Darstellung und Eigenschaften von Dichlorvinylencarbonat

Abstract

Dichlorvinylencarbonat (DCVC) (3) ist ein neuartiges Derivat der GlyoxylsBure, deren Derivate durch Solvolyse daraus leicht zuganglich sind. Die Darstellung dieser Verbindung sowie einige ihrer Grundzustandseigenschaften werden beschrieben. Dichlorovinylene carbonate (DCVC) is a novel derivative of glyoxylic acid. Its derivatives are readily accessible from DCVC by solvolysis. The preparation of the compound as well as some of its ground state properties are described. Ausgehend von dem leicht zuganglichen Athylencarbonat (1) gelang uns die Darstellung des Dichlorvinylencarbonats (DCVC) (3), wie wir in einer Kurzmitteilung berichtetenl). Auf der Grundlage der von Ellingboe und Melbyz) gegebenen Vorschrift zur Chlorierung von 1 wurde das Tetrachlorathylencarbonat (2) hergestellt, das anschlieknd durch Behandlung mit verkupfertem Zinkpulver oder Zinkspanen in Ather unter Zusatz katalytischer Mengen Dimethylformamid in DCVC (3) (85 %) -1 iibergefuhrt wurde. hv c1-, -1 2 3 A. Photochemische Chlorierung des Athylencarbonats im einzelnen untersucht:Der Verlauf der Photochlorierung von khylencarbonat (1) war bisher noch nicht Der quantitative Verlauf der Reaktion unter den von uns gewahlten Bedingungen ist in Abbild. 1 durch die Abhangigkeit der prozentualen Zusammensetzung der intermediiir nachweisbaren Verbindungen 1, 2, 4 und 5 von der aufgenommenen Chlormenge dargestellt.

Swern Oxidation of Bicyclo[2.2.1]hept-5-ene-2,3-diol and Its Pyrazine-fused Derivatives: An Improved Synthesis of Bicyclo[2.2.1]hept-5-ene-2,3-dione and An Unexpected Ring-Opening Reaction

“…Dichlorovinylene carbonate (1) can be prepared by the reductive dechlorination reaction of tetrachloroethylene carbonate [3]. However, the synthesis of tetrachloroethylene carbonate is troublesome because the use of a large amount of chlorine gas is required [3]. Furthermore, we could not reproduce the reported yield of the Diels-Alder re-action of 1 with cyclopentadiene: the adduct 2 was obtained only in 40-50% yields whereas 65-70% yields were claimed in the literature [3].…”

“…Dichlorovinylene carbonate (1) can be prepared by the reductive dechlorination reaction of tetrachloroethylene carbonate [3]. However, the synthesis of tetrachloroethylene carbonate is troublesome because the use of a large amount of chlorine gas is required [3].…”

“…However, the synthesis of tetrachloroethylene carbonate is troublesome because the use of a large amount of chlorine gas is required [3]. Furthermore, we could not reproduce the reported yield of the Diels-Alder re-action of 1 with cyclopentadiene: the adduct 2 was obtained only in 40-50% yields whereas 65-70% yields were claimed in the literature [3]. Thus, we report here an improved synthesis of 1 starting from more readily available vinylene carbonate (4) [4].…”

“…The organic phase was dried with sodium sulfate. After removal of the solvent, the resulting yellow oil was distilled under vacuum to give 3 (5.31 g, 73%) as a yellow oil which solidified after cooling: bp 129°C (10 Torr); mp 40°C (lit [3] A similar reaction of 6 (0.65 g, 5.8 mmol) with dimethyl sulfoxide (1.19 g, 15 mmol) and oxalyl chloride (1.65 g, 13 mmol), followed by the addition of triethylamine (2.70 g, 27 mmol) provided 3 (0.43 g, 61%).…”

Synthesis and Self-Assembly of Conjugated Polymer Precursors Containing Dichlorocarbonate Groups by Living Ring-Opening Metathesis Polymerization

“…One promising class of monomers for the facile generation of conjugated polymers via ROMP are norbornenes 1 9 and 2 10 (Chart 1). These monomers can be readily prepared via Diels-Alder reaction of cyclopentadiene or furan with dichlorovinylene carbonate.…”