Synthesis of diazonaphthoquinones from naphthols by diazo-transfer reaction

Article abstract of DOI:10.1246/bcsj.20150021

Various orthodiazonaphthoquinones (1-diazo-2(1H)-naphthalenones and 2-diazo-1(2H)-naphthalenones) were synthesized using the diazo-transfer reaction between the appropriate naphthol and 2-azido-1,3-dimethylimidazolinium chloride (ADMC). The ADMC was prepa

Full text of DOI:10.1246/bcsj.20150021

Synthesis of Diazonaphthoquinones from
Naphthols by Diazo-Transfer Reaction
Mitsuru Kitamura,* Rie Sakata, Norifumi Tashiro, Azusa Ikegami, and Tatsuo Okauchi
Department of Applied Chemistry, Kyushu Institute of Technology,
1-1 Sensuicho, Tobata, Kitakyushu, Fukuoka 804-8550
E-mail: kita@che.kyutech.ac.jp
Received: January 15, 2015; Accepted: February 25, 2015; Web Released: March 4, 2015
Various orthodiazonaphthoquinones (1-diazo-2(1H)-naphthalenones and 2-diazo-1(2H)-naphthalenones) were
synthesized using the diazo-transfer reaction between the appropriate naphthol and 2-azido-1,3-dimethylimidazolinium
chloride (ADMC). The ADMC was prepared by the reaction between 2-chloro-1,3-dimethylimidazolinium chloride and
sodium azide. The diazo-transfer reaction selectively introduced the diazo group at the C(2) position of 1-naphthol or the
C(1) position of 2-naphthol. The naphthalenediols that were tested, except for 1,3-naphthalenediol, also reacted with
ADMC to afford the corresponding monodiazotized compound. X-ray analyses suggested that the diazonaphthoquinones
did not have diazoniumnaphtholate structures but had diazocarbonyl structures.
Orthodiazonaphthoquinones (1-diazo-2(1H)-naphthalenones
1 and 2-diazo-1(2H)-naphthalenones 2, Figure 1) are relatively
stable cyclic α-diazocarbonyl compounds,1 and they are exclu-
sively used as photoresists (e.g., the novolak-diazonaphthoqui-
none resist).2 α-Diazocarbonyl compounds are often used in
organic syntheses involving carbene and carbenoid intermedi-
ates;3 therefore, it is expected that diazonaphthoquinones could
reliably be used as aromatic units for the synthesis of bioactive
aromatic natural products and aromatic functional materials
through the corresponding carbene or carbenoid intermediates.
However, although the Wolff rearrangement of orthodiazo-
naphthoquinones, which is the key reaction for photoresists,
has been widely investigated,4 the development of other reac-
tions and the application of diazonaphthoquinones as aromatic
building blocks are found to be limited,5 partly because of the
difficulties involved in synthesizing diazonaphthoquinones.1
In general, orthodiazonaphthoquinones are synthesized from
naphthols in several steps. Routes for synthesizing 1-diazo-
naphthoquinones 1 are shown in Scheme 1, which shows that 1
can be synthesized via aminonaphthols (Route a)6 or orthoqui-
nones (Route b).7 Neither of these routes are short, and both
require a regioselective transformation, such as amination in
Route a and hydrazonation in Route b, to occur. The diazo-
transfer reaction involving naphthol is the shortest direct syn-
thetic method (Route c),3,8 but this method is not commonly
used to synthesize diazonaphthoquinones. To the best of our
knowledge, 2-azido-3-ethylbenzothiazolium tetrafluoroborate
(3), synthesized by Balli et al., is the reagent with which
naphthol undergoes the most efficient diazo-transfer reaction.9
1-Diazo-2(1H)-naphthalenone (1a) has been synthesized from
2-naphthol (4a) using the thiazolium salt 3, although the yield
was not high (22%) (eq 1).
N3
N2
+
C2H5
S
N
OH
+
O
–
BF4
ð1Þ
MeOH
H2O
4a
3
1a 22%
Recently, we have reported that 2-azido-1,3-dimethylimid-
azolinium salts 5 act as efficient reagents for diazo-transfer
reactions with 1,3-dicarbonyl compounds (Table 1).10 2-Azido-
1,3-dimethylimidazolinium chloride (ADMC, 5a) has been
prepared through the N-nitrosation of N-aminoguanidine 6 in
an aqueous medium (Method A) or through the reaction
between 2-chloro-1,3-dimethylimidazolinium chloride (DMC,
7) and sodium azide in a nonaqueous solvent (Method B). The
corresponding phosphate, 2-azido-1,3-dimethylimidazolinium
phosphate (ADMP) 5b, has been isolated as a crystal, and it
has been found to be a stable and safe reagent.11 ADMC 5a
and ADMP 5b reacted with 1,3-dicarbonyl compounds under
mild conditions in the presence of Et3N to give 2-diazo-1,3-
dicarbonyl compounds in high yields. These 2-diazo-1,3-
dicarbonyl compounds were easily isolated because the by-
products of the reactions are highly soluble in water.
In a further study of the diazo-transfer reactions of the imida-
zolinium salts 5,12-14 we found that ADMC 5a is able to trans-
fer a diazo group to naphthols.13 The outcomes of this reaction
are described in this study.
N2
O
O
N2
Results and Discussion
We started with the reaction between ADMC 5a (prepared
using Method A) and 2-naphthol (4a) (Table 2). A solution of
ADMC 5a was prepared by stirring a mixture of guanidine 6
R
R
1
2
Figure 1. Diazonaphthoquinones.
824 | Bull. Chem. Soc. Jpn. 2015, 88, 824–833 | doi:10.1246/bcsj.20150021
© 2015 The Chemical Society of Japan

NH2
Table 2. Diazo-Transfer Reaction between ADMC 5a and
2-Naphthol (4a) Using Method Aa)
OH
OH
amination
NH2
N
route a
HCl aq., NaNO2
R
R
R
R
0 °C, 30 min
• 2HCl
MeN
NMe
ADMC 5a
oxidation
N-nitrosation
route b
+
6•2HCl
O
O
N2
OH
route c:
OH
N2
O
4a
Diazo-
transfer
Na2CO3 aq.
base
R
0 °C, 30 min
–H+
TsNH-NH2
THF
1a
NNHTs
O
N2
O
Yield/%
HCl
NaNO2
Entry
Base
Et3N
1 M NaOH aq.
1 M NaOH aq.
/equiv
/equiv
1a
4a
1
2
3
3
3
5
2.2
2.2
5
10
38
52
88
56
44
–TolSO2H
R
1
Scheme 1. Synthesis of 1-diazonaphthoquinones 1.
a) Molar ratio: 6¢2HCl/4a/base = 1.1/1/2.
Table 1. Diazo-Transfer Reactions between 2-Azido-
1,3-dimethylimidazolinium Salts 5 and 1,3-Dicarbonyl
Compounds
sodium hydroxide solution; therefore, we changed to perform-
ing the diazo-transfer reaction in an aprotic solvent in
Method B.
X–
N3
2-Naphthol (4a) was treated with 1.1 equiv of ADMC 5a
(prepared by the reaction between DMC 7 and sodium azide
(Method B) in CH3CN at 0 °C) in THF in the presence of a base
(Table 3, Entries 1-13). Using Et3N as a base led to diazo-
naphthoquinone 1a being obtained in 58% yield (Entry 1). The
effects of using different bases were remarkable. Using a base
with a similar basicity to Et3N, such as i-Pr2NEt2 or K2CO3, led
to 1a being obtained in a good yield (Entries 2 and 4), but using
Et2NH led to 1a being obtained in a poor yield (Entry 3). Less
basic bases, such as aromatic bases, were not suitable for the
production of diazonaphthoquinone 1a (Entries 5-7). Using
DBU (1,8-diazabicyclo[5.4.0]undec-7-ene) as a base led to 4a
being consumed and a large amount of an unknown product
being observed when the product mixture was analyzed by
thin layer chromatography (TLC) (Entry 8). However, these
unknown products were not found, and 4a was recovered in
66% yield, when the reaction was quenched by adding water.
The yield of 1a increased to 80% when Et3N was used as the
base and the reaction was performed at ¹20 °C, and the yield
of 1a increased to 86% when 1.5 equiv of ADMC 5a was
added (Entries 10 and 11). The reaction was accelerated when
30 mol % of 15-crown-5 was added (Entry 12). The reaction
mixtures used in Entries 1-12 were not clear solutions, prob-
ably because of the poor solubility of sodium azide in the
solvent mixture (CH3CN and THF) that was used. The reaction
mixture was a clear solution when methanol was added, but this
caused the yield of 1a to decrease (Entry 13).
+
O
O
+
MeN
NMe
Ph
5a X = Cl (ADMC)a)
5b X = PF6 (ADMP)
O
O
Et3N
THF
Ph
N2
0 °C, 10 min
NH2
Cl–
N
MeN
6
Cl
+
NMe
MeN
NMe
7
Entry
X
5
Methoda)
Yield/%
1
2
3
Cl
Cl
PF6
5a
5a
5b
A
B
®
quant.
98
91
a) Methods for preparing ADMC 5a. Method A: 6¢2HCl, HCl
aq., NaNO2, 0 °C, 30 min; Na2CO3 aq. Method B: DMC 7,
NaN3, CH3CN, 0 °C, 30 min.
and sodium nitrite in aqueous hydrochloric acid at 0 °C for 30
min. The pH of the mixture was adjusted to a value of 10 by
adding saturated aqueous Na2CO3. Then, 2-naphthol (4a) was
reacted with 5a under different conditions. Adding 2-naphthol
(4a) and Et3N at twice the molar concentration of 4a in tetra-
hydrofuran (THF) led to the diazo-transfer product diazonaph-
thoquinone 1a being obtained in 10% yield after stirring the
mixture for 30 min (Entry 1). Adding sodium hydroxide rather
than Et3N led to diazonaphthoquinone 1a being obtained in
38% yield (Entry 2). Adding an excess of N-nitrosation rea-
gents (HCl aq. and NaNO2) increased the yield of diazonaph-
thoquinone 1a to 52% (Entry 3). However, diazonaphthoqui-
none 1a was found to decompose to naphthol 4a in an aqueous
The reaction of 1-naphthol (8a) was then examined (Entries
14-17). 2-Diazo-1(2H)-naphthalenone (2a) was obtained
regioselectively when 1-naphthol (8a) was used as a starting
material, and adding 30 mol % of 15-crown-5 again effectively
accelerated the reaction (Entries 14 and 15). However, adding
too much of the crown ether was not effective in promoting the
formation of diazonaphthoquinone 8a (compare Entry 15 with
Entries 16 and 17).
Bull. Chem. Soc. Jpn. 2015, 88, 824–833 | doi:10.1246/bcsj.20150021
© 2015 The Chemical Society of Japan | 825

Table 3. Diazo-Transfer Reactions between ADMC 5a and Naphthols 4a and 8a Using Method B
2-naphthol (4a)
–
or
+
N
Cl–
O
N
N2
Cl–
1-naphthol (8a)
Cl
NaN3
additive
N2
N
O
base
+
MeN
NMe
or
MeN
NMe
CH3CN
THF
Temp, 30 min
Temp, Time
5a
1a
2a
Product (Yield/%a))
1a (58) 4a (16)
7
Entry
Naphthol
Additive/equiv
Base
Temp/°C
Time
1b)
4a
4a
4a
4a
4a
4a
4a
4a
4a
4a
4a
4a
4a
®
®
®
®
®
®
®
®
®
®
®
Et3N
0
0
0
0
0
0
0
0
0
1 h
1 h
1 h
1 h
1 h
1 h
1 h
1 h
1 h
1 h
1 h
2b)
i-Pr2NEt
Et2NH
K2CO3
DMAP
imidazole
pyridine
DBU
1a (52)
1a (4)
1a (53)
1a (12)
1a (5)
1a (trace)
1a (0)
1a (0)
4a (30)
4a (41)
4a (21)
4a (24)
4a (59)
4a (77)
4a (66)
4a (84)
3b)
4b)
5b)
6b)
7b)
8b)
9b)
®
Et3N
Et3N
Et3N
Et3N
10b)
11c)
12c)
13b)
¹20
¹20
¹20
¹20
1a (80)
1a (86)
1a (87)
1a (12)
15-Crown-5 (0.3)
MeOH
20 min
1 h
4a (87)
14c)
15c)
16c)
17c)
8a
8a
8a
8a
®
Et3N
Et3N
Et3N
Et3N
¹20
¹20
¹20
¹20
40 min
30 min
15 min
1 h
2a (76)
2a (83)
2a (72)d)
2a (41)d)
15-Crown-5 (0.3)
15-Crown-5 (1.3)
15-Crown-5 (2)
18e)
4a
Et3N
0
1 h
1a (27)
4a (43)
a) Isolated yield. b) Molar ratio: 7/NaN3/naphthol 4a or 8a/Et3N = 1.1/1.2/1/2. c) Molar ratio: 7/NaN3/naphthol
4a or 8a/Et3N = 1.5/1.7/1/2. d) The yield was determined by 1H NMR spectroscopy using 1,1,2,2-tetrachloroethane
as an internal standard. e) ADMP 5b was used instead of ADMC 5a. Molar ratio: ADMP 5b/4a/Et3N = 1.1/1/2.
In contrast with the case of diazo-transfer reactions with
1,3-dicarbonyl compounds (Table 1, Entry 3), ADMP 5b was
unsuitable for a diazo-transfer reaction with naphthol under
the optimized reaction conditions for ADMC 5a (Table 3,
Entry 18).
by 1-diazonaphthoquinone 1a, but reacting 1-formyl-2-naph-
thol (12) with ADMC 5a at room temperature for a prolonged
period led to the formation of 1-cyano-2-naphthol (14) in 70%
yield (Scheme 2). The nitrile 14 would have been formed via
13 because 13 was confirmed to transform to 14 by the reaction
with Et3N in THF at room temperature for 3 h.
We investigated the diazotization of various naphthol deriv-
atives to determine the scope and limitations of the method.
The results of performing the reaction using various
naphthols (mono-ols) are shown in Table 4. 1-Unsubstituted
2-naphthols were converted into 1-diazonaphthoquinone in
good yields (Entries 1-5), while 1-substituted 2-naphthols did
not yield the corresponding diazo compounds (Entries 6 and 7).
2-Unsubstituted 1-naphthols gave 2-diazo derivatives in good
yields, and the presence of substituents at the C(3) or C(4)
positions on the 1-naphthol did not influence the yield (Entries
8-11). 5,8-Dimethoxy-1-naphthols were also transformed into
the corresponding diazonaphthoquinones in good yields (En-
tries 12 and 13). The reaction became complex when the 1-
naphthol had a substituent at the C(2) position, and we were not
able to identify the compounds that were obtained (Entry 14).
Anthrone (equivalent to anthracene-9-ol) gave the corre-
sponding diazo compound 9 in good yield (Entry 15), but
phenol could not be used in the diazotization reaction
(Entry 16).
The reaction with naphthalenediols was then examined
(Table 5). The formation of monodiazotized compounds was
not detected when 1,3-naphthalenediol (15a) was treated with
1.5 equiv of ADMC 5a, but the bis-diazotized compound 16
was obtained in 61% yield. The yield of the bis-diazotized
compound 16 increased to 80% when 3.0 equiv of 5a was used
(Entry 1). 1,5-Naphthalenediol (15b) was consumed by treat-
ing it with the azide imidazolinium 5a, but the products were
difficult to isolate. 5-Acetoxy-2-diazo-1(2H)-naphthalenone
(17) was obtained in 56% yield when 1,5-naphthalenediol was
diazotized using ADMC 5a and the subsequent acetylation
(using Ac2O, in pyridine) of the product (Entry 2). Acetylation
was performed after the diazo-transfer reaction with ADMC
5a in all of the subsequent reactions with naphthalenediols so
that the products could easily be isolated. The bis-diazotized
compound was not obtained after the reaction of 15b even
though an excess of the diazotizing reagent 5a was used. A
monodiazotized compound was obtained regioselectively when
1,6-naphthalenediol (15c) was reacted (Entry 3). The diazo-
transfer reaction of 1,7-naphthalenediol (15d) gave several
Interestingly, 1-formyl-2-naphthol (12) reacted with ADMC
5a at ¹20 °C to give isooxazole 13 in 70% yield accompanied
826 | Bull. Chem. Soc. Jpn. 2015, 88, 824–833 | doi:10.1246/bcsj.20150021
© 2015 The Chemical Society of Japan

Table 4. Reactions of Naphthols with ADMC 5aa)
Entry
ArOH
Time
Product
Yield/%b)
N2
OH
R
O
R
1
2
3
4
4b (R = CH2OTBS)
4c (R = CO2CH3)
4d (R = CO2Ph)
0.5 h
1 h
1 h
1b (R = CH2OTBS)
1c (R = CO2CH3)
1d (R = CO2Ph)
1e (R = CONHPh)
N2
81
75
62
60 [93]c)
4e (R = CONHPh)
1 h
OH
O
Br
5
1 h
4f
Br
1f
79
Br
OH
d)
6
7
3 h
2 h
®
4g
e)
BINOL (4h)
®
OH
O
N2
R1
R1
R2
R2
8
9
10
11
8b (R1 = H, R2 = OMe)
8c (R1 = H, R2 = Cl)
8d (R1 = CH2OTBS, R2 = H)
8e (R1 = CO2CH3, R2 = H)
OMe OH
1 h
1 h
1 h
2 h
2b (R1 = H, R2 = OMe)
2c (R1 = H, R2 = Cl)
2d (R1 = CH2OTBS, R2 = H)
2e (R1 = CO2CH3, R2 = H)
OMe O
73
81
72
98
N2
R
R
OMe
OMe
12f)
13
8f (R = (E)-CH=CH-Ph)
8g (R = CO2C2H5)
3 h
4 h
2f (R = (E)-CH=CH-Ph)
2g (R = CO2C2H5)
89
60
OH
n-Bu
d)
14
1 h
®
8h
O
O
15
16
10 min
9
[86]c),g)
N2
10
OH
2 hh)
®
e)
11
a) Unless otherwise noted, the reactions were carried out at ¹20 °C by stirring a mixture of ArOH (1 equiv) and Et3N
(2 equiv) in THF with a solution of ADMC 5a (1.5 equiv), which was prepared using DMC 7 (1.5 equiv), sodium
azide (NaN3) (1.7 equiv), and 15-crown-5 (30 mol %) in CH3CN. b) Isolated yield. c) The yield was determined by
1H NMR spectroscopy using 1,1,2,2-tetrachloroethane as an internal standard. d) Complex mixture. No compounds
were identified. e) Ar-OH was recovered. f) Molar ratio: 7/NaN3/8f/Et3N = 5/5/1/5. g) Anthraquinone was
obtained in 7% yield. h) At room temperature.
products, and 19 and 20 were obtained as a 2:1 mixture in 60%
yield and 19 was isolated in 12% yield (Entry 4). The 2,6-
naphthalenediol 15e and the 2,7-naphthalenediol 15f gave the
monodiazotized compounds 21 and 22, respectively (Entries 5
and 6).
The optimized equilibrium geometry of 2-azido-1,3-dimeth-
ylimidazolinium 23 is shown in Figure 2 (B3LYP/6-31G**).
There is no imaginary frequency in the calculated spectrum.
Both the LUMO (solid) and the electron density surfaces
(transparent) are shown in Figure 2b. The LUMO protrudes
Bull. Chem. Soc. Jpn. 2015, 88, 824–833 | doi:10.1246/bcsj.20150021
© 2015 The Chemical Society of Japan | 827

N
O
N2
5a (1.5 equiv)a)
Et3N (2.0 equiv)
O
+
THF
–20 °C
30 min
13 70%
1a 10 %
CHO
OH
5a (1.5 equiv)a)
Et3N (2.0 equiv)
CN
12
OH
THF
–20 °C
rt
14 70%
4 h
Scheme 2. Reaction between 1-formyl-2-naphthol (12) and ADMC 5a.
Table 5. Reactions of Naphthalenediols 15 with ADMC 5aa)
Entry
Naphthalenediol
15
Time
Product (Yield/%)b)
O
OH
N2
1
15a
10 min
O
OH
OH
16 (80)c)
N2
O
N2
2d)
15b
15c
1 h
1 h
17 (56)
OH
OH
OAc
O
N2
3d)
18 (41)
HO
AcO
AcO
O
N2
OH
19 (12 [40]e))
4d)
15d
30 min
HO
N2 OAc
O
20 ([20]e))
N2
N2
OH
O
5d)
15e
1 h
HO
HO
21 (31)
AcO
AcO
OH
O
6d)
15f
30 min
22 (40)
a) Unless otherwise noted, the reactions were carried out at ¹20 °C by stirring a mixture of ArOH and Et3N (2 equiv)
in THF with a solution of ADMC 5a (1.5 equiv), which was prepared from DMC 7 (1.5 equiv), sodium azide
(1.7 equiv), and 15-crown-5 (30 mol %) in CH3CN. b) Isolated yield. c) 3.0 equiv of 5a was used. d) After the
diazotization reaction was performed, the crude products were treated with acetic anhydride and pyridine. e) The yield
1
was determined by H NMR spectroscopy.
from the electron density surface around the terminal nitrogen.
This figure suggests that a soft nucleophile would preferentially
attack the terminal nitrogen of 5a electrostatically.15 A natu-
ral population analysis of 23 calculated at the same level of
theory is shown in Table 6 (B3LYP/6-31G**). Large positive
charge is localized at C(1) in 23, which suggests that a hard
nucleophile would attack C(1), preferably through a charge-
controlled reaction.15
A plausible mechanism for the reaction between ADMC
5a and 2-naphthol 4a in the presence of a base is shown in
Scheme 3. The reaction pathway depends on the base used.
Naphtholate I will be formed from naphthol 4a and the base at
828 | Bull. Chem. Soc. Jpn. 2015, 88, 824–833 | doi:10.1246/bcsj.20150021
© 2015 The Chemical Society of Japan

–
N
+
N
N
N(5)
+
H3CN
NCH3
N(4)
23
N(3)
C(1)
N(1)
C(5)
C(4)
N(2)
C(3)
C(2)
(a)
(b)
Figure 2. Optimized equilibrium geometry (B3LYP/6-31G**) of 2-azido-1,3-dimethylimidazolinium (ADM) 23 obtained using
Spartan 08. (a) Optimized equilibrium geometry with numbers. (b) The LUMO (solid) and the electron density surface
(transparent).
Table 6. Natural Population Analysis (B3LYP/6-31G**) for
2-Azido-1,3-dimethylimidazolinium (ADM) 23
4a
HO
Atom
Natural chargea)
base•H+
base
N(1)
N(2)
N(3)
N(4)
N(5)
C(1)
C(2)
C(3)
C(4)
C(5)
¹0.421426
¹0.390391
¹0.344347
0.223098
0.133719
0.672485
¹0.268080
¹0.271542
¹0.499865
¹0.491281
I
–O
O
a
N
–
N
N
H
attack at a
+
+
Cl–
N
Cl–
N
N
N
N
N
b
+
MeN
NMe MeN
NMe
MeN NMe
5a
II
NH
a) Sum of atomic charges = 1.000000.
attack at b
MeN
NMe
25
equilibrium when the base used has a conjugate acid with an
acidity similar to that of naphthol (pKa µ 10). Naphtholate I
will then attack the terminal nitrogen in 5a (the position a in
5a) to form intermediate II. Intermediate II will then undergo
intramolecular proton abstraction to afford the corresponding
diazo compound 1a and guanidine 25. The reverse reaction
will occur when naphtholate I attacks the central carbon in
the guanidinium (the position b in 5a), and naphtholate I and
naphthol 4a will be reformed at equilibrium. In contrast, naph-
ArO N3
MeN
NMe
O
N
N
O
24
+
–
N
N
Ar = 2-naphthyl
1a
Scheme 3. Plausible reaction mechanism.
tholate I will be kinetically formed when a strong base (pKaH
>
1.3355(19) ¡, respectively, for 1a, and 1.1168(14) and
1.3482(14) ¡, respectively, for 2a. The N(1)-N(2) bond lengths
are longer and the C-N(1) bond lengths are shorter than those
in a benzenediazonium salt (the N(1)-N(2) and C-N(1) bond
lengths in benzenediazonium tetrafluoroborate are 1.083 and
1.415 ¡, respectively).20 The ketone C=O bond lengths are
1.2474(19) ¡ in 1a and 1.2409(13) ¡ in 2a, and these lengths
are close to the length of a double bond. The C=O bond lengths
in benzoquinone are around 1.2 ¡ (1.195 ¡ for chloranil),21
while the aromatic C-O bond lengths are around 1.37-1.40 ¡
(1.373(8) ¡ for 3,5-dichlorophenol).22 Allen examined the
relationships between N-N bond lengths and N-C bond lengths
in diazo and diazonium compounds (compounds with a C-N¸N
substructure).16d The average N-N and N-C bond lengths in
α-diazoketones were found to be 1.115(3) and 1.328(5) ¡,
10) is used, and a hard oxygen nucleophile will attack the most
positive position b in 5a to form 24. In this case, the reverse
reaction will be slow because naphtholate I is predominantly
formed from naphthol 2a. Naphtholate I will hardly be formed
when a weak base is used; therefore diazonaphthoquinone 1a
will not be formed efficiently.
X-ray structural data for diazoquinone have been reported in
several publications,16 but there are few reports of structural
data for diazonaphthoquinones.7g,17 We succeeded in deter-
mining X-ray structural data for the simple diazonaphthoqui-
nones 1a18 and 2a19 (Figures 3 and 4). The CN2 moiety is
almost linear, with C-N(1)-N(2) bond angles of 175.50(14)
and 176.92(11)° for 1a and 2a, respectively (Table 7). The
N(1)-N(2) and C-N(1) bond lengths are 1.1210(19) and
Bull. Chem. Soc. Jpn. 2015, 88, 824–833 | doi:10.1246/bcsj.20150021
© 2015 The Chemical Society of Japan | 829

Table 7. Selected Geometric Parameters for 1a and 2a;
Distances in ¡, Angle in °
N(2)
N(1)
1a
1.2474(19)b) 1.2409(13)c)
1.1210(19) 1.1168(14)
1.3355(19)d) 1.3482(14)e)
2aa)
O(1)-C
N(1)-N(2)
N(1)-C
[1.240(4)]
[1.106(5)]
[1.339(5)]
[1.451(5)]
[1.413(5)]
[1.342(5)]
[1.438(5)]
[1.400(5)]
[1.460(5)]
C(1)
O(1)
C(1)-C(2)
C(2)-C(3)
C(3)-C(4)
C(4)-C(5)
C(5)-C(10)
C(10)-C(1)
1.449(2)
1.458(2)
1.359(2)
1.444(2)
1.418(2)
1.448(2)
1.4468(15)
1.4307(16)
1.3495(17)
1.4431(16)
1.4195(15)
1.4779(14)
C(10)
C(2)
C(3)
C(5)
C(4)
N(2)-N(1)-C
175.50(14)f) 176.92(11)g)
[176.2(4)]
[112.7(3)]
[124.7(3)]
[121.0(3)]
[117.9(3)]
[121.8(3)]
Figure 3. ORTEP of diazonaphthoquinone 1a. The thermal
ellipsoids are set at 50%. Hydrogen atoms are omitted
for clarity.
C(2)-C(1)-C(10)
C(1)-C(2)-C(3)
C(4)-C(5)-C(10)
C(6)-C(5)-C(10)
C(1)-C(10)-C(5)
126.40(13)
113.42(13)
119.17(13)
118.48(13)
115.66(12)
112.93(9)
125.66(9)
120.76(9)
117.95(10)
121.04(9)
O(1)
a) The values in square brackets are quoted from Ref. 17. b)
Distance of O(1)-C(2). c) Distance of O(1)-C(1). d) Distance
of N(1)-C(1). e) Distance of N(1)-C(2). f) Angle of N(2)-
N(1)-C(1). g) Angle of N(2)-N(1)-C(2).
N(2)
C(1)
N(1)
C(10)
C(2)
C(3)
melting points are uncorrected. Elemental analyses were
recorded on a Yanaco MT-5, and carried out at Center for
Instrumental Analysis, Faculty of Engineering, Kyusyu Insti-
tute of Technology. Column chromatography was performed
on silica gel (Kanto silica gel 60N or Fuji Silysia Silica gel
PSQ-100B). 2-Chloro-1.3-dimethyl-2-imidazolinium chloride
was purchased from TCI or prepared following a literature
procedure.24
C(5)
C(4)
Figure 4. ORTEP of diazonaphthoquinone 2a. The thermal
ellipsoids are set at 50%. Hydrogen atoms are omitted
for clarity.
respectively, and the N-N and N-C bond lengths in benzoyl-
phenyldiazomethane were found to be 1.132(5) and 1.325(5) ¡,
respectively.23 These data suggest that the diazonaphthoqui-
nones 1a and 2a do not have diazoniumnaphtholate structures
but have structures of diazo carbonyl compounds in the solid
state.
Caution: Although we have never had any trouble with
azidoimidazolinium salts 5, azide compounds are potentially
explosive.25 Reaction with 5 should be carried out in a well-
ventilated hood, and should be conducted behind a safety
shield.
Density Functional Calculations. Computational studies
were carried out using DFT calculations on Spartan 08 plat-
form. Optimized equilibrium geometry was found by B3LYP
functional and 6-31G** basis set. A natural population ana-
lysis was calculated at the same level of theory (B3LYP/
6-31G**).
Typical Procedure for the Preparation of Diazonaphtho-
quinones by the Reaction of 2-Naphthol (4a) with 2-Azide-
1,3-dimethylimidazolinium Chloride (Method A, Table 2,
Run 3): To a solution of 1,3-dimethylimidazolidinonehydra-
zone dihydrochloride (6¢2HCl) (228 mg, 1.1 mmol) in water
(2.7 mL) was added conc. hydrochloric acid (0.45 mL, 5.4
mmol). To the mixture, sodium nitrite (346 mg, 5.0 mmol) in
water was added slowly at 0 °C, and the mixture was stirred for
20 min. After the mixture was added aqueous sodium carbonate
solution until pH ca. 10, an aqueous solution of 2-naphthol (4a,
162 mg, 1.0 mmol) and 1 M NaOH aq. (1.0 mL, 2.0 mmol) was
added to the mixture, which was stirred for 30 min. From the
mixture, organic materials were extracted three times with
CH2Cl2. The combined extracts were washed with brine, and
dried over anhydrous sodium sulfate. The solvent was removed
in vacuo to afford crude compounds, which were purified by
Conclusion
In conclusion, we have developed a general method for
synthesizing diazonaphthoquinones by treating naphthol deriv-
atives with 2-azido-1,3-dimethylimidazolinium chloride 5a.
The ease with which 5a is prepared and the common use of
naphthol imply that this method is likely to find widespread
use in organic synthesis and material chemistry, such as for
preparing photoresists.
Experimental
General. All reactions were carried out under a nitrogen
atmosphere unless otherwise noted. 1H NMR (400.1 MHz,
500.0 MHz) and 13C NMR (100.6 MHz, 125.7 MHz) spectra
were recorded on a Bruker Avance 400 or JEOL JNM-A500 in
CDCl3 or DMSO-d6 solutions [In CDCl3, CHCl3 (for 1H, ¤ =
7.26) or CDCl3 (for 13C, ¤ = 77.0) was used as an internal
standard. In DMSO-d6, DMSO-d6 (for 13C, ¤ = 39.95) was
used as an internal standard.]. IR spectra were recorded on a
JEOL JIR-WINSPEC50. High-resolution mass spectra were
obtained with a JEOL JMS-SX102A mass spectrometer. The
830 | Bull. Chem. Soc. Jpn. 2015, 88, 824–833 | doi:10.1246/bcsj.20150021
© 2015 The Chemical Society of Japan

flash column chromatography (silica gel: hexane/ethyl acetate)
to give diazonaphthoquinone 1a in 52% yield.
Typical Procedure for the Preparation of Diazonaphtho-
quinones by the Reaction of Naphthols with 2-Azide-1,3-
dimethylimidazolinium Chloride (Method B, Table 3,
1H NMR (400 MHz, CDCl3): ¤ 11.7 (s, 1H), 8.9 (s, 1H), 7.8
(d, 1H, J = 7.8 Hz), 7.75 (d, 2H, J = 8.0 Hz), 7.62 (ddd, 1H,
J = 7.8, 7.4, 1.1 Hz), 7.37-7.28 (m, 3H), 7.31 (d, 1H, J = 7.8
Hz), 7.12 (t, 1H, J = 7.8 Hz); 13C NMR (101 MHz, CDCl3): ¤
179.5, 161.3, 145.7, 138.3, 132.3, 132.0, 129.0, 128.7, 125.5,
125.2, 124.4, 124.3, 120.4, 119.1, 80.8; HRMS (FAB+):
Found: m/z 290.0912. Calcd for C17H12N3O2: (M + H)+,
290.0929; mp 152-153 °C (dec).
Run 12):
To a solution of 2-chloro-1,3-dimethylimidaz-
olinium chloride 7 (228 mg, 1.35 mmol) in acetonitrile (2 mL),
sodium azide (99.4 mg, 1.5 mmol) and 15-crown-5 ether (0.06
ml, 0.3 mmol) was added at ¹20 °C and the mixture was stirred
for 30 min. 2-Naphthol 14a (130 mg, 0.90 mmol) and tri-
ethylamine (0.25 mL, 1.8 mmol) in THF (4 mL) was added to
the mixture, which was stirred for 20 min. The reaction was
quenched with water, and organic materials were extracted
three times with CH2Cl2. The combined extracts were washed
with water and brine, and then, dried over anhydrous sodium
sulfate. The solvent was removed in vacuo to afford crude
compounds. The crude materials were purified by flash column
chromatography (silica gel: hexane/ethyl acetate = 4/1) to
give diazonaphthoquinone 1a in 87% yield.
6-Bromo-1-diazo-2(1H)-naphthalenone (1f): IR (ATR):
¹1
2111, 1700, 1610, 1541, 1479, 1082, 820 cm
;
1H NMR
(400 MHz, CDCl3): ¤ 7.71 (d, 1H, J = 2.0 Hz), 7.60 (dd, 1H,
J = 8.5, 2.0 Hz), 7.54 (d, 1H, J = 9.8 Hz), 7.15 (d, 1H, J = 8.5
Hz), 6.69 (d, 1H, J = 9.8 Hz); 13C NMR (101 MHz, CDCl3):
¤ 179.5, 138.9, 132.5, 132.3, 127.1, 127.0, 125.9, 121.0,
117.8; Anal. Found: C, 48.23; H, 2.16; N, 11.04%. Calcd for
C10H5BrN2O: C, 48.22, H, 2.02; N, 11.25%; mp 105-115 °C
(dec).
2-Diazo-1(2H)-naphthalenone (2a):
IR (ATR): 2917,
2850, 2348, 2113, 1689, 1619, 1562 cm¹1; 1H NMR (400 MHz,
CDCl3): ¤ 8.33 (d, 1H, J = 8.0 Hz), 7.59 (ddd, 1H, J = 8.0, 7.2,
1.4 Hz), 7.49 (d, 1H, J = 7.2 Hz), 7.47 (ddd, 1H, J = 8.0, 7.2,
1.4 Hz), 6.89 (d, 1H, J = 9.3 Hz), 6.58 (d, 1H, J = 9.3 Hz);
13C NMR (101 MHz, CDCl3): ¤ 180.2, 137.47, 132.6, 129.5,
128.2, 127.2, 125.3, 117.3, 116.2, 74.2; Anal. Found: C, 70.20;
H, 3.68; N, 16.74%. Calcd for C10H6N2O3: C, 70.58; H, 3.55;
N, 16.46%; mp 73.5-74 °C (dec).
1-Diazo-2(1H)-naphthalenone (1a):
IR (ATR): 2333,
2221, 2084, 1616, 1558, 1479, 1452, 1394, 1346, 1304, 1251,
¹1
1203, 819, 613 cm
;
1H NMR (400 MHz, CDCl3): ¤ 7.62
(d, 1H, J = 9.8 Hz), 7.57 (dd, 1H, J = 7.8, 1.2 Hz), 7.51 (ddd,
1H, J = 7.8, 7.8, 1.2 Hz), 7.28 (brd, 1H, J = 7.8 Hz), 7.27 (ddd,
1H, J = 7.8, 7.8, 1.2 Hz), 6.65 (d, 1H, J = 9.8 Hz); 13C NMR
(101 MHz, CDCl3): ¤ 180.2, 140.2, 130.0, 129.7, 127.1, 125.9,
125.6, 124.7, 119.6, 77.2; Anal. Found: C, 70.76; H, 3.70; N,
16.39%. Calcd for C10H6N2O: C, 70.58; H, 3.55; N, 16.46%.
3-(tert-Butyldimethylsiloxymethyl)-1-diazo-2(1H)-naph-
thalenone (1b): IR (KBr): 3446, 3055, 2954, 2856, 2099,
4-Methoxy-2-diazo-1(2H)-naphthalenone (2b):
IR
(ATR): 2364, 2337, 2136, 2025, 2084, 1733, 1623, 1610,
¹1
1556, 1471, 1448, 1332, 1155, 1128, 1095, 1035, 956 cm
;
1H NMR (400 MHz, CDCl3): ¤ 8.33 (dd, 1H, J = 7.8, 1.1 Hz),
7.96 (d, 1H, J = 7.9 Hz), 7.66 (ddd, 1H, J = 7.9, 7.8, 1.3 Hz),
7.51 (ddd, 1H, J = 7.9, 7.8, 1.1 Hz), 5.9 (s, 1H), 3.88 (s, 3H);
13C NMR (101 MHz, CDCl3): ¤ 180.1, 144.4, 133.0, 132.6,
129.8, 127.9, 125.5, 122.5, 87.8, 74.6, 55.6; HRMS (FAB+):
Found: m/z 201.0696. Calcd for C11H9N2O2: (M + H)+,
201.0664; mp 104-105 °C (dec).
1
1587, 1119 cm¹1; H NMR (400 MHz, CDCl3): ¤ 7.73 (t, 1H,
J = 1.6 Hz), 7.61 (d, 1H, J = 7.3 Hz), 7.45 (ddd, 1H, J = 8.5,
7.5, 1.0 Hz), 7.28-7.24 (m, 2H), 4.40 (d, 2H, J = 1.7 Hz), 0.99
(s, 9H), 0.15 (s, 6H); 13C NMR (101 MHz, CDCl3): ¤ 179.1,
136.7, 134.5, 129.8, 128.8, 126.2, 125.6, 124.6, 119.3, 76.6,
60.3, 26.0, 18.4, ¹5.4 ppm; HRMS (FAB+): m/z [M + H]+
Calcd for C17H23N2O2Si 315.1529, found 315.1539.
4-Chloro-2-diazo-1(2H)-naphthalenone (2c): IR (ATR):
¹1
Methyl 4-Diazo-3,4-dihydro-3-oxo-2-naphthalenecarbox-
2343, 2121, 1741, 1610, 1537 cm ;
1H NMR (400 MHz,
ylate (1c): IR (ATR): 2117, 1725, 1706, 1614, 1552, 1481,
1454, 1430, 1207, 1143, 1089 cm
CDCl3): ¤ 8.38 (dd, 1H, J = 8.0, 1.0 Hz), 7.96 (dd, 1H, J =
8.0, 1.0 Hz), 7.75 (ddd, 1H, J = 8.0, 8.0, 1.0 Hz), 7.56 (ddd,
1H, J = 8.0, 8.0, 1.0 Hz), 7.04 (s, 1H); 13C NMR (101 MHz,
CDCl3): ¤ 178.9, 134.9, 133.2, 130.2, 128.2, 125.9, 125.3,
118.0, 114.2, 79.89; HRMS (FAB+): Found: m/z 205.0176.
Calcd for C10H5ClN2O2: (M + H)+, 205.0169; mp 155-160 °C
(dec).
3-(tert-Butyldimethylsiloxymethyl)-2-diazo-1(2H)-naph-
thalenone (2d): IR (KBr): 3446, 2929, 2858, 2117, 1624
cm¹1; 1H NMR (400 MHz, CDCl3): ¤ 8.30 (d, 1H, J = 7.4 Hz),
7.60 (ddd, 1H, J = 8.4, 7.0, 1.4 Hz), 7.46-7.42 (m, 2H), 6.44
(s, 1H), 4.70 (d, 2H, J = 0.8 Hz), 0.92 (s, 9H), 0.11 (s, 6H);
13C NMR (101 MHz, CDCl3): ¤ 180.6, 136.6, 132.6, 129.8,
128.7, 127.9, 126.9, 125.3, 114.2, 77.7, 63.8, 25.7, 18.2,
¹5.5 ppm; HRMS (EI+): m/z [M]+ Calcd for C17H22N2O2Si
314.1451, found 314.1442.
¹1
;
1H NMR (400 MHz,
CDCl3): ¤ 8.39 (s, 1H), 7.69 (d, 1H, J = 7.8 Hz), 7.61 (ddd,
1H, J = 7.8, 7.8, 1.1 Hz), 7.31 (dd, 1H, J = 7.8, 7.8 Hz), 7.29
(d, 1H, J = 7.8 Hz), 3.94 (s, 3H); 13C NMR (101 MHz, CDCl3):
¤ 175.7, 165.3, 145.3, 131.9, 131.7, 129.2, 126.0, 125.0, 123.7,
119.3, 80.0, 52.5; Anal. Found: C, 63.23; H, 3.62; N, 12.34%.
Calcd for C12H8N2O3: C, 63.16, H, 3.53; N, 12.28%; mp 92.5-
94 °C (dec).
Phenyl 4-Diazo-3,4-dihydro-3-oxo-2-naphthalenecarbox-
¹1
ylate (1d): IR (KBr): 3446, 2089, 1729, 1625, 1209 cm
;
1H NMR (400 MHz, CDCl3): ¤ 8.57 (s, 1H), 7.76 (d, 1H, J =
7.7 Hz), 7.65 (ddd, 1H, J = 8.0, 7.4, 1.1 Hz), 7.43 (dd, 2H, J =
8.3, 7.4 Hz), 7.35 (dd, 2H, J = 8.5, 7.7 Hz), 7.29-7.25 (m, 3H);
13C NMR (101 MHz, DMSO-d6): ¤ 174.8, 163.1, 150.9, 145.6,
132.6, 132.3, 130.0, 129.8, 126.4, 125.34, 125.29, 123.4,
122.3, 121.2, 80.8 ppm; HRMS (EI+): m/z [M]+ Calcd for
C17H10N2O3 290.0691, found 290.0688.
Methyl 3-Diazo-3,4-dihydro-4-oxo-2-naphthalenecarbox-
ylate (2e): IR (KBr): 3061, 2954, 2105, 1708, 1614, 1442,
1
4-Diazo-3,4-dihydro-3-oxo-N-phenyl-2-naphthalenecar-
1239 cm¹1; H NMR (400 MHz, CDCl3): ¤ 8.35 (dd, 1H, J =
boxamide (1e):9 IR (ATR): 3026, 2844, 2690, 2476, 2360,
6.7, 0.7 Hz), 7.68 (ddd, 1H, J = 8.1, 7.0, 1.4 Hz), 7.61 (d, 1H,
J = 6.2 Hz), 7.58 (ddd, 1H, J = 7.9, 6.7, 1.2 Hz), 7.45 (s, 1H),
¹1
2283, 2106, 1676, 1595, 1589, 1358, 1209, 790.7 cm
;
Bull. Chem. Soc. Jpn. 2015, 88, 824–833 | doi:10.1246/bcsj.20150021
© 2015 The Chemical Society of Japan | 831

3.22 (s, 3H); 13C NMR (125 MHz, CDCl3): ¤ 179.4, 164.0,
134.8, 133.0, 131.0, 130.0, 129.8, 125.8, 123.2, 119.1, 76.8,
53.0 ppm; HRMS (EI+): m/z [M]+ Calcd for C12H8N2O3
228.0535, found 228.0538.
added at ¹20 °C and the mixture was stirred for 30 min. 1,5-
Naphthalene diol 15b (144 mg, 0.9 mmol) and triethylamine
(0.25 mL, 1.8 mmol) in THF (4 mL) was added to the mixture,
which was stirred for 1 h. To the mixture, acetic anhydride
(0.17 mL, 1.8 mmol) and triethylamine (4.0 mL, 29 mmol) was
added, and the mixture was stirred until diazonaphthoquinone
was consumed by monitoring with TLC. The reaction was
quenched with water, and organic materials were extracted
three times with CH2Cl2. The combined extracts were washed
with water and brine, and then, dried over anhydrous sodium
sulfate. The solvent was removed in vacuo to afford crude
compounds. The crude materials were purified by flash column
chromatography (silica gel: hexane/ethyl acetate = 4/1) to
give 17 in 56% yield.
2-Diazo-5,8-dimethoxy-3-[(E)-2-phenylethenyl]-1(2H)-
naphthalenone (2f): IR (KBr): 2917, 2848, 2682, 2943, 2086,
1
1616, 1454, 1265, 1106 cm¹1; H NMR (500 MHz, CDCl3): ¤
7.53 (d, 2H, J = 7.0 Hz), 7.41-7.28 (m, 5H), 7.02 (d, 1H,
J = 9.0 Hz), 6.98 (d, 1H, J = 16.0 Hz), 6.85 (d, 1H, J = 8.5 Hz),
3.96 (s, 3H), 3.93 (s, 3H); 13C NMR (126 MHz, CDCl3): ¤
174.4, 152.5, 149.1, 136.3, 132.5, 129.0, 128.8, 128.5, 126.8,
126.2, 122.8, 116.6, 113.1, 109.1, 89.2, 56.4, 56.2 ppm.
3-Diazo-3,4-dihydro-5,8-dimethoxy-4-oxo-2-naphthalene-
carboxylic Acid Methyl Ester (2g): IR (ATR): 2918, 2848,
2241, 2104, 1709, 1614, 1578, 1462, 1373, 1255, 1105, 980;
1H NMR (400 MHz, CDCl3): ¤ 7.87 (s, 1H), 7.09 (d, 1H, J =
9.0 Hz), 7.01 (d, 1H, J = 9.0 Hz), 3.95 (s, 6H), 3.93 (s, 3H);
13C NMR (101 MHz, CDCl3): ¤ 163.9, 153.1, 150.1, 126.9,
120.5, 118.3, 117.0, 114.2, 112.8, 77.2, 56.7, 56.2, 52.7;
HRMS (FAB+): Found: m/z 289.0835. Calcd for C14H13N2O5:
(M + H)+ 289.0824; mp 165.5-166 °C (dec).
5-Acethoxy-2-diazo-1(2H)-naphthalenone (17):
IR
(ATR): 2924, 2412, 2200, 2098, 1749, 1608, 1581, 1450,
1408, 1373, 1321, 1265, 1211, 1165, 1024, 933 cm¹1; 1H NMR
(400 MHz, CDCl3): ¤ 8.23 (ddd, 1H, J = 7.9, 1.3, 1.0 Hz), 7.46
(dd, 1H, J = 7.9, 7.9 Hz), 7.39 (dd, 1H, J = 7.9, 1.3 Hz), 6.93
(d, 1H, J = 9.6 Hz), 6.61 (dd, 1H, J = 9.6, 1.0 Hz), 2.41 (s, 3H);
13C NMR (101 MHz, CDCl3): ¤ 179.2, 169.1, 146.6, 130.9,
130.3, 127.2, 126.0, 123.3, 117.2, 110.2, 77.8, 20.9; Anal.
Found: C, 62.78; H, 3.58; N, 12.65%. Calcd for C12H8N2O3: C,
63.16; H, 3.53; N, 12.28%; mp 103-105 °C (dec).
10-Diazo-9(10H)-anthracenone (10):9
1H NMR (400
MHz, CDCl3): ¤ 8.52 (d, 2H, J = 8.0 Hz), 7.68 (ddd, 2H,
J = 7.1, 7.2, 1.4 Hz), 7.39 (ddd, 2H, J = 7.6, 7.6, 1.0 Hz), 7.31
(d, 2H, J = 8.0 Hz); HRMS (FAB+): Found: m/z 221.0718
Calcd for C14H9N2O: (M + H)+, 221.0715.
6-Acethoxy-2-diazo-1(2H)-naphthalenone (18):
IR
(ATR): 3064, 2916, 2850, 2104, 1757, 1606, 1566, 1471,
Naphth[1,2-d]isoxazole (13):26 IR (ATR): 3097, 3064,
2916, 2848, 1975, 1913, 1764, 1670, 1664, 629, 1581, 1560,
1531, 1512, 1485, 1466, 1446, 1431, 1392, 1342, 1331, 1288,
1265, 1253, 1221, 1207, 1167, 1138, 1088, 1001, 962;
1H NMR (400 MHz, CDCl3): ¤ 9.10 (d, 1H, J = 1.0 Hz), 8.14
(d, 1H, J = 8.3 Hz), 7.99 (brd, 1H, J = 8.3 Hz), 7.96 (d, 1H,
J = 9.1 Hz), 7.73 (dd, 1H, J = 9.1, 0.9 Hz), 7.69 (ddd, 1H,
J = 9.1, 7.1, 1.2 Hz), 7.57 (ddd, 1H, J = 9.1, 7.1, 1.2 Hz);
13C NMR (101 MHz, CDCl3): ¤ 162.2, 144.9, 131.7, 130.4,
129.0, 128.6, 126.7, 125.6, 123.2, 116.4, 110.2; Anal. Found:
C, 77.94; H, 4.33; N, 8.14%. Calcd for C11H7NO: C, 78.09; H,
4.17; N, 8.28%; mp 77.5 °C.
1444, 1429, 1367, 1298, 1192, 1011, 957 cm¹1; H NMR (400
1
MHz, CDCl3): ¤ 8.34 (d, 1H, J = 8.7 Hz), 7.23 (d, 1H, J =
2.2 Hz), 7.17 (dd, 1H, J = 8.7, 2.2 Hz), 6.91 (d, 1H, J =
9.3 Hz), 6.50 (d, 1H, J = 9.3 Hz), 2.34 (s, 3H); 13C NMR (101
MHz, CDCl3): ¤ 179.1, 168.9, 153.9, 138.9, 127.4, 126.5,
120.1, 117.5, 116.7, 77.5, 21.1; HRMS (FAB+): Found: m/z
229.0645. Calcd for C12H9N2O3: (M + H)+, 229.0613; mp
107-115 °C.
7-Acethoxy-2-diazo-1(2H)-naphthalenone (19):
IR
¹1
(neat): 2109, 1761, 1624, 1580, 1213 cm
;
1H NMR (400
MHz, CDCl3): ¤ 8.01 (d, 1H, J = 2.4 Hz), 7.51 (d, 1H, J =
8.5 Hz), 7.36 (dd, 1H, J = 8.5, 2.4 Hz), 6.87 (d, 1H, J =
9.4 Hz), 6.57 (d, 1H, J = 9.4 Hz), 2.34 (s, 3H);13C NMR (101
MHz, CDCl3): ¤ 179.1, 169.3, 149.4, 135.3, 130.4, 129.5,
126.5, 117.6, 116.4, 116.2, 77.1, 21.0; HRMS (FAB+): Found:
m/z 229.0645. Calcd for C12H9N2O3: (M + H)+, 229.0613.
1-Cyano-2-naphthol (14):27 1H NMR (400 MHz, CDCl3):
¤ 8.03 (d, 1H, J = 8.3 Hz), 7.95 (d, 1H, J = 9.0 Hz), 7.82
(d, 1H, J = 8.1 Hz), 7.65 (ddd, 1H, J = 8.2, 7.0, 1.2 Hz), 7.46
(ddd, 1H, J = 8.1, 7.1, 1.0 Hz), 7.18 (d, 1H, J = 9.0 Hz);
13C NMR (101 MHz, CDCl3): ¤ 162.2, 135.3, 132.9, 129.1,
128.6, 128.0, 125.2, 123.9, 117.4, 115.7, 92.7.
6-Acethoxy-1-diazo-2(1H)-naphthalenone (21):
IR
(ATR): 3423, 2923, 2852, 2096, 1766, 1624, 1572, 1483,
2,4-Bis(diazo)-1,3(2H,4H)-naphthalenedione (16):4g IR
1363, 1217, 1147, 1020, 906 cm¹1; H NMR: ¤ 7.59 (d, 1H,
1
¹1
(ATR): 2919, 2597, 2348, 2088, 2026, 1687, 1591 cm
;
J = 9.8 Hz), 7.36-7.34 (m, 1H), 7.28-7.26 (m, 2H), 6.71 (d,
1H, J = 9.8 Hz), 2.34 (s, 3H); 13C NMR: ¤ 179.9, 169.4, 147.5,
139.4, 126.8, 126.2, 124.7, 123.7, 122.3, 120.6, 68.1, 21.0;
HRMS (FAB+): Found: m/z 229.0640. Calcd for C12H9N2O3:
(M + H)+, 229.0613; mp 143-148 °C (dec).
1H NMR (400 MHz, CDCl3): ¤ 8.24 (dd, 1H, J = 8.0, 1.2 Hz),
7.65 (ddd, 1H, J = 8.0, 8.0, 1.2 Hz), 7.33 (ddd, 1H, J = 8.0,
8.0, 1.0 Hz), 7.15 (brd, 1H, J = 8.0 Hz); 13C NMR (101 MHz,
CDCl3): ¤ 176.6, 173.6, 134.3, 127.7, 127.4, 125.6, 120.1,
120.1, 84.2; HRMS (FAB+): Found: m/z 213.0387. Calcd for
C10H4N4O2: (M + H)+, 213.0414; mp 180-183 °C.
7-Acethoxy-1-diazo-2(1H)-naphthalenone (22):
IR
(ATR): 2212, 2088, 1765, 1714, 1622, 1575, 1487, 1440,
1
Typical Procedure for the Preparation of Diazonaphtho-
quinones Having Acetoxy Group by the Reaction of Naph-
thalenediols with 2-Azide-1,3-dimethylimidazolinium Chlo-
ride 5a and the Successive Acetylation (Table 5, Run 2). To
a solution of 2-chloro-1,3-dimethylimidazolinium chloride 7
(228 mg, 1.35 mmol) in acetonitrile (2 mL), sodium azide (99.4
mg, 1.5 mmol) and 15-crown-5 ether (0.06 ml, 0.3 mmol) was
1394, 1369, 1288, 1213, 1009, 918 cm¹1; H NMR: ¤ 7.59 (d,
1H, J = 9.8 Hz), 7.55 (d, 1H, J = 8.4 Hz), 7.01 (d, 1H, J =
2.0 Hz), 6.98 (dd, 1H, J = 8.4, 2.0 Hz), 6.61 (d, 1H, J =
9.8 Hz), 2.33 (s, 3H); 13C NMR: ¤ 179.7, 169.0, 151.8, 139.6,
131.2, 128.7, 125.6, 123.3, 118.7, 112.5, 77.5, 21.1; HRMS
(FAB+): Found: m/z 229.0629. Calcd for C12H9N2O3:
(M + H)+, 229.0613; mp 103-105 °C (dec).
832 | Bull. Chem. Soc. Jpn. 2015, 88, 824–833 | doi:10.1246/bcsj.20150021
© 2015 The Chemical Society of Japan

Seidl, M. N. da Silva, M. C. B. V. da Souza, A. V. Pinto, J. L.
Wardell, S. M. S. V. Wardell, Magn. Reson. Chem. 2006, 44, 481.
This work was supported by a Grant-in-Aid from the
Ministry of Education, Culture, Sports, Science and Technol-
ogy of Japan. This work was performed under the Cooperative
Research Program of “Network Joint Research Center for
Materials and Devices.”
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Bull. Chem. Soc. Jpn. 2015, 88, 824–833 | doi:10.1246/bcsj.20150021
© 2015 The Chemical Society of Japan | 833