Org. Synth. 1951, 31, 82
DOI: 10.15227/orgsyn.031.0082
[Propane, 1,3-dibromo-2,2-bis(bromomethyl)-]
Submitted by Hershel L. Herzog1
Checked by T. L. Cairns and D. W. Woodward.
1. Procedure
In a 5-l. three-necked round-bottomed flask equipped with a powerful mechanical stirrer (Note 1), a thermometer, and a 1-l. dropping funnel are placed 130 g. (0.96 mole) of technical grade pentaerythritol (Note 2) and 650 ml. of pyridine. The stirrer is started, and to the resulting suspension is added dropwise 750 g. (4.24 moles) of benzenesulfonyl chloride (Note 3) at such a rate that the temperature of the reaction does not rise above 30–35°. The addition requires about 2 hours. The resulting slurry is stirred at 40° for 1 hour after the addition is complete. The slurry is then added slowly (Note 4) to a vigorously stirred solution of 800 ml. of concentrated hydrochloric acid in 1 l. of water and 2 l. of methanol contained in a 9 by 15 in. battery jar. The resulting suspension of granular white pentaerythrityl benzenesulfonate is cooled by addition of 500 g. of ice, filtered with suction, and washed with 5 l. of water and then with 1 l. of cold methanol in two portions.
The crude, slightly wet pentaerythrityl benzenesulfonate is added to 1 l. of diethylene glycol (Note 5) in a 4-l. Erlenmeyer flask equipped with a Hershberg stirrer. Then 600 g. (5.8 moles) of sodium bromide is added, and the mixture is heated in an oil bath at 140–150° with slow stirring (60–120 r.p.m.) overnight. The resulting orange mixture is allowed to cool to about 90°, 2 l. of ice water is added rapidly with stirring, and finally the mixture is cooled to 10° by direct addition of ice. The precipitate is filtered with suction, washed with 2 l. of water, and pressed dry. The yield is 315–323 g. of a crude tan crystalline solid, m.p. 147–149°. The solid is dissolved in 2 l. of boiling acetone and filtered by gravity on a steam-heated funnel. On cooling, the solution deposits colorless glistening plates, which are filtered with suction and washed with 100 ml. of cold 95% ethanol, yielding 150–160 g. of pentaerythrityl tetrabromide, m.p. 159–160° (Note 6). By repeated concentration and cooling of the mother liquor, an additional 90–100 g. of pentaerythrityl tetrabromide, m.p. 156.5–158° (Note 6), is obtained. The combined yield is 228–260 g. (68–78%) (Note 7).
2. Notes
1. A powerful stirrer is necessary to mix the reactants, particularly in the later stages of the reaction when the mixture is quite viscous. The submitter and checkers used a "Lightnin" stirrer.
2. Heyden Chemical Corporation technical grade pentaerythritol (Pentek) was found to be satisfactory. It contains about 90% pentaerythritol, the remainder being principally dipentaerythritol.
3. Eastman Kodak Company practical grade benzenesulfonyl chloride was used.
4. Crystallization is extremely slow at first and becomes satisfactory only when the mixture is well seeded. It is well to remove a small portion first and work it up in the hydrochloric acid solution with a spatula to induce crystallization. The mixture should be added slowly at first but more rapidly toward the end.
5. Eastman Kodak Company practical grade diethylene glycol was used.
6. The checkers observed melting points about 2° lower.
7. The yield is based on the assumption that 90% of the starting material is pentaerythritol.
3. Discussion
The procedure given was developed by Buchman, Herzog, and Fujimoto.2 Pentaerythrityl bromide has also been prepared from phosphorus tribromide and pentaerythritol,3 and by the action of hydrobromic acid on pentaerythrityl tetraacetate in acetic acid.4
This preparation is referenced from:

References and Notes
  1. California Institute of Technology, Pasadena, California.
  2. Buchman, Herzog, and Fujimoto, unpublished results.
  3. Org. Syntheses Coll. Vol. 2, 476 (1943).
  4. Perkin and Simonsen, J. Chem. Soc., 87, 860 (1905).

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


ethanol (64-17-5)

hydrochloric acid (7647-01-0)

acetic acid (64-19-7)

methanol (67-56-1)


sodium bromide (7647-15-6)

phosphorus tribromide (7789-60-8)

acetone (67-64-1)

Benzenesulfonyl chloride (98-09-9)

pyridine (110-86-1)

Pentaerythritol (115-77-5)

Pentaerythrityl bromide,
Pentaerythrityl tetrabromide,
Propane, 1,3-dibromo-2,2-bis(bromomethyl)- (3229-00-3)

pentaerythrityl tetraacetate (597-71-7)

diethylene glycol (111-46-6)

pentaerythrityl benzenesulfonate