Some acid-catalysed reactions of indol-3-yl and indol-2-yl disubstituted methanols

Article abstract of DOI:10.1135/cccc2009023

1-Substituted indol-3-yl and indol-2-yl disubstituted methanols do not undergo acidcatalysed trimerisation to yield indolocyclotriveratrylenes, unlike the related primary 1-substituted indol-3-yl-and -2-ylmethanols. The 1-substituted indol-3-ylmethanols 1

Full text of DOI:10.1135/cccc2009023

Acid-Catalysed Reactions
1137
SOME ACID-CATALYSED REACTIONS OF INDOL-3-YL AND
INDOL-2-YL DISUBSTITUTED METHANOLS
1
2
3,
Mardi SANTOSO , Naresh KUMAR and David StClair BLACK *
School of Chemistry, The University of New South Wales, UNSW Sydney, NSW 2052, Australia;
1
2
3
e-mail: msantoso@its.ac.id, n.kumar@unsw.edu.au, d.black@unsw.edu.au
Received February 28, 2009
Accepted May 22, 2009
Publish ed on lin e July 17, 2009
Dedicated to Dr. Alfred Bader on the occasion of his 85th birthday.
1-Substituted in dol-3-yl an d in dol-2-yl disubstituted m eth an ols do n ot un dergo acid-
catalysed trim erisation to yield in dolocyclotriveratrylen es, un like th e related prim ary
1-substituted in dol-3-yl- an d -2-ylm eth an ols. Th e 1-substituted in dol-3-ylm eth an ols 10 an d
11 gave diin dol-3-ylm eth an es 12 an d 13, respectively, on treatm en t with p-toluen esulfon ic
acid in dich lorom eth an e. In con trast, th e in dol-2-ylm eth an ols 22 an d 23 gave th e reduced
in dolo[3,2-b]carbazoles 24 an d 25, respectively, on treatm en t with boron trifluoride eth erate
in ben zen e. An X-ray crystal structure of com poun d 24 is described.
Keyw ord s: In doles; Diin dol-3-ylm eth an es; In dolocarbazoles; Acid-catalysed addition reac-
tion s; Isatin s; Keton e reduction .
Sim ple N-substituted in dole-3- or in dole-2-m eth an ols 1 an d 2 h ave been
sh own to un dergo acid-catalysed cyclotrim erisation reaction s, usually in -
volvin g p-toluen esulfon ic acid in dich lorom eth an e, to form “in dolocyclo-
triveratrylen es” or [2,3;2,3;2,3]calix[3]in doles 3 in yields approxim atin g
40% 1 (Sch em e 1).
SCHEME 1
Collect. Czech. Chem. Commun. 2009, Vol. 74, Nos. 7–8, pp. 1137–1150
© 2009 Institute of Organic Chemistry and Biochemistry
doi:10.1135/cccc2009023

1138
Santoso, Kumar, Black:
It is assum ed th at th ese reaction s proceed th rough th e in term ediacy of
prim ary ben zylic cation s. It was con sequen tly of in terest to study sim ilar
reaction s th at would in volve secon dary ben zylic cation in term ediates,
wh ich could arise from sim ilar acid-catalysed reaction s of in dole-3- or
-2-m eth an ols. Th e in troduction of an addition al substituen t on th e carbon
atom bearin g th e h ydroxy group gives an en orm ous scope of possibilities.
We h ave in vestigated a sm all variety of such substituen ts an d th e results of
our experim en ts are described h erein .
On e way in wh ich such secon dary ben zylic cation s can be gen erated is
th rough acid-catalysed addition s of aldeh ydes to in doles. We h ave previ-
ously in vestigated th e reaction s of th e activated paren t 4,6-dim eth oxy-
in dole with arom atic aldeh ydes un der th e in fluen ce of ph osph oryl ch loride
as th e acid catalyst2. In th is study, cyclodim erisation occurred sm ooth ly to
give in dolo[3,2-b]carbazoles, via th e in term ediacy of reduced derivatives
wh ich were readily oxidised un der th e reaction con dition s. Sim ilar reduced
in dolo[3,2-b]carbazoles h ave been form ed by reaction of diin dol-3-yl-
m eth an es with aldeh ydes an d keton es3,4. In all th ese cases, th e in dole com -
poun ds were un substituted at n itrogen . As th e form ation of in dolocyclo-
triveratrylen es usually requires th e presen ce of a substituen t at th e in dole
n itrogen atom , it was decided to m ake th is an essen tial part of th e study in -
volvin g secon dary m eth an ol derivatives.
RESULTS AND DISCUSSION
Preparation and Acid-Catalysed Reactions of Indol-3-yl
Disubstituted Methanols
All th e disubstituted m eth an ol derivatives were gen erated by th e reduction
of related keton es usin g sodium boroh ydride in eth an ol. Reduction of
3-acetyl-1-ben zylin dole5 (4) gave th e n ew m eth an ol com poun d 6 in 96%
yield (Sch em e 2). Most in dolem eth an ol com poun ds are quite sen sitive, an d
SCHEME 2
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Acid-Catalysed Reactions
1139
th erefore difficult to obtain fully pure. For in stan ce, th e related N-m eth yl
derivative of com poun d 7, form ed by reduction of th e N-m eth yl derivative
of com poun d 5, h as been reported to be un stable an d to un dergo polym eri-
sation 6. Alth ough th e m eth an ol 6 could be obtain ed pure, on treatm en t
with p-toluen esulfon ic acid or h ydroch loric acid in dich lorom eth an e, it
gave com plex reaction m ixtures wh ich could n ot be separated.
It was h oped th at m ore stable m eth an ols could be form ed from 3-ben zoyl-
in doles, so th e N-m eth yl- an d N-allylin doles, 8 an d 9, respectively, were
reduced to th e m eth an ols 10 an d 11, respectively, in very h igh yields.
Com poun d 10 was fully ch aracterised, but com poun d 11 could n ot be
obtain ed an alytically pure. Treatm en t of m eth an ols 10 an d 11 with
p-toluen esulfon ic acid gave th e diin dol-3-ylm eth an es 12 an d 13, respec-
tively, in good yields, accom pan ied by 4-ch loroben zaldeh yde as a by-
product (Sch em e 3).
SCHEME 3
In doles react readily at C3 with oxalyl ch loride. Con sequen tly, 1-m eth yl-
in dole was con verted in to th e glyoxylic am ide 14, by quen ch in g th e in ter-
m ediate glyoxyloyl ch loride with 3,5-dim eth oxyan ilin e. Th e related 4,6-
dim eth oxyin dole was sim ilarly con verted in to th e glyoxylic am ide 15,
quen ch in g th is tim e with pyrrolidin e. Reaction of 4,6-dim eth oxyin dole
with oxalyl ch loride h as been reported7 to give th e in dole-7-glyoxyloyl
ch loride, but in our h an ds, a m ixture of 3- an d 7-isom ers was form ed an d
th e resultin g am ides could be separated by ch rom atograph y. Reduction of
th e keto-am ides 14 an d 15 gave h igh yields of th e respective alcoh ols 16
an d 17 (Sch em e 4), but th ese could n ot be obtain ed pure, an d on direct
treatm en t with acid gave com plex reaction m ixtures. It is perh aps n ot sur-
prisin g th at th ese alcoh ols are sen sitive to acid, as th e resultin g ben zylic
cation s would be destabilised by th e adjacen t carbon yl groups.
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Santoso, Kumar, Black:
SCHEME 4
Preparation and Acid-Catalysed Reactions of Indol-2-yl
Disubstituted Methanols
Th e required in dol-2-ylm eth an ols can be prepared by reduction of 2-acyl-
in doles. Th e syn th etic route developed8 from N-ph en acylisatin s was used to
prepare th e kn own 2-ben zoylin dole9 18 an d 2-ben zoyl-4,6-dim eth oxy-
in dole8,10,11 19. Th ese were N-alkylated with allyl ch loride an d sodium io-
dide to give com poun ds 20 an d 21, respectively, in very h igh yields.
Reduction of th e products with sodium boroh ydride afforded th e previ-
ously un reported m eth an ols 22 an d 23, th e form er but n ot th e latter bein g
fully ch aracterised. In th ese cases th e stan dard con dition s of p-toluen e-
sulfon ic acid in dich lorom eth an e gave a product m ixture, but treatm en t of
th e two m eth an ols 22 an d 23 with boron trifluoride eth erate in ben zen e
gave good yields of th e reduced in dolocarbazoles 24 an d 25, respectively
(Sch em e 5).
Th e “dim eric” structure of com poun d 24 was clear from th e m ass spectro-
scopic data wh ich sh owed a m olecular ion at m/z 490. Th e detailed struc-
ture was establish ed by NMR spectroscopy an d X-ray crystallograph y. Th e
1H NMR spectrum sh owed a sin gle m eth in e proton reson an ce at δ 5.75 ppm ,
con sisten t with th e dih ydroin dolo[3,2-b]carbazole structure, an d also rulin g
out th e altern ative dih ydroin dolo[2,3-b]carbazole structure, wh ich would
sh ow two differen t m eth in e proton s. Th e X-ray crystal structure sh owed
th at th e dih ydroin dolocarbazole fram ework is essen tially plan ar, an d th at
th e two ph en yl substituen ts are syn to each oth er (Fig. 1). Sim ilarly, com -
poun d 25 sh owed a m olecular ion at m/z 610, an d th e 1H NMR spectrum
displayed a sin gle m eth in e proton reson an ce at δ 5.84 ppm .
Earlier in vestigation s h ave sh own th at th e h eatin g in eth an ol of 2-
(1-h ydroxyeth yl)-1-m eth ylin dole with Am berlite IR-120 ion exch an ge resin
gave a 55% yield of crude 5,6,11,12-tetram eth yl-6,12-dih ydroin dolo[3,2-b]-
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Acid-Catalysed Reactions
1141
SCHEME 5
FIG. 1
ORTEP diagram of structure 24. Hydrogen atom s an d th e solven t m olecule are om m ited for
clarity
Collect. Czech. Chem. Commun. 2009, Vol. 74, Nos. 7–8, pp. 1137–1150

1142
Santoso, Kumar, Black:
carbazole12. Furth er related in dolocarbazole structures can be form ed in
acid-catalysed reaction s of sim ilar substrates in wh ich th e h ydroxy group is
replaced by a ben zim idazol-1-yl group13
.
CONCLUSION
Acid-catalysed reaction s of in dol-3- an d in dol-2-yl disubstituted m eth an ols
do n ot yield in dolocyclotriveratrylen es. Th e 3-m eth an ols 10 an d 11 gave
diin dol-3-ylm eth an es 12 an d 13, respectively, wh ile th e 2-m eth an ols 22
an d 23 gave th e reduced in dolo[3,2-b]carbazoles 24 an d 25, respectively.
EXPERIMENTAL
Meltin g poin ts were m easured usin g a Mel-Tem p m eltin g poin t apparatus, an d are un cor-
rected. Microan alyses were perform ed by th e Microan alytical Un it, Research Sch ool of
Ch em istry, Th e Australian Nation al Un iversity. 1H an d 13C NMR spectra (δ, ppm ; J, Hz) were
obtain ed on a Bruker AC300F (300 MHz) spectrom eter. Mass spectra were recorded on eith er
an AEI MS 12 (EI) or a Fin n egan MAT (MALDI) spectrom eter. IR spectra (ν, cm –1) were re-
corded with a Perkin –Elm er 298 IR spectrom eter. UV-Vis spectra were recorded usin g a
Hitach i U-3200 spectrom eter. Colum n ch rom atograph y was carried out usin g Merck 70–230
m esh silica gel, wh ilst preparative th in layer ch rom atograph y was perform ed usin g Merck
silica gel 7730 60GF254. Flash ch rom atograph y14 was carried out usin g Merck 60H silica gel.
1-(1-Ben zylin dol-3-yl)eth an ol (6)
A m ixture of 3-acetyl-1-ben zylin dole5 (4) (0.76 g, 3.05 m m ol) an d sodium boroh ydride (0.60 g,
15.86 m m ol) in absolute eth an ol was h eated un der reflux for 2 h . After coolin g, a sm all
am oun t of 10% sodium h ydroxide was added an d th e solven t was evaporated un der reduced
pressure. Water was added an d th e resultin g wh ite precipitate was filtered off, wash ed with
water an d dried to afford th e alcoh ol 6 as a yellowish solid (0.74 g, 96%), m .p. 76–77 °C. IR
(Nujol): 3350, 1610, 1550, 1460, 1380, 1340, 1300, 1260, 1180, 1130, 1080, 1040, 990, 880,
820, 790, 770, 740, 700. UV (MeOH (ε)): 222 (35,500), 285 (6,500). 1H NMR (300 MHz,
CDCl3): 1.70 d, 3 H, J = 6.2 (Me); 1.98 d, 1 H, J = 4.6 (OH); 5.28 s, 3 H (CH2 an d CHOH);
7.10–7.31 m , 9 H (ArH); 7.82 m , 1 H (ArH). 13C NMR (75 MHz, CDCl3): 23.77, Me; 49.98,
CH2; 64.10, CHOH; 109.85, 119.44, 119.79, 122.06, 124.74, 126.86, 127.64, 128.74, ArCH;
120.32, 126.41, 136.99, 137.34, ArC. MS (EI), m/z (%): 252 (5), 251 (25) [M• +], 236 (40), 91
(100). For C17H17NO·0.25H2O calculated: 79.8% C, 6.9% H, 5.5% N; foun d: 79.6% C, 6.8% H,
5.4% N.
3-(4-Ch loroben zoyl)-1-m eth ylin dole (8)
Method A: 3-(4-Ch loroben zoyl)in dole (0.12 g, 0.47 m m ol) an d fresh ly crush ed potassium
h ydroxide (0.11 g, 1.96 m m ol) in dry dim eth yl sulfoxide (25 m l) were stirred at room tem -
perature for 1 h . Iodom eth an e (0.02 m l, 0.32 m m ol) was added an d th e m ixture was stirred
for an addition al 1 h . Water was added an d th e resultin g wh ite precipitate was filtered off,
wash ed with water an d dried (0.11 g, 85%), m . p. 144–145 °C. IR (Nujol): 1610, 1580, 1505,
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1450, 1365, 1260, 1225, 1150, 1120, 1080, 1060, 1030, 1000, 965, 870, 840, 770, 745, 720,
690. UV (MeOH (ε)): 254 (21,600), 322 (19,400). 1H NMR (300 MHz, CDCl3): 3.85 s, 3 H,
Me; 7.33–7.78 m , 7 H, ArH; 7.51 s, 1 H (H2); 8.36–8.42 m , 1 H (ArH). 13C NMR (75 MHz,
CDCl3): 33.62, Me; 109.69, 122.72, 122.87, 123.83, 128.57, 130.11, 137.61, ArCH; 115.49,
127.14, 137.31 (2×), 139.27, ArC; 189.39, CO. MS (EI), m/z (%): 271 (10) [M• +
(30) [M• + 35Cl], 158 (100), 77 (100).
,
37Cl], 269
,
Method B: 4-Ch loro-N,N-dim eth ylben zam ide (1.44 g, 7.84 m m ol) was stirred an d warm ed
at 60 °C, ph osph oryl ch loride (0.88 m l, 9.44 m m ol) was added an d th e m ixture was stirred
for 5 m in . 1-Meth ylin dole (1.03 g, 7.85 m m ol) was added an d th e m ixture was h eated at 80 °C
for 2 h . Aqueous sodium h ydroxide (10%) was added to th e m ixture an d th e product was
extracted with dich lorom eth an e. Th e com bin ed extract was wash ed with brin e, dried over
an h ydrous m agn esium sulfate an d th e solven t was rem oved un der reduced pressure. Th e
crude product was purified usin g colum n ch rom atograph y with dich lorom eth an e eluen t to
yield th e keton e 8 as a wh ite solid (1.41 g, 67%).
1-Allyl-3-(4-ch loroben zoyl)in dole (9)
4-Ch loro-N,N-dim eth ylben zam ide (1.55 g, 8.44 m m ol) was stirred an d warm ed at 60 °C,
ph osph oryl ch loride (0.88 m l, 9.44 m m ol) was added an d th e m ixture was stirred for 5 m in .
1-Allylin dole (1.27 g, 8.08 m m m ol) was added an d th e m ixture was h eated at 80 °C for 2 h .
Aqueous sodium h ydroxide (10%) was added to th e cooled m ixture an d th e product was ex-
tracted with dich lorom eth an e. Th e com bin ed extract was wash ed with brin e, dried over an -
h ydrous m agn esium sulfate an d th e solven t was rem oved un der reduced pressure. Th e crude
product was purified usin g colum n ch rom atograph y with dich lorom eth an e eluen t to yield
th e keton e 9 as a wh ite solid (1.53 g, 67%), m .p. 126–127 °C. IR (Nujol): 1610, 1580, 1455,
1370, 1190, 1170, 1080, 1000, 935, 870, 840, 765, 740. UV (MeOH (ε)): 254 (33,500), 321
(27,600). 1H NMR (300 MHz, CDCl3): 4.76 d, 2 H, J = 5.6 (H1′); 5.17 d, 1 H, J = 16.9 (H3′);
5.29 d, 1 H, J = 10.81 (H3′); 5.93–6.06 m , 1 H (H2′); 7.31–7.77 m , 8 H (ArH); 8.38–8.41 m ,
1 H (ArH). 13C NMR (75 MHz, CDCl3): 49.45, C1′; 118.74, C3′; 134.90, C2′; 110.14, 122.70,
122.86, 123.79, 128.54, 130.08, 136.90, ArCH; 115.70, 127.23, 136.97, 137.30, 139.13, ArC;
189.40, CO. MS (EI), m/z (%): 297 (5) [M• + 37Cl], 295 (10) [M• + 35Cl], 184 (30), 41 (100).
, ,
For C18H14ClNO·0.25H2O calculated: 72.0% C, 4.9% H, 4.7% N; foun d: 72.3% C, 4.8% H,
4.6% N.
(4-Ch loroph en yl)(1-m eth ylin dol-3-yl)m eth an ol (10)
3-(4-Ch loroben zoyl)-1-m eth ylin dole (8) 0.70 g, 2.60 m m ol) was dissolved in tetrah ydrofuran
(50 m l), sodium boroh ydride (2.46 g, 0.065 m ol) was added an d followed by addition of ab-
solute eth an ol (20 m l). Th e m ixture was h eated un der reflux for 2 h an d, after coolin g, th e
solven t was evaporated un der reduced pressure to dryn ess. Th e residue was suspen ded in
aqueous sodium h ydroxide (10%) an d th e resultin g wh ite precipitate was filtered off,
wash ed with water an d dried to afford th e alcoh ol as a wh ite solid (0.70 g, 99%), m .p.
109–110 °C. IR (Nujol): 3300, 1580, 1540, 1450, 1370, 1320, 1300, 1230, 1190, 1140, 1120,
1080, 1050, 1010, 980, 810, 730. UV (MeOH, (ε)): 223 (58,800), 285 (7,400). 1H NMR
(300 MHz, CDCl3): 3.73 s, 3 H (Me); 6.11 d, 1 H, J = 4.1 (CHOH); 6.79 s, 1 H (H2); 7.11 m ,
1 H (ArH); 7.23–7.34 m , 4 H (ArH); 7.44 m , 2 H (ArH); 7.57 m , 1 H (ArH). 13C NMR
(75 MHz, CDCl3): 32.73, CH3; 69.44, CHOH; 109.47, 119.57, 119.59, 122.14, 127.44, 127.83,
128.36, ArCH; 117.93, 126.12, 132.94, 137.44, 142.22, ArC. MS (EI), m/z (%): 273 (20) [M• +
,
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Santoso, Kumar, Black:
37Cl], 272 (10) [M• +
,
35Cl], 271 (65) [M• +
,
35Cl], 254 (55), 160 (35), 139 (25), 132 (100), 130
(20), 117 (35), 77 (30). For C16H14ClNO·0.33H2O calculated: 69.2% C, 5.3% H, 5.0% N;
foun d: 69.2% C, 5.3% H, 5.0% N.
(1-Allylin dol-3-yl)(4-ch loroph en yl)m eth an ol (11)
1-Allyl-3-(4-ch loroben zoyl)in dole (9) (0.35 g, 1.18 m m ol) was dissolved in tetrah ydrofuran
(30 m l), sodium boroh ydride (0.35 g, 9.25 m m ol) was added an d followed by addition of ab-
solute eth an ol (20 m l). Th e m ixture was refluxed for 2 h an d, after coolin g, th e solven t was
evaporated un der reduced pressure to dryn ess. Th e residue was suspen ded in aqueous so-
dium h ydroxide (10%) an d th e product was extracted several tim es with dich lorom eth an e.
Th e com bin ed extracts were dried over an h ydrous sodium sulfate, an d th e solven t was evap-
orated un der reduced pressure to give th e title alcoh ol as a yellowish oil (0.33 g, 94%). IR
(n eat): 3340, 3060, 2920, 2860, 1460, 1265, 1180, 1090, 1040, 1020, 925, 800, 745. UV
(CH2Cl2 (ε)): 229 (132,000), 273 (26,800). 1H NMR (300 MHz, CDCl3): 4.67 d, 2 H, J = 5.6
(H1′); 5.11 d, 1 H, J = 16.9 (H3′); 5.21 d, 1 H, J = 10.2 (H3′); 5.91–6.04 m , 1 H (H2′); 6.13 s,
1 H (CHOH); 6.87 s, 1 H (H2); 7.10 an d 7.23 2 m (H6 an d H5); 7.30–7.34 m , 3 H (ArH); 7.44
m , 2 H (ArH); 7.57 m , 1 H (ArH). 13C NMR (75 MHz, CDCl3): 48.91, C1′; 69.59, CHOH;
117.58, C3′; 133.20, C2′; 109.90, 119.72, 119.75, 122.20, 126.38, 127.90, 128.42, ArCH;
118.34, 126.34, 133.00, 136.92, 142.18, ArC. MS (EI), m/z (%): 299 (20) [M• +
,
37Cl], 297 (55)
[M• + 35Cl], 282 (20), 280 (55), 186 (35), 184 (50), 158 (65), 156 (30), 139 (75), 130 (45), 117
,
(45), 111 (50), 111 (50), 41 (100).
(4-Ch loroph en yl)bis(1-m eth ylin dol-3-yl)m eth an e (12)
(4-Ch loroph en yl)(1-m eth ylin dol-3-yl)m eth an ol (10) (0.20 g, 0.74 m m ol) in dich lorom eth an e
was treated with a sm all am oun t of p-toluen esulfon ic acid m on oh ydrate, an d stirred at room
tem perature for 1 h . Th e solven t was rem oved un der reduced pressure an d th e crude product
was purified usin g colum n ch rom atograph y with dich lorom eth an e/ligh t petroleum (1:1)
eluen t to afford th e product as a wh ite solid (0.10 g, 71%), m .p. 204–205 °C. IR (Nujol):
1640, 1600, 1580, 1460, 1420, 1380, 1320, 1220, 1200, 1150, 1120, 1080, 1010, 920, 860,
830, 800, 730, 700. UV (CH2Cl2 (ε)): 231 (66,600), 293 (16,300). 1H NMR (300 MHz, CDCl3):
3.71 s, 6 H, Me; 5.91 s, 1 H (CH bridgin g); 6.56 s, 2 H (H2); 7.05 m , 2 H (ArH); 7.23–7.35 m ,
8 H (ArH); 7.41 m , 2 H (ArH). 13C NMR (75 MHz, CDCl3): 32.66, Me; 39.55, CH bridgin g;
109.15, 118.78, 119.93, 121.59, 128.32 (2×), 130.06, ArCH; 117.77, 127.30, 131.68, 137.45,
143.04, ArC. MS (EI), m/z (%): 386 (30) [M• + 37Cl], 384 (95) [M• + 35Cl], 383 (30), 274 (20),
, ,
273 (100), 257 (20), 253 (30). For C25H21ClN2 calculated: 78.0% C, 5.5% H, 7.3% N; foun d:
77.7% C, 5.7% H, 7.1% N.
Bis(1-allylin dol-3-yl)(4-ch loroph en yl)m eth an e (13)
(1-Allylin dol-3-yl)(4-ch loroph en yl)m eth an ol (11) (0.42 g, 1.41 m m ol) in dich lorom eth an e
was treated with a sm all am oun t of p-toluen esulfon ic acid m on oh ydrate or h ydroch loric
acid, an d stirred at room tem perature for 1 h . Th e solven t was rem oved un der reduced pres-
sure an d th e crude product was purified by colum n ch rom atograph y (dich lorom eth an e/ligh t
petroleum , 1:1) to afford th e product as a wh ite solid (0.21 g, 68%), m .p. 297–299 °C. IR
(Nujol): 3040, 1455, 1365, 1335, 1190, 1150, 1080, 1010, 990, 920, 860, 740. UV (CH2Cl2
(ε)): 230 (48,100), 293 (11,000). 1H NMR (300 MHz, CDCl3): 4.65 m , 4 H (H1′); 5.06 m , 2 H
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(H3′); 5.18 m , 2 H (H3′); 5.90–6.01 m , 3 H (H2′ an d CH bridgin g); 6.60 s, 2 H (H2); 7.03 m ,
2 H (ArH); 7.19–7.41 m , 10 H (ArH). 13C NMR (75 MHz, CDCl3): 39.66, CH bridgin g; 48.73,
C1′; 116.93, C3′; 130.10, C2′; 109.61, 118.97, 120.04, 121.63, 127.35, 128.37, 133.65, ArCH;
118.09, 127.57, 131.71, 136.90, 142.91, ArC. MS (ES), m/z (%): 439 (30) [M• +
[M• + 35Cl], 435 (100), 280 (25).
,
37Cl], 437 (90)
,
N-(3,5-Dim eth oxyph en yl)-1-m eth ylin dol-3-ylglyoxylam ide (14)
1-Meth ylin dole (1.99 g, 15.17 m m ol) in an h ydrous eth er (35 m l) was cooled in ice, an d
treated dropwise wh ile stirrin g with a solution of oxalyl ch loride (1.46 m l, 16.74 m m ol) in
an h ydrous eth er (5 m l). After stirrin g in ice for 1 h , th e glyoxyloyl ch loride was collected by
filtration . It was dissolved in an h ydrous eth er (50 m l) an d treated dropwise with a solution
of 3,5-dim eth oxyan ilin e (2.61 g, 17.04 m m ol) in an h ydrous eth er (50 m l) with ice coolin g.
It was stirred in ice for addition al 1 h , an d th e resultin g precipitate was filtered off, wash ed
with water an d dried to afford th e keto-am ide as a yellowish solid (3.39 g, 66%), m .p.
165–166 °C. IR (Nujol): 3340, 1690, 1600, 1460, 1370, 1290, 1260, 1200, 1120, 1080, 1050,
1010, 980, 940, 850, 820, 790, 770, 750, 680. UV (MeOH (ε)): 263 (5,400), 276 (4,800), 338
(9,500). 1H NMR (300 MHz, CDCl3): 3.81 s, 6 H (OMe); 3.86 s, 3 H (Me); 6.30 t, 1 H (ArH);
6.96 d, 2 H (ArH); 7.36–7.38 m , 3 H (ArH); 8.43–8.46 m , 1 H (ArH); 9.00 s, 1 H (H2); 9.35 bs,
1 H (NH). 13C NMR (75 MHz, CDCl3): 33.73, Me; 55.43, OMe; 97.56, 98.18, 109.97, 122.66,
123.61, 124.03, 142.24, ArCH; 111.65, 127.74, 137.08, 138.69, 160.19, 161.20, 179.46, ArC.
MS (EI), m/z (%): 338 (5) [M• +], 158 (100). For C19H17N2O4 calculated: 67.4% C, 5.4% H,
8.3% N; foun d: 67.4% C, 5.5% H, 8.3% N.
1-(4,6-Dim eth oxy-1-m eth ylin dol-3-ylglyoxyloyl)pyrrolidin e (15)
4,6-Dim eth oxyin dole (0.59 g, 3.33 m m ol) in an h ydrous eth er (25 m l) was cooled in ice, an d
treated dropwise wh ile stirrin g with a solution of oxalyl ch loride (0.32 m l, 3.78 m m ol) in
an h ydrous eth er (5 m l). After stirrin g in ice for 1 h , th e resultin g yellow precipitate was fil-
tered off to yield crude m aterial wh ich was suspen ded in an h ydrous eth er (20 m l), an d
treated dropwise wh ile stirrin g with a solution of pyrrolidin e (0.31 m l, 3.71 m m ol) in an h y-
drous eth er (5 m l) with ice coolin g. After stirrin g in ice for 1 h , th e resultin g precipitate was
filtered off an d purified usin g flash ch rom atograph y with eth yl acetate to afford
(4,6-dim eth oxyin dol-3-ylglyoxyloyl)pyrrolidin e as an oran ge solid (0.27 g, 27%), m .p.
169–170 °C. IR (Nujol): 3330, 1590, 1450, 1370, 1270, 1210, 1140, 1030, 840, 800, 780. UV
(MeOH (ε)): 253 (16,800), 348 (32,200). 1H NMR (300 MHz, CDCl3): 1.89–1.91 m , 4 H (CH2);
3.57–3.65 m , 4 H (CH2); 3.77 an d 3.86 2 s, 6 H (OMe); 6.11 d, 1 H, J = 1.5 (H5); 6.39 d, 1 H,
J = 1.5 (H7); 7.47 s, 1 H (H2); 9.87 bs, 1 H (NH). 13C NMR (75 MHz, CDCl3): 23.86, 26.07,
45.84, 47.26, CH2; 55.33 an d 55.51, OMe; 86.12, C5; 93.17, C7; 113.07, C2; 114.69, 130.69,
140.79, 155.75, 162.03, 164.15, 180.38, ArC. MS (EI), m/z (%): 302 (25) [M• +], 204 (100), 176
(25), 149 (40). For C16H18N2O4 calculated: 63.6% C, 6.0% H, 9.3% N; foun d: 63.4% C,
6.1% H, 9.0% N.
(4,6-Dim eth oxyin dol-3-ylglyoxyloyl)pyrrolidin e (0.21 g, 0.69 m m ol) an d fresh ly crush ed
potassium h ydroxide (0.15 g, 2.67 m m ol) in dry dim eth yl sulfoxide (15 m l) were stirred at
room tem perature for 1 h . Iodom eth an e (0.09 m l, 1.45 m m ol) was added an d th e m ixture
was stirred for an addition al 1 h . Water was added an d th e product was extracted with di-
ch lorom eth an e several tim es. Th e com bin ed extracts were wash ed with brin e several tim es,
dried over an h ydrous m agn esium sulfate an d evaporated un der reduced pressure. Th e crude
Collect. Czech. Chem. Commun. 2009, Vol. 74, Nos. 7–8, pp. 1137–1150

1146
Santoso, Kumar, Black:
product was purified usin g colum n ch rom atograph y with eth yl acetate/ligh t petroleum (1:1)
eluen t to afford th e keto-am ide 15 as a yellow solid (0.18 g, 82 %), m .p. 180–181 °C. IR
(Nujol): 1620, 1585, 1460, 1380, 1350, 1320, 1260, 1210, 1150, 1070, 1040, 820, 760, 720.
UV (MeOH (ε)): 251 (18,100), 341 (34,400). 1H NMR (300 MHz, CDCl3): 1.90–1.98 m , 4 H
(CH2); 3.49 t, 2 H (CH2); 3.63 t, 2 H (CH2); 3.89 s, 6 H (OMe); 4.05 s, 3 H (Me); 6.16 d, 1 H,
J = 1.6 (H5); 6.30 d, 1 H, J = 1.6 (H7); 7.37 s, 2 H (H2). 13C NMR (75 MHz, CDCl3): 24.14,
25.97, 45.35, 47.01, CH2; 32.34, Me; 55.47 an d 55.67, OMe; 84.08, C5; 93.16, C7; 115.48,
C2; 113.35, 129.92, 143.42, 155.86, 162.16, 165.27, 183.10, ArC. MS (EI), m/z (%): 316 (20)
[M• +], 218 (100), 149 (85), 137 (20), 121 (20). For C17H20N2O4 calculated: 64.5% C, 6.4% H,
8.9% N; foun d: 64.7% C, 6.5% H, 8.8% N.
N-(3,5-Dim eth oxyph en yl)-2-h ydroxy-2-(1-m eth ylin dol-3-yl)acetam ide (16)
N-(3,5-Dim eth oxyph en yl)-1-m eth ylin dol-3-ylglyoxylam ide (14) (0.87g, 2.57 m m ol) was dis-
solved in tetrah ydrofuran (40 m l), an d sodium boroh ydride (0.49 g, 12.95 m m ol) an d abso-
lute eth an ol (20 m l) were added. Th e m ixture was stirred at room tem perature for 2.5 h , an d
th e colourless solution was evaporated to dryn ess. Th e residue was suspen ded in aqueous
sodium h ydroxide (10%) an d th e resultin g wh ite precipitate was filtered off, wash ed with
water an d dried to yield th e alcoh ol 16 (0.84 g, 97%), m .p. 63–64 °C. IR (Nujol): 3350, 1660,
1600, 1530, 1460, 1380, 1340, 1260, 1200, 1150, 1080, 1010, 820, 740. UV (CH2Cl2 (ε)): 229
(33,000), 253 (11,500). 1H NMR (300 MHz, CDCl3): 3.68 s, 3 H (Me); 3.73 s, 6 H (OMe);
5.35 s, 1 H (CHOH); 6.23 t, 1 H (ArH); 6.78 m , 2 H (ArH); 7.07–7.30 m , 4 H (ArH); 7.65 m ,
1 H (ArH). 13C NMR (75 MHz, CDCl3): 32.87, Me; 55.43, OMe; 68.72, CHOH; 97.10, 98.08,
109.74, 119.27, 120.18, 122.46, 128.63, ArCH; 112.30, 125.88, 137.47, 139.06, 161.13, ArC;
170.71, CO. MS (EI), m/z (%): 340 (5) [M• +], 160 (95), 153 (100), 152 (20), 132 (35), 124
(65), 117 (35).
1-[2-(4,6-Dim eth oxy-1-m eth ylin dol-3-yl)-2-h ydroxyacetyl]pyrrolidin e (17)
1-(4,6-Dim eth oxy-1-m eth ylin dol-3-ylglyoxyloyl)pyrrolidin e (15) (0.12 g, 0.38 m m ol) an d
sodium boroh ydride (0.36 g, 9.52 m m ol) in absolute eth an ol (45 m l) was stirred for 3 h .
A sm all am oun t of 10% sodium h ydroxide was added an d th e solven t was evaporated. Th e
wh ite precipitate was filtered off, wash ed with water an d dried to afford th e title com poun d
as a wh ite solid (0.11 g, 92%). 1H NMR (300 MHz, CDCl3 + [(CD3)2SO]): 1.52–1.58 m , 4 H
(CH2); 2.71–3.35 m , 4 H (CH2); 3.43 s, 3 H (Me); 3.56, 3.58 2 s, 6 H (OMe); 4.34 d, 1 H, J =
5.6 (CHOH); 5.01 d, 1 H, J = 5.6 (CHOH); 5.89 d, 1 H (H5); 6.02 s, 1 H (H2); 6.09 d, 1 H
(H7). 13C NMR (75 MHz, CDCl3 + [(CD3)2SO]): 23.14, 25.17, 45.32, 45.99, CH2; 29.84, Me;
54.58 an d 54.98, OMe; 65.31, CHOH; 84.62, C5; 90.90, C7; 98.32, C2; 111.20, 132.85,
138.78, ArC; 153.01 an d 157.14, C-OMe; 168.60, CO.
2-Ben zoylin dole (18)
A solution of sodium h ydroxide (1.29 g, 32.25 m m ol) in m eth an ol (75 m l) was added to
isatin (4.65 g, 0.032 m ol) an d th e m ixture was refluxed for 1 h . After coolin g, th e m eth an ol
was evaporated, an d th e residue was suspen ded in dry dim eth ylform am ide (30 m l). A solu-
tion of ph en acyl brom ide (6.47 g, 0.033 m ol) in dry dim eth ylform am ide (20 m l) was added
an d th e m ixture was h eated at 100 °C for 16 h . It was cooled an d th en poured in to a m ix-
ture of ice an d 10% h ydroch loric acid (40 m l). Th e resultin g precipitate was filtered off,
Collect. Czech. Chem. Commun. 2009, Vol. 74, Nos. 7–8, pp. 1137–1150

Acid-Catalysed Reactions
1147
wash ed with water, dried, suspen ded in 20% aqueous sodium h ydroxide solution (100 m l)
an d refluxed for 12 h . After coolin g, th e m ixture was diluted with water an d th e product
was extracted with dich lorom eth an e. Th e com bin ed extract was dried over an h ydrous
m agn esium sulfate, evaporated un der reduced pressure an d recrystallized from dich loro-
m eth an e/ligh t petroleum to afford th e title com poun d as a wh ite solid (3.13 g, 44%), m .p.
147–148 °C (lit.9 gives 149–150 °C). 1H NMR (300 MHz, CDCl3): 7.15–7.20 m , 2 H (ArH);
7.36–7.41 m , 1 H (ArH); 7.47–7.66 m , 4 H (ArH); 7.73 m , 1 H (ArH); 7.99 m , 2 H (ArH);
9.28 bs, 1 H (NH). 13C NMR (75 MHz, CDCl3): 112.30, 112.97, 120.93, 123.13, 126.44,
128.40, 129.22 an d 132.29, ArCH; 127.63, 134.30, 137.32, 138.01, ArC; 187.35, CO.
1-Allyl-2-ben zoylin dole (20)
2-Ben zoylin dole 18 (0.84 g, 3.80 m m ol) an d fresh ly crush ed potassium h ydroxide (0.85 g,
0.015 m ol) in dry dim eth yl sulfoxide (15 m l) were stirred for 1 h . Allyl ch loride (0.62 m l,
7.61 m m ol) an d sodium iodide (1.14 g, 7.61 m m ol) were added an d th e m ixture was stirred
for 1 h . Water was added an d th e m ixture was extracted with dich lorom eth an e. Th e com -
bin ed extract was wash ed with brin e, dried over an h ydrous m agn esium sulfate an d evapo-
rated un der reduced pressure. Th e crude product was purified usin g flash ch rom atograph y
with ch loroform /ligh t petroleum (1:1) eluen t to afford th e keton e 20 as a yellowish solid
(0.93 g, 93%), m .p. 66–67 °C. IR (Nujol): 3060, 1640, 1520, 1460, 1380, 1340, 1270, 1210,
1170, 1140, 1000, 930, 825, 800, 745, 730, 705, 690. UV (CH2Cl2 (ε)): 227 (30,800), 250
(24,200), 319 (33,500). 1H NMR (300 MHz, CDCl3): 5.03 m , 1 H (H3′); 5.16 m , 1 H (H3′);
5.28 m , 2 H (H1′); 6.04–6.17 m , 1 H (H2′); 7.06 s, 1 H (H3); 7.20 m , 1 H (ArH); 7.38–7.64 m ,
5 H (ArH); 7.71 m , 1 H (ArH); 7.94 m , 2 H (ArH). 13C NMR (75 MHz, CDCl3): 46.98, C1′;
116.12, C3′; 134.03, C2′; 110.72, 115.29, 120.85, 122.96, 125.91, 128.10, 129.62, 132.07,
ArCH; 128.55, 134.38, 139.30,139.74, ArC; 188.36, CO. MS (EI), m/z (%): 261 (25) [M• +], 105
(40), 78 (35), 77 (100), 41 (68). For C18H15NO calculated: 82.7% C, 5.8% H, 5.4% N; foun d:
82.3% C, 5.9% H, 5.2% N.
1-Allyl-2-ben zoyl-4,6-dim eth oxyin dole (21)
2-Ben zoyl-4,6-dim eth oxyin dole10 (19) (0.56 g, 1.99 m m ol) an d fresh ly crush ed potassium
h ydroxide (0.45 g, 8.02 m m ol) in dry dim eth yl sulfoxide (10 m l) were stirred for 1 h . Allyl
ch loride (0.33 m l, 4.05 m m ol) an d sodium iodide (1.19 g, 7.94 m m ol) were added an d th e
m ixture was stirred for an addition al 1 h . Water was added an d th e precipitate was filtered
off, wash ed with water an d dried to afford th e keton e 21 as a yellow solid (0.62 g, 97%),
m .p. 112 °C. IR (Nujol): 1600, 1580, 1445, 1370, 1270, 1240, 1200, 1180, 1150, 1110, 1080,
990, 925, 910, 890, 800, 730, 715, 690. UV (MeOH (ε)): 255 (18,500), 350 (20,900). 1H NMR
(300 MHz, (CD3)2SO): 3.83 s, 6 H, OMe; 4.87 m , 1 H (H3′); 5.06 m , 1 H (H3′); 5.21 m , 2 H
(H1′); 5.96–6.05 m , 1 H (H2′); 6.26, 6.63, 6.86 3 s, 3 H (H5, H3, H7); 7.51–7.66 m , 3 H
(ArH); 7.78 m , 2 H (ArH). 13C NMR (300 MHz, (CD3)2SO): 46.79, C1′; 115.92, C3′; 134.87,
C2′; 55.59 an d 55.89, OMe; 85.80, C5; 93.24, C7; 113.48, C3; 128.59, 129.29, 132.20, ArCH;
111.92, 132.20, 139.45, 141.91, ArC; 155.07 an d 161.09, C-OMe; 186.60, CO. MS (EI), m/z
(%): 322 (25) [M• + + 1], 321 (100) [M• +], 244 (20), 105 (90), 77 (90), 41 (75). For C20H19NO3
calculated: 74.7% C, 6.0% H, 4.4% N; foun d: 74.6% C, 5.9% H, 4.6% N.
Collect. Czech. Chem. Commun. 2009, Vol. 74, Nos. 7–8, pp. 1137–1150

1148
Santoso, Kumar, Black:
(1-Allylin dol-3-yl)ph en ylm eth an ol (22)
1-Allyl-2-ben zoylin dole (20) (0.93 g, 3.56 m m ol) an d sodium boroh ydride (0.72 g, 19.03 m m ol)
in absolute eth an ol (40 m l) were stirred for 1 h . Th e m ixture was evaporated un der reduced
pressure to dryn ess, th e residue was suspen ded in aqueous sodium h ydroxide (10%) an d th e
resultin g precipitate was filtered off, wash ed with water an d dried to yield th e alcoh ol 22 as
a wh ite solid (0.76 g, 81%), m . p. 94–95 °C. IR (Nujol): 3400, 1450, 1400, 1370, 1310, 1260,
1200, 1160, 1130, 985, 920, 840, 790, 740, 730, 710. UV (MeOH (ε)): 224 (36,500), 277
(8,200). 1H NMR (300 MHz, CDCl3): 4.69–4.87 m , 2 H (H1′); 4.92 m , 1 H (H3′); 5.13 m , 1 H
(H3′); 5.81–5.93 m , 1 H (H2′); 6.01 d, 1 H, J = 4.9 (CHOH); 6.32 s, 1 H (H3); 7.18 m , 1 H
(ArH); 7.25–7.49 m , 7 H (ArH); 7.63 m , 1 H (ArH). 13C NMR (75 MHz, CDCl3): 45.97, C1′;
116.11, C3′; 133.62, C2′; 69.65, CHOH; 102.07, 109.67, 119.66, 120.83, 121.93, 126.60,
127.82, 128.35, ArCH; 127.14, 137.61, 141.05, 141.21, ArC. MS (EI), m/z (%): 266 (20)
[M• + + 1], 263 (100) [M• +], 246 (30), 221 (20), 204 (55), 186 (20), 168 (40), 158 (70), 156
(50), 144 (35), 130 (40), 117 (50), 105 (85), 77 (60), 41 (45). For C18H17NO·0.5H2O calcu-
lated: 79.4% C, 6.7% H, 5.1% N; foun d: 79.2% C, 6.5% H, 5.1% N.
(1-Allyl-4,6-dim eth oxyin dol-2-yl)ph en ylm eth an ol (23)
A m ixture of 1-allyl-2-ben zoyl-4,6-dim eth oxyin dole (21) (0.38 g, 1.18 m m ol) an d sodium
boroh ydride (0.22 g, 5.82 m m ol) in absolute eth an ol (50 m l) was stirred for 1 h . Th e m ix-
ture was evaporated to dryn ess an d th e residue was suspen ded in aqueous sodium h ydroxide
(5%). Th e resultin g precipitate was filtered off, wash ed with water an d dried to afford th e
title alcoh ol as a wh ite solid (0.37 g, 97%), m . p. 119–120 °C. IR (Nujol): 3420, 1650, 1640,
1595, 1450, 1375, 1250, 1205, 1160, 1140, 1085, 1040, 980, 910, 790, 765, 740, 720, 695.
UV (MeOH (ε)): 226 (13,800), 276 (4,300). 1H NMR (300 MHz, CDCl3): 3.83 an d 3.87 2 s,
6 H (OMe); 4.62–4.81 m , 2 H (H3′); 4.86 m , 1 H (H1′); 5.09 m , 1 H (H1′); 5.78–5.95 m , 1 H
(H2′); 5.94 d, 1 H, J = 4.9 (CHOH); 6.20 d, 1 H, J = 1.7 (H5); 6.23 s, 1 H (H3); 6.33 d, 1 H,
J = 1.7 (H7); 7.26–7.44 m , 5 H (ArH). 13C NMR (75 MHz, CDCl3): 46.17, C1′; 116.00, C3′;
133.60, C2′; 55.22 an d 55.62, OMe; 85.74, C5; 91.47, C7; 99.60, C3; 126.49, 127.65, 128.28,
ArCH; 112.08, 138.43, 139.07, 141.39, ArC; 153.74 an d 157.65, C-OMe. MS (EI), m/z (%):
323 (60) [M• +], 306 (20), 105 (100), 77 (40), 41 (55).
5,11-Diallyl-6,12-diph en yl-6,12-dih ydro-5H,11H-in dolo[3,2-b]carbazole (24)
(1-Allylin dol-3-yl)ph en ylm eth an ol (22) (0.06 g, 0.23 m m ol) in ben zen e was treated with a
catalytic am oun t of boron trifluoride dieth yl eth erate an d stirred for 30 m in . Th e solution
was evaporated an d th e crude product was purified usin g flash ch rom atograph y with di-
ch lorom eth an e eluen t to yield th e com poun d 24 as a wh ite solid (0.04 g, 71%), m .p.
308–309 °C. IR (Nujol): 1450, 1370, 1160, 1010, 990, 915, 860, 800, 770, 730, 720, 700. UV
(CH2Cl2 (ε)): 234 (56,100), 287 (17,500), 294 sh (16,400). 1H NMR (300 MHz, CDCl3):
4.41–4.74 m , 4 H (H1′); 4.79 m , 2 H (H3′); 4.96 m , 2 H (H3′); 5.35–5.47 m , 2 H (H2′); 5.76 s,
2 H (CH bridgin g); 6.97 m , 2 H (ArH); 7.06–7.29 m , 10 H (ArH); 7.36 m , 4 H (ArH); 7.47 m ,
2 H (ArH). 13C NMR (75 MHz, CDCl3): 40.03, CH bridgin g; 45.96, C1′; 115.89, C3′; 133.10,
C2′; 109.35, 118.99, 119.08, 121.18, 126.55, 128.57, 128.85, ArCH; 112.07, 125.74, 135.75,
137.63, 143.65, ArC. MS (EI), m/z (%): 491 (35) [M• + + 1], 490 (100) [M• +], 449 (30), 413
(70), 372 (25), 331 (75). For C36H30N2·0.5CH2Cl2 calculated: 82.2% C, 5.9% H, 5.3% N;
Collect. Czech. Chem. Commun. 2009, Vol. 74, Nos. 7–8, pp. 1137–1150

Acid-Catalysed Reactions
1149
foun d: 82.2% C, 5.8% H, 5.2% N. Crystals for a sin gle crystal X-ray determ in ation were ob-
tain ed by recrystallization from dich lorom eth an e/ligh t petroleum .
5,11-Diallyl-1,3,7,9-tetram eth oxy-6,12-diph en yl-6,12-dih ydro-
5H,11H-in dolo[3,2-b]carbazole (25)
(1-Allyl-4,6-dim eth oxyin dol-2-yl)ph en ylm eth an ol (23) (0.10 g, 0.31 m m ol) in ben zen e was
treated with a catalytic am oun t of boron trifluoride dieth yl eth erate an d stirred for 1 h . Th e
solven t was evaporated an d th e crude product was purified usin g flash ch rom atograph y with
dich lorom eth an e eluen t to afford th e com poun d 25 as a wh ite solid (0.07 g, 74%), m .p.
118–119 °C. IR (Nujol): 1600, 1580, 1450, 1375, 1250, 1200, 1150, 1050, 920, 800, 700. UV
(CH2Cl2 (ε)): 234 (93,800), 281 (30,500), 344 (4,400). 1H NMR (300 MHz, CDCl3): 3.81 an d
3.94 2 s, 12 H (OMe); 4.58 d, 4 H (H1′); 4.85 m , 2 H (H3′); 4.98 m , 2 H (H3′); 5.50–5.61 m ,
2 H (H2′); 5.84 s, 2 H (CH bridgin g); 6.22 d, 2 H, J = 1.8 (H5); 6.30 d, 2 H, J = 1.8 (H7);
7.09–7.27 m , 6 H (ArH); 7.45 m , 4 H (ArH). 13C NMR (75 MHz, CDCl3): 39.44, CH bridgin g;
45.89, C1′; 116.19, C3′; 133.12, C2′; 54.63 an d 55.67, OMe; 85.99, C5; 91.25, C7; 125.96,
127.70, 129.58, ArCH; 112.61, 127.45, 135.34, 138.58, 144.48, ArC; 154.09 an d 156.77,
C-OMe. MS (EI), m/z (%): 610 (25) [M• +], 533 (30), 305 (35), 91 (85), 77 (70), 41 (100). For
C
40H38N2O4 calculated: 78.7% C, 6.3% H, 4.6% N; foun d: 78.7% C, 6.4% H, 4.5% N.
Crystallograph ic Study on Com poun d 24
Crystal data. C36H30N2·(CH2Cl2)0.5, M = 533.1, triclin ic, space group P1, a = 10.830(5) Å,
b = 11.408(4) Å, c = 12.847(5) Å, α = 66.88(3)°, β = 80.77(3)°, γ = 76.53(3)°, V = 1415(1) Å3,
DC = 1.25 g cm –3, Z = 2, µCu = 13.92 cm –1. Crystal size 0.21 × 0.24 × 0.24 m m , 2θm ax = 140°,
m in im um an d m axim um tran sm ission factors 0.72 an d 0.79. Th e n um ber of reflection s was
4272 con sidered observed out of 5371 un ique data. Fin al residuals R, Rw were 0.052, 0.070
for th e observed data.
Structure determination. Reflection data were m easured with an En raf–Non ius CAD-4
diffractom eter in θ/2θ scan m ode usin g graph ite m on och rom atized copper radiation (λ =
1.54184 Å). Data were corrected for absorption usin g th e an alytical m eth od of De Meulen aer
an d Tom pa15. Reflection s with I > 3σ(I) were con sidered observed. Th e structure was deter-
m in ed by direct ph asin g an d Fourier m eth ods. Th e solven t m olecule with occupan cy 0.5
was disordered about a cen tre of sym m etry, an d was refin ed as a rigid body with idealised
geom etry. Hydrogen atom s were in cluded in calculated position s an d were assign ed th erm al
param eters equal to th ose of th e atom to wh ich th ey were bon ded. Position al an d
an isotropic th erm al param eters for th e n on -h ydrogen atom s were refin ed usin g full-m atrix
least-squares. Reflection weigh ts used were 1/σ2(Fo), with σ(Fo) bein g derived from σ(Io) =
2
[σ2(Io) + (0.04Io)2]1/2. Th e weigh ted residual is defin ed as Rw = (∑w∆2/∑wF0
)
1/2. Atom ic scat-
terin g factors an d an om alous dispersion param eters were from In tern ation al Tables for X-ray
17
Crystallograph y16. Structure solution s were by SIR92
an d refin em en t used RAELS 18
.
ORTEP-II 19 run n in g on Power MacIn tosh was used for th e structural diagram s, an d a DEC
Alph a-AXP Workstation was used for calculation s.
CCDC 721778 con tain s th e supplem en tary crystallograph ic data for th is paper. Th ese
data can be obtain ed free of ch arge via www.ccdc.cam .ac.uk/con ts/retrievin g.h tm l (or from
th e Cam bridge Crystallograph ic Data Cen tre, 12, Un ion Road, Cam bridge, CB2 1EZ, UK;
fax: +44 1223 336033; or deposit@ccdc.cam .ac.uk).
Collect. Czech. Chem. Commun. 2009, Vol. 74, Nos. 7–8, pp. 1137–1150

1150
Santoso, Kumar, Black:
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