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Org. Synth. 1927, 7, 4
DOI: 10.15227/orgsyn.007.0004
p-ARSONOPHENOXYACETIC ACID
[Acetic acid, p-arsonophenoxy-]
Submitted by C. S. Palmer and E. B. Kester.
Checked by J. B. Conant
1. Procedure
In a 2-l. round-bottomed flask are placed 218 g. (1 mole) of p-hydroxyphenylarsonic acid (Note 1) and 375 cc. of water. A solution of 180 g. (4.5 moles) (Note 2) of sodium hydroxide in 375 cc. of water is added, and the mixture shaken until a homogeneous solution is obtained. After cooling to 40–50° there is added 189 g. (2 moles) of chloroacetic acid in small portions (Note 3) with stirring, and the clear solution is refluxed for four hours. At the end of this time the mixture is cooled to 20°, filtered to remove a slight flocculent precipitate, and the p-arsonophenoxyacetic acid precipitated (Note 4) by the addition of 200 cc. (2.1 moles) of hydrochloric acid (sp. gr. 1.19).
The product is filtered on a 10-cm. Büchner funnel and washed with three successive 100-cc. portions of cold water. It is then crystallized from 2 l. of hot water (Note 5), filtered, and washed twice with 100-cc. portions of cold water, once with 25 cc. of acetone, and once with 25 cc. of ether. After drying at 110° for one hour, there remains a pure white, anhydrous product weighing 110–120 g. (40–43 per cent of the theoretical amount) (Note 6). An arsenic analysis shows the product to be about 99 per cent pure.
2. Notes
1. Commercial phenolarsonic acid may be used, or 240 g. of sodium p-hydroxyphenylarsonate (p. 490) and 140 g. of sodium hydroxide may be substituted for the acid and the larger amount of base.
2. The use of less than 4.5 moles of alkali lowers the yield; an increase in the alkali concentration does not increase the yield.
3. Unless the chloroacetic acid is added cautiously, there may be a violent reaction and the yield of p-arsonophenoxyacetic acid is lowered.
4. The product sometimes does not precipitate readily without vigorous agitation and rubbing the inside wall of the vessel with a stirring rod.
5. It is sometimes necessary to use decolorizing carbon in order to get a white recrystallized product.
6. The odor of phenol is strong at the end of the reaction, but most of the p-hydroxyphenylarsonic acid which does not react with the chloroacetic acid is not hydrolyzed and can be recovered in the filtrate from the p-arsonophenoxyacetic acid.
3. Discussion
p-Arsonophenoxyacetic acid can be made by heating aqueous sodium p-hydroxyphenylarsonate, 2 moles of chloroacetic acid, and 4 moles of sodium hydroxide.1

References and Notes
  1. Meister, Lucius and Brüning, Ger. pat. 216,270 [Frdl. 9, 1047 (1908–10)].

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

hydrochloric acid (7647-01-0)

ether (60-29-7)

sodium hydroxide (1310-73-2)

phenol (108-95-2)

chloroacetic acid (79-11-8)

acetone (67-64-1)

phenolarsonic acid

decolorizing carbon (7782-42-5)

p-ARSONOPHENOXYACETIC ACID,
Acetic acid, p-arsonophenoxy- (53663-15-3)

p-hydroxyphenylarsonic acid (98-14-6)

sodium p-hydroxyphenylarsonate (53663-20-0)