A Publication
of Reliable Methods
for the Preparation
of Organic Compounds
Annual Volume
Org. Synth. 1952, 32, 88
DOI: 10.15227/orgsyn.032.0088
[1,5-Naphthalenedisulfonyl chloride]
Submitted by P. D. Caesar1
Checked by R. T. Arnold and George P. Scott.
1. Procedure
In a 1-l. round-bottomed flask is placed a mixture of 204.3 g. (1 mole) of finely divided phosphorus pentachloride and 132.8 g. (0.4 mole) of the disodium salt of naphthalene-1,5-disulfonic acid which has been dried previously at 140° for 48 hours (Note 1). The flask is provided with an air condenser which is fitted at the top with a calcium chloride drying tube. It is then placed in an oil bath which is heated to 110°, and the mixture is maintained at that temperature for 1 hour. The condenser is removed for brief intervals now and then during the heating period, and the reactants are stirred by means of a glass rod. At the end of the heating period, the product is a thick paste.
The flask and contents are placed on a steam cone and heated for 2 hours under vacuum (furnished by a water aspirator) (Note 2) in order to remove the phosphorus oxychloride formed in this process as well as most of the unreacted phosphorus pentachloride. The dry cake is pulverized in a mortar and transferred to a 4-l. beaker. To this is added 750 ml. of distilled water and 2 l. of chloroform. The mixture is placed on a steam bath, heated to boiling, and stirred vigorously until nearly all the solid dissolves. By means of a separatory funnel the layers are separated while still hot. The chloroform solution is again heated to boiling and filtered through a large fluted filter into an Erlenmeyer flask.
After sufficient chloroform has been evaporated to give a solution volume approximating 250 ml., the solution is cooled in an ice bath and the crystalline product collected on a filter. By further concentration of the mother liquor, an additional quantity of naphthalene-1,5-disulfonyl chloride is obtained. A total yield of 85–115 g. (65–88%) of recrystallized material results; m.p. 181–183°.
2. Notes
1. The powdered solids should be thoroughly mixed before heating. This may be done by inserting a rubber stopper into the neck of the reaction flask and shaking vigorously for about 2 minutes. However, an appreciable pressure develops in the flask and care must be taken in removing the stopper.
2. The reaction flask should be connected to the receiver by a tube of large bore and equipped, preferably, with ground-glass fittings. Two traps between the receiver and the aspirator are desirable to assure no contact between the phosphorus chlorides and water.
3. Discussion
Naphthalene-1,5-disulfonyl chloride has been prepared by the reaction of naphthalene with chlorosulfonic acid; 2,3,4,5,6,7 however, the yields are generally poor and the conditions difficult to reproduce. It also has been obtained by treating disodium 1,5-naphthalene-disulfonate with chlorosulfonic acid.8 The present method has been published.9
This preparation is referenced from:

References and Notes
  1. University of Illinois, Urbana, Illinois.
  2. Armstrong, J. Chem. Soc., 24, 173 (1871).
  3. Armstrong, Ber., 15, 204 (1882).
  4. Corbellini, Giorn. chim. ind. applicata, 9, 118 (1927) [C. A., 22, 2938 (1928)].
  5. Pollak, Heimberg-Krauss, Katscher, and Lustig, Monatsh., 55, 358 (1930).
  6. General Tire & Rubber Co., Brit. pat. 802,654 [C. A., 53 11330 (1959)].
  7. Marotta and Swisher (to Monsanto Chemical Co.), U. S. pat. 2,827,487 [C. A., 52, 16324 (1958)].
  8. Spryskov and Apar'eva, Zhur. Obshchei Khim. (J. Gen. Chem.), 19, 1576 (1949) [C. A., 44, 1082 (1950)].
  9. Marvel and Caesar, J. Am. Chem. Soc., 73, 1097 (1951).

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

chlorosulfonic acid (7790-94-5)

phosphorus pentachloride (10026-13-8)

chloroform (67-66-3)

Phosphorus Oxychloride (21295-50-1)

Naphthalene (91-20-3)

Naphthalene-1,5-disulfonyl chloride,
1,5-Naphthalenedisulfonyl chloride (1928-01-4)

disodium 1,5-naphthalene-disulfonate,
disodium salt of naphthalene-1,5-disulfonic acid