1
972 J . Org. Chem., Vol. 61, No. 6, 1996
Cui et al.
2
-Naphthol (Aldrich, 98%) was purified by precipitation with
2-acetamidonaphthalene (mp 133-134 °C; lit.16 mp 132 °C),
concd HCl from aqueous base and recrystallization (benzene/
3
1.9 g (14 mmol) of anhyd AlCl , and 25 mL of methylene
4
5
heptane) to yield mp 122.5-123.0 °C (lit. mp 122-123 °C).
-Naphthyl acetate (Aldrich, 98%) was distilled (by 111 °C/
.9 mm) and recrystallized twice from hexane to yield white
crystals, mp 71.0-71.5 °C (lit. mp 71-72 °C, 70 °C ).
2
chloride were stirred in a round bottom flask at ambient
temperature for 1 h under a dry atmosphere. Sequentially,
50 mL of ice-cold water and 15 mL of concd HCl were added
slowly. The organic layer was separated and evaporated to
2
0
4
6
47
-Na p h th yl Myr ista te (1b). 2-Naphthol (7.0 g, 49 mmol)
residue. The residue was dissolved in ether, dried (anhyd Na
2
-
and myristoyl chloride (Aldrich 98%, 15 mL, 55 mmol) were
dissolved in 20 mL of benzene and were refluxed for 3 h under
a dry atmosphere. Standard workup and recrystallization (2×)
from 1-butanol afforded 2-naphthyl myristate as white crystals
SO ), and eluted on a silica gel column with 1/1 (v/v) hexane/
4
ethyl acetate to afford 0.7 g (65%) of colorless crystals, mp 89-
90 °C. IR (KBr): 3292, 3040, 2933, 2847, 1675, 1665, 1584
-
1
1
cm
(t, J ) 7.1 Hz), 2.20 (s), 1.81 (q), 1.77-1.10 (m), 0.87 ppm (t,
J ) 7.0 Hz). Mass m/z calcd for C26 395, found 395.
.
3
H NMR (CDCl /TMS): δ 8.46-7.40 (m), 7.50 (s), 3.05
(
1
2
15.0 g, 87%): mp 64.5-65.0 °C. IR (CCl
4
): 3061, 2926, 2855,
/TMS): δ 7.67-7.20 (m),
.61 (t, J ) 7.5 Hz), 1.84 (q, J ) 7.2 Hz), 1.54-1.27 (m), 0.88
-
1
1
761, 1632 cm
.
H NMR (CDCl
3
H37NO
2
2-Am in o-8-m yr istoyln a p h th a len e. 2-Acetamido-8-myris-
toylnaphthalene (0.5 g, 1.3 mmol), 5.0 mL of glacial acetic acid,
and 1.0 mL of 18 N sulfuric acid were refluxed in a round
bottom flask for 4 h and cooled to room temperature. Water
(10 mL) and then sufficient 30% aqueous NaOH were added
to cause precipitation of 0.45 (95%) of yellow solid, mp 97-
-
5
(
2
t, J ) 6.6 Hz). UV/vis (ethyl acetate, 9.2 × 10 M) λmax(ꢀ)
76 (3790), 304 (309), 318 nm (276). Mass m/z calcd for
354, found 354.
-Myr istoyl-2-n a p h th ol (1-3b) was synthesized by a modi-
fication of the method of Fries for the preparation of 1-acetyl-
24 34 2
C H O
1
1
3
-1
1
2
-naphthol. After recrystallization of the crude product from
100 °C. IR (KBr): 3372, 2927, 2848, 1679, 1621 cm
NMR (CDCl /TMS): δ 8.37-7.13 (m), 6.60 (s), 2.82 (t, J ) 7.2
Hz), 1.80 (q), 1.80-1.10 (m), 0.85 ppm (t, J ) 7.0 Hz). Mass
m/z calcd for C24 35NO 353, found 353.
.
H
hexane, a yellow solid, mp 43.5-44.5 °C, was obtained in 60%
3
yield. IR (CCl
CDCl /TMS): δ 12.22 9s), 8.05-7.13 (m), 3.17 (t, J ) 7.2 Hz),
.81 (q, J ) 6.9 Hz), 1.55-1.25 (m), 0.88 ppm (t, J ) 6.3 Hz).
4
): 3060, 2990, 2950, 2890, 1650 cm-
1
. H NMR
1
(
1
3
H
8-Myr istoyl-2-n a p h th ol (8-3b). Sodium nitrite (0.11 g, 1.6
mmol), 0.5 g (1.4 mmol) of 2-amino-8-myristoylnaphthalene,
and 20 mL of glacial acetic acid were stirred at 16 °C for 20
min, heated to boiling, and cooled to room temperature. Water
(50 mL) and the mixture was extracted with ethyl ether (3 ×
-
5
UV/vis (ethyl acetate, 7.6 × 10 M): λmax(ꢀ) 254 (6690), 312
3740), 338 (2720), 360 (2760). Mass m/z calcd for C24
54, found 354.
(
34 2
H O
3
2
-Meth oxy-6-m yr istoyln a p h th a len e, mp 73.0-73.5 °C,
was prepared from 2-methoxynaphthalene and myristoyl
chloride in 33% yield by a modification of the method for the
2
20 mL). The organic layers were combined, dried (anhyd Na -
4
SO ), and treated with Darco decolorizing carbon. The residue
4
8
preparation of 6-acetyl-2-methoxynaphthalene.
IR (CCl
4
):
obtained after removing ether was eluted on a silica gel column
10/1 (v/v) hexane/ethyl acetate. Recrystallization from metha-
nol/water afforded 0.15 g (30%) of 8-myristoyl-2-naphthyl
acetate, mp 50-51 °C, as light yellow, cottonlike needles. It
3
090, 2920, 2850, 1700, 1630, 1600 cm-1
.
1
H NMR (CDCl /
3
TMS): δ 8.40-7.15 (m), 3.95 (s), 3.07 (t, J ) 7.5 Hz), 1.78 (q,
J ) 7.2 Hz), 1.55-1.26 (m), 0.88 ppm (t, J ) 6.3 Hz). UV/vis
-
5
16
(
2
3
ethyl acetate, 5.4 × 10 M) λmax(ꢀ) 242 (8800), 246 (8000),
was hydrolyzed and separated by semipreparative TLC
60 (26000), 306 (nm) 10500). Mass m/z calcd for C25
H
36
O
2
(Kieselgel 60; eluent 10/1 (v/v) hexane/ethyl acetate). The
yellow oil solidified (mp 56-57 °C) after refrigeration at -15
68, found 368.
°
cm
C for 24 h. IR (KBr): 3225, 2925, 2850, 1650, 1608, 1600
6
-Myr istoyl-2-n a p h th ol (6-3b). The procedure for dem-
-
1
1
.
3
H NMR (CDCl /TMS): δ 8.27-7.17 (m), 6.09 (br s),
ethylation of 2-methoxy-6-myristoylnaphthalene was adapted
from the one used with 6-acetyl-2-methoxynaphthalene.17
3.06 (t, J ) 7.3 Hz), 1.77 (q, J ) 7.7 Hz), 1.70-1.10 (m), 0.87
-
4
ppm (t, J ) 7.0 Hz). UV/vis (methanol, 2.16 × 10 M): λmax
ꢀ) 348 (4100), 230 (32000). Mass m/z calcd for C24 354,
found 354.
1-Acetyl-2-n a p h th ol (1-3a ).13 2-Naphthyl acetate (1.0 g,
.4 mmol) and 1.5 g (12 mmol) of anhydr AlCl were heated in
-
Yellow-brown needles, mp 99.0-99.5 °C, were obtained in 68%
yield after two recrystallizations of the crude product from
(
34 2
H O
-
1
ethyl acetate. IR (CCl
4
): 3590, 3040, 2910, 2850, 1700 cm
;
-1
1
IR (KBr): 1660 cm
.
H NMR (CDCl /TMS): δ 8.41-7.15 (m),
3
5
3
5
1
1
.18 (br s), 3.08 (t, J ) 7.2 Hz), 1.78 (q, Q ) 7.2 Hz), 1.39-
a round bottom flask for 5 h at 70 °C under a dry atmosphere
and then cooled to room temperature. Dilute HCl was added,
and the mixture was extracted with ether. The ether layer
.26 (m), 0.88 (t, J ) 6.3 Hz). UV/vis (ethyl acetate, 1.9 ×
-
5
0
M) λmax(ꢀ) 260 (24300), 312 nm (8950). Mass m/z calcd
for C24
34 2
H O 354, found 354.
2 4
was dried (anhyd Na SO ) and evaporated to a residue. Two
3
-Myr istoyl-2-n a p h th ol (3-3b). Under an argon atmo-
recrystallizations from hexane afforded 0.3 g (30%) of a light
sphere, 0.6 mL of a 10.0 M solution of n-butyllithium in hexane
was added rapidly by syringe to a cold (dry ice/acetone bath)
solution of 1.0 mL (4 mmol) of 1-bromotridecane in 20 mL of
dry THF. It was stirred for 15 min at 0 °C, and then a solution
of 0.15 g (0.8 mmol) of 3-hydroxy-2-naphthoic acid (Aldrich,
yellow solid, mp 62.0-63.0 °C (lit.13 mp 64 °C). HPLC analyses
-
1
4
indicated ca. 95% purity. IR (CCl ): 3040, 2980, 1630 cm .
1
H NMR (CDCl
s). UV/vis (ethyl acetate, 6.9 × 10 M): λmax(ꢀ) 254 (9200),
02 (6800), 356 nm (4030). Mass m/z calcd for C12 186,
found 186.
-Acetyl-2-n a p h th ol (3-3a ) was prepared by the method
3
/TMS): δ 13.50 (br s), 8.11-7.13 (m), 2.88 ppm
-
5
(
3
10 2
H O
9
8%) in 5.0 mL of dry THF (5.0 mL) was injected via syringe.
After being stirred for 30 min at 0 °C, the reaction mixture
was poured into 150 mL of dilute HCl and extracted with 100
mL of ethyl ether. The ether was washed thrice with water
3
1
4
of Rubottom and Kim in 38% yield: mp 109.0-111.5 °C (lit.
1
5
49
mp 110.0-111.8 °C, 112 °C ). UV/vis (ethyl acetate, 1.8 ×
and dried (anhyd Na
the ether, was eluted on a 60-200 mesh silica gel column with
50 mL of hexane and then 1/40 (v/v) ethyl acetate/hexane.
2 4
SO ). The residue, after evaporation of
-5
1
0
M): λmax(ꢀ) 256 (44000), 290 (20000), 384 nm (1800). Mass
m/z calcd for C12 10O2 186, found 186.
-Acetyl-2-m eth oxyn a p h th a len e. Under a dry atmo-
sphere, 8.5 g (64 mmol) of powdered anhyd AlCl was added
H
1
5
0
6
Further purification by semipreparative TLC (Kieselgel 60;
eluent: 1/40 (v/v) hexane/ethyl acetate) afforded a yellow solid
which became yellow-green needles (0.1 g, 36%), mp 78.5-
3
gradually with stirring to an ice-cold solution of 5.0 g (32 mmol)
of 2-methoxynaphthalene (Aldrich, 98%) and 2.4 mL (43 mmol)
of acetyl chloride in 20 mL of nitrobenzene. After the mixture
was stirred for 24 h, ice and dilute HCl were added, and the
nitrobenzene was removed by steam distillation. The remain-
ing liquid was extracted with chloroform. The fraction of the
organic layer distilling at 195-200 °C/10 mm was recrystal-
lized twice from hexane to afford 2.8 g (49%) of 6-acetyl-2-
7
2
8
1
9.0 °C, after recrystallization from hexane. IR (CCl
4
): 3080,
930, 2855, 1657 cm-1
1
.
H NMR (CDCl /TMS): δ 11.72 (s),
3
.40-7.29 (m), 3.18 (t, J ) 7.0 Hz). UV/vis (methanol, 1.1 ×
-
5
0
M): λmax(ꢀ) 245 (56000), 291 (11500), 310 (12000), 384
354, found 354.
-Aceta m id o-8-m yr istoyln a p h th a len e. Myristoyl chlo-
ride (Aldrich, 98%; 0.9 g, 3.6 mmol), 0.5 g (2.7 mmol) of
nm (2400). Mass m/z calcd for C24
34 2
H O
2
5
0
methoxynaphthalene as white flakes, mp 103.0-104.5° (lit.
mp 104-105 °C). IR (CCl ): 3050, 3010, 2890, 2850, 1690,
4
(
(
(
(
45) Franzen, H. Ber. 1917, 50, 104.
46) Chattaway, F. D. J . Chem. Soc. 1931, 2495.
47) Hodgson, H. H. J . Chem. Soc. 1942, 747.
48) Haworth, R. D.; Sheldrik, G. J . Chem. Soc. 1934, 864.
(49) Fries, K. Ber. 1925, 58, 2835.
(50) Baker, W.; Carruthers, G. N. J . Chem. Soc. 1938, 479.