Thiete 1,1-dioxide and 3-Chlorothiete 1,1-dioxide could be produced through the following synthetic routes.

A. 1,1-dioxide. The pH of a solution of tungstic acid (WO₃ · H₂O) (1.1 g, 0.044 mol) 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) 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. 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. 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.) tetrachloride (300 mL) is added to the flask and the suspension is irradiated by a 250-W sunlamp positioned as close as possible to the reaction flask without touching it while chlorine is bubbled through the solution for 15 min at a moderate rate. 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. 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 (300 mL) 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 to give a white solid (4.5–4.8 g, 75–81%); mp 49–50°C (lit. 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. (350 mL) is added and the solution is irradiated with a 250-W sunlamp while chlorine is bubbled through the stirred mixture for 1 hr. 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°C. 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°C.