Org. Synth. 1984, 62, 210
DOI: 10.15227/orgsyn.062.0210
THIETE 1,1-DIOXIDE AND 3-CHLOROTHIETE 1,1-DIOXIDE
[2H-Thiete 1,1-dioxide and 2H-thiete, 3-chloro- 1,1-dioxide]
Submitted by Thomas C. Sedergran and Donald C. Dittmer
1.
Checked by M. F. Semmelhack, Elena M. Bingham, William A. Sheppard, and Joseph J. Bozell.
1. Procedure
A.
Thietane 1,1-dioxide. The pH of a solution of
tungstic acid (WO3 · H2O) (1.1 g, 0.044 mol) (Note 1) in 280 mL of distilled water is adjusted to 11.5 by addition of
10% aqueous sodium hydroxide; the white suspension of the tungstate catalyst is added to a
1-L, round-bottomed flask fitted with a mechanical stirrer and a pressure-equalizing addition funnel. The
tungstic acid–water mixture is cooled to 0–10°C by means of an
ice–salt bath;
glacial acetic acid (50 mL) and trimethylene sulfide (thietane) (47.5 g, 0.641 mol, d 1.028) (Note 2) are added. The chilled mixture is stirred, and
30% hydrogen peroxide (189 mL) is added carefully by means of the addition funnel over a period of 2 hr
(Note 3). The mixture is stirred at 0–10°C for an additional hour, transferred to an
evaporating dish, and heated to near dryness on a
steam bath. The resulting solid material is triturated five times with
100-mL portions of hot chloroform; any catalyst is removed by filtration. The
chloroform solutions are combined and dried over anhydrous
magnesium sulfate and the solvent is removed via a
rotary evaporator to give a white solid (
60.3–63.7 g,
0.57–0.60 mol,
88.7–93.7%), mp
74–76°C (lit.
2 mp
75.5–76°C).
B.
3-Chlorothietane 1,1-dioxide. Thietane 1,1-dioxide (14.0 g, 0.132 mol) is placed in a
three-necked, 500-mL, round-bottomed flask fitted with a magnetic stirrer, reflux condenser and a chlorine bubbler.
Caution! (Since chlorine is poisonous, the reaction involving it should be done in a good hood.) Carbon tetrachloride (300 mL) is added to the flask
(Note 4) and the suspension is irradiated by a 250-W sunlamp positioned as close as possible to the reaction flask without touching it
(Note 5) while
chlorine is bubbled through the solution for 15 min at a moderate rate
(Note 6). A copious white precipitate forms and irradiation and addition of
chlorine must be stopped at this point (or 10 min after the first appearance of a precipitate) to avoid dichlorination. The reaction mixture is cooled to room temperature and filtered to give a white, fluffy product (
5.4–8.1 g,
30–44%) that is crystallized from
chloroform, mp
136–137°C (lit.
3 mp
136.5–137.5°C).
C.
Thiete 1,1-dioxide. A sample of
3-chlorothietane 1,1-dioxide (8.0 g, 0.057 mol) is dissolved in dry
toluene (300 mL) (Note 7) in a
500-mL, two-necked, round-bottomed flask equipped with a reflux condenser, magnetic stirrer, heating mantle (or silicone oil bath), and thermometer. The reaction is heated to 60°C and
triethylamine (28.7 g, 0.28 mol, 39.5 mL) is added through the condenser. The reaction mixture is stirred for 4 hr and
triethylamine hydrochloride is removed by filtration and washed with
toluene (100 mL).
Toluene is removed on a rotary evaporator and the residue is recrystallized from
diethyl ether–ethanol (Note 8) to give a white solid (
4.5–4.8 g,
75–81%); mp
49–50°C (lit.
3 mp
52–54°C).
D.
3,3-Dichlorothietane 1,1-dioxide. Thietane 1,1-dioxide (5.0 g, 0.047 mol) is placed in a
500-mL, three-necked, round-bottomed flask equipped with a reflux condenser, magnetic stirrer, and chlorine gas bubbler.
Carbon tetrachloride (350 mL) is added and the solution is irradiated with a 250-W sunlamp
(Note 5) while
chlorine is bubbled through the stirred mixture for 1 hr
(Note 9). Irradiation and
chlorine addition are stopped and the reaction mixture is allowed to cool to room temperature. The product is collected by filtration as a white solid (
4.0–4.4 g,
49–53%), mp
156–158°C4 (Note 10). the product can be used without further purification or recrystallized from
chloroform.
E.
3-Chlorothiete 1,1-dioxide. A solution of
3,3-dichlorothietane 1,1-dioxide (4.0 g, 0.023 mol) in
toluene (150 mL) is placed in a
250-mL, round-bottomed, two-necked flask equipped with a heating mantle (or silicone oil bath), magnetic stirrer, reflux condenser, and thermometer. The solution is heated to 60°C and
triethylamine (2.54 g, 0.025 mol, 3.5 mL) is added dropwise through the condenser over a 10-min period. The solution is stirred for 2 hr at 60°C and cooled to room temperature. The
triethylamine hydrochloride is collected by filtration and washed with hot
toluene (50 mL). Removal of
toluene on a rotary evaporator gives a white solid (
2.7–3.0 g,
84–93%) that is recrystallized from
chloroform-hexane, mp
118–120°C4 (Note 11).
2. Notes
1.
The
tungstic acid was used as supplied by the Eastman Kodak Company.
2.
The
trimethylene sulfide was used as supplied by the Aldrich Chemical Company.
3.
The addition rate of the
hydrogen peroxide must be adjusted so that the temperature of the reaction mixture does not rise above 10°C. The yield is reduced if the temperature is allowed to rise above that point. The endpoint of the reaction, when excess
peroxide is present, can be determined with potassium iodide–starch test paper. The yield also is reduced if more than a slight excess of
hydrogen peroxide is used.
4.
The sulfone is not completely dissolved at this point. The prescribed ratio of sulfone to
carbon tetrachloride (0.0467 g mL) is important. If it is less (i.e., more
carbon tetrachloride relative to sulfone), considerable
3,3-dichlorothietane 1,1-dioxide will be formed.
5.
Any commercial sunlamp is satisfactory and should be used with eye protection.
Carbon tetrachloride boils gently because of the heat from the lamp.
6.
The submitters suggested adding the
chlorine at such a rate that a constant yellow color is maintained in the solution or suspension. The checkers found that, depending on the rate of
chlorine introduction, it took from 10 to 35 min for the appearance of the white precipitate. In each run, the monochlorinated product was contaminated with a small amount (5–10% by NMR integration) of either starting material or dichlorinated product. The checkers found that the optimum yield of monochlorinated product was obtained when the
chlorine was bubbled into the solution through a ¼-in. glass tube at a rate estimated to be between 5–15 bubbles per second. The suspended sulfone dissolves as the reaction proceeds.
7.
Toluene was dried over Linde 4A molecular sieves.
Benzene may be used also.
8.
The product is heated in about
25–30 mL of diethyl ether, and
ethanol is added dropwise until a solution is obtained. The checkers found that the thiete sulfone could also be crystallized by gently heating the crude material in
diethyl ether (~ 100 mL) until it dissolves, followed by cooling to −15°C.
9.
If the reaction time is less than 1 hr, a mixture of
monochloro- and dichlorosulfone is obtained.
10.
The spectral properties of the product are as follows: IR (KBr disk) cm
−1: 2950 (m), 1370 (m, SO
2), 1310 (m), 1210 (m), 1140 (m, SO
2), 970 (m), 940 (m), 820 (w);
1H NMR (chloroform-
d) δ: 5.0 (s, 4 H, CH
2SO
2CH
2).
11.
The spectral properties of the product are as follows: IR (KBr disk) cm
−1: 1540 (m, >C=C<), 1400 (w), 1300 (s, SO
2), 1210 (s), 1140 (s, SO
2), 1020 (m), 770 (m);
1H NMR (chloroform-
d) δ: 4.6 (s, 2 H, CH
2-SO
2), 6.8 (s, 1 H, CH=C).
3. Discussion
This preparation of
thiete 1,1-dioxide is more direct and less tedious than previous methods.
3,5,6Oxidation of
trimethylene sulfide catalyzed by
tungstic acid7 is preferred to the uncatalyzed reaction; yields are better and the reaction time is shortened by elimination of an induction period.
Selective chlorination of the 3-position of
thietane 1,1-dioxide may be a consequence of
hydrogen atom abstraction by a
chlorine atom. Such reactions of
chlorine atoms are believed to be influenced by polar effects, with preferential
hydrogen abstraction occurring remotely from an electron withdrawing group.
8 The free-radical chain reaction may be propagated by attack of the 3-thietanyl 1,1-dioxide radical on molecular
chlorine.
Conversion of
3-chlorothietane 1,1-dioxide to the 3-(
N,N-dimethylamino) derivative followed by reduction, quaternization, and Hofmann elimination affords a convenient route to the highly reactive
thiete (thiacyclobutene).
5,9The following compounds have been obtained from
thiete 1,1-dioxide: substituted cycloheptatrienes,
10 benzyl α-toluenethiosulfinate,
11 pyrazoles,
12 naphthothiete 1,1-dioxides,
13 and 3-substituted thietane 1,1-dioxides.
14 It is a dienophile in Diels–Alder reactions
10,13,15 and undergoes cycloadditions with enamines, dienamines, and ynamines.
16 Thiete 1,1-dioxide is a source of the novel intermediate, vinylsulfene (CH
2=CHCH=SO
2), which undergoes cycloadditions to strained olefinic double bonds,
17 reacts with
phenol to give
allyl sulfonate derivatives
18 or cyclizes unimolecularly to give an unsaturated sultene.
18 Platinum19 and
iron20 complexes of
thiete 1,1-dioxide have been reported.
3-Chlorothiete 1,1-dioxide is a useful intermediate for the preparation of other 3-substituted thiete 1,1-dioxides via addition–elimination reactions.
4 It also undergoes Diels–Alder reactions with
1,3-butadiene and with
1,3-diphenylisobenzofuran.
4
Appendix
Chemical Abstracts Nomenclature (Collective Index Number);
(Registry Number)
H2O
monochloro- and dichlorosulfone
thiete (thiacyclobutene)
ethanol (64-17-5)
acetic acid (64-19-7)
Benzene (71-43-2)
diethyl ether (60-29-7)
hydrogen (1333-74-0)
sodium hydroxide (1310-73-2)
chloroform (67-66-3)
iron (7439-89-6)
phenol (108-95-2)
carbon tetrachloride (56-23-5)
platinum (7440-06-4)
chlorine (7782-50-5)
toluene (108-88-3)
hydrogen peroxide,
peroxide (7722-84-1)
Triethylamine hydrochloride (554-68-7)
magnesium sulfate (7487-88-9)
1,3-Butadiene (106-99-0)
triethylamine (121-44-8)
benzyl α-toluenethiosulfinate
allyl sulfonate
1,3-diphenylisobenzofuran (5471-63-6)
chloroform-hexane
Thiete 1,1-dioxide,
2H-Thiete 1,1-dioxide (7285-32-7)
3-Chlorothiete 1,1-dioxide,
2H-thiete, 3-chloro- 1,1-dioxide (90344-86-8)
tungstic acid
trimethylene sulfide,
thietane (287-27-4)
Thietane 1,1-dioxide (5687-92-3)
3-Chlorothietane 1,1-dioxide (15953-83-0)
3,3-Dichlorothietane 1,1-dioxide (90344-85-7)
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