Thiones as reactive intermediates in condensations of diketones with aromatics mediated by tetraphosphorus decasulfide

Article abstract of DOI:10.1080/10426500214887

Phenanthrene-9,10-quinone and P₄S₁₀ react with phenols on being heated to give oxathiins, e.g., 9 the dioxin 22, ethers, e.g., 14 arylphenanthrenols, e.g., 10 and furanols, e.g., 17 in addition to sulfides, e.g., 26 and disulfides, e

Full text of DOI:10.1080/10426500214887

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Phosphorus, Sulfur, and Silicon and the Related
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Thiones as Reactive Intermediates in Condensations of
Diketones with Aromatics Mediated by Tetraphosphorus
Decasulfide
a
a
Brian J. Morrison & Oliver C. Musgrave
a
The University , Old Aberdeen, Scotland
Published online: 27 Oct 2010.
To cite this article: Brian J. Morrison & Oliver C. Musgrave (2002) Thiones as Reactive Intermediates in Condensations of
Diketones with Aromatics Mediated by Tetraphosphorus Decasulfide, Phosphorus, Sulfur, and Silicon and the Related Elements,
177:12, 2725-2744, DOI: 10.1080/10426500214887
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Phosphorus, Sulfur and Silicon, 2002, Vol. 177:2725–2744
Copyright �C 2002 Taylor & Francis
1
042-6507/02 $12.00 + .00
DOI: 10.1080/10426500290146730
THIONES AS REACTIVE INTERMEDIATES
IN CONDENSATIONS OF DIKETONES
WITH AROMATICS MEDIATED BY
TETRAPHOSPHORUS DECASULFIDE
Brian J. Morrison and Oliver C. Musgrave
The University, Old Aberdeen, Scotland
(Received December 31, 2001; accepted March 14, 2002)
Phenanthrene-9,10-quinone and P S react with phenols on being
4
10
heated to give oxathiins, e.g., 9 the dioxin 22, ethers, e.g., 14 arylphenan-
threnols, e.g., 10 and furanols, e.g., 17 in addition to sulfides, e.g., 26
and disulfides, e.g., 25. Under similar conditions benzil gives thiophene
derivatives, e.g., 2. Most of the reactions appear to proceed via thione
intermediates but some of the products are also formed when P S is
4
10
absent.
Keywords: Diketones; furans; tetraphosphorus decasulfide; thiones;
thiophenes
INTRODUCTION
Condensations of diketones with aromatics have provided several types
1,2
of polycarbocyclic compounds. With the object of preparing polycyclics
containing thiophene rings, we have investigated reactions between
aromatic 1,2-diketones and phenols in the presence of tetraphosphorus
decasulfide, P4S10.
RESULTS AND DISCUSSION
The reaction between benzil, P4S10 and either phenol or catechol at
�
1
70 C gave 2-phenylbenzothiophene 1 (14.7%) and tetraphenylthio-
phene 2 (24.8%). The phenols took no part in the reaction and when
omitted the same products were obtained together with a small amount
(
3.9%) of the thienothiophene 3. A similar reaction between thenil,3
Address correspondence to O. C. Musgrave, Chemistry Department, The University,
Old Aberdeen AB24 3UE, Scotland, United Kingdom. E-mail: o.c.musgrave@abdn.ac.uk
2
725

2
726
B. J. Morrison and O. C. Musgrave
phenol, and P4S10 gave a little (1.8%) of the thienothiophene 4 the UV
4
absorption of which resembled that of the parent thienothiophene 5.
Intramolecular cyclisation again occurred and the phenol was not in-
corporated into the product.
To encourage intermolecular reaction we replaced benzil by
phenanthrene-9,10-quinone in which the carbonyl groups are part of
a rigid structure and have a cis orientation. The quinone reacted with
�
phenol and P4S10 at 160 C to give the oxathiin 7 (10.6%) (where ‘A’
represents the partial formula 6), the ether 14 (16.1%), and the diol
10 (21.5%). The UV absorption shown by the diol 10 and by the other
arylphenanthrenols 11–13 produced in related reactions closely resem-
5
bles that of phenanthren-9-ol and indicates the nature of the major
aromatic system present. As with all the other phenanthrene deriva-
tives described here, only a partial interpretation of the NMR signals
for the aromatic protons of these compounds is possible. Some of the
6
low-field signals can be assigned to the “bay” protons at C-4 and C-5,
7
and to those at C-1 and C-8 if heteroatom substituents are present in
the peri positions as in the oxathiin 7. In the diol 10 the aryl protons of
0
0
the hydroxyphenyl group appear as a deceptively simple AA XX system
0
and so establish that the hydroxy group is at C-4 . Of the two hydroxy
proton signals at � 5.50 and 8.50, the former can be assigned to the hy-
droxy group is at C-9 which is shielded by the ring current of the C-10
aryl substituent. The hydroxy protons of the simple analogue biphenyl-
0
8
2
,2 -diol give a signal at � 5.65. In the diacetate of 10 the protons of
the C-9 acetoxy group are shielded in a similar manner, the signal at �
9
2
.10 being close to that shown by 2-acetoxybiphenyl at � 2.08.
The reaction of catechol with phenanthrenequinone and P4S10 gave
two products, the dioxin 22 (18.6%) and the furanol 17 (38.7%). The
0
0
NMR spectrum of the former shows a highly symmetrical AA XX mul-
tiplet for the four aryl protons of the o-phenylenedioxy group so con-
firming the symmetrical structure of the molecule. The UV absorption
of the acetate of the furanol 17 resembles closely that1 of the unsub-
stituted furan 16 and indicates the nature of the polycyclic aromatic
system present. The other acetates derived from the related furanols
0
1
8–21 show similar UV spectra. The NMR spectrum of the furanol 17
shows the expected three-proton AMX system for the protons at C-11,
12, and -13; the signal at lowest field (� 7.97) results from the proton at
-
C-13 which is close to C-1 and is further deshielded by the ring current
in the phenanthrene system.
�
Phenanthrenequinone also reacted with catechol at 160 C in the ab-
sence of P4S10 to give the dioxin 22 and the furanol 17, both in much
lower yield, and the triol 11 (15.9%). The structure of the last-named
in which arylation has occurred ortho to an hydroxy group rather than

Thiones as Reactive Intermediates in Condensations
2727
para follows from its NMR and mass spectra. Thus the aryl protons
of the dihydroxyphenyl group show signals typical of an AMX sys-
tem, the coupling constants resembling those found for the correspond-
ing protons in the furanol 17. The presence of hydroxy groups at C-9
0
and -2 explains the ready loss of water from the molecular ion to

2
728
B. J. Morrison and O. C. Musgrave
produce a polycyclic furan ion-radical the subsequent fragmentation
of which resembles that of the molecular ion derived from the fura-
nol 17. The NMR spectrum of the triacetate derived from the triol
1
1 shows proton signals at � 1.82, 2.17, and 2.31 the first two of
which we assign to the protons of the acetoxy groups at C-9 and
C-2 , respectively, both of which are shielded by the adjoining aromatic
0
rings.
The reaction of resorcinol with phenanthrenequinone in the pres-
ence of P4S10 gave the expected products, the furanol 18 (58.0%) and
the triol 12 (9.0%). When the reaction was repeated with the omission
of the P4S10 the same products were obtained but in significantly dif-
ferent yields (5.0% and 27.0% respectively). Hydroquinone behaved in
a similar fashion giving the furanol 19 (30.8%), the triol 13 (9.6%), and
a little of an oxathiinol which we isolated as the acetate 8 which shows
UV absorption resembling that of the unsubstituted oxathiin 7.
Phloroglucinol reacted with phenanthrenequinone and P4S10 at
20 C to produce the furandiol 21 (11.4%) which gives an aromatic pro-
�
2
ton NMR signal at unusually low field (ca. � 9.87). We assign this to H-1
1
1
which is strongly deshielded by the nearby hydroxy group at C-13. The
deshielding of the C-13 acetoxy protons of the corresponding diacetate
is likewise a consequence of the proximity of the phenanthrene ring sys-
tem. Several products resulted from the reactions between pyrogallol
�
and phenanthrenequinone. With P4S10 at 160 C we obtained the mono
hydroxy furans 17 (7.5%) and 18 (12.5%) which we had previously pre-
pared from catechol and resorcinol. When the P4S10 was omitted the
products were the expected furandiol 20 (12.4%) and the correspond-
ing uncyclised tetraol which we isolated as the tetra-acetate 23 (13.6%)
because it rapidly underwent aerial oxidation.
The products from the reactions of naphthols with phenan-
threnequinone and P4S10 proved to be more diverse. 1-Naphthol gave
the naphthofuran 24 (74.8%), the disulfide 25 (11.0%), and the naph-
thylthiophenanthrene 26 (2.2%). The UV absorption of the naphthofu-
ran shows a marked resemblance to that of its benzenoid analogue
16. The NMR spectrum of the monosulfide 26 shows a two-proton
multiplet centered at � 8.43 which we assign to the peri protons at
0
C-8 and -8 . In the absence of P4S10 1-naphthol reacted with phenan-
threnequinone to give the expected products, the naphthofuran 24
(
6.9%) and the corresponding diol 27 (47.2%). The NMR signals for the
shielded hydroxy protons of the latter appear at � 5.43 and 5.58 while
the mass spectrum shows the characteristic ready loss of water from
the molecular ion. 2-Naphthol behaved in a completely different fash-
ion. It failed to react when heated with phenanthrenequinone alone and

Thiones as Reactive Intermediates in Condensations
2729
in the presence of P4S10 gave the ether 28 (7.9%) and small amounts
of the sulfide 29, the disulfides 30 and 31, and the naphthylthionaph-
thol 32. There was no evidence of any phenanthrene-naphthalene bond
formation.
Lawesson’s reagent,12 the dimer of p-methoxyphenylthionophos-
phinesulfide, resembles P4S10 in its abiliity to convert ketones into
thiones, and we briefly examined its effect on reactions between
�
phenanthrenequinone and various phenols at 160 C. Phenol itself pro-
duced no recognisable products but catechol gave the dioxin 22 (3.5%),
the disulfide 31 (12.9%), the furanol 17 (14.4%), the oxathiinol 9 (4.1%),
and the hydroxyether 15 (8.4%). The oxathiinol and the hydroxyether
show UV absorption resembling that of the parent compounds 7 and 14
respectively. Similar reactions with resorcinol and with hydroquinone
gave the furanols 18 (45.7%) and 19 (56.5%).
We also examined the reactions of P4S10 with other cyclic dicarbonyl
compounds. Acenaphthenequinone gave a little of the thiophene 33
while o-chloranil afforded a compound C12HCl7OS (3.3%) which we for-
mulate as the hydroxydibenzothiophene 34, and which is presumably
derived from the corresponding octa-chloro compound 35. Calculations
based on the dimensions of dibenzothiophene13 show that the chlorine
atoms at C-4 and -5 in 35 overlap considerably. Replacement of one of
these by the less bulky hydroxy group at some point in the reaction pro-
cedure would be facilitated as this would reduce the distortion present
in the molecule.
The plethora of products obtained together with the wide range of
yields suggest that more than one reaction mechanism is involved.
The sulfur-containing compounds clearly result from the mono- and di-
14
thiones formed from the reactants and P4S10. Now the thione group
+
�
� +
15
can behave as a dipolar system [R2C- S ↔ R2C- S] or as a diradical
˙
˙
R2C-S and mechanisms involving such entities can account for all the
products obtained in the present work. Thus the dithione formed from
benzil may be represented as the diradical 36; double ring-closure and
subsequent dehydrogenation by sulfur would give the thienothiophene
3
. The formation of many of the other products involves a reduction
step which appears to be the extrusion of sulfur from the molecule.
For example monocyclization of the diradical 36 and thiiran formation
gives the diradical 37 which by hydrogen atom migration and loss of
sulfur from the thiiran group, gives the thiophene 1. The thienothio-
phene 4 can be derived in a similar manner from thenil. Dimerisation of
the diradical 36 would lead to the tricyclic structure 38 which would lose
1
6
1
7
sulfur from both the thiiran and dithietan rings giving the thiophene
. The thiophenes 33 and 35 would be formed in a similar manner.
2

2
730
B. J. Morrison and O. C. Musgrave
The 2-naphthyl sulfides and disulfides appear to result from the thione
1
8
3
9 corresponding to the keto tautomer of 2-naphthol. “Polar” dimer-
ization of this and subsequent elimination of hydrogen sulfide would
give the sulfide 29 while reaction with 2-naphthol and loss of hydro-
gen sulfide would lead to the ether 28. “Radical” dimerization of the
thione followed by dehydrogenation by sulfur would provide the disul-
fide 30 while a comparable radical substitution reaction between the
thione and 2-naphthol would lead to the hydroxysulfide 32. The disul-
fide 31 presumably results from a radical dimerization of the dithione
formed from phenanthrenequinone which leads to a diradical such as

Thiones as Reactive Intermediates in Condensations
2731
40. Abstraction of hydrogen from the phenol present in the reaction
followed by extrusion of sulfur then occurs. In its reaction with phenan-
threnequinone and P4S10 1-naphthol resembled its 2-isomer in giving
the disulfide 25 but it also afforded the mixed sulfide 26. We suggest
that in the latter case the thione produced from the keto tautomer of
1
-naphthol adds by a radical process to the dithione derived from
phenanthrenequinone to give, after hydrogen atom migration, the dithi-
etan 41 which finally loses two atoms of sulfur.
The formation of the oxathiin 7 could proceed via the adduct 42
which would then undergo successive cyclization, hydrogen atom mi-
gration, and loss of hydrogen sulfide. Hydrogen atom migration from
sulfur to carbon in the diradical 42 and subsequent loss of sulfur from
the resulting dithietan would give the ether 14. The formation of the
carbon-carbon bond in the phenanthrenediol 10 suggests that the phe-
nol present undergoes electrophilic attack by the monothione to give
the dipolar species 43 which after cyclization to a hydroxythiiran and
loss of sulfur provides the diol. Although the ether 14 and the diol 10 do
not contain sulfur their formation nevertheless requires the presence
of P4S10 (and consequently the production of the intermediate thiones)
because phenol and phenanthrenequinone failed to react when heated
together. The dioxin 22 appears to result from nucleophilic addition of
both hydroxy groups of catechol to the dithione followed by elimination
of hydrogen sulfide and sulfur from the intermediate dithiol 44. A sim-
ilar addition involving only one of the hydroxy groups and subsequent
cyclization would provide the isomeric dithiol 45, which would fragment
in a similar manner to give the furanol 17. The formation of the products
from the other phenols can be explained by similar reaction sequences.
The unexpected monohydric furanols 17 and 18 obtained from pyro-
gallol must result from the thiones derived from the keto tautomers of
the furandiol 20. For example the thione 46 could undergo hydrogen
migration and thiiran formation followed by extrusion of sulfur to give
the furanol 18.
When P4S10 was omitted the combined yields of all the products from
the reactions of catechol and of resorcinol with phenanthrenequinone
were considerably lower than when P4S10 was present. Presumably the
formation of the triol 11 now occurred via the intermediate hydrox-
yketone 47 which then underwent reduction by the excess of catechol
present followed by dehydration. We associate the relatively high yield
of the triol 13 with its being derived from hydroquinone which is a par-
ticularly good reducing agent. Similar conventional mechanisms each
involving a reduction step can be devised for the formation of the fura-
nols obtained under comparable conditions.

2
732
B. J. Morrison and O. C. Musgrave
The efficient conversion of anthraquinone into anthracene (76.9%)
by treatment with P4S10 in the presence of phenol appears to occur via
the corresponding dithione. This would abstract hydrogen atoms from
the phenol forming the dithietan 48 which would then lose sulfur.
EXPERIMENTAL
IR spectra were recorded for KBr discs and UV absorption spectra for
methanolic solutions (except where indicated); ε values are given in
3
� 1
� 1
1
units of dm mol cm and infl denotes an inflexion. H NMR spectra
were measured at 220 MHz for solutions in deuterochloroform (unless
otherwise stated) with tetramethylsilane as internal standard. Mass
spectra were obtained using electron impact at 70 eV. TLC and PLC
were performed using Merck Kieselgel GF254. “Light petroleum” refers
�
to the fraction b.p. 60–80 C. The yields of products are based on the
initial weights of the dicarbonyl compounds (or, where appropriate, of
the naphthols) used and were not optimalized.
Reaction of Benzil with P S to Give 1, 2, and 3
4
10
(
a) A mixture of benzil (5 g, 23.81 mmol), phenol (5 g, 53.19 mmol),
and P4S10 (Aldrich, 5 g, 11.26 mmol) was heated under nitrogen at
1
�
70 C with stirring for 2 h and poured into water. Extraction with
chloroform afforded a solid which on being subjected to PLC using
light petroleum gave two bands. The faster-moving of these afforded 2-
�
+
phenylbenzothiophene 1 (734 mg, 3.50 mmol, 14.7%), m.p. 173–174 C
19
�
(
2
lit., 175–176 C) which crystallized from light petroleum (Found: M ,
+
10.0495. Calc. for C14H10S: M, 210.0502); m/z 210 (100%, M ), 178
5, M-S), 165 (10, M-CHS), and 105 (5, M ); �max (Et2O)/nm 234 (log ε
2+
(

Thiones as Reactive Intermediates in Condensations
2733
�
4
7
.31), 256 (4.11), 260infl (4.10), 301 (4.37), and 318infl (4.14); �max/cm 1
58 and 688 (5 adjacent ArH) and 745 (4 adjacent ArH); �H 7.1–8.0
(
(
m, ArH). The slower-moving band afforded tetraphenylthiophene 2
�
20
�
1.143 g, 2.95 mmol, 24.8%) m.p. 183–184 C (lit., 184–185 C) from
+
light petroleum. (Found: M , 388.1289. Calc. for C28H20S: M, 388.1286);
m/z 388 (100%, M ), 354 (10, M-H2S), 310 (3, M-C6H6), and 278 (2, 310-
+
�
1
S); �max (Et2O)/nm 248 (log ε 4.43), and 313 (4.22); �max/cm 760, 750,
08, and 696 (5 adjacent ArH); �H 7.0–7.4 (m, ArH).
b) A similar reaction between benzil and P4S10 alone gave three
7
(
products after PLC. The fastest-moving component crystallized from
light petroleum to give benzthieno[3,2-b]benzothiophene 3 (220 mg,
�
21
�
+
0
2
(
.92 mmol, 3.9%) m.p. 210–212 C (lit., 215–216 ) (Found: M ,
+
40.0062. Calc. for C14H8S2: M, 240.0066); m/z 240 (100%, M ), 208
5, M-S), 195 (3, M-CHS), and 120 (5, M ); �max (Et2O)/nm 240 (log ε
2+
4
3
.19), 256 (4.17), 264 (4.21), 296infl (4.18), 306 (4.22), 316infl (4.07), and
30 (3.87); �max/cm 742 (4 adjacent ArH), �H 7.25–7.58 and 7.65–7.97
�
1
(
(
both 4H, m, ArH). The other products were the phenylthiophenes 1
572 mg, 2.72 mmol, 11.5%) and 2 (1.035 g, 2.67 mmol, 22.4%).
Reaction of 2,2’-Thenil with P S to Give 4
4
10
The product from a similar reaction between 2,2 -thenil3 (2 g,
0
9
1
.01 mmol), phenol (4 g, 42.55 mmol), and P4S10 (2 g, 4.50 mmol) at
60 C was dissolved in chloroform and washed with aqueous sodium
�
hydroxide. The alkali-insoluble material on being subjected to PLC us-
ing light petroleum gave 2-(2 -thienyl)thieno[3,2-b]thiophene 4 (35 mg,
0
�
+
0
2
.16 mmol, 1.8%), m.p. 96–98 C (from light petroleum). (Found: M ,
21.9631. C10H6S3 requires M, 221.9631); m/z 222 (100%, M ), 190 (28,
+
M-S), 177 (52, M-CHS), 164 (10, M-C2H2S), and 145 (17, 177-S); �max/nm
�
1
2
1
53 (log ε 3.82), 306infl (3.96), 327 (4.07) and 343infl (3.90); �max/cm
610 aromatic C C), 805 and 695 (3 and 2 adjacent ArH); �H 7.00–7.06
(
1H, m, ArH) and 7.19–7.37 (5H, m, ArH).
REACTIONS OF PHENANTHRENEQUINONE AND P S
4
10
WITH PHENOLS
P4S10 (1 g, 2.25 mmol) was added to a stirred mixture of phenan-
�
threnequinone (1 g, 4.81 mmol) and the phenol (4 g) at 160 C under
�
nitrogen. After being heated at 160 C for 2 h the mixture was poured
into water, extracted with chloroform, and the chloroform layer was
washed with aqueous sodium hydroxide. Acidification of the latter af-
forded the phenolic components. Both the neutral and the phenolic frac-
tions were separated by PLC (which also removed sulfur) using light

2
734
B. J. Morrison and O. C. Musgrave
petroleum and chloroform respectively, and the components were puri-
fied by crystallization.
1
. With Phenol (42.55 mmol) to Give 7, 10, and 14
The neutral fraction gave rise to two bands, the faster-moving
component crystallizing from chloroform-light petroleum to give
benzo[b]phenanthro[9,10-e]oxathiin 7 as plates (153 mg, 0.51 mmol,
�
+
1
3
2
2
0.6%) m.p. 167–168.5 C (Found: M , 300.0607. C20H12OS requires M,
+
00.0608); m/z 300 (71%, M ), 271 (10, M-CHO), 268 (100, M-S), 239 (29,
2
+
2+
2+
68-CHO), 150 (10, M ), 134 (17, 268 ), and 119.5 (15, 239 ); �max/nm
48 (log ε 4.71), 264infl (4.71), 293infl (3.92), 309 (3.88), 321 (3.90), 341
�
1
(
3.49), 348infl (3.42), and 354 (3.40); �max/cm 1628 and 1604 (aromatic
C C), 760 and 745 (4 adjacent ArH); �H 7.00–7.25 (2H, m, ArH), 7.38–
7
5
.78 (5H, m, ArH), 7.92–8.02 (1H, m, ArH), and 8.27–8.75 (4H, m, 1-, 4-,
-, and 8-H). The slower-moving component crystallized from benzene-
ethanol to give 9-phenoxyphenanthrene 14 (209 mg, 0.78 mmol, 16.1%)
as needles m.p. and mixture m.p. with an authentic specimen 79–80 C
�
22
�
+
(
lit, 80–81 ) (Found: M , 270.1047. Calc. for C20H14O: M, 270.1044);
+
m/z 270 (100%, M ), 241 (18, M-CHO), 176 (11, M-PhOH), and 165
(
2
1
14, M-PhCO); �max/nm 247infl (log ε 4.66), 253 (4.68), 273infl (4.15),
87 (3.91), 298 (3.92), 335 (2.97), and 352 (3.00); �max/cm 1630, 1594,
588 (aromatic C C), 768, 727, and 692 (5 adjacent ArH), and 752 (4
�
1
adjacent ArH); �H 7.04–7.23 (4H, m, ArH), 7.28–7.42 (2H, m, ArH),
7
4
.45–7.77 (5H, m, ArH), 8.27–8.38 (1H, m, 8-H) and 8.55–8.73 (2H, m,
- and 5-H).
The alkali-soluble fraction afforded a solid which crystallized from
0
chloroform-light petroleum to give 10-phenylphenanthrene-4 ,9-diol 10
�
+
(
296 mg, 1.03 mmol, 21.5%) m.p. 165–167 C (Found: M , 286.0995.
+
C20H14O2 requires: M, 286.0993); m/z 286 (100%, M ), 257 (8, M-CHO),
2
18 (36, M-C4H4O), 126 (16, 218-C6H4O), and 94 (12, C6H6O); �max/nm
51 (log ε 4.51), 274infl (4.16), 300infl (3,86), 343 (3.17), and 361 (3.11);
2
�
1
�
max/cm 3400 (phenolic OH), 1595 (aromatic C C), 830 (2 adjacent
ArH) and 760 (4 adjacent ArH); �H 5.50 (1H, brs, 9-OH), 6.61, 6.66,
0
0
0
0
0
0
6
.97, and 7.02 (each 1H, s, AA XX , 3 -, 5 -, and 2 -, 6 -H), 7.33–7.56 (3H,
m, ArH), 7.61–7.85 (3H, m, ArH), 8.03–8.15 (2H, m, 4- and 5-H), and
0
�
8
.50 (1H, brs, 4 -OH). The diacetate m.p. 128–130 C crystallized from
+
chloroform-light petroleum [Found: (M -CH2CO), 328.1102. C22H16O3
requires: M, 328.1099]; m/z 370 (1%, M ), 328 (68, M-CH2CO), 286 (100,
+
3
28-CH2CO), 257 (32, 286-CHO), 239 (11, 257-H2O), and 218 (20, 286-
C4H4O); �max/nm 241infl (log ε 4.93), 259infl (4.44), 268infl (4.37) and
3
�
1
35 (3.73); �max/cm 1755 and 1720 (aryl acetate CO), 1608 (aromatic
C C), 825 (2 adjacent ArH), and 747 (4 adjacent ArH); �H 2.10 and

Thiones as Reactive Intermediates in Condensations
2735
0
2
8
.35 (each 3H, s, 9- and 4 -MeCO2Ar), 6.92–7.98 (10 H, m, ArH), and
.65–8.90 (2H, m, 4- and 5-H).
2
. With Catechol (36.36 mmol) to Give 11, 17, and 22
The neutral fraction, after further PLC using light petroleum-
chloroform, crystallized from the same solvent to give benzo[b]-
phenanthro[9,10-e]dioxin 22 as needles (254 mg, 0.89 mmol, 18.6%)
�
+
m.p. 212–214 C (Found: M , 284.0837. C20H12O2 requires M,
+
2
2
84.0837); m/z 284 (100%, M ), 255 (45, M-CHO), 226 (15, M-2CHO),
02 (4, M-C4H2O2), 142 (18, M ), 113 (14, 226 ), and 101 (8, 202 );
max/nm 236infl (log ε 4.54), 243 (4.58), 256infl (4.22), 265infl (4.13),
35 (3.52), and 371infl (3.10); �max/cm 1597 (aromatic C C), and 751
4 adjacent ArH); �H 6.81–7.10 (4H, AA XX m, 10-, 11-, 12-, and 13-H),
.15–7.70 (4H, m, ArH), 8.12–8.25 (2H, m, 1- and 8-H), and 8.48–8.70
2+
2+
2+
�
�
1
3
(
0
0
7
(
2H, m, 4- and 5-H).
The alkali-soluble fraction crystallized from light petroleum-
chloroform to give benzo[b]phenanthro[9,10-d]furan-10-ol 17 as needles
�
+
(
528 mg, 1.86 mmol, 38.7%) m.p. 265–267 C (Found: M , 284.0837.
+
C20H12O2 requires: M, 284.0837.); m/z 284 (100%, M ), 255 (6, M-
2+
CHO), 226 (22, M-2CHO), 178 (11, C14H10), 142 (17, M ), and 113
17, 2262 ); �max/nm 250 (log ε 4.65), 264 (4.64), 281 (4.12), 308 (4.15),
+
(
3
1
�
1
20 (4.08), 341 (3.41), and 359 (3.55); �max/cm 3400 (phenolic OH),
592 (aromatic C C), 780 (3 adjacent ArH) and 755 (4 adjacent ArH);
�
H [(CD3)2CO + 10% (CD3)2SO], 7.09 (1H, dd, J 1 and 8, 11-H), 7.32
1H, dd, J 8 and 8, 12-H), 7.67–7.91 (4H, m, ArH), 7.97 (1H, dd, J 1
and 8, 13-H), 8.50–8.58 (1H, m, 1-H), 8.70–8.76 (1H, m, 8-H), and 8.88–
.07 (2H, m, 4- and 5-H). The acetate crystallized from light petroleum
(
9
�
+
as needles m.p. 170–171 C (Found: M , 326.0942. C22H14O3 requires:
M, 326.0943); m/z 326 (24%, M ), 284 (100, M-CH2CO), 255 (6, 284-
+
CHO), and 226 (11, 255-CHO); �max/nm 240infl (log ε 4.43), 252 (4.57),
2
3
61 (4.56), 282 (4.02), 296 (4.01), 306 (4.14), 319 (4.15), 339 (3.40), and
53 (3.37); �max/cm 1764 (aryl acetate CO), 1591 (aromatic C C), 759
�
1
(
3 adjacent ArH), and 731 (4 adjacent ArH); �H 2.53 (3H, s, MeCO2Ar),
.22–7.28 (1H, m, 11-H), 7.39–7.48 (1H, m, 12-H), 7.60–7.82 (4H, m,
7
ArH), 8.17–8.26 (1H, m, 13-H), 8.44–8.51 (1H, m, 1-H), 8.54–8.61 (1H,
m, 8-H), and 8.67–8.77 (2H, m, 4- and 5-H).
When the above experiment was repeated using only catechol and
phenanthrenequinone the yields of the dioxin 22 (1.5%) and of the fura-
nol 17 (3.1%) were much lower. The phenolic fraction now afforded a sec-
ond product which crystallized from chloroform-light petroleum to give
0
0
1
1
0-phenylphenanthrene-2 ,3 ,9-triol 11 as needles (231 mg, 0.76 mmol,
�
+
5.9%) m.p. 184–186 C (Found: M , 302.0941. C20H14O3 requires:

2
736
B. J. Morrison and O. C. Musgrave
+
M, 302.0943); m/z 302 (100%, M ), 284 (5, M-H2O), 273 (8, M-CHO),
2+
2
1
55 (6, 284-CHO), 226 (6, 255-CHO), 165 (8, C13H9), 142 (13, 284 ),
27.5 (7, 2552 ), and 113 (14, 226 ); �max/nm 255 (log ε 4.60), 272infl
+
2+
�
1
(
4.16), 301 (3.95), 341 (3.34), and 358 (3.23); �max/cm 3460 (phenolic
OH), 1618 and 1595 (aromatic C C), 761 and 757 (3 and 4 adjacent
0
ArH); �H [(CD3)2CO] 6.72 (1H, dd, J 1.5 and 9, 4 -H), 6.87 (1H, dd, J 9
0
0
and 9, 5 -H), 6.98 (1H, dd, J 1.5 and 9, 6 -H), 7.30–8.00 (6H, m, ArH and
ArOH), 8.36–8.47 (1H, m, 8-H), and 8.67–8.95 (2H, m, 4- and 5-H). The
triacetate crystallized from chloroform-light petroleum as needles, m.p.
55–156 C (Found: M , 428.1264. C26H20O6 requires: M, 428.1260); m/z
28 (2%, M ), 386 (74, M-CH2CO), 344 (51, M-2CH2CO), 302 (100, M-
�
+
1
4
3
+
CH2CO), 284 (20, 302-H2O), 273 (12, 302-CHO), 255 (8, 284-CHO),
and 226 (6, 255-CHO); �max/nm 249infl (log ε 4.50), 255 (4.55), 268infl
�
1
(
4.10), 274infl (3.96), 287 (3.84), and 298 (3.86); �max/cm 1760 (aryl ac-
etate CO), 1599 (aromatic C C), 794 and 760, (3 and 4 adjacent ArH);
0
0
�
H 1.82, 2.17, and 2.31 (each 3H, s, 9-, 2 -, and 3 -MeCO2Ar), 7.20–7.75
8H, m, ArH), 7.82–7.89 (1H, m, 8-H), and 8.67–8.77 (2H, m, 4- and
-H).
(
5
3
. With Resorcinol (36.36 mmol) to Give 12 and 18
There was no neutral fraction. The alkali-soluble fraction afforded
two products the faster-moving of which crystallized from chloroform
to give benzo[b]phenanthro[9,10-d]furan-11-ol 18 as needles (793 mg,
�
+
2
.79 mmol, 58.0%) m.p. 227–228 C (Found: M , 284.0845, C20H12O2
+
requires: M, 284.0837); m/z 284 (100%, M ), 255 (7, M-CHO), 226 (10,
M-2CHO), 142 (21, M ), 127.5 (4, 255 ), and 113 (8, 226 ); �max/nm
60 (log ε 4.61), 283infl (4.18), 298 (3.95), 320 (4.22), 332 (4.28), 346infl
3.65), and 366 (3.43); �max/cm 3300 (phenolic OH), 1596 (aromatic
C C). 806 (2 adjacent ArH), and 754 (4 adjacent ArH); �H [(CD3)2CO]
.07 (1H, dd, J 2 and 10, 12-H), 7.27 (1H, d, J 2, 10-H), 7.35–7.78 (5H,
m, ArH and ArOH), 8.26 (1H, d, J 10, 13-H), 8.30–8.37 (1H, m, 1-H),
2
+
2+
2+
2
(
�
1
7
8
.56–8.63 (1H, m, 8-H), and 8.66–8.82 (2H, m, 4- and 5-H). The acetate,
�
m.p. 197–200 C, crystallized from chloroform-light petroleum (Found:
+
+
M , 326.0940. C22H14O3 requires: M, 326.0943); m/z 326 (15%, M ), 284
100, M-CH2CO), 255 (6, 284-CHO), and 226 (11, 255-CHO); �max/nm
42infl (log ε 4.50), 252 (4.66), 282 (4.15), 296 (4.08), 309 (4.26), 322
(
2
�
1
(
4.31), 341 (3.53), and 360 (3.45); �max/cm 1758 (aryl acetate CO),
589 (aromatic C C), 808 (2 adjacent ArH), and 761 (4 adjacent ArH);
H 2.41 (3H, s, MeCO2Ar), 7.26 (1H, dd, J 2 and 9, 12-H), 7.34 (1H, d,
J 2, 10-H), 7.53–7.97 (4H, m, ArH), 8.34 (1H, d, J 9, 13-H, and 8.47–8.97
4H, m, 1-, 4-, 5-, and 8-H).
1
�
(

Thiones as Reactive Intermediates in Condensations
2737
0
0
The slower-moving band gave 10-phenylphenanthrene-2 ,4 ,9-triol
�
+
1
2 (130 mg, 0.43 mmol, 9.0%) m.p. 175–177 C (Found: M , 302.0944.
C20H14O3 requires: M, 302.0942); m/z 302 (100%, M ), 284 (11, M-
+
H2O), 273 (8, M-CHO), 255 (5, 273-H2O), 231(8, 273-C2H2O), 215 (6,
2+
M-3CHO), 165 (7, C13H9), and 142 (7, 284 ); �max/nm 251 (log ε 4.41),
�
1
2
77 (4.11), 310infl (3.87), 344 (3.05) and 362 (2.87); �max/cm 3350
(
(
phenolic OH), 1595 (aromatic C C), 840 (2 adjacent ArH) and 757
4 adjacent ArH); �H [(CD3)2CO] 6.37–6.76 (2H, m, ArH), 7.02–7.09 (1H,
m, ArH), 7.37–8.30 (7H, m, ArH and ArOH), 8.40–8.57 (2H, m, ArH and
ArOH), 8.70–8.84 (2H, m, 4- and 5-H).
Repetition of the reaction without the addition of P4S10 gave the
furanol 18 (5.0%) and the triol 12 (27.0%).
4
. With Hydroquinone (36.36 mmol) to Give 8, 13, and 19
There was no neutral fraction but the phenolic fraction afforded three
products. The fastest-moving of these crystallized from light petroleum-
chloroform to give benzo[b]phenanthro[9,10-d]furan-12-ol 19 as needles
�
+
(
420 mg, 1.48 mmol, 30.8%) m.p. 218–219 C (Found: M , 284.0828.
+
C20H12O2 requires: M, 284.0837); m/z 284 (100%, M ), 255 (6, M-CHO),
26 (9, M-2CHO), 142 (19, M ), and 113 (11, 226 ); �max/nm 259 (log
2+
2+
2
ε 4.46), 285 (3.89), 310infl (4.13), 315 (4.16), 327 (4.19), 341infl (3.62),
�
1
and 361 (3.31); �max/cm 3260 (phenolic OH), 1611 and 1586 (aromatic
C C), 806 (2 adjacent ArH), and 745 (4 adjacent ArH); �H [(CD3)2CO]
7
.08 (1H, dd, J 2 and 10, 11-H), 7.64 (1H, d, J 10, 10-H), 7.68–7.86 (5H,
m, ArH and ArOH), 7.90 (1H, d, J 2, 13-H), 8.41–8.48 (1H, m, 1-H),
8
.58–8.66 (1H, m, 8-H), and 8.84–8.93 (2H, m, 4- and 5-H). The acetate,
�
m.p. 187–188.5 C, crystallized from chloroform-light petroleum (Found:
+
+
M , 326.0944. C22H14O3 requires: M, 326.0943); m/z 326 (28%, M ), 284
100, M-CH2CO), 255 (10, 284-CHO), and 226 (14, 255-CHO); �max/nm
(
2
3
54 (log ε 4.56), 263infl (4.53), 281 (3.98), 299infl (3.99), 308 (4.18),
21.5 (4.24), 340 (3.46), and 358 (3.43); �max/cm 1751 (aryl acetate
�
1
CO), 1613 and 1587 (aromatic C C), 812 (2 adjacent ArH), and 750
4 adjacent ArH); �H 2.41 (3H, s, MeCO2Ar), 7.11–7.20 (1H, m, 11-H),
(
7
8
.53–7.77 (5H, m, ArH), 7.97 (1H, brs, 13-H), 8.32–8.43 (2H, m, 1- and
-H), and 8.55–8.69 (2H, m, 4- and 5-H).
The next fraction afforded a mixture of phenols which, after acety-
lation and further PLC using light petroleum-chloroform (9:1), gave
benzo[b]phenanthro[9,10-e]oxathiin-12-yl acetate 8 (10 mg, 0.03 mmol,
�
+
0
.6%) as needles, m.p. 181–183 C (Found: M , 358.0671. C22H14O3S
+
requires: M, 358.0663); m/z 358 (54%, M ), 316 (100, M-CH2CO), 287
(
6, 316-CHO), 284 (23, 316-S), 258 (12, 287-CHO), 255 (6, 284-CHO),

2
738
B. J. Morrison and O. C. Musgrave
and 226 (7, 255-CHO); �max/nm 244infl (log ε 4.52), 285 (4.39). 307infl
�
1
(
4.10), 322infl (4.02), and 344infl (3.82); �max/cm 1765 (aryl acetate
CO), 1594 (aromatic C C), 811 (2 adjacent ArH), and 762 (4 adjacent
ArH); �H 2.26 (3H, s, MeCO2Ar), 6.85–7.96 (7H, m, ArH), 8.31–8.40 (1H,
m, 8-H), 8.44–8.52 (1H, m, 1-H), and 8.57–8.71 (2H, m, 4- and 5-H).
The slowest-moving fraction crystallized from chloroform to give 10-
0
�
0
phenylphenanthrene-2 ,5 ,9-triol 13 (140 mg, 0.46 mmol, 9.6%) as nee-
+
dles, m.p. 190.5–191.5 C (Found: M , 302.0941. C20H14O3 requires: M,
+
3
02.0943); m/z 302 (100%, M ), 284 (9, M-H2O), 273 (7, M-CHO), 255
(
6, 273-H2O), 226 (6, 255-CHO), 202 (9, C16H10), 189 (7, C15H9), 165 (9,
2
+
2+
2+
C13H9), 142 (16, 284 ), 127.5 (6, 255 ), and 113 (11, 226 ); �max/nm
52 (log ε 4.56), 273infl (4.14), 303 (4.04), 341 (3.18), and 358 (3.18);
2
�
�
1
max/cm 3300 (phenolic OH), 1595 (aromatic C C), 816 (2 adjacent
0
0
ArH), and 756 (4 adjacent ArH); �H [(CD3)2CO] 6.69–7.02 (3H, m, 3 -,4 -,
and 6 -H), 7.38–8.02 (8H, m, ArH and ArOH), 8.37–8.50 (1H, m, 8-H),
0
and 8.66–8.87 (2H, m, 4- and 5-H).
Repetition of the reaction with the omission of P4S10 gave the furanol
9 (10.2%) and the triol 13 (45.1%).
1
�
5
. With Phloroglucinol (31.75 mmol) at 220 C to Give 21
The phenolic fraction afforded benzo[b]phenanthro[9,10-d]furan-11,13-
diol 21 (148 mg, 0.49 mmol, 11.4%) which crystallized from chloroform
�
+
as needles m.p. 235–238 C (Found: M , 300.0774. C20H12O3 requires
+
2+
M, 300.0786); m/z 300 (100%, M ), 271 (4, M-CHO), and 150 (22, M );
max/nm 254 (log ε 4.03), 265 (4.03), 320 (3.57), 331 (3.58), 352infl (3.01)
�
�
1
and 368 (2.81); �max/cm 3445 (phenolic OH), 1628 (aromatic C C),
and 754 (4 adjacent ArH); �H [(CD3)2CO] 6.62 and 6.83 (each 1H, d,
J 1.5, 12- and 10-H), 7.59–7.85 (4H, m, ArH), 8.37–8.44 (1H, m, 8-H),
8
9
.72–8.97 (3H, m, 4- and 5-H and 11-OH), 9.79 (1H, brs, 13-OH), and
�
.83–9.92 (1H, m, 1-H). The diacetate had m.p. 191–193 C (Found:
+
+
M , 384.0994. C24H16O5 requires M, 384.0997); m/z 384 (24%, M ),
42 (25, M-CH2CO), 300 (100, M-2CH2CO), 271 (8, 300-CHO), and 213
8, 300-3CHO); �max/nm 242infl (log ε 4.43), 253 (4.60), 261infl (4.58),
81infl (4.12), 298infl (4.01), 311 (4.17), 323 (4.17), 340 (3.41), and 358
3
(
2
�
1
(
3.32); �max/cm 1761 (aryl acetate CO), 1621 and 1580 (aromatic C C),
and 758 (4 adjacent ArH); �H 2.39 and 2.58 (each 3H, s, 11- and 13-
MeCO2Ar), 7.06 and 7.48 (each 1H, brs, 10- and 12-H), 7.60–7.75 (4H,
m, ArH), 8.40–8.47 (1H, m, 8-H), 8.66–8.77 (2H, m, 4- and 5-H), and
8
.96–9.03 (1H, m, 1-H).
Repetition of the reaction in the absence of P4S10 gave the same
furandiol 21 in lower (4.2%) yield.

Thiones as Reactive Intermediates in Condensations
2739
6
. With Pyrogallol (31.75 mmol) to Give 17, 18, 20, and 23
The phenolic fraction afforded the furanol 17 (103 mg, 0.38 mmol, 7.5%)
and its isomer 18 (170 mg, 0.60 mmol, 12.5%) identical with the prod-
ucts obtained from the reactions with catechol and with resorcinol.
Repetition of the reaction without the addition of P4S10 gave a phe-
nolic fraction which was separated by PLC using chloroform-acetone
(
9:1). The faster-moving component crystallized from chloroform to give
benzo[b]phenanthro[9,10-d]furan-10,11-diol 20 (179 mg, 0.60 mmol,
�
+
1
2.4%) as needles m.p. 235–237 C (Found: M , 300.0774. C20H12O3 re-
+
quires: M, 300.0785); m/z 300 (100%, M ), 226 (9, M-CHO CO OH),
and 150 (20, M2 ); �max/nm 252 (log ε 4.54), 277infl (4.23), 318 (3.98),
+
�
1
3
1
27 (3.98), 348infl (3.51), and 364 (3.39); �max/cm 3320 (phenolic OH).
610 (aromatic C C), 790 (2 adjacent ArH), 755 and 740 (4 adjacent
ArH); �H[(CD3)2CO] 7.11 (1H, d, J 8, 12-H), 7.65–7.80 (6H, m, ArH),
.83 (1H, d, J 8, 13-H), 8.43–8.51 (1H, m, 1-H), 8.65–8.72 (1H, m, 8-H),
7
and 8.86–8.95 (2H, m, 4- and 5-H).
The slower-moving component (253 mg) darkened on exposure to
the air and was therefore acetylated. PLC using chloroform gave
0
0
0
1
0
0-phenylphenanthrene-2 ,3 ,4 ,9-tetrayl tetra-acetate 23 (179 mg,
�
.37 mmol, 13.6%), m.p. 196–199 C after crystallization from
chloroform-light petroleum. [Found: (M-CH2CO) , 444.1200. C26H20O7
requires: M, 444.1209]: m/z 486 (1%, M ), 444 (79, M-CH2CO), 402 (64,
+
+
4
3
44-CH2CO), 360 (64, 402-CH2CO), 318 (100, 360-CH2CO), 300 (25,
18-H2O), 289 (17, 318-CHO), 271 (7, 289-H2O), 231 (7, 289-2CHO),
and 165 (8, C13H9); �max/nm 243infl (log ε 4.52), 261infl (4.42), 271infl
�
1
(
4.32), and 329 (3.69); �max/cm 1775 (aryl acetate CO), 1602 (aromatic
C C), 822 (2 adjacent ArH), and 752 (4 adjacent ArH); �H 1.95, 2.18,
0
0
0
2
.35, and 2.38 (each 3H, s, 9-, 2 -, 3 -, and 4 -MeCO2Ar.), 6.97 (1H, d,
0
J 8, 5 -H), 7.15-7.83 (6H, m, ArH), 7.92–7.99 (1H, m, 8-H), and 8.54–8.76
(
2H, m, 4- and 5-H).
7
. With 1-Naphthol (27.78 mmol) to Give 24, 25,
6, and 27
2
The neutral fraction afforded three components the fastest-moving of
0
which was 1,1 -dinaphthyl disulfide 25 (487 mg, 1.53 mmol, 11.0%)
�
23
�
which crystallized from light petroleum in plates, m.p. 91 C (lit., 91 C)
Found: M , 318.0528 Calc. for C20H14S2: M, 318.0537); m/z 318 (52%,
M ), 286 (9, M-S), 254 (9, M-2S), 159 (100, M-C10H7S), and 115 (97,
C9H7); �max/nm 305 (log ε 3.80); �max/cm 1588 (aromatic C C), 789 (3
adjacent ArH), and 768 (4 adjacent ArH); �H 7.08–7.85 (12H, m, ArH),
+
(
+
�
1
0
and 8.24–8.44 (2H, m, 8- and 8 -H).

2
740
B. J. Morrison and O. C. Musgrave
The next product was 9-(1-naphthylthio)phenanthrene 26 (35 mg,
0
.01 mmol, 2.2%) which crystallized from light petroleum-chloroform
�
+
in plates m.p. 59–60 C (Found: M , 336.0968. C24H16S requires: M,
+
3
(
(
36.0973); m/z 336 (100%, M ), 335 (17, M-H), 302 (26, M-H2S), 210
17, M-C10H6), 209 (18, M-C10H7), 168 (11, M2 ), 165 (33, C13H9), 160
+
32, C10H8S), 159 (39, C10H7S), 128 (9, C10H8), and 115 (45, C9H7);
�
1
�
max/nm 256 (log ε 4.74), 263infl (4.71), and 344 (3.52); �max/cm 1582
(
aromatic C C), 785 (3 adjacent ArH), 764, 759, and 742 (4 adjacent
0
ArH); �H 7.17–7.91 (12H, m, ArH), 8.35–8.52 (2H, m, 8- and 8 -H), and
8
.55–8.79 (2H, m, 4- and 5-H).
The slowest-moving component crystallized from light petroleum-
chloroform to give naphtho[1,2-b]phenanthro]9,10-d]furan 24 (1.143 g,
�
+
3
.50 mmol, 74.8%) as plates, m.p. 208–210 C (Found: M , 318.1049.
+
C24H14O requires: M, 318.1045); m/z 318 (100%, M ) 289 (16, M-
CHO), 159 (20, M ), 144.5 (10, 289 ); �max/nm 252 (log ε 4.53), 267
2
+
2+
(
(
4.56), 278infl (4.47), 316 (4.08), 326 (4.08), 333 (402), 340 (3.80), 348
�
1
3.82), and 360 (3.20); �max/cm
1610 (aromatic C C), 803 (2
adjacent ArH), 765, 755, and 742 (4 adjacent ArH); �H (C6D6)
.20–7.84 (9H, m, ArH), 8.09–8.18 (1H, m, ArH) and 8.41–8.60
4H, m, ArH). The phenolic fraction contained only unchanged
7
(
1
-naphthol.
Repetition of the reaction without the addition of P4S10 gave a neutral
fraction containing the furan 24 (6.9%). The phenolic fraction afforded
0
0
1
0-(2 -naphthyl)phenanthrene-1 ,9-diol 27 (763 mg, 2.27 mmol, 47.2%)
�
m.p. 201–203 C which crystallized from light petroleum-chloroform
Found: M , 336.1158. C24H16O2 requires: M, 336.1150); m/z 336 (100%,
+
(
+
M ), 318 (18, M-H2O), 307 (12, M-CHO), 289 (20, 318-CHO), 278 (5,
07-CHO), 165 (23, C13H9), and 159 (12, 3182 ); �max/nm 238 (log ε
+
3
4
3
.73), 252 (4.72), 278 (4.39), 300 (4.16), 310infl (4.12), 323infl (3.90),
41 (3.44), and 360 (3.36); �max/cm 3505 (phenolic OH), 1595 (aro-
�
1
matic C C), 808 (2 adjacent ArH), 760 and 748 (4 adjacent ArH); �H
5
.43 and 5.58 (each 1H, s, ArOH), 7.29–7.90 (10H, m, ArH), 8.30–8.45
0
(
2H, m, 8- and 8 -H), and 8.60–8.75 (2H, m, 4- and 5-H). The diacetate
�
crystallized from light petroleum-chloroform in needles m.p. 178–180 C
+
(
Found: M , 420.1361. C28H20O4 requires M, 420.1361); m/z 420 (1%,
+
M ), 378 (33, M-CH2CO), 336 (100, 378-CH2CO), 318 (17, 336-H2O), 307
(
8, 336-CHO), 289 (10, 307-H2O) and 165 (10, C13H9); �max/nm 228 (log ε
.78), 251infl (4.69), 256 (4.72), 271infl (4.41), and 298 (4.12); �max/cm
�
1
4
1
7
9
5
764 (aryl acetate CO), 1596 (aromatic C C), 809 (2 adjacent ArH),
0
61 and 750 (4 adjacent ArH); �H 1.94 and 2.07 (each 3H, s, 1 - and
-MeCO2Ar), 7.40–8.01 (12H, m, ArH), and 8.69–8.80 (2H, m, 4- and
-H).

Thiones as Reactive Intermediates in Condensations
2741
8
. With 2-Naphthol (27.78 mmol) to Give 28, 29, 30, 31,
and 32
The neutral fraction gave rise to four bands, the fastest-moving of which
0
was 2,2 -dinaphthyl disulfide 30 (205 mg, 0.64 mmol, 4.6%) which crys-
�
24
tallized from light petroleum in plates, m.p. 138–139 C (lit., 139–
40 C) (Found: M , 318.0544. Calc. for C20H14S2: M, 318.0537); m/z 318
63%, M ), 254 (14, M-2S), 160 (57, M-C10H6S), 159 (77, M-C10H7S), 128
12, C10H8), and 115 (100, C9H7); �max/nm 248 (log ε 3.51); �max/cm
�
+
1
(
(
+
�
1
1
583 (aromatic C C), 813 (2 adjacent ArH), and 738 (4 adjacent ArH),
0
�H 7.35–8.10 (m, ArH). The next band afforded 2,2 -dinaphthyl sulfide
2
9 (172 mg, 0.60 mmol, 4.3%) which crystallized from light petroleum
�
25
�
+
in plates m.p. 148–150 C (lit., 151 C) (Found: M , 286.0811. Calc.
for C20H14S: M, 286.0816); m/z 286 (100%, M ), 284 (32, M-2H), 252
+
2
+
2+
(
2
15, 284-S), 143 (11, M ), 142 (9, 284 ), and 115 (20, C9H7); �max/nm
30 (log ε 4.68), 256 (4.52), 275infl (4.24), 305 (4.03), and 332 (3.65);
�
1
�max/cm 1620 and 1587 (aromatic C C), 812 (2 adjacent ArH), and 738
(
4 adjacent ArH); �H 7.28–8.08 (10H, m, ArH), 8.47–9.11 (4H, m, ArH).
0
The third band gave 2,2 -dinaphthyl ether 28 (295 mg, 1.09 mmol, 7.9%)
which crystallized from light petroleum in needles m.p. 104–105 C
�
26
�
+
(
lit., 105 C) (Found: M , 270.1046. Calc. for C20H14O: M, 270.1044);
+
2+
m/z 270 (100%, M ), 241 (20, M-CHO), 239 (9, 241-2H), 135 (14, M ),
27 (19, C10H7), and 115 (11, C9H7); �max/nm 235 (log ε 4.81), 263infl
1
(
�
1
4.54), 274infl (4.42), 286infl (4.20), 313 (3.68), and 328 (3.70); �max/cm
1
625 and 1592 (aromatic C C), 809 (2 adjacent ArH), and 744 (4
0
adjacent ArH); �H 7.26–7.90 (m, ArH). The final band afforded 9,9 -
diphenanthryl disulfide 31 (19 mg, 0.05 mmol, 1.9%) which crystallized
from light petroleum-chloroform in plates, m.p. 189–190 C (lit., 202–
�
27
�
+
2
04 C for a sample with a poor carbon analysis) (Found: M , 418.0832.
+
Calc. for C28H18S2: M, 418.0848); m/z 418 (31%, M ), 386 (33, M-S), 354
(
9, M-2S), 352 (354-2H), 210 (73, C14H10S), 209 (73, C14H9S), 178 (18,
10-S), 176 (17, 210-H2S), and 165 (100, C13H9); �max/nm (CHCl3) 259
2
�
1
(
log ε 4.63), 301infl (4.10), and 352infl (3.57); �max/cm 1600 (aromatic
C C), and 739 (4 adjacent ArH); �H 7.45–8.00 (12H, m, ArH), 8.47–8.53
0
0
0
(
2H, m, 8- and 8 -H), and 8.59–8.85 (4H, m, 4-, 4 -, 5-, and 5 -H).
0
The phenolic fraction gave 1-(2 -naphthylthio)-2-naphthol 32 (25 mg,
.08 mmol, 0.6%) m.p. 92 C (lit., 92 C) which crystallized from light
petroleum-chloroform (Found: M , 302.0756. Calc. For C20H14OS: M,
02.0763); m/z 302 (91%, M ). 269 (15, M-HS), 268 (6, M-H2S), 241 (7,
�
28
�
0
+
+
3
2+
M-S-CHO), 239 (6, 268-CHO), 151 (11, M ), 128 (100, C10H8), and 115
(
(
19, C9H7); �max/nm 233 (log ε 4.82), 238infl (4.74), 284 (4.08), 292infl
4.04), 325 (3.69), and 338 (3.73); �max/cm 3360 (phenolic OH), 1618
�
1
and 1592 (aromatic C C), 818 (2 adjacent ArH), and 743 (4 adjacent

2
742
B. J. Morrison and O. C. Musgrave
ArH); �H 7.06–7.95 (13H, m, ArH and ArOH), and 8.14–8.26 (1H, m,
�
8
-H). The acetate m.p. 118–120 C crystallized from light petroleum-
+
chloroform. (Found: M , 344.0868. C22H16O2S requires: M, 344.0871);
m/z 344 (44%, M ), 302 (100, M-CH2CO), 269 (19, 302-HS), 239 (10, 269-
+
CH2O), 144 (11, C10H8O), 128 (94, C10H8), and 115 (17, C9H7); �max/nm
2
44infl (log ε 4.52), 285 (4.39), 307infl (4.10), 322infl (4.02) and 334infl
�
1
(3.82); �max/cm 1760 (aryl acetate CO), 1590 (aromatic C C), 810
2 adjacent ArH), 762 and 743 (4 adjacent ArH); �H 2.25 (3H, s,
(
MeCO2Ar), 7.13–7.74 (10H, m, ArH), 7.84–8.02 (2H, m, ArH), and 8.41–
.51 (1H, m, 8-H).
8
REACTIONS OF PHENANTHRENEQUINONE WITH
LAWESSON’S REAGENT (p-METHOXYPHENYL-
THIONOPHOSPHINE SULFIDE DIMER) AND PHENOLS
1
. With Catechol to Give 9, 11, 15, 17, 22, and 31
Lawesson’s reagent12 (2.03 g, 5.0 mmol) was added to a stirred mixture
of phenanthrenequinone (1 g, 4.81 mmol) and catechol (5 g, 45.5 mmol)
�
�
at 160 C. The mixture was heated at 160 C for 4 h and then treated as
described above for the corresponding reactions with P4S10. The neutral
fraction afforded the dioxin 22 (48 mg, 0.17 mmol, 3.5%) and the disul-
fide 31 (130 mg, 0.31 mmol, 12.9%). The phenolic fraction gave three
products, the fastest-moving being the furanol 17 (196 mg, 0.69 mmol,
0
1
4.4%). The next band afforded 9-phenoxyphenanthren-2 ol 15 (115 mg,
0
.40 mmol, 8.4%) which crystallized from light petroleum-chloroform
�
+
in needles m.p. 103–105 C (Found: M , 286.0997. C20H14O2 requires:
M, 286.0993); m/z 286 (100%, M ), 257 (6, M-CHO), 239 (6, 257-H2O),
+
1
96 (16, C14H12O), 178 (57, C14H10), 176 (22, C14H8), and 165 (22,
C13H9); �max/nm 252 (log ε 4.59), 280infl (4.13), 304 (3.98), 334 (3.51)
�
1
and 349 (3.39); �max/cm 3450 (phenolic OH), 1594 (aromatic C C),
60 and 747 (4 adjacent ArH), �H [(CD3)2SO] 7.35–8.11 (9H, m, ArH
7
and ArOH), 8.67–8.77 (1H, m, ArH), and 8.77–9.16 (4H, m, 4-, 5-, 8-,
and 10-H). The slowest-moving band gave benzo[b]phenanthro[9,10-
e]oxathiin-10-ol 9 (63 mg, 0.20 mmol, 4.1%) which crystallized from
�
+
light petroleum-chloroform as needles m.p. 186–188 C (Found: M ,
+
3
(
16.0561. C20H12O2S requires: M, 316.0558); m/z 316 (100%, M ), 287
11, M-CHO), 284 (20, M-S), 259 (8. 287-CO), 158 (9, M2 ); �max/nm
+
2
30infl (log ε 4.16), 249 (4.67), 275infl (4.36), 335 (3.56), and 358infl
�
1
(
3.32); �max/cm 3440 (phenolic OH), 1601 and 1583 (aromatic C C),
768 (3 adjacent ArH), and 748 (4 adjacent ArH); �H [(CD3)2CO] 6.79–
7.04 (3H, m, ArH), 7.61–7.86 (4H, m, ArH), 7.97–8.09 (1H, m, 8-H),
8.65–8.87 (3H, m, 1-, 4-, and 5-H), and 9.04 (1H, brs, ArOH).

Thiones as Reactive Intermediates in Condensations
2743
2
. With Resorcinol (45.5 mmol) to Give 18 and
with Hydroquinone (36.36 mmol) to Give 19
The molten product from a similar reaction using resorcinol in place
of catechol was poured into chloroform and washed with 2M-sodium
hydroxide solution. Acidification of the latter and subsequent PLC gave
the furanol 18 (624 mg, 2.20 mmol, 45.7%). Hydroquinone gave the
furanol 19 (771 mg, 2.7 mmol, 56.5%)
REACTIONS OF OTHER DIKETONES WITH P S
4
10
1
. With Acenaphthenequinone to Give 33
P4S10 (1.2 g, 2.70 mmol) was added slowly to a stirred mixture of
acenaphthenequinone (1 g, 5.49 mmol) and phenol (4 g, 42.55 mmol)
�
at 160 C under nitrogen. Treatment as in the reactions with
phenanthrenequinone gave a neutral fraction which afforded di-
1
2
3
,2-acenaphthenothiophene 33 (20 mg, 0.06 mmol, 2.2%) m.p. 278–
80 C (lit., 279–280 C) (Found: M , 332.0661. Calc. for C24H12S: M,
32.0659) identical with an authentic specimen.
�
29
�
+
2
. With o-Chloranil to Give 34
A similar reaction between o-chloranil (1.23 g, 5.0 mmol) and P4S10
(
4
0.23 g, 0.52 mmol) gave 1,2,3,5,6,7,8-heptachlorodibenzothiophen-
�
+
-ol 34 (30 mg, 0.07 mmol, 3.3%) m.p. >350 C (Found: M , 437.7518.
35
+
C12H Cl7OS requires: M, 437.7568); m/z 438 (46%, M ), and 375 (15,
M-CO-Cl): �max/nm 245 (log ε 4.32), 305 (3.49), and 349infl (2.77);
�
1
�
max/cm
(Nujol) 3440 (phenolic OH), and 1630 (aromatic C C); �H
�
[
(CD3)2CO] No signal. The acetate m.p. 226–228 C crystallized from
+
35
acetone-methanol (Found: M , 479.7677. C14H3 Cl7 O2S requires:
M, 479.7674); m/z 480 (6%, M ), and 438 (46, M-CH2CO); �max/nm
2
1
+
�
1
27 (log ε 4.61), 242infl (4.70), 249 (4.75) and 314 (3.62); �max/�cm
762 (aryl acetate CO), 1610 and 1597 (aromatic C C); �H 243 (s,
MeCO2Ar).
3
. With Anthraquinone to Give Anthracene
The neutral fraction from the reaction between P4S10 (2.05 g,
4
4
.62 mmol), anthraquinone (1.9 g, 9.13 mmol), and phenol (4 g,
2.55 mmol) at 160 C after PLC and crystallization from chloroform
�
gave anthracene (1.25 g, 7.02 mmol, 76.9%) m.p. and mixture m.p. 215–
2
�
30
�
16 C (lit., 216–216.5 C).

2
744
B. J. Morrison and O. C. Musgrave
Benzo[b]phenanthro[9,10-d ]furan 16
This10 had �max/nm 242infl (log ε 4.38), 265.5 (4.69), 281 (4.26), 295
(
4.24), 307 (4.38), 320 (4.43), 341 (3.60), and 358 (3.60).
REFERENCES
[
[
1] (a) O. C. Musgrave and C. J. Webster, J. Chem. Soc., 855 (1971); (b) D. L. Manson
and O. C. Musgrave, J. Chem. Soc., 1011 (1963).
2] (a) I. M. Davidson and O. C. Musgrave, J. Chem. Soc., 3154 (1963); (b) I. M. Davidson,
O. C. Musgrave, and D. L. Manson, J. Chem. Soc., 3040 (1965).
[
[
3] S. Z. Cardon and H. P. Lankelma, J. Amer. Chem. Soc., 70, 4248 (1948).
4] Y. L. Gol’dfarb, V. P. Litvinov, and S. A. Ozolin, Bull. Acad. Sci. USSR, Div. Chem.
Sci., 486 (1965).
[5] P. Ramart-Lucas, M. J. Matti, and T. Guilmart, Bull. Soc. Chim. Fr., 1215 (1948).
[6] P. M. G. Bavin, K. D. Bartle, and J. A. S. Smith, Tetrahedron, 21, 1087 (1965).
[7] A. Zweig, J. E. Lancaster, and M. T. Neglia, Tetrahedron, 23, 2577 (1967).
[8] B. Brzezinski, P. Radziejewski, J. Olejnik, and G. Zundel, J. Phys. Chem., 97, 6590
(1993).
[
9] Y. Ishii, C. Gao, W.-X. Xu, M. Iwasaki, and M. Hidai, J. Org. Chem., 58, 6818 (1993).
[
[
10] J. N. Chatterjea, V. N. Mehrotra, and S. K. Roy, Chem. Ber., 96, 1156 (1963).
11] cf. S. Winstein, P. Carter, F. A. L. Anet, and A. J. R. Bourn, J. Amer. Chem. Soc., 87,
5
247 (1965).
[
12] B. S. Pedersen, S. Scheibye, N. H. Nilsson, and S.-O. Lawesson, Bull. Soc. Chim.
Belg., 87, 223 (1978).
[13] R. M. Schaffrin and J. Trotter, J. Chem. Soc.(A), 1561 (1970).
[14] W. M. MacGregor and D. S. Sherrington, Chem. Soc. Rev., 22, 199 (1993).
[15] A. Ohno, Organic Chemistry of Sulfur, edited by S. Oae (Plenum Press, New York,
1
977), p. 189.
16] U. Zoller, Heterocyclic Compounds. Small Ring Heterocycles, edited by A. Hassner
Wiley, New York, 1983), vol. 42, pt. 1, p. 403.
17] H. E. Simmons, D. C. Blomstrom, and R. D. Vest, J. Amer. Chem. Soc., 84, 4782
1962).
18] S. Forsen and M. Nilsson, The Chemistry of the Carbonyl Group, edited by J. Zabicky
Interscience, London, 1970), vol. 2, p. 157.
19] J. E. Banfield, W. Davies, N. W. Gamble, and S. Middleton, J. Chem. Soc., 4791
1956).
20] J. Perregaard, I. Thomsen, and S.-O. Lawesson, Acta Chem. Scand., Ser. B, 29, 538
1975).
[
[
[
[
[
(
(
(
(
(
[
[
[
[
[
[
[
21] H. Behringer and E. Meinetsberger, Liebig’s Ann. Chem., 1729 (1981).
22] G. Wittig, W. Uhlenbrock, and P. Weinhold, Chem. Ber., 95, 1692 (1962).
23] R. Leuckart, J. Prakt. Chem., 41, 179 (1890).
24] J. Troeger and W. Meine, Ber., 35, 2164 (1902).
25] F. Krafft and R. Schonherr, Ber., 22, 821 (1889).
26] C. Graebe, Ber., 13, 1849 (1880).
27] K. Sindelar, J. Holubek, M. Ryska, I. Koruna, and M. Protiva, Collect. Czech Chem.
Commun., 51, 2848 (1986).
[
[
[
28] L. G. S. Brooker and S. Smiles, J. Chem. Soc., 1723 (1926).
29] K. Dziewonski, Ber., 36, 962 (1903).
30] W. H. McVicker, J. K. Marsh, and A. W. Stewart, J. Chem. Soc., 127, 999 (1925).