The Conjugated Steroids

Carboxyalthioacrylates

“…We report here upon one group of such compounds, the carboxyalkylthioacrylic acids (I, R = , X = -COOH), their esters and half-esters, and other derivatives. The compounds (1)(2)(3)(4)(5)(6)(7)(8)(9)(10)(11)(12)(13)(14)(15) prepared are listed in Table I. (1) A grant from Bristol Laboratories, Syracuse, N. Y.…”

“…The diacids (3,4) and their half-esters (1,2) reacted smoothly with oxalyl chloride. No indication of cistrans isomerization was revealed by nmr spectra of the unpurified acid chlorides.…”

“…shown by nmr to be mostly the trans isomer 2. Distillation of this was attended by considerable decomposition and afforded only 2.0 g (5%) of írans-ethyl 3-(2'-carboxyethylthio)acrylate (2): bp 152°( 0.8 mm); n25n 1.5319; ir (liquid film) 5.87, 6.33, 7.67, 10.6 µ; nmr (A-60, CDC13) 1.26 (t, 3 H, J = 7 Hz, -OCH2CH3), 2.94 (symmetrical multiplet, 4 H, -SCH2CH2-OOOH), 4.17 (q,2H,7 = 7 Hz, -OCH2CH3), 5.75 (d, 1 H, J = 15 Hz, =CHCOOEt), 7.67 (d, 1 H, J = 15 Hz, -SCH=); uv ®°278 nm(e 18,300). cis-3-(2'-Carboxyethylthio)acrylic Acid (3).-Propiolic acid (2.0 g, 29 mmol) and 3-mercaptopropionic acid (3.03 g, 29 mmol) were dissolved in an EtOH-water (1:3) mixture (50 ml) containing KOH (3.2 g, 58 mmol).…”

The isolation of 3β-hydroxy-Δ5-steroids from the urine of normal men

“…Since the work of Ronzoni (1952), Dingemanse et al (1952) and Cohen & Oneson (1953 dehydroepiandrosterone has been recognized as one of the major constituents of the 17-oxo steroid fraction of the urine of normal people. However, the possibility that other 3p-hydroxy-A5-steroids might be present in the urine of normal people has not previously been systematically investigated.…”

Stringent requirement for electrophiles in the facile solvolytic hydrolysis of neutral sulfate ester salts

“…The pKVs of a series of substituted phenyl phenacyl sulfones (2) were determined. With variation of the phenylsulfonyl substituents, the sulfone acidities followed a linear correlation with <r. The p value for this correlation was +2.01, indicating that electron-withdrawing substituents increase sulfone acidity and that this system is very responsive to substituent changes.…”