = 7.2 Hz), 8.03 d (1H, 5-H, J = 8.4 Hz),
7.53 m (2H, 6-H, 7-H), 7.90 d (1H, 8-H, J = 8 Hz). 13C
NMR spectrum, δC, ppm: 10.48 (CH3), 21.87
(CH2CH3), 66.68 (OCH2), 125.24 (C3), 126.53 (C6),
126.62 (C7), 127.21 (C8), 128.48 (C5), 130.06 (C2),
130.25 (C1), 132.48 (C4a), 133.22 (C4), 133.91 (C8a),
168.93 (C=O). Mass spectrum, m/z (Irel, %): 214 (72)
[M]+, 172 (100), 155 (95), 127 (56), 115 (5).
(3H, CH3), 8.7 d (1H, 2-H, J = 9.0 Hz), 7.69 d.d (1H,
3-H, J = 7.0, 9.0 Hz), 8.23 d (1H, 4-H, J = 7.0 Hz),
8.00 d (1H, 5-H, J = 8.0 Hz), 7.5 m (1H, 6-H), 7.58 m
(1H, 7-H), 7.9 d (1H, 8-H, J = 8.0 Hz). 13C NMR spec-
trum, δC, ppm: 52.19 (CH3), 126.27 (C6), 125.34 (C3),
126.39 (C7), 127.19 (C8), 128.36 (C5), 128.77 (C1),
130.44 (C2), 132.59 (C8a), 132.69 (C4), 133.47 (C4a),
167.32 (C=O). Mass spectrum, m/z (Irel, %): 186.17
(69) [M]+, 155 (100), 127 (81), 126 (15), 77 (10), 75 (5).
Methyl naphthalene-2-carboxylate (1f). Yield
1
27%, mp 76–78°C; published data [12]: mp 77°C. H
Propyl naphthalene-2-carboxylate (1b). Yield
NMR spectrum, δ, ppm: 3.93 s (3H, CH3), 7.7 d (1H,
3-H, J = 7.0 Hz), 8.19 d (1H, 4-H, J = 7.0 Hz), 7.83 d
(1H, 5-H, J = 8.0 Hz), 7.48 m (1H, 6-H), 7.4 m (1H,
7-H), 7.8 d (1H, 8-H, J = 8.0 Hz), 8.6 s (1H, 1-H). 13C
NMR spectrum, δC, ppm: 52.28 (CH3), 125.34 (C6),
125.43 (C3), 126.80 (C4a), 127.19 (C4), 127.88 (C7),
128.68 (C5), 129.40 (C1), 131.16 (C8), 132.59 (C8a),
135.57 (C2), 167.90 (C=O). Mass spectrum, m/z (Irel,
%): 186.17 (69) [M]+, 155 (100), 127 (80), 126 (15),
40 (16).
1
73%, bp 107–109°C (0.2 mm). H NMR spectrum, δ,
ppm: 1.08 t (3H, CH2CH3, J = 7.2 Hz), 2.03 m (2H,
CH2CH3), 4.30 t (2H, OCH2, J = 6.8 Hz), 8.60 s (1H,
1-H), 7.68 d (1H, 3-H, J = 8.0 Hz), 8.20 d (1H, 4-H,
J = 7.0 Hz), 7.80 d (1H, 5-H, J = 8.0 Hz), 7.50 m (2H,
6-H, 7-H), 8.04 d (1H, 8-H, J = 8 Hz). 13C NMR
spectrum, δC, ppm: 10.50 (CH3), 22.15 (CH2CH3),
66.61 (OCH2), 125.26 (C6), 125.80 (C3), 127.22 (C4),
127.51 (C8a), 127.75 (C7), 128.51 (C5), 129.33 (C1),
131.37 (C8), 132.53 (C4a), 135.49 (C2), 167.63 (C=O).
Mass spectrum, m/z (Irel, %): 214 (48) [M]+, 207 (29),
172 (94), 163 (13), 155 (100), 127 (59), 115 (7).
Ethyl naphthalene-1-carboxylate (1g). Yield
27%, bp 165–166°C (10 mm); published data [12]: bp
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SYNTHESIS OF NAPHTHALENECARBOXYLIC AND NAPHTHALENEDICARBOXYLIC ACIDS
395
1
310°C. H NMR spectrum, δ, ppm: 1.40 t (3H, CH3,
ACKNOWLEDGMENTS
J = 7.6 Hz), 4.4 q (2H, OCH2, J = 3.7 Hz), 8.97 d (1H,
2-H, J = 9.0 Hz), 7.63 d.d (1H, 3-H, J = 7.0, 9.0 Hz),
8.21 d (1H, 4-H, J = 7.0 Hz), 8.00 d (1H, 5-H, J =
8.0 Hz), 7.5 m (1H, 6-H), 7.5 m (1H, 7-H), 7.87 d (1H,
8-H, J = 8.0 Hz). 13C NMR spectrum, δC, ppm: 14.40
(CH3), 61.04 (CH2O), 125.27 (C3), 126.17 (C6), 126.60
(C7), 127.44 (C8), 128.16 (C5). 129.33 (C1), 130.11
(C2), 131.37 (C8a), 133.23 (C4), 133.85 (C4a), 167.59
(C=O). Mass spectrum, m/z (Irel, %): 200.10 (71) [M]+,
172 (15), 156 (17), 155 (100), 127 (68), 126 (13).
This study was performed using the facilities of the
Agidel Joint Center at the Institute of Petrochemistry
and Catalysis, Russian Academy of Sciences.
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spectrum, δ, ppm: 1.11 t (3H, CH2CH3, J = 7.6 Hz),
1.88 m (2H, CH2CH3), 2.96 s (3H, 1-CH3), 2.95 s (3H,
8-CH3), 4.40 t (2H, OCH2, J = 6.4 Hz), 7.29 d (1H,
2-H, J = 8.0 Hz), 7.35 d (1H, 7-H, J = 8.0 Hz), 7.45 t
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8.77 d (1H, 5-H, J = 8.4 Hz). 13C NMR spectrum, δC,
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soedinenii
naftalinovogo
ryada,
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Goskhimizdat, 1963, pp. 480, 482.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 3 2017