Scientia Sinica

No. 1 CHANG: STUDIES ON FUSED RING SYSTEMS II 53

1,2,3,4,9,10,11,12-octahydrophenanthrenes which they called keto ester A, employing the same series of reactions. ‘From this racemic estrone, after resolution through /-menthoxy-acetate, natural estrone was obtained. Consequently our work stopped at this point, and we began to look for other routes for the synthesis of estrone.

EXPERIMENTAL™

m-lodoanisole (I1)—This compound was prepared according to the method of Votocek and Matejka™!. A mixture of 123 g of m-anisidine, 500 g of ice and 240 ml of 1:1 sulfuric acid was cooled to 5°. A solution of 70 g of sodium nitrite in 200 ml of water was added slowly with stirring. After all the sodium nitrite solution had been added, the reaction mixture was poured into a solution of 200 g of potassium iodide in 400 ml of water and 100 ml of concentrated sulfuric acid with stirring. After the reaction mixture was left standing at room temperature overnight, it was steam distilled. The product was extracted with benzene and the benzene extract was first washed with sodium bisulfite solution and then with water. After being dried with anhydrous magnesium sulfate, the solvent was removed and the residue dis-

tilled; b. p. 130° (20 mm); yield, 193 g.

B-m-Anisylethyl Alcohol (II)—This compound was prepared according to the method of Bachmann and Thomas"!, except that a solution of ethylene oxide in anhydrous ether was used instead of gaseous form. Light yellow oil was obtained as the product, b. p. 118-123° (2 mm).

B-m-Anisylethyl Bromide (II1)—Using the method of Bachmann and Thomas®!, this compound was obtained as light yellow oil; b. p. 158-160° (8 mm).

B-m-Anisylethylmalonic Ester (IV)—According to the method of Bachmann and coworkers"!, this compound was obtained as light yellow oil; b. p. 188-192° (0.4 mm).

Ethyl 5-Keto-6,6-dicarbethoxy-8-m-anisyloctanoate (V).—This compound was prepared according to the method of Bachmann and coworkers!) with a few slight modifications. To a suspension of 9.2 g of powdered sodium in 300 ml of thiophene-free benzene, a solution of 118 g of the substituted malonic ester (IV) in 100 ml of pure benzene was added. The mixture was refluxed till all the sodium had reacted. The mixture was cooled with ice water and 90g of ethyl glutaryl chloride was added slowly with stirring. After the mixture was left standing at room temperature overnight, it was poured into 400 ml of water. Then the two layers were separated and the aqueous layer was extracted once with benzene. The combined benzene

*The experimental work was carried out at the University of Michigan.