Synthesis of ω-Substituted Alkanethiols and (Bromomethyl)methylthiomalonates

✍ Scribed by Michael J. Pfammatter; Vuk Siljegovic; Tamis Darbre; Reinhart Keese

• Publisher: John Wiley and Sons
• Year: 2001
• Tongue: German
• Weight: 151 KB
• Volume: 84
• Category: Article
• ISSN: 0018-019X
• DOI: 10.1002/1522-2675(20010321)84:3<678::aid-hlca678>3.0.co;2-y

✦ Synopsis

Several multifunctional derivatives of methylthiomalonic acid ( 2-(thiocarboxy)acetic acid), i.e. 20a, b, 21, 22a, b, and 24, were prepared from thiols bearing a functionalized head group, i.e. from 9a, b, 12, and 16d, f (Schemes 4 and 5). The association constants of the two dithio podands 8b and 11 with K were determined. Scheme 2 a) CHCl 2 OMe or SO 2 Cl 2 . b) 5a ± c, Et 3 N. c) Zn, AcOH. d) 10, CHCl 2 OMe, CH 2 Cl 2 , Et 3 N.

1 ) Upon heating to 150 ± 1538, compound 14f developed a smectic mesophase (probably smectic A) and decomposed below the clearing point at T b 1958. Compound 14b decomposed at 166 ± 1688, but developed a mesophase upon quick cooling to 155 ± 1608. We thank Prof. R. Miethchen, University of Rostock, for this analysis. Scheme 3 a) 5b (n 8) or 5f (n 12), MeOH, reflux. b) 5d (n 10), MeOH; Ac 2 O, pyridine. c) Ac 2 O, pyridine for 14f. d) Zn, AcOH, and 15d or 15f.