Org. Synth. 1936, 16, 81
DOI: 10.15227/orgsyn.016.0081
Submitted by R. W. Bost and E. W. Constable.
Checked by Reynold C. Fuson and C. F. Woodward.
1. Procedure
A mixture of 326 g. (3.9 moles) of a 36 per cent formaldehyde solution (Note 1) and 700 cc. of concentrated hydrochloric acid (sp. gr. 1.18) is placed in a tall glass cylinder (Note 2), and hydrogen sulfide is passed through the solution until no more precipitate is formed. In order to facilitate the process, the accumulated mass of crystals is removed from time to time by filtration. The time required for completion of the reaction varies from twelve to twenty-four hours. A crude yield of 176 g. (98 per cent of the theoretical amount) of fine, nearly colorless needles melting at 210–213° is obtained.
The product is purified by the inverted filtration method. The apparatus used is shown in Fig. 20. A 2-l. round-bottomed flask is equipped with a reflux condenser and a bent glass tube, 8–10 mm. in diameter (Note 3). To the lower end of this tube is attached, by means of a cork, a 25-mm. tip prepared from a paper Soxhlet thimble and packed with glass wool. A 2-l. conical flask serves as a receiver for the hot filtrate.
Fig. 20
Fig. 20
The crude product is placed in the round-bottomed flask, 1 l. of benzene is added, and heat is applied until the solvent boils vigorously. After a few minutes the source of heat is withdrawn and the mixture is allowed to become quiet. The filtering thimble, which up to this point is kept at the top of the flask (see Fig. 20), is now lowered to its normal position and the conical flask is attached. Gentle suction is applied, and the liquid is drawn over into the conical flask. The hot solution is removed, allowed to cool, and filtered. In the meantime, the extraction process is repeated with a second 1-l. portion of benzene. The two portions of benzene are used alternately over and over in the manner described until all the crude product has been recrystallized. This requires about ten separate extractions, using each 1-l. portion of benzene five times.
The yield of pure product, melting at 214–215°, is 165–169 g. (92–94 per cent of the theoretical amount).
2. Notes
1. The formaldehyde content of the solution is determined by analysis, for which the iodimetric method of Borgstrom and Horsch1 is recommended. The yield is calculated upon the basis of the amount of formaldehyde actually present, as shown by analysis. Since commercial solutions of formaldehyde contain methyl alcohol, the formaldehyde present cannot be estimated accurately by reference to specific-gravity tables—compare Org. Syn. Coll. Vol. I, 1941, 378, Note 1.
2. A tall cylindrical vessel ensures good contact between the solution and the gas bubbling through it. Hydrogen sulfide from a commercial cylinder was used.
3. Successful use of the inverted filtration method requires attention to these details: (a) use of a sufficiently wide transfer tube; (b) minimum exposure of tubing between the flasks; (c) rapid transfer of the hot solution; (d) avoidance of too strong an application of suction.
The inverted filtration device is convenient for simple recrystallizations as well as repeated extractions. It is of particular advantage for the manipulation of volatile, inflammable solvents and of lachrymatory solutions.
3. Discussion
sym.-Trithiane has been prepared by treating carbon bisulfide,2 ethyl isothiocyanate,3 or potassium thiocyanate3 with zinc and hydrochloric acid; by heating methylene iodide with alcoholic sodium hydrosulfide;4 and by treating aqueous formaldehyde with hydrogen sulfide and concentrated hydrochloric acid.5

References and Notes
  1. Borgstrom and Horsch, J. Am. Chem. Soc. 45, 1493 (1923).
  2. Girard, Compt. rend. 43, 396 (1856); Ann. 100, 306 (1856).
  3. Hofmann, Ber. 1, 176, 179 (1868).
  4. Husemann, Ann. 126, 293 (1863).
  5. Hofmann, ibid. 145, 360 (1868); Baumann, Ber. 23, 67 (1890).

Chemical Abstracts Nomenclature (Collective Index Number);
(Registry Number)

hydrochloric acid (7647-01-0)

Benzene (71-43-2)

methyl alcohol (67-56-1)

formaldehyde (50-00-0)

hydrogen sulfide (7783-06-4)

zinc (7440-66-6)

potassium thiocyanate (333-20-0)

Methylene iodide (75-11-6)

carbon bisulfide

sodium hydrosulfide

ethyl isothiocyanate (542-85-8)

sym.-TRITHIANE (291-21-4)