Thioncarbonsäureester, I. Monothionmalonsäureester

Abstract

Ausgehend vom Cyanessigsaure-athylester wurden uber die Stufe der Imidsaureester-hydrochloride 1 a-f die Monothionmalonsaureester 2a-f dargestellt. Die Thionmalonsaureester unterliegen ebenso wie methylenaktive Thioamide einer Thion-Enthiol-Tautomerie. Sie werden in Gegenwart von Natriumalkoholat bevorzugt a m Schwefel alkyliert. Ihre Methylenaktivitat I l l 3 sich durch Michael-Addition und Knoevenagel-Kondensation nachweisen.Im Unterschied zu den Monothiocarbonsauren, in denen die Thiolform domi-niertW), lassen sich in ihren Derivaten Thion-und Thiolform fixiereo, so dab Thioncarbonsaureamide 4-7), Thionsaureanhydride 8) und Thioncarbonsaureester 4,9-15) eine Untersuchung der Reaktivitat der Thiocarbonylgruppe im Vergleich zu den analogen Sauerstoffverbindungen erlauben.Uns interessierte im Zusammenhang mit unseren Untersuchungen an CH-aciden Thioamiden 7,16-18) das reaktive Verhalten weiterer Mono-und Dithio-P-dicarbonylverbindungen, wie sie z. B. in den Thionmalonsaureestern gegeben sind. Derartige 1 ) G . Strickmann, Arbeit im vertieften organ. Praktikum und Teil d. Diplomarb., Humboldt-Univ. Berlin 1965 und 1966. 2 ) Vortrag zur Haupttagung der Chernischen Gesellschaft 1966 in Leipzig, gehalten am 2. Nov. 1966; s.

A new chiral heterocyclic 1,1-enediamine as a precursor to piperidines

“…Infrared spectra were recorded on a Pye-Unicam SP3-100 or a Philips PU9706 spectrometer in chloroform unless otherwise stated. Nuclear magnetic resonance (NMR) spectra were recorded using the following instruments: 1 H spectra at 250 MHz on a Bruker WM250 PFT or at 400 MHz on a Bruker AM400 PFT; 13 C spectra on a Bruker FX90 at 22.5 MHz, a Bruker WM250 PFT at 62.5 MHz, or a Bruker AM400 PFT at 100 MHz and multiplicites were determined using DEPT sequences. NMR Spectra were recorded for solutions in deuteriochloroform with tetramethylsilane as an internal standard unless otherwise stated.…”

Cathodic Reduction of O-Ethyl S-Phenacyl Dithiocarbonate

“…1 H NMR (300 MHz) and 13 C NMR (75.4 MHz) spectra were recorded on a Varian Unity 300 apparatus with deuteriochloroform as internal standard. Mass spectra (EI, ionising voltage 70 eV) were determined using a Hewlett-Packard Model 5988A mass-selective detector equipped with a Hewlett-Packard MS Chem Station.…”

“…spectra were obtained, as dispersions in KBr, on a Perkin-Elmer Model 583 spectrometer. 1 H NMR (300 MHz) and 13 C NMR (75.4 MHz) spectra were recorded on a Varian Unity 300 apparatus with deuteriochloroform as internal standard. Chemical shifts are given in ppm.…”

“…[13] They are stable oils wich are extracted completely into aqueous sodium hydroxide but not into aqueous sodium carbonate. [13] They are stable oils wich are extracted completely into aqueous sodium hydroxide but not into aqueous sodium carbonate.…”

“…The β-oxo-thionesters have been synthesised by several methods. [13] They are stable oils wich are extracted completely into aqueous sodium hydroxide but not into aqueous sodium carbonate. They are therefore quite acidic with pK a values comparable with those of β-oxo-esters.…”