Arnold R Hirsch Deceased716 Valmont St, New Orleans, LA 70115

4172076, Oct 23, 1979

Feb 13, 1978

5/877569

Arnold L. Hirsch - Oak Park IL
Josef Pikl - Glassboro NJ

Diamond Shamrock Corporation - Cleveland OH

C07J 1700
C07J 900

26023955R

Steroidal acids of the formula ##STR1## are prepared from steroidal ketones of the formula ##STR2## wherein R. sub. 1 is hydrogen; hydroxy; lower alkyloxy; tetrahydropyranyloxy; aryloxy; alkyl; alkanoyloxy or aroyloxy; R. sub. 2 is hydrogen; hydroxy; lower alkyloxy; tetrahydropyranyloxy; aryloxy; alkyl; alkanoyloxy or aroyloxy; R. sub. 3 is hydrogen; hydroxy; lower alkyloxy; tetrahydropyranyloxy; aryloxy; alkyl; alkanoyloxy or aroyloxy; with the proviso that R. sub. 1 and R. sub. 2 together or R. sub. 2 and R. sub. 3 together may form a carbon-carbon bond; R. sub. 4 is --(CH. sub. 2). sub. n CO(CH. sub. 2). sub. m CH. sub. 3 ; R. sub. 5 is --(CH. sub. 2). sub. n+m+1 COOH; R. sub. 6 is hydrogen; hydroxy; lower alkyloxy; tetrahydropyranyloxy; aryloxy; alkyl; alkanoyloxy or aroyloxy; and n is 0 to 4, m is 0 to 4 and sum of n+m is 0 to 4 in the formula (I) and (II) above and these formulas include isomers and homologs of the above mentioned compounds: by reacting 1 m of ketone with 1 to 70 m sulfur and 1 to 80 m of ammonia, primary amine or secondary amine to produce a thioamide which is then hydrolyzed to an acid. These acids are useful as intermediates in the synthesis of Vitamin D derivatives.

4199518, Apr 22, 1980

Mar 30, 1978

5/891846

William R. Glave - Chicago IL
Richard L. Johnson - Melrose Park IL
Arnold L. Hirsch - Oak Park IL

Diamond Shamrock Corporation - Dallas TX

C07J 900

2603972

Improved yields of 1. alpha. ,3. beta. -dihydroxy-steroid-5-enes are obtained by the addition of the alkali metal/liquid ammonia reduction products of 1. alpha. ,2. alpha. -epoxy-4,6-dien-3-one steroids to a quenching agent such as liquid ammonia/ammonium chloride mixture. Specific steroids reduced by these procedures include 1. alpha. ,2. alpha. -epoxycholesta-4,6-dien-3-one and 25-hydroxy-1. alpha. ,2. alpha. -epoxycholesta-4,6-dien-3-one.

4287129, Sep 1, 1981

Jul 28, 1980

6/172925

William H. Klausmeier - Elmhurst IL
Richard L. Johnson - Northlake IL
Arnold L. Hirsch - Oak Park IL

Diamond Shamrock Corp. - Dallas TX

C07J 900

2603971

Enol acetylation is carried out on a variety of 1,4,6-trien-3-ones to form 1,3,5,7 tetraene structures from which 1. alpha. -hydroxy-7-dehydro steroids are obtained. The compounds are intermediates used in the preparation of vitamin D. sub. 3 metabolites such as 1. alpha. ,25-dihydroxyvitamin D. sub. 3 and 1. alpha. -hydroxyvitamin D. sub. 3.