B. Bis[2,2,2-trifluoro-1-phenyl-1-(trifluoromethyl)ethoxy] diphenyl sulfurane
. Carbon tetrachloride
is distilled directly from phosphorous pentoxide
into a dry, 2-l., three-necked flask
, fitted with stoppers, until 700 ml. is collected. The flask is quickly fitted with an adapter for use as a nitrogen-inlet
, a mechanical stirrer
, and an adapter for solid addition (Note 5)
which is attached to the 500-ml. flask containing the potassium alkoxide from Part A. A positive pressure of dry nitrogen
is used to maintain inert atmosphere conditions. A white slurry is obtained when the powdered alkoxide is added at room temperature to the stirred carbon tetrachloride
. Since all of the alkoxide does not transfer, the tared, 500-ml. flask is reweighed, and the amount added to the reaction vessel is determined by difference (Note 6)
. The adaptor used for solid addition is quickly exchanged for a septum.
To a stirred suspension of 105 g. (0.372 mole) of the alkoxide, 34.7 g. (31.0 ml., 0.186 mole) of diphenyl sulfide
is added by syringe. Bromine, 29.9 g. (9.6 ml., 0.186 mole)
, is then added by syringe over a 5-minute period, giving a red-brown mixture which gradually fades to a pale yellow within 30 minutes. Stirring is continued at room temperature for 2.5 hours, leaving a pale-yellow solution and a copious precipitate of potassium bromide
containing some potassium alkoxide.
A glove bag is equipped with a spatula, a tared, 1-l., single-necked round-bottomed flask
, a 350-ml. Buchner funnel
with filter paper, a 1-l. flask, a vacuum adapter, an aspirator hose (Note 7)
, and a flask containing 100 ml. of dry carbon tetrachloride
. Filtration of the reaction mixture under a nitrogen
atmosphere can be achieved by pouring the solution into the filter funnel via
one neck of the three-necked flask, which is inserted through a hole in the glove bag. The potassium bromide
is removed and washed with two 50-ml. portions of dry carbon tetrachloride
. The filtrate is then transferred to the 1-l. flask, fitted with the vacuum adapter. After removal of the sulfurane solution from the glove bag (Note 8)
, the flask is quickly placed on a rotary evaporator (Note 9)
and concentrated to a semisolid. Drying under reduced pressure (10−2
mm.) for 24 hours results in crude sulfurane (115–119 g.
) as slightly yellow crystals.
The flask containing the crude sulfurane is transferred to the nitrogen
atmosphere of the glove bag which contains a powder funnel, a fluted filter paper, a 1-l., single-necked, round-bottomed flask, a 250-ml. graduated cylinder
, a 1-l. flask containing 700 ml. of dry pentane (Note 10)
, and a 500-ml. flask containing 250 ml. of dry diethyl ether (Note 10)
. After dissolving the sulfurane in 150 ml. of ether
, 500 ml. of pentane
is added, giving a cloudy solution that clarifies when filtered directly into the 1-l. flask. The flask, is stoppered with the vacuum adapter and removed from the bag. At this time everything but the pentane
is removed from the glove bag and the following items are added: a 600-ml., medium-frit sintered-glass funnel
, a 1-l., single-necked, round-bottomed flask, a tared, 500-ml., single-necked round-bottomed flask
, a vacuum adaptor, two spatulas, and a powder funnel. The sulfurane solution is concentrated to ca.
350 ml. at reduced pressure and a temperature not exceeding 40° (Note 9)
, using a magnetic stirrer to prevent bumping as the solvent is evaporated through the vacuum adapter. After a drying tube
is connected to the adapter, the flask is cooled in an acetone–dry ice bath to induce crystallization; swirling the flask during the crystallization prevents crystals from adhering to the sides. When crystallization is complete, the flask is exchanged for the three-necked flask inserted into the side of the glove bag. Cooling in the acetone–dry ice bath is continued while the neck of the flask penetrates the glove bag. The crystals, collected in the sintered-glass funnel by vacuum filtration, are washed with one 50-ml. portion of cold (−78°) pentane
and transferred to the 500-ml. flask. After fitting with the vacuum adapter, the flask is removed from the bag and the crystals dried under reduced pressure (10−2
mm.) until the powdered, white sulfurane is at constant weight (76–79 g.
, m.p. 103–108°
). Further crystallization from the mother liquors, after concentration by rotary evaporation to one-half the original volume, gives up to 7 g.
of crude sulfurane (m.p. < 95°
) for a total yield of 79–83 g.
) (Note 11)
. Recrystallization by the same method as above gives analytically pure material, m.p. 109.5–110.5°