Optimization of the synthesis of phenanthrene-2- and -3-sulfonyl chlorides

Article abstract of DOI:10.1134/S1070428012040148

Sulfonation of phenanthrene with sulfuric acid, followed by neutralization with sodium hydroxide, gave a mixture of isomeric sodium phenanthrenesulfonates in an overall yield of 83%. Sodium phenanthrene- 2-, -3-, and -9-sulfonates were isolated in 17, 43, and 4% yield, respectively. Sulfonation of phenanthrene with ClSO₃H or SO₃ did not improve the yields of phenanthrene-2- and -3-sulfonic acids. Treatment of sodium phenanthrene-2- and -3-sulfonates with PCl₅-POCl₃ or SOCl₂-DMF afforded the corresponding sulfonyl chlorides in 89 and 87 or 69 and 70% yield, respectively. Pure phenanthrene-2- and -3-sulfonyl chlorides were also synthesized in 27 and 51% yield by reaction of a mixture of 2- and 3-sulfonates with PCl₅-POCl₃. Pleiades Publishing, Ltd., 2012.

Full text of DOI:10.1134/S1070428012040148

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2012, Vol. 48, No. 4, pp. 547–551. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © V.V. Russkikh, E.A. Khokhrina, V.V. Shelkovnikov, 2012, published in Zhurnal Organicheskoi Khimii, 2012, Vol. 48, No. 4,
pp. 549–553.
Optimization of the Synthesis
of Phenanthrene-2- and -3-sulfonyl Chlorides
V. V. Russkikh, E. A. Khokhrina, and V. V. Shelkovnikov
Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Division, Russian Academy of Sciences,
pr. Akademika Lavrent’eva 9, Novosibirsk, 630090 Russia
e-mail: vsh@nioch.nsc.ru
Received April 11, 2011
Abstract—Sulfonation of phenanthrene with sulfuric acid, followed by neutralization with sodium hydroxide,
gave a mixture of isomeric sodium phenanthrenesulfonates in an overall yield of 83%. Sodium phenanthrene-
2-, -3-, and -9-sulfonates were isolated in 17, 43, and 4% yield, respectively. Sulfonation of phenanthrene
with ClSO3H or SO3 did not improve the yields of phenanthrene-2- and -3-sulfonic acids. Treatment of sodium
phenanthrene-2- and -3-sulfonates with PCl5–POCl3 or SOCl2–DMF afforded the corresponding sulfonyl
chlorides in 89 and 87 or 69 and 70% yield, respectively. Pure phenanthrene-2- and -3-sulfonyl chlorides were
also synthesized in 27 and 51% yield by reaction of a mixture of 2- and 3-sulfonates with PCl5–POCl3.
DOI: 10.1134/S1070428012040148
Phenanthrene-2- and 3-sulfonyl chlorides are initial
compounds in the synthesis of a number of sulfur-
containing phenanthrenes [1, 2] and their subsequent
transformation into substituted 9,10-phenanthrene-
quinones exhibiting photochemical activity. For ex-
ample, 9,10-phenanthrenequinone was used as a com-
ponent of light-sensitive materials [3]. However, the
series of available photoactive derivatives of 9,10-phe-
nanthrenequinone [4] is limited due to the lack of con-
venient procedures for their synthesis. Phenanthrene-2-
and 3-sulfonyl chlorides can be obtained from the cor-
responding sulfonic acids. The yield of phenanthrene-
3-sulfonyl chloride from potassium phenanthrene-3-
sulfonate was 6% calculated on the initial phenan-
threne [2].
nanthrene-2-sulfonate in 17–21% yield, and potassium
phenanthrene-3-sulfonate was isolated in 24–26%
yield. The same compounds were later isolated in
slightly lower yields, 16 and 21%, respectively [7].
According to Ioffe [8], the yields of barium phenan-
threne-2-sulfonate and potassium phenanthrene-3-sul-
fonate were 29 and 32%, respectively; raising the
temperature to 135°C increased the yield of 2-sulfonic
acid [8].
The formation of disulfonic acids is the main side
process complicating the synthesis of phenanthrene
monosulfonic acids by sulfonation of phenanthrene.
Therefore, we performed sulfonation of phenanthrene
with sulfuric acid under conditions favoring formation
of monosulfonic acids, i.e., the reaction was carried out
at 135°C and was terminated after 25–30 min when the
residual amount of phenanthrene was about 2%. Sul-
furic acid was added under vigorous stirring to molten
phenanthrene to a molar ratio of 1.6:1. The residual
amount of phenanthrene was controlled by the solu-
bility of a sample of the reaction mixture in water [8].
The present work was aimed at optimizing the
synthesis of phenanthrene-2- and 3-sulfonyl chlorides
via sulfonation of phenanthrene as intermediate step.
Sulfonation of phenanthrene (I) can give rise to four
mono- and twelve disulfonic acids [5]. Salts of these
acids are capable of forming supersaturated aqueous
solutions, which hinders separation of isomeric prod-
ucts by fractional crystallization.
Taking into account the amount of unreacted phe-
nanthrene (2%), its purity (93%), and inorganic im-
purity (NaCl, 23%), the yield of sodium monosul-
fonates was 83%, the ratio of the 2- and 3-isomers
being 1:2. By fractional crystallization we isolated
sodium phenanthren-2- and -3-sulfonates in 17 and
Fieser [6] developed a procedure for the sulfonation
of phenanthrene in sulfuric acid with predominant
formation of monosulfo derivatives. Following this
procedure, the 2-isomer was isolated as barium phe-
547

RUSSKIKH et al.
548
Scheme 1.
SO3Na
SO3Na
(1) H2SO4
(2) NaOH
+
+
SO3Na
I
II
III
IV
43% yield, respectively. In addition, 4% of sodium
phenanthrene-9-sulfonate was isolated from the mother
liquors (Scheme 1). There was no need of obtaining
the corresponding barium and potassium salts for sub-
sequent synthesis of phenanthrene-2- and 3-sulfonyl
chlorides.
[10, 11]. Cerfontain et al. [10] reported on the forma-
tion of a mixture of 1-, 2-, 3-, and 9-substituted iso-
mers at a ratio of 6:1:2:7.6 in the reaction of phenan-
threne with sulfuric anhydride in nitromethane at 0°C,
and a mixture of the same compounds at a ratio of
1:1.2:6:5.6 (yield 69%) was obtained by sulfonation
of phenanthrene with sulfuric anhydride–dioxane in
dichloroethane at 20°C [11].
The isomer ratio in the product mixtures was
determined by 1H NMR spectroscopy in D2O from the
intensities of characteristic signals at δ 8.02 d (1-H, J =
2.2 Hz, II), 8.79 br.s (4-H, III), and 8.19 ppm, s (10-H,
IV). The purity of the isolated sodium phenanthrene-
sulfonates was estimated by the absence of signals of
The isomer ratio roughly conforms to the reactivity
indices, i.e., electron densities of the frontier orbital or
cation localization energies for the respective positions
of phenanthrene molecule: 9 > 1 > 3 > 2 [12]. Insofar
as the sulfonation process is reversible, the isomer
ratio is determined by kinetic or thermodynamic con-
trol over the process, which depends on the tempera-
ture and reaction time.
1
other isomers in the H NMR spectra and by the
melting points of the corresponding salts with
p-toluidine.
Katritzky et al. [9] reported on the sulfonation of
phenanthrene with sulfuric anhydride in nitrobenzene
at 25°C which gave 81% of a compound which was
assigned the structure of phenanthrene-2-sulfonic acid
IIa. We reproduced the synthesis described in [9] and
obtained a mixture of 1-, 2-, 3-, and 9-sulfonic acids in
an overall yield of 77% at a ratio of 2:1:10:5.6. The
1H NMR spectrum of the phenanthrene sulfonation
product (in DMSO-d6) was given in [9] without assign-
ment of signals and analysis of their fine structure, and
the downfield signal (m, 1H) was located at δ 9.15–
9.18 ppm in that spectrum. According to our data, phe-
nanthrene-2-sulfonic acid (IIa) in DMSO-d6 is charac-
terized by a downfield multiplet at δ 8.75–8.84 ppm
(m, 2H) due to 4-H and 5-H, while the 1-H proton
characteristically resonates at δ 8.24 ppm as a broad-
ened singlet (cf. [10]). A four-proton multiplet was
Apart from sulfuric acid, sulfonation of aromatic
compounds can be performed with the use of chloro-
sulfonic acid. Pschorr [13] described such reaction in
boiling chloroform and isolated 2- and 3-isomers as
lead salts in 85% yield. We carried out analogous
reaction at a reactant molar ratio of 1:1 and obtained
a mixture of isomeric phenanthrenesulfonates II–IV in
5, 39, and 20% yield, respectively. Heating of the mix-
ture to 135°C after removal of chloroform increased
the yield of II and III to 77%, while the yield of IV
decreased to 3%.
We believe that the procedures for phenanthrene
sulfonation with chlorosulfonic acid or sulfuric anhy-
dride are not advantageous from the viewpoint of
preparation of phenanthrene-2- and 3-sulfonic acids, as
compared to the above described sulfonation of phe-
nanthrene with sulfuric acid.
13
observed at δ 8.14–8.23 ppm [9]. The C NMR spec-
trum of compound IIa, recorded by us, also differed
from that given in [9]. The melting point of the sul-
fonation product was given in [9], but its salt with
p-toluidine was not obtained, though its melting point
is a characteristic parameter for identification of phe-
nanthrenesulfonic acids [6, 8].
Chlorosulfonic acid may be used to obtain sulfonyl
chlorides directly from aromatic substrates [14]. The
reaction is accompanied by liberation of H2SO4 and is
reversible. Chlorosulfonic acid is taken in excess (4–
5 equiv) to displace the equilibrium toward formation
of sulfonyl chloride. As applied to phenanthrene, the
presence of excess chlorosulfonic acid will favor
formation of disulfonic acids and bis(sulfonyl
Our results on the sulfonation of phenanthrene with
sulfuric anhydride with formation of a mixture of iso-
meric sulfonic acids are consistent with the data of
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 4 2012

OPTIMIZATION OF THE SYNTHESIS OF PHENANTHRENE-2- ...
549
Scheme 2.
Thus phenanthrene-2- and -3-sulfonyl chlorides can
be synthesized via sulfonation of phenanthrene and
subsequent chlorination without intermediate isolation
of pure phenanthren-2- and -3-sulfonic acids as barium
and potassium salts. Phenanthrene-2- and -3-sulfonyl
chlorides were prepared by reaction of a mixture of
sodium phenanthrene-2- and -3-sulfonates with PCl5–
POCl3, followed by fractional crystallization of iso-
meric sulfonyl chlorides from organic solvents.
SO2Cl
SOCl2–DMF
II
V
SO2Cl
SOCl2–DMF
III
EXPERIMENTAL
VI
The UV spectra were recorded on a Hewlett
Packard 8453 spectrophotometer. The IR spectra were
measured in KBr on a Bruker Vector 22 instrument.
The 1H and 13C NMR spectra were obtained on Bruker
chlorides). Therefore, it is preferable to synthesize
phenanthrene-2- and 3-sulfonyl chlorides in a stepwise
mode through the corresponding monosulfonates.
1
AV-300 (300.13 MHz for H) and AM-400 spectrom-
1
eters (400.13 MHz for H and 100.63 MHz for 13C)
To convert sulfonates II and III into sulfonyl
chlorides we tried both PCl5–POCl3 [1, 2] and SOCl2–
DMF (Vilsmeier reagent) [15]; the latter was not used
previously for the synthesis of phenanthrenesulfonic
acid derivatives (Scheme 2). Pure sulfonates II and III
were thus converted into sulfonyl chlorides V and VI
in 69 and 70% yield, respectively. The use of PCl5–
POCl3 ensured higher yields of V and VI (89 and 87%,
respectively); however, the procedure utilizing SOCl2–
DMF is more convenient as compared to PCl5–POCl3.
from solutions in D2O (II–IV) using tert-butyl alcohol
as internal reference (δ 1.25 ppm) or DMSO-d6 (IIa)
and CDCl3 (V, VI) using the residual proton signal of
the solvent as reference (DMSO-d5, δ 2.50 ppm;
CHCl3, δ 7.24 ppm).
Phenanthrene (I) of pure grade contained (GC–MS)
92.6% of the main substance, 2.6% of anthracene,
1.4% of methylphenanthrene, and 1.2% of dibenzo-
thiophene.
1
Compounds V and VI displayed in the H NMR
Sulfonation of phenanthrene (I) with sulfuric
acid. Phenanthrene (I), 17.82 g (0.1 mol), was melted
on heating to 110°C, 8.65 ml (0.16 mol) of 93% H2SO4
was added dropwise under vigorous stirring, maintain-
ing the temperature below 125°C, and the mixture was
stirred for 20 min at 135°C and poured into 145 ml of
water. The solution was neutralized to pH 7 by adding
9 g of NaOH in 16 ml of water and cooled in an ice
bath. The precipitate was filtered off, thoroughly
squeezed, washed with a solution of 18 g of NaCl in
100 ml of water to remove sodium disulfonates, and
dried. The product was 26.76 g of a mixture of sodium
phenanthrene-2- and -3-sulfonates at a ratio of 1:2.
The filtrate was evaporated to a volume of 100 ml to
isolate an additional amount, 4.67 g, of a mixture of
sodium phenanthrene-3- and -9-sulfonates at a ratio of
4:5 (1H NMR). The products were finely ground and
treated with chloroform to isolate 0.38 g (2%) of un-
reacted phenanthrene I. Found for the product mixture,
%: Cl 14.40. Calculated, %: NaCl 23.01.
spectra characteristic signals which allowed us to
estimate their ratio in a mixture on a quantitative level,
δ, ppm: 8.56 d (1-H, J = 2.4 Hz, V) and 9.29 d (4-H,
J = 1.5 Hz, VI). To optimize conditions for the syn-
thesis of sulfonyl chlorides V and VI, a mixture of
sulfonates II and III obtained by sulfonation of phe-
nanthrene with H2SO4 was brought into reaction with
PCl5–POCl3. The resulting mixture of sulfonyl chlo-
rides V and VI (1:2) was separated by crystallization
from CHCl3–CCl4 (1:1). After additional recrystalliza-
tion from chloroform, crystalline isomer V contained
no impurity of VI. Removal of the solvent mixture
from the mother liquor, followed by crystallization of
the residue from methanol and carbon tetrachloride
gave pure sulfonyl chloride VI. The yields of V and VI
were 27 and 51%, respectively. The procedure for
isomer separation by crystallization from organic sol-
vents is more convenient and more efficient than that
implying preliminary separation of sulfonates II and
III by fractional crystallization from aqueous solution.
The yields of V and VI prepared from a mixture of
isomeric sodium phenanthrenesulfonates were 21 and
40%, respectively (calculated on the initial phenan-
threne; cf. 6% of VI [2]).
Sodium phenanthrene-2-sulfonate (II). A mixture
of sodium phenanthrene-2- and -3-sulfonates, 26.38 g,
and 130 ml of water was heated to the boiling point
and filtered. The undissolved material was recrystal-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 4 2012

RUSSKIKH et al.
550
lized from 250 ml of water, washed with water on
a filter, and dried. Yield 4.48 g (17%). p-Toluidinium
salt, mp 290°C; published data [6]: mp 291°C.
1H NMR spectrum (D2O), δ, ppm: 7.43 m (4H, 6-H,
7-H, 9-H, 10-H), 7.62 m (1H, 8-H), 7.71 d.d (1H, 3-H,
J = 9.2, 2.2 Hz), 8.02 d (1H, 1-H, J = 2.2 Hz), 8.25 m
(1H, 5-H), 8.33 d (1H, 4-H, J = 9.2 Hz).
cooled to 6°C, and 2 g (25 mmol) of gaseous sulfuric
anhydride was supplied under vigorous stirring. The
mixture was cooled from 40 to 25°C, kept for 4 h, and
treated with water (3×25 ml). The aqueous phase was
separated, neutralized to pH 7 with NaOH, and
evaporated, and the residue was washed with 15 ml of
water. The product, 5.36 g (77%), contained phenan-
threne-1-, -2-, -3-, and -9-sulfonic acids at a ratio of
2:1:10:5.6 (1H NMR).
Phenanthrene-2-sulfonic acid (IIa) was obtained
by ion-exchange chromatography of aqueous sodium
salt II on KU-1 cation exchanger. mp 150–151°C (from
nitrobenzene–toluene); published data [9]: mp 149–
151°C; p-toluidinium salt, mp 290°C; published data
Sulfonation of phenanthrene (I) with chlorosul-
fonic acid. a. A solution of 1.78 g (10 mmol) of
phenanthrene (I) in 25 ml of anhydrous chloroform
was heated to the boiling point, 1.17 g (10 mmol) of
chlorosulfonic acid was added dropwise, and the mix-
ture was evaporated on a water bath. The residue was
treated with water (3×10 ml), the aqueous solution
was neutralized to pH 7 with NaOH and evaporated,
and the residue was washed with 5 ml of water to
isolate 1.75 g (59%) of a mixture of sodium phenan-
threne-3- and -9-sulfonates at a ratio of 2:1 (1H NMR).
The residue obtained after removal of chloroform was
repeatedly treated with hot water, the aqueous extract
was adjusted to pH 7 by adding NaOH and evaporated,
and the residue was recrystallized from water. Yield of
sodium phenanthrene-2-sulfonate (II) 0.15 g (5%).
b. After evaporation of the reaction mixture, the
residue was heated to 135°C and kept for 20 min at
that temperature, 15 ml of water was added, and the
mixture was neutralized to pH 7 with a solution of
NaOH. A mixture of sodium sulfonates II and III was
isolated as described above for the sulfonation with
H2SO4; yield 2.81 g (77%), ratio II :III = 1:2. The
mother liquor was evaporated, and the residue was
recrystallized thrice from water to isolate 0.09 g (3%)
of sodium phenanthrene-9-sulfonate (IV).
1
[6]: mp 291°C. H NMR spectrum (DMSO-d6), δ,
ppm: 7.59–7.73 m (2H, 6-H, 7-H), 7.84 d (1H, 9-H,
J9, 10 = 8.0 Hz), 7.89 d (1H, 10-H, J10, 9 = 8.0 Hz),
7.92 d (1H, 8-H, J8,7 = 8.2 Hz), 7.97 d (1H, 3-H, J3,4
=
8.0 Hz), 8.24 s (1H, 1-H), 8.75–8.84 m (2H, 4-H, 5-H).
13C NMR spectrum (DMSO-d6), δC, ppm: 123.05,
123.38, 124.68, 125.34, 127.27, 127.30, 127.34, 127.59,
128.80, 129.68, 130.14, 131.14, 132.09, 145.88.
Sodium phenanthrene-3-sulfonate (III). The
mother liquors obtained after isolation of sodium salt
II were combined and evaporated. The crystalline
residue was squeezed on a filter, washed with 30 ml of
water, and crystallized from 100 ml of water. Yield
11.62 g (43%); p-toluidinium salt, mp 219°C; pub-
1
lished data [6]: mp 222°C. H NMR spectrum (D2O),
δ, ppm: 7.30 d (1H, 9-H, J = 9.4 Hz), 7.39 d (1H,
10-H, J = 9.4 Hz), 7.47 m (2H, 6-H, 7-H), 7.60 d.m
(1H, 8-H, J = 8.0 Hz), 7.76 d (1H, 1-H, J = 8.9 Hz),
7.84 d.d (1H, 2-H, J = 8.7, 2.2 Hz), 8.31 d.m (1H, 5-H,
J = 8.3 Hz), 8.79 br.s (1H, 4-H).
Sodium phenanthrene-9-sulfonate (IV). The
mother liquor obtained after isolation of sodium salt
III was evaporated, and the moist residue was
squeezed on a filter, washed with 20 ml of water, and
dried to isolate 4.07 g (15%) of a mixture of 2- and
3-sulfonates II and III at a ratio of 1:4. The washings
were combined and evaporated, and the residue was
combined with 4.67 g of preliminarily isolated mixture
III/IV (see above) and recrystallized thrice from water.
Yield 1.12 g (4%), p-toluidinium salt, mp 228°C;
Phenanthrene-2-sulfonyl chloride (V). a. Phos-
phoryl chloride, 1.5 ml, and phosphorus(V) chloride,
3.12 g (15 mmol), were added to 2.96 g (10 mmol) of
sodium salt II preliminarily dried at 150°C. The
mixture was thoroughly ground using a glass rod and
heated for 1 h at 100°C. The mixture was then cooled,
30 g of finely crushed ice was added, and the precip-
itate was filtered off, washed with water, and dried.
Yield 2.46 g (89%), mp 155–156°C (from CHCl3);
published data [1]: mp 156°C. UV spectrum (EtOH),
1
published data [7]: mp 229°C. H NMR spectrum
(D2O), δ, ppm: 7.33 m (2H, 2-H, 3-H), 7.50 m (1H,
6-H), 7.64 m (2H, 1-H, 7-H), 8.09 m (1H, 4-H), 8.19 s
(1H, 10-H), 8.26 d (1H, 5-H, J = 8.4 Hz), 8.56 d (1H,
8-H, J = 8.7 Hz).
λ
max, nm: 217, 260, 356. IR spectrum, ν, cm–1: 1374,
1
1164 (SO2). H NMR spectrum (CDCl3), δ, ppm:
7.73 m (2H, 6-H, 7-H), 7.74 d (1H, 9-H, J = 8.5 Hz),
7.88 d (1H, 10-H, J = 8.5 Hz), 7.93 m (1H, 8-H),
8.16 d.d (1H, 3-H, J = 9.2, 2.2 Hz), 8.56 d (1H, 1-H, J =
2.4 Hz), 8.67 m (1H, 5-H), 8.85 d (1H, 4-H, J = 9.3 Hz).
Sulfonation of phenanthrene (I) with sulfuric
anhydride. A solution of 4.75 g (25 mmol) of com-
pound I in 25 ml of anhydrous nitrobenzene was
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 4 2012

OPTIMIZATION OF THE SYNTHESIS OF PHENANTHRENE-2- ...
b. Anhydrous sodium phenanthrene-2-sulfonate,
REFERENCES
551
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and extracted with chloroform (3×10 ml), the extract
was dried over CaCl2 and evaporated, and the residue
was recrystallized from chloroform. Yield 0.19 g
(69%), mp 155–156°C.
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procedure was analogous to the synthesis of sulfonyl
chloride V (method a). Yield 2.07 g (87%), mp 108–
109°C (from CCl4) [2]. UV spectrum (EtOH), λmax
,
nm: 213, 222, 248, 312. IR spectrum, ν, cm–1: 1379,
1
p. 1822.
1176 (SO2). H NMR spectrum (CDCl3), δ, ppm:
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8.03 d (1H, 1-H, J = 8.7 Hz), 8.12 d.d (1H, 2-H, J =
8.7, 1.8 Hz), 8.65 d (1H, 5-H, J = 7.2 Hz), 9.29 d (1H,
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a solution of 0.24 g (2 mmol) of SOCl2 in 50 ml of
anhydrous chloroform, 0.07 g (1 mmol) of DMF was
added, and the mixture was heated for 30 min under
reflux. The product was isolated as described above for
compound V (method b). Yield 0.21 g (70%), mp 108–
109°C (from CCl4).
1957, vol. 22, p. 1649.
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c. The mother liquor obtained after isolation of
crystalline sulfonyl chloride V (method c) from isomer
mixture V/VI was evaporated, and the residue was
crystallized first from methanol and then from carbon
tetrachloride. Yield 7.33 g (51%), mp 108–109°C.
14. Reutov, O.A., Kurts, A.L., and Butin, K.P., Organi-
cheskaya khimiya (Organic Chemistry), Moscow:
BINOM, 2004, vol. 2.
15. Fieser, L.F. and Fieser, M., Reagents for Organic
Synthesis, New York: Wiley, 1968, vol. 1.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 4 2012