TrisannelatedBenzeneSynthesisbyCopper(II)Chloride
J. Chin. Chem. Soc., Vol. 49, No. 1, 2002 93
Trisannelation of Cycloalkanones and Acetophenone: A
Typical Procedure. Synthesisof1,2,3,4,5,6,7,8,9,10,11,12-
dodecahydrotriphenylene DTP (4)
Triphenylbenzene (TPB) (12a)
Acetophenone in a sim i lar re ac tion refluxing for 4 h at
140 C. Com pound12a wasseparatedbyPTLC, thetopband
un der UV lamp was sep a rated, washed with ace tic acid, gave
To a flame dried 50 mL round bot tom flask equipped
with a re flux con denser was added 1 g (7.4 mmol) of an hy-
drous cop per(II) chlo ride and 10 mL (97 mmol) of cyclo hex-
anone(freshlydistilledanddriedoverzeolite).Theresulting
so lu tion was stirred and al lowed to re flux at 155 C for 3 h;
thecolorofsolutionwasinitiallyyelloworange, butafter15
to 20 min. of refluxing changed to dark pur ple. Dur ing this
periodtheHClgaswasevolvedandwhiteCuClprecipitateis
formed. Theresultingsolutionwaswashedwith3 20 mL of
wa ter and ex tracted with 3 20 mL of ether, dried over
1
2
white crystal needles mp = 170 C (lit. 171.5-175 C)
(0.234 g, 39% yield), IR (KBr): 3050 (w), 2920 (m), 1580 (m)
-
1 1
4
cm , H NMR (CCl ) : 7.25-7.75 (m, 18H) ppm.
Preparation of 1,3,5-tri(2-naphtyl)benzene 12b
To a flame dried 25 mL round bot tom flask equipped
with a re flux con denser was added 0.03 g (0.19 mmol) an hy-
drous CuCl and 0.4 g (2.9 mmol) 2-acetonaphthalene in 5
2
mLtoluene.Theresultingsolutionwasstirredandallowedto
re flux at 180-249 C for 6 h. The color of the so lu tion was ini-
tially yel low or ange, but af ter 15 min. of refluxing changed to
dark pur ple. Dur ing this time the HCl gas evolved and a white
CuCl pre cip i tate was formed. The re sult ing so lu tion was
MgSO
ri fied by silicagel col umn and recrystallized from CHCl
hexane(7:3v/v)togive 4as a white crys tal (0.54 g, 66%): mp
4
,filteredandevaporated.Theremainingsolidwaspu-
3
-
8
c
=
1
229 C (lit mp = 230 C). IR (KBr): 2925 (vs), 2850 (s),
-
1 1
450 (m), 1430 (s), 1310 (m), 1570 (m), 1250 (m) cm , H
4
washed with 3 10 mL ether filterate and dried over MgSO .
1
3
NMR (CCl
4
), : 2.45 (s, 12H), 1.7 (s, 12H) ppm., C NMR
The sol vent was re moved by pump, the brown viscose syrup
left, purified by silicagel column, (0.132 g, 33%) mp =
115-120 C. IR (KBr): 3050 (w), 3250 (m), 1418 (m), 1190
(CDCl
3
), : 132.4, 27, 23 ppm., MS: m/z 240 (M+, 70), 239
(
60), 198 (30), 184 (35), 66 (26), 65 (100); calcd for C18
H
24
-
1
1
m/e 240.1878, found, 240.1874.
(s), 1145 (m), 1120 (s), 720 (vs), 695 (s) cm . H NMR
CDCl ): ; 6.8-7.7 (m, 24H) ppm.
(
3
Separation of 2-(1-cyclohex-1 -enyl)cyclohexanone (6)
A por tion of the crude solid was pu ri fied by silicagel
Preparation of 9-phenyl-1,2,3,4,5,6,7,8-octahydro-
phenanthrene 20
8
-10mmHg
PTLCusingEtOAc:ligroin(1:5)bp
= 147-148 C. IR
(
neat) 3060 (vs), 2800-3000 (s), 1717 (s), 1680 (vs), 1450 (s)
To a 25 mL flame dried flask equipped with a re flux
con denser was added 1.2 g (10 mmol) acetophenone. To this
was added a mix ture of 1.96 g (1.1 mmol) 2-(1-cyclohexa-
1 -enyl)cyclohexanone 4 and 0.27 g (2 mmol) anhydrous
-
1 1
cm , H NMR (CDCl
3
), 5.45 (m, 1H), 1.5-3.05 (m, 17H).
2
-(Cyclopentylidene)cyclopentanone 10 and 1,2,3,4,5,6-
hexahydrotricyclopenta[a,c,e]benzene (Trindan) 9
Thesameprocedureasatypicalprocedurewasused;l0
was iso lated by PTLC on silicagel eluent EtOAc:lig ro in (1:10
2
CuCl . The re sult ing so lu tion was stirred and al lowed to re-
flux at 130-140 C for 2 h. The color of the so lu tion was
intially yel low or ange, af ter 15 min re flux changed to dark
pur ple. Dur ing this pe riod the HCl gas was evolved and a
white CuCl pre cip i tate was formed. The re sult ing so lu tion
v/v), IR (CCl
4
): 2950 (vs), 2850 (s), 1695 (s), 1640 (m), 1445
-
1
1
(
m), 1260 (m) cm , H NMR (CDCl ), : 1.35-3 (m, 14H)
3
ppm.
4
was washed with 3 10 mL ether,dried over MgSO ; the sol-
vent was re moved with a pump. The crude res i due was pu ri-
fiedbysilicagelcolumnusingpetroleumetheraseluent(0.89
Trindan 9
Separated from crude solid by PTLC on silicagel
eluent EtOAc:lig ro in (1:10 v/v) top bond with blue color un-
g, 31%). IR (CCl
4
): 3050 (w), 2900 (s), 2830 (s), 1430 (s)
cm , H NMR (CDCl ): ; 7-8 (m, 6H), 0.5-2.3 (m, 16H).,
calcd for C 20 22 m/e 262.1721, found 262.172.
-
1 1
3
der UV lamp, and recrystallized from H
2
O:EtOAc gave crys-
H
1
1
tal nee dles (0.35 g, 43%), mp = 96 C (lit = 97.5-98 C); IR
(
KBr): 2940 (vs), 2830 (s), 1640 (w), 1445 (m), 1295 (m),
Preparation of 2,6,10-Trimethyl-1,2,3,4,5,6,7,8,9,10,11,12-
dodecahydrotriphenylenes 17 and 18
-
1 1
1
420 (m), 1270 (m) cm , H NMR (CCl ), 2.9-2.5 (t, 12H,
4
1
3
J = 7.3 Hz), 1.8-3.2 (m, 6H) ppm., C NMR (CDCl
37.3, 31.1, 25.4., MS:m/z 198 (M+, 2), 184 (2), 91 (60), 41
70), 43 (95), 56 (100); calcd. for C15 18 m/e 198.1408,
3
), :
Atypicalprocedureasusedfor4 was ap plied (0.320g,
~40%). IR (KBr): 2940 (vs), 2920 (s), 2834 (s), 1445 (m),
1
-
1 1
(
H
1430 (s), 1369 (m) cm , H NMR (CDCl
3
): 2.6-2.3 (m, 3H),
1
3
found 198.1405.
2.1-1.6 (m, 18H), 1.1 (m, 9H)., C NMR (CDCl ) (17) ;
3