Chemoselective method for the synthesis of 4-allyl-4-hydroxycyclohexa-2,5-dienone derivatives from 1,4-quinones by an indium-mediated allylation protocol

Article abstract of DOI:10.1016/S0040-4020(02)00133-3

Allyl indium halide on reaction with 1,4-quinones produced 4-allyl-4-hydroxycyclohexa-2,5-dienone derivatives. Unsymmetrical quinones show high chemoselectivity in addition of allyl indium halide reagent to the carbonyl group.

Full text of DOI:10.1016/S0040-4020(02)00133-3

TETRAHEDRON
Pergamon
Tetrahedron 58 =2002) 2847±2852
Chemoselective method for the synthesis of 4-allyl-4-
hydroxycyclohexa-2,5-dienone derivatives from 1,4-quinones
by an indium-mediated allylation protocol
Dipanjan Pan, Sajal K. Mal, Gandhi K. Kar and Jayanta K. Rayp
Department of Chemistry, Indian Institute of Technology, Kharagpur 721 302, West Bengal, India
Received 24 November 2001; accepted 7 February 2002
AbstractÐAllyl indium halide on reaction with 1,4-quinones produced 4-allyl-4-hydroxycyclohexa-2,5-dienone derivatives. Unsymme-
trical quinones show high chemoselectivity in addition of allyl indium halide reagent to the carbonyl group. q 2002 Elsevier Science Ltd. All
rights reserved.
The use of allyl indium halides1 as organometallic reagents
for the allyl group transfer has gained importance in the last
few years due to its generality, mild, easy and high yielding
reaction conditions. Various homoallylic alcohols2,3 homo-
allylvinylcyclopropanes4 and gem diallylbutenolides/
phthalides5 have been synthesised by reaction of such
reagents with suitable aldehydes/ketones,2 hydrazones,6
azetidinones,7 epoxides,8 acid anhydrides5 etc. In connec-
tion with our studies toward the preparation of sol±gel
glass9 through polymerisation of triethoxysilane derivatives
of polyarenes we were in need of some polyallylated
polyarene systems, which can easily be converted to
the triethoxysilane derivatives via hydrosilylation with
=EtO)3SiH and Spier's catalyst =Fig. 1).10
synthesis of some 4-allyl-4-hydroxycyclohexa-2,5-dienone
derivatives by reaction of suitable 1,4-quinone derivatives
with allyl indium iodides =Scheme 1). Thus 1,2-dihydroxy-
9,10-anthraquinone =alizarin) =1) =1equiv.) was treated with
allylindium iodide generated in situ by reaction with indium
metal =1.05 equiv.) and allyl bromide =1.55 equiv.) in the
presence of NaI =1.55 equiv.) in DMF =3 mL) to furnish
10-allyl-3,4,10-trihydroxy-10H-anthracen-9-one =6) in 71 %
yield. =Table 1, entry 1) Out of the two carbonyl groups only
one was found to react with the reagent while the other
remained unaffected despite the use of excess of reagents.
Similarly compound 2 under the said reaction condition
Though the reaction of allyl indium halide with 1,2-or 1,3
diketones11,12 are known, to the best of our knowledge, there
are two reports13a,b on studies of the reaction of allyl indium
halides with 1,4-diketones or 1,4 benzoquinone derivative
only. However there is a report on allylation of 1,4-quinones
using Cd as catalyst.13c Here we report our results on the
Scheme 1.
Figure 1.
Keywords: 1,4-quinone derivatives; allyl indium halide; allylation; chemoselective addition; 2,5-cyclohexadienones.
Corresponding author. Tel.: 191-3222-83326; fax: 191-3222-755303; e-mail: jkray@chem.iitkgp.ernet.in
p
0040±4020/02/$ - see front matter q 2002 Elsevier Science Ltd. All rights reserved.
PII: S0040-4020=02)00133-3

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D. Pan et al. / Tetrahedron 58 '2002) 2847±2852
Table 1. Allylation of anthraquinone derivatives
However the reactions of 1,4-benzoquinones or 1,4-
naphthoquinones with allylindium reagents were not so
smooth and non-uniform results were obtained depending
on the substrate and reaction conditions employed =Figure 4)
=Table 2).
Entry
Anthraquinone derivative
Product =yield %)a
1
2
3
4
5
1
2
3
4
5
6 =71)
7 =66)
8 =61)
9 =70)
10 =68)
Thus, reactions of p-benzoquinone =11) with allylindium
iodide at room temperature or at 2238C afforded no cyclo-
hexadienone derivatives but the 2-allylhydroquinone 18
as the only isolable product =Table 2, entry 6) whereas its
a
Isolated yield.
Table 2. Allylation of 1,4-benzoquinone and 1,4-naphthoquinone derivatives
Entry
1,4-Benzo-/naphthoquinone
derivatives
Product =yield)
Room temperature
2238C
6
7
8
9
10
11
12
13
11
12
13
14
15
15
16
17
181other products =72%)
19 =69%)
18 =73%)
20 =61%)
21 =74%)
22 =59%)
24 =51%)
±
22 =50%)
23 =69%)
25 =63%)
26127 =73%) =1.6:1)
±
±
26127 =73%) =1.6:1)
28129 =73%) =1:1.4)
afforded 7 as a white solid in very good yield =entry 2).
Other 1,4-quinone derivatives also behaved in a similar
way =Figure 3) =entries 3,4 and entry 5) where 2-methyl
allylindium halide was used for allylation. In the case of
unsymmetrical quinones high chemoselectivity was
observed towards the addition of the reagent on the carbonyl
group in close proximity to the OH/OR group =entries 1±4).
This is probably due to the participation of the lone pair of
electrons of oxygen in coordination with the reagent. The
reactions were very clean and produced the desired product
in high yield. The results are summarised in Table 1.
2,5-dimethyl analogue =12) under identical conditions
produced
4-allyl-4-hydroxy-2,5-dimethylcyclohex-2,5-
dienone =20), at 2238C and the product formed at room
temperature was found to be the hydroquinone derivative
19 =entry 7). Compound 19 is possibly formed via re-
arrangement of 20 as indicated by the fact that when pure
20 is stirred at room temperature with SiO2 in chloroform, it
is converted to 19. A possible pathway for such conversion
may be as in Scheme 2.
In entry 6, use of low temperature furnished a cleaner
product in high yield whereas the reaction at room tempera-
ture furnished 18 along with some unidenti®ed side products
in very minor amounts.
In the case of compound 13 the addition was found to be
directed by the presence of the heteroatom at 2-position of
the carbonyl moiety. Thus compound 13, on treatment with
allyl bromide/In/NaI in DMF at 2238C produced 21 as the
only isolable product in 74% yield where the allyl group
reacted with the C1-carbonyl group adjacent to the SPh
Scheme 2.
Figure 2. Representative 1H NMR data of compound 9.

D. Pan et al. / Tetrahedron 58 '2002) 2847±2852
2849
Figure 3.
moiety and the other carbonyl moiety C4 remained unaf-
fected =entry 8). Compound 14 also reacted in a similar
fashion to furnish compound 22 as the only isolable product
both at room temperature and at 2238C, however the yield
at 2238C was better =,59%) compared to that at room
temperature =50%) =entry 9). In the case of 1,4-naphtho-
quinones such as compound 15, allylation =at room tempera-
ture) with allyl/2-methylallyl indium halides furnished
4-hydroxycyclohexadienone derivatives 23 and 25, respec-
tively, while the reaction of allyl indium halide with 15 at
Figure 4.

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D. Pan et al. / Tetrahedron 58 '2002) 2847±2852
2238C produced 2-allyl-1,4-dihydroxynaphthalene =24) as
the only product in 51% yield =entries 10 and 11). In the case
of 16 or 17 the reaction was found to be less chemoselective
due to the increased peri interaction. Thus compound 16 on
reaction with allylbromide/In/NaI in DMF at 2238C and at
room temperature produced a mixture of 26 and 27 in the
ratio 1.6:1. Here the major product 26 resulted through the
allylation of the C1 carbonyl assisted by ±SPh participation
with the allyl indium reagent =entry 12). Interestingly, the
ratio of products 28 and 29 formed from allylation of
8-methoxy-2-phenylsulfanyl-1,4-naphthoquinone =17) was
just the reverse of the above result =entry 13). Here, to the
presence of an extra methoxy group at position 8 of the
naphthoquinone moiety further increased the peri inter-
action at the C1 carbonyl.
acetate and the organic layer was thoroughly washed with
water and dried =Na2SO4). Removal of solvent under
reduced pressure followed by puri®cation of the residue
obtained furnished the 4-hydroxy-4-allyl cyclohexa-2,5-
dienone derivatives or the hydroquinone derivatives in
35±74% yield.
1.2.1. 10-Allyl-3,4,10-trihydroxy-10H-anthracen-9-one
+6). Yellow solid, mp 152±1548C =CHCl3±petroleum
ether 60±808C), yield 71%; IR =KBr) nmax 3199 =br), 3303
=br), 3393 =br) cm21; 1H NMR =CDCl3) d 2.74 =dd, 1H, Jˆ
7.4, 12.8 Hz), 2.99 =dd, 1H, Jˆ7.2, 12.8 Hz), 3.25±4.10 =br,
1H, exchangeable with D2O), 4.58 =brd, 1H, Jˆ16.8 Hz),
4.76 =dd, 1H, Jˆ1.8, 10.1 Hz), 4.95±5.12 =m, 1H), 6.10±
6.40 =br, 1H, exchangeable with D2O), 6.95 =d, 1H, Jˆ
8.5 Hz), 7.39±7.47 =m, 1H), 7.60±7.68 =m, 1H), 7.66 =d,
1H, Jˆ8.5 Hz), 7.78 =d, 1H, Jˆ7.7 Hz), 8.07 =d, 1H, Jˆ
7.8 Hz), 8.91=brs, 1H, exchangeable with D 2O); 13C NMR
=CDCl3) d 48.45, 75.99, 115.21, 120.51, 121.27, 124.73,
127.03, 128.57, 129.50, 130.58, 133.31, 141.30, 144.62,
150.07, 180.39. Anal. Calcd for C17H14O4: C, 72.34; H,
4.96. Found: C, 72.05; H, 4.78.
Thus despite the co-ordination of ±SPh group with the
reagent the steric factors controlled the product and it is
the less hindered carbonyl group at C4 that reacted in prefer-
ence over the other carbonyl group to form a mixture of 28
and 29 in the ratio of 1:1.4 in the reaction mixture =entry 13)
=ratio of the products in each case was determined from the
1H NMR spectra).
1.2.2. 10-Allyl-4,10-dihydroxy-3-methoxy-10H-anthra-
cen-9-one +7). Yellow viscous liquid, yield 66%; IR
The results are summarised in Table 2. The compounds
were characterised by usual spectroscopic methods and
analysis. A representative H NMR data of compound 9 is
shown in Fig. 2. Thus we describe a high yielding general
method for the synthesis of 4-hydroxy-4-allylcyclohexa-
2,5-dienone derivatives of 1,4-quinones by an indium
mediated allylation protocol =Figs. 3 and 4).
1
=KBr) nmax 1642, 3387 =br) cm21; H NMR =CDCl3) d
1
2.70 =dd, 1H, Jˆ7.3, 12.7 Hz), 3.00 =dd, 1H, Jˆ7.4,
12.7 Hz), 3.88 =s, 3H), 4.44±4.70 =m, 2H), 4.80 =brs, 1H),
4.92±5.06 =m, 1H), 6.87 =d, 1H, Jˆ8.7 Hz), 7.38±7.46
=m, 1H), 7.57±7.66 =m, 2H), 7.73 =d, 1H, Jˆ8.7 Hz), 7.81
=brd, 1H, Jˆ7.7 Hz), 8.09 =dd, 1H, Jˆ1.3, 7.8 Hz). Anal.
Calcd for C18H16O4: C, 72.97; H, 5.40. Found: C, 72.68; H,
5.15.
1. Experimental
1.1. General
1.2.3. 10-Allyl-3-allyloxy-4,10-dihydroxy-10H-anthra-
cen-9-one +8). Yellow oil =column chromatography,
CH2Cl2±etherˆ8:2), yield 61%; IR =KBr) nmax 1639, 3199
1
=br), 3393 =br) cm21; H NMR =CDCl3) d 1.71 =brs, 1H),
All melting points are uncorrected and recorded in one-side
open glass capillaries using a sulfuric acid bath. Dimethyl
formamide was dried and distilled prior to use according to
the standard procedure. Indium metal was purchased from
SRL India Ltd. NMR spectra were recorded on 200 or
2.77 =dd, 1H, Jˆ7.3, 12.7 Hz), 3.12 =dd, 1H, Jˆ7.3,
12.7 Hz), 4.49±4.81 =m, 4H), 4.94±5.11 =m, 1H), 5.35±
5.51 =m, 2H), 6.04±6.12 =m, 1H), 6.98 =d, 1H, Jˆ
8.6 Hz), 7.34 =brs, 1H), 7.42±7.49 =m, 1H), 7.61±7.69 =m,
1H), 7.83 =d, 1H, Jˆ8.6 Hz), 7.86 =brd, 1H, Jˆ7.9 Hz), 8.17
=brd, 1H, Jˆ7.8 Hz); 13C NMR =CDCl3) d 49.47, 69.86,
73.71, 111.63, 119.02, 119.43, 120.60, 124.90, 125.52,
126.49, 127.84, 130.17, 130.48, 131.30, 132.02, 133.14,
142.52, 145.29, 149.84, 182.39. Anal. Calcd for C20H18O4:
C, 74.53; H, 5.59. Found: C, 74.24; H, 5.41.
Ê
500 MHz Bruker spectrometer in CDCl3 =dried with 4 A
molecular sieves) as solvent. Coupling constant =J) values
are given in Hz. IR spectra were recorded on a Perkin±
Elmer 800 machine. Elemental values were obtained from
CDRI, Lucknow. TLC was performed on pre-coated silica
gel plates =Fluka). Yields of the products refer to spectro-
scopically homogenous substances.
1.2.4. 10-Allyl-3,4-bis-allyloxy-10-hydroxy-10H-anthra-
cen-9-one +9). Yellow oil =column chromatography,
CH2Cl2±etherˆ8:2), yield 70%; IR =KBr) nmax 1661, 3429
1.2. General method for the synthesis of 4-hydroxy-4-
allyl cyclohexa-2,5-dienone derivatives
=br) cm21
;
1H NMR =CDCl3) d 2.80 =dd, 1H, Jˆ7.6,
12.8 Hz), 2.96 =dd, 1H, Jˆ7.6, 12.8 Hz), 4.53 =dd, 1H, Jˆ
1.3, 17.0 Hz), 4.70±4.73 =m, 3H), 4.84 =d, 2H, Jˆ5.6 Hz),
5.03±5.11 =m, 1H), 5.29 =brs, 1H, exchangeable with D2O),
5.37 =dd, 1H, Jˆ0.7, 10.5 Hz), 5.41 =brd, 1H, Jˆ10.5 Hz),
5.48 =dd, 1H, Jˆ1.5, 17.2 Hz), 5.53 =dd, 1H, Jˆ1.1,
17.2 Hz), 6.08±6.15 =m, 1H), 6.18±6.26 =m, 1H), 7.06 =d,
1H, Jˆ8.7 Hz), 7.45 =brt, 1H, Jˆ7.8 Hz), 7.67 =m, 1H), 7.93
=brd, 1H, Jˆ8.0 Hz), 8.07 =d, 1H, Jˆ8.7 Hz), 8.19 =dd, 1H,
Jˆ1.4, 7.8 Hz). Anal. Calcd for C23H22O4: C, 76.24; H,
6.08. Found: C, 76.08; H, 5.89.
To a stirred suspension of In-metal =1.05 mmol) and sodium
iodide =1.55 mmol), in dry DMF =2±3 mL) at room
temperature allyl bromide =or 2-methyl allyl bromide)
=1.55 mmol) was added dropwise. The stirring was con-
tinued at room temperature until all the indium metal
dissolved. To this a solution of 1,4-quinone derivatives in
DMF =1±2 mL) was added dropwise and stirred further for
3±5 h =completion of the reaction was checked by TLC).
The reaction mixture was quenched with a few drops of dil
HCl and diluted with water. It was then extracted with ethyl

D. Pan et al. / Tetrahedron 58 '2002) 2847±2852
2851
1.2.5. 10-Hydroxy-10-+2-methyl-allyl)-10H-anthracen-9-
one +10). White solid, mp 116±1188C =CHCl3±petroleum
ether 60±808C), yield 68%; IR =KBr) nmax 1658, 3490
ture mp 142±1438C)16 yield 51%; 3.48±3.52 =m, 2H), 5.08±
5.27 =m, 2H), 4.9±5.3 =br, 2H), 5.95±6.11 =m, 1H), 6.61 =s,
1H), 7.45±7.55 =m, 2H), 8.05±8.15 =m, 2H).
1
=brs) cm21; H NMR =CDCl3) d 0.93 =d, 3H, Jˆ1.0 Hz),
1.2.13. 4-Hydroxy-4-+2-methyl-allyl)-4H-naphthalen-1-
one +25). White solid, mp 81±838C, =CHCl3±petroleum
ether 60±808C), yield 63%; IR =KBr) nmax 1648, 3375
2.69 =s, 3H), 3.86 =brs, 1H), 4.56 =m, 1H), 7.43±7.51 =m,
2H), 7.62±7.70 =m, 2H), 7.93 =brd, 2H, Jˆ7.3 Hz), 8.18 =dd,
2H, Jˆ1.4, 7.7 Hz); 13C NMR =CDCl3) d 23.68, 56.62,
73.14, 117.03, 125.97, 128.89, 128.12, 131.38, 133.26,
139.26, 139.33, 147.02, 180.11. Anal. Calcd for C18H16O2:
C, 81.81; H, 6.06. Found: C, 81.63; H, 5.84.
1
=br) cm21; H NMR =CDCl3) d 1.47 =s, 3H), 1.67 =brs,
1H), 2.55±2.76 =m, 2H), 4.52±4.53 =m, 1H), 4.80±4.83
=m, 1H), 6.32 =d, 1H, Jˆ10.3 Hz), 6.97 =d, 1H, Jˆ
10.3 Hz), 7.38±7.46 =m, 1H), 7.58±7.66 =m, 1H), 7.76
=dd, 1H, Jˆ1.2, 7.7 Hz), 8.03 =dd, 1H, Jˆ1.3, 7.8 Hz).
Anal. Calcd for C14H14O2: C, 78.50; H, 6.54. Found: C,
78.27; H, 6.28.
1.2.6. 2-Allyl-benzene-1,4-diol +18). White solid, mp 90±928C
=CHCl3±petroleum ether 60±808C), =Literature mp 938C),14
1
yield 73%; IR =KBr) nmax 3460 cm21; H NMR =CDCl3) d
3.33 =d, 2H, Jˆ6.3 Hz), 4.41 =brs, 1 H), 4.35 =brs, 1 H), 5.09±
1.2.14. 4-Allyl-4-hydroxy-3-phenylsulfanyl-4H-naphtha-
len-1-one +26). =Isolated), yellow viscous oil =column
chromatography, CH2Cl2±etherˆ8:2), yield 35%; IR
5.18 =m, 2H), 5.90±6.10 =m, 1H), 6.57±6.75 =m, 3H).
1.2.7. 3-Allyl-2,5-dimethyl-benzene-1,4-diol +19). White
solid, mp 138±1408C =CHCl3±petroleum ether 60±808C),
=Literature mp 141±1428C),15 yield 69%; 1H NMR =CDCl3)
d 2.15 =s, 3H), 2.18 =s, 3H), 3.41±3.45 =m, 2H), 4.35 =brs,
1H, exchangeable with D2O), 4.41=brs, 1H, exchangeable
with D2O), 4.96±5.10 =m, 2H), 5.85±6.02 =m, 1H), 6.50 =s,
1H). Anal. Calcd for C11H14O2: C, 74.16; H, 7.87. Found: C,
73.87; H, 7.59.
1
=KBr) nmax 1659, 3376 =br) cm21; H NMR =CDCl3) d
2.70 =brs, 1H, OH), 2.87 =dd, 1H, Jˆ7.7, 12.9 Hz), 3.04
=dd, 1H, Jˆ7.8, 12.8 Hz), 4.86±4.98 =m, 2H), 5.05±5.30
=m, 1H), 5.72 =s, 1H), 7.38±7.57 =m, 6H), 7.57±7.65 =m,
1H), 7.78 =dd, 1H, Jˆ1.1, 7.9 Hz), 8.05 =dd, 1H, Jˆ1.3,
7.7 Hz); 13C NMR =CDCl3) d 50.15, 74.87, 119.96,
121.52, 125.27, 126.03, 127.99, 128.11, 130.06, 130.15,
130.46, 132.29, 135.89, 145.69, 180.89. Anal. Calcd for
C19H16O2S: C, 74.03; H, 5.19. Found: C, 73.82; H, 4.86.
1.2.8. 4-Allyl-4-hydroxy-2,5-dimethyl-cyclohexa-2,5-
dienone +20). Pale yellow solid, mp 56±588C =Literature
1
mp 608C),13a yield 61%; H NMR =CDCl3) d 1.77 =d, 3H,
1.2.15. 4-Allyl-4-hydroxy-3-phenylsulfanyl-4H-naphtha-
len-1-one +26) and 4-allyl-4-hydroxy-2-phenylsulfanyl-
4H-naphthalen-1-one +27). =Mixture, ratio 1.6:1, as indi-
Jˆ1.3 Hz), 1.97 =d, 3H, 1.25 Hz), 2.45 =d, 2H, Jˆ7 Hz),
3.27 =brs, 1H), 4.96±5.10 =m, 2H), 5.27±5.48 =m, 1H),
5.89 =d, 1H, Jˆ1.3 Hz), 6.53 =d, 1H, Jˆ1.4 Hz).
1
cated from H NMR, when the reaction was carried out at
2238C), yellow oil, yield 73%; H NMR =CDCl3) d 2.55
1
=brd, Jˆ7.3 Hz, allylic CH2 of 27), 2.8 =m) and 3.05 =m)
=allylic CH2 of 26), 4.81±4.98 =m, vinylic CH2), 5.05±5.9
=m, vinylic CH), 5.66 =s) and 6.11 =s) =H3 and H2 of 27 and
26, respectively), 7.35±7.77 =aromatic), 7.75 =dd, Jˆ1.1,
7.8 Hz), 8.05 =dd, Jˆ1.4, 7.7 Hz) =aromatic).
1.2.9. 4-Allyl-4-hydroxy-3-phenylsulfanylcyclohexa-2,5-
dienone +21). Viscous oil =column chromatography,
CH2Cl2±etherˆ8:2), yield 74%; IR =KBr) nmax 1652,
1
3520 cm21; H NMR =CDCl3) d 2.52 =brs, 1H), 2.76±2.83
=m, 2H), 5.13±5.27 =m, 2H), 5.50±5.55 =m, 2H), 6.16 =dd,
1H, Jˆ1.4, 9.8 Hz), 6.82 =d, 1H, Jˆ9.9 Hz), 7.45±7.48 =m,
5H). Anal. Calcd for C15H14O2S: C, 69.77; H, 5.43. Found:
C, 69.52; H, 5.12.
1.2.16. 4-Allyl-4-hydroxy-5-methoxy-3-phenylsulfanyl-
4H-naphthalen-1-one +28) and 4-allyl-4-hydroxy-8-
methoxy-2-phenylsulfanyl-4H-naphthalen-1-one
+29).
=Mixture, ratio 1:1.4 as indicated from H NMR), yellow
1
1.2.10. 4-Allyl-4-hydroxy-3-p-tolylsulfanylcyclohexa-2,5-
dienone +22). White solid; mp 110±1128C =CHCl3±petro-
leum ether 60±808C), yield 59%; 1H NMR =CDCl3) d 2.40
=s, 3H), 2.51 =brs, 1H), 2.77 =m, 2H), 5.11±5.25 =m, 2H),
5.48 =d, 1H, Jˆ1.7 Hz), 5.49±5.59 =m, 1H), 6.14 =dd, 1H,
Jˆ1.8, 9.8 Hz), 6.79 =d, 1H, Jˆ10.1 Hz), 7.22±7.37 =m,
4H). Anal. Calcd for C16H16O2S: C, 70.59; H, 5.88.
Found: C, 70.31; H, 5.62.
1
oil, yield 73%; H NMR =CDCl3) d 2.52 =brd, Jˆ7.3 Hz,
allylic CH2 of minor isomer 28), 3.05±3.25 =m, allylic CH2
of 29), 3.95 =s, OCH3 of 28), 4.03 =s, OCH3 of 29), 4.85±5.1
=m, vinylic CH2), 5.10±5.4 =m, vinylic CH), 5.15 =s, OH,
exchangeable with D2O), 5.73 =s, H3 of major isomer 29),
5.96 =s, H2 of minor isomer 28), 6.95 =brd, Jˆ8.3, H6 of
minor isomer 28), 7.15 =brd, Jˆ7.4 Hz, H7 of major isomer
29), 7.18±7.56 =m, aromatic), 7.75 =brd, H8 of minor isomer
28).
1.2.11. 4-Allyl-4-hydroxy-4H-naphthalen-1-one +23).
White solid, mp 78±808C, =CHCl3±petroleum ether 60±
808C) =literature mp 81±828C)16 yield 69%; IR =KBr) nmax
1678, 3360 cm21; 1H NMR =CDCl3) d 1.74 =brs, 1H), 2.64±
2.69 =m, 2H), 4.88±5.03 =m, 2H), 5.35±5.45 =m, 1H), 6.31
=d, 1H, Jˆ10.3 Hz), 6.93 =d, 1H, Jˆ10.3 Hz), 7.37±7.45 =m,
1H), 7.56±7.67 =m, 1H), 7.72 =dd, 1H, Jˆ1.2, 7.8 Hz), 8.01
=dd, 1H, Jˆ1.2, 7.8 Hz). Anal. Calcd for C13H12O2: C,
78.00; H, 6.00. Found: C, 77.78; H, 5.78.
Acknowledgements
Financial support from CSIR and DST, New Delhi is grate-
fully acknowledged.
References
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