Molecules 1997, 2, 7 – 10

molecules ISSN 1420-3049

Synthesis of New 2-(1,3-Dithianyl)phenols and

Hexakis-[p-(1,3-dithian-2-yl)phenoxy]cyclotriphosphazene

Stibrányi Ladislav a*, Zúziová Jozefínaa and Prónayová Nadezdab

a Departmentof Organic Chemistry, Faculty of Chemical Technology, Slovak Technical University, Bratislava, SK - 812 37
Slovak Republic. Fax 00 427 368 560 ([email protected])

b Central
Laboratory for Spectroscopy, Faculty of Chemical Technology, Slovak Technical University, Bratislava, SK - 812
37 Slovak Republic

Received: 14 October 1996 / Accepted: 27 November 1996 / Published: 29 January 1997

Abstract: 2-Chloro-1,3-dithiane was obtained by the chlorination of 1,3-dithiane with N-chlorosuccinimide.

Reactions of 2-chloro-1,3-dithiane with various substituted phenols lead to 2-(1,3-dithianyl)phenols (3). Hexakis-
[p-(1,3-dithian-2-yl)phenoxy]cyclotriphosphazene (6) was obtained by reaction with hexachlorotriazacyclo-
triphosphazene (5).

Keywords: 1,3,5,2,4,6,-Triazatriphosphorine, 1,3-dithiane, phenol, electrophilic substitution.

Introduction to the synthesis of functionalized organophosphazenes is one

that involves the reaction of a halogenophosphazene with a
Only a few examples of direct introduction of a 2-(1,3- functional reagent. Many aryloxyphosphazenes are already
dithianyl) group into aromatic compounds were found in known [5,6] , but none has been prepared that bears 1,3-
literature. Electrophilic aromatic substitution reactions of dithianyl units. Trying to use 1,3-dithiane in the chemistry of
2-chloro-1,3-dithiane is of interest since a protected formyl cyclotriphosphazenes we studied the reaction of 2-(p-
group is introduced in one step. 1,3-Dithiane was used as hydroxyphenyl)-1,3-dithiane, prepared according to lit. [2],
the sulfide for the preparation of o-aminobenzaldehyde de- with hexachlorocyclotriphosphazene. The nucleophilic reac-
rivatives [1]. Japanese authors described some interesting tions of substituted phenols with halophosphazenes in THF
reactions of 2-chloro-1,3-dithiane with excess phenol or in the presence of sodium hydride and catalytical amount of
N,N-dimethylaniline [2]. The highly specific method for the tetrabutylammonium bromide [7] and using 2-butanone as a
ortho formylation of p-substituted phenols via correspond- solvent in the presence of potassium hydrogen carbonate [6]
ing 1,3-dithiane was described [3]. Kruse reported on the are described. Also the reaction of phosphazenes with so-
reactions of 2-chloro-1,3-dithiane with phenols and elec- dium or potassium salt of the corresponding phenols in THF
tron-rich aromatic compounds [4]. The most obvious route [8] or in the mixture THF-DMF [9] are known.

* To whom correspondence should be addressed

© 1997 MDPI. All rights reserved
8 Molecules 1997, 2

OH
OH compound was confirmed by 31P, 1H, 13C NMR spectroscopy
H Cl
and by IR spectra and elemental analysis.
S S
+ R2 R2 The reaction of 2-chloro-1,3-dithiane with o-, m- and
two p-substituted phenols using modified conditions made
R1 R1
possible the preparation of new 2-(1,3-dithian-2-yl) phenol
S S derivatives 3a-3k (Table 1). The synthetized compounds were
isolated by column chromatography in 20–40 % yields. Be-
sides the products of electrophilic substitution on aromatic
1 2 3a-k phenol ring we observed also the formation of the well known
1,3-bis(1´,3´-dithian-2-yl-2´-thio) propane and S-[3-(1´,3´-
Scheme 1.
dithian-2-yl-2´-thio)]propyl thioformate.
The reaction course was controlled by TLC, after the
Results and Discussion starting phenol was consumed and the reaction mixture was
worked up. The reactions took from 16 to 88 hrs to com-
We found, that using the above mentioned reaction condi- plete depending on the phenol substituent and its position.
tions for the preparation of hexasubstituted derivative 6 the 2,6-Dimethylphenol was observed to be the most reactive of
reaction did not yield the expected product. In our hands the all used phenols, m- and p- halo substituted phenols showed
best results were obtained in a mixture of solvents DMF- unexpected low reactivity. In the case of 4-unsubstituted
acetonitrile in the ratio 2:1, the presence of potassium car- phenols the reaction took place in that free position. The
bonate and a catalytical amount of sodium iodide. The pro- observed chemical shifts were compared with the calculated
cedure for preparation of hexakis-[p-(1,3-dithian -2- ones by ACD/LabsTM for chemistry method with PC compu-
yl)phenoxy]cyclotriphosphazene using the above conditions ter. They were also compared with chemical shifts, calcu-
led to the required product. The structure of the obtained lated depending on effect of substituent and its position at

Table 1. Physicochemical data of compounds 3a-k. The given positions in numbers of the groups are relative to the OH group.

Compound R1 R2 R Formula M.p. Yield Calcd/found

Mr °C % C H S
3a 2-CH3 6-CH3 4-dithianyl C12H16OS2 182-185 43 60.00 6.71 26.69
240.24 59.78 6.56 26.20
3b 3-CH3 4-CH3 6-dithianyl C12H16OS2 129-132 23 60.00 6.71 26.69
240.24 59.45 6.42 26.34
3c 3-CH3 5-C2H5 4-dithianyl C13H18OS2 139-141 24 61.42 7.14 25.22
254.25 61.05 6.88 25.05
3d 2-sec-C4H9 H 4-dithianyl C14H20OS2 96-98 19 62.68 7.51 23.90
268.26 62.51 7.33 23.85
3e 3-tert-C4H9 H 6-dithianyl C14H20OS2 112-114 43 62.68 7.51 23.90
268.26 62.44 7.24 23.57
3f 2-C6H12 H 4-dithianyl C16H22OS2 120-123 30 65.31 7.48 21.79
294.23 65.11 7.50 21.66
3g 2-CH3O H 4-dithianyl C11H14O2S2 140-143 29 54.54 5.83 26.47
242.23 54.74 5.67 26.25
3h 3-iso-C3H7O H 4-dithianyl C13H18O2S2 119-121 19 57.78 6.71 23.73
270.25 57.26 6.48 23.60
3i 2-Cl H 6-dithianyl C10H11ClOS2 103-106 17 48.69 4.49 25.99
246.67 48.30 4.45 25.75
3j 4-Br H 2-dithianyl C10H11BrOS2 136-138 33 41.25 3.81 22.02
291.20 40.97 3.34 21.74
3k 3-F H 4-dithianyl C10H11FOS2 122-123 22 51.98 4.80 27.75
231.09 51.59 4.78 27.58
Molecules 1997, 2 9
phenol ring [10] using index of 13C NMR Spectra Data. All Table 2. Measured 13C NMR spectral data of compounds
these data were also used for determination of phenol ring 3a-k
position attacked by the 1,3-dithian-2-yl electrophilic group.
2-(4-Hydroxyphenyl)-1,3-dithiane reacted with 13C
Compound NMR chemical shifts, in ppm
hexachlorocyclotriphosphazene in DMF-acetonitrile (2:1)
using potassium carbonate as a base and a new 3a 152.3, 130.7, 127.9, 123.3, 51.0, 32.3, 25.2, 15.9
hexasubstituted cyclotriphosphazene was prepared in 85%
yield. The others prepared 1,3-dithian-2-yl substituted 3b 151.6, 138.5, 129.6, 128.6, 120.8, 118.1, 46.4,
phenols reacted with hexachlorocyclotriphosphazene in a 31.7, 24.8, 19.4
more complicated fashion and these reactions are under study. 3c 154.7, 141.1, 137.3, 115.2, 113.6, 48.4, 33.0,
28.1, 25.6, 21.4, 15.6
Experimental 3d 153.2, 133.6, 131.3, 126.7, 125.9, 115.4, 51.2,
34.0, 32.3, 29.6, 25.0
Melting points were determined on the Kofler hot stage. 1H 3e 153.7, 153.5, 128.5, 120.5, 117.8, 114.3, 46.7,
NMR spectra were obtained with a Tesla BS 487 (80 MHz) 34.5, 31.5, 31.1, 24.7
instrument and 13C NMR spectra with a Varian VXR-300
3f 152.8, 133.9, 131.3, 126.4, 125.9, 115.4, 51.1,
(75 MHz) in deuteriochloroform with tetramethylsilane as
37.2, 32.8, 32.2, 26.9, 26.2
an internal standard. 31P NMR spectra were measured on a
Jeol FX 100 (46 MHz) with phosphoric acid as an internal 3g 146.5, 145.7, 131.0, 120.8, 114.4, 110.2, 55.9,
standard. Chemical shifts are given in ppm (δ-scale). IR spec- 51.2, 32.2, 25.0
tra were recorded on FTIR PU 9802/25 (Philips) spectro- 3h 156.2, 155.7, 130.1, 120.4, 115.0, 102.6, 71.1,
photometer using KBr technique (ν in cm-1). The TLC analy- 47.7, 43.0, 32.4, 26.8
ses were carried out on Silufol 60 F 254 sheets in the follow- 3i 151.3, 132.4, 128.4, 128.0, 119.4, 116.3, 50.0,
ing solvent system: chloroform-methanol 7:3, or 1:1, for 32.0, 24.9
phosphazene cyclohexane-benzene 9:1. Spots were detected 3j 153.6, 132.8, 131.7, 125.8, 119.1, 112.5, 46.6,
by UV light at 254 nm, or by spraying with mixture aniline- 31.5, 24.6
pyridine 2:1. For column chromatography, silica gel 60–120 3k 164.3, 157.0, 130.2, 118.4, 112.0, 102.7, 42.7,
µm was used. Starting hexachlorotriazacyclotripho-sphazene 32.2, 24.9
(m.p.=113–115°C) was prepared from phosphorus
pentachloride by treatment ammonium chloride according
to a described procedure [11]. OH
Cl Cl
P
N N
General procedure for preparation of 2-(1,3-dithianyl)- +
phenols (3a-k) Cl P P Cl
N
Cl Cl
S S
A well stirred solution of 1,3-dithiane (25 mmol) in benzene
(60 ml) was cooled to 10 °C, and N-chlorosuccinimide (27
mmol) was added under atmosphere of nitrogen. After stir- 4 5
ring for 15 min at room temperature the solution of corre-
sponding phenol (25 mmol) in benzene (40 ml) was dropwise
added so that the temperature remained within 20 °C to 30
°C. Then the mixture was stirred another 24–96 h at room S S
temperature. The precipitated N-succinimide was filtered off S S
and the solvent was evaporated in vacuo, the residue was
chromatographed on silica gel column (250 g) in chloroform
or in chloroform/methanol (7:3,v/v). Yields and spectroscopic S O O S
P
data were given in the Tables. N N
S O S
P O
P
Hexakis-[p-(1,3-Dithian-2-yl)phenoxy]cyclotriphosphazene O
N
O
(6)

A solution of hexachlorotriazacyclotriphosphazene (5 mmol) S

S
in acetonitrile (30 ml) was added dropwise during 20 min to S
S
a stirred suspension of 2-(p-hydroxyphenyl)-1,3-dithiane (30
mmol) potasium carbonate (30 mmol) and sodium iodide (0.2 6
Scheme 2.
10 Molecules 1997, 2

mmol) in dimethylformamide (60 ml). The mixture was

heated at 70 °C for 12 h under stirring and exclusion of 3. Gassman, G. P.; Amick, R. D. J. Am.. Chem. Soc. 1978,
moisture. The solvent was evaporated in vacuo and the resi- 100, 7611.
due was extracted with chloroform (100 ml), filtered and the 4. Kruse, C. G.; Wijsman, A., van der Gen, A. J. Org.
filtrate was concentrated. The residue was chromatographed Chem. 1979, 44, 1847.
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to afford 600 mg (85 %) of viscous oil (6). 1980, 19, 1026.
IR (KBr ): 1661, 1512, 1505, 1202, 1184, 1163, 955, 768. 6. Pond, D. M.; Wang, R. H. S. U.S. 3,936,418 (1976),
1H NMR (CDCl ): 1.8–2.1(m, 4H), 2.86–3.2(m, 4H), 5.18
3
Chem.Abstr. 1976, 84, 151551.
(s, 1H), 6.76–7.36 (q, 4H). 13C NMR (CDCl 3): 24.5, 31.6, 7. Munsey, S. M.; Natale, R. N. Heterocycles 1990, 31,
50.3, 115.4, 128.6, 132.7, 155.4. 31P NMR (CDCl 3): 8.64 851.
(s). Anal. Calcd for C60H66O6P3N3S12 : C, 51.38 H, 4.71 N, 8. Dieck, R. L.; Quinn, E. J. (Amstrong Cork Co.) U.S.
2.99 Found : C, 51.00 H, 4.25 N, 3.17. 4,108,805 (1978), Chem. Abstr. 1979, 90, 72830.
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96, 3003.
2. Arai, K.; Oki, M. Bull. Soc. Chem. Jpn. 1976, 49, 553. Sample Availability: Samples available from the author.