Ethylene sulfide

Material Protection. The graft copolymers of ethylene sulfide on polyethyleneimine can be used as an antifouHng anticorrosion substrate for iron (439). PEIs or their derivatives are also used in electrolysis baths as brighteners in the electrochemical deposition of metals (440,441). 

Diborane reacts with ethylene oxide at —80° C to form diethoxyborane and a soHd polymer containing approximately eight ethylene oxide units per molecule (88). Potassium thiocyanate or thiourea react ia aqueous solution with ethylene oxide to give ethylene sulfide (89). 

Fig. 14-7. Distribution of sensitivity to ethylene sulfide odor in 33 individuals. The abscissa is the percentage of the individuals who detected the presence of ethylene sulfide at various levels. Source Dravnicks, A., and Jarke, F., J. Air PoIIut. Control Assoc. 30, 1284-1289 (19801.

Tung et al21> have reported on the use of a polymeric thiol transfer agent for use in block copolymer production. Various methods have been used for the anion thiol conversion. Near quantitative yields of thiol arc reported to have been obtained by terminating anionic polymerization with ethylene sulfide and derivatives (Scheme 7.27). Transfer constants for the polymeric thiols are reported to be similar to those of analogous low molecular weight compounds.273... 

Ethylene carbonate, reaction with potassium thiocyanate, 42, 59 Ethylene sulfide, 42, S9 Ethyl formate, reaction with cyclo-hexylamine, 41, 14 Ethyl- -hexylamine, 43, 47 5-(2-Ethylhexyl)-l,2,3,4,5-pentachloro-cyclopentadiene, 43, 93 Ethylhydrazinium hydrogen oxalate,... 

A nickel-promoted C—S bond cleavage has been reported,860 which occurs when solutions of the Ni1 complex of (330) are electrogenerated. The product was identified by cyclic voltammetry and spectroscopy as [Ni(C6H4S2)2]2. EPR and NMR evidence suggests a one-electron mechanism, involving reduction to a 19-electron Ni1 species, electron transfer, and concomitant C—S bond cleavage, extrusion of ethylene followed by a further one-electron reduction and extrusion of ethylene sulfide. 

Daco-derived ligands, in particular derivatives alkylated with ethylene sulfide to provide pendent mercaptoethyl groups, have been used in model compounds for the active site of Ni11-containing hydrogenases.1407 1409... 

See Other INDUCTION PERIOD INCIDENTS, RUNAWAY REACTIONS 10840. Thiirane (Ethylene sulfide)... 

Colorless liquid that gradually polymerizes. It may be stabilized with 0.5% butylmer-captan. Ethylene sulfide is hazardous through inhalation and ingestion, and produces local skin/eye impacts. 

Potassium thiocyanate reacts in aqueous solution of ethylene oxide to form ethylene sulfide, C2H4S. 

Ethylene sulfide Ethylene thiourea 2-Ethylhexyl aerylate Ethyl methanesulfonate A-Ethyl-A-nitrosourea... 

The conformational energy E(op) associated with gauche states about CH2-CH2 bonds in polyethylene sulfide) (PSE) is estimated from the RIS analysis of experimental dipole moments and their temperature coefficients corresponding to the alternating copolymer of pentamethylene sulfide and ethylene sulfide (PXS) as well as to 1,2-bis(butylthio)ethane. 

Mean-square dipole moments of polylthiodiethylene gycol), an alternating copolymer of ethylene oxide and ethylene sulfide, are determined from dielectric constant measurements on dilute solutions of the polymer in benzene. Since the configuration-dependent properties of one of the parent homopolymers, PES, are unknown, because of its insolubility in ordinary solvents, the results are preferably compared with those of POE chains. It is found that the dipole moments of polylthiodiethylene glycol) are somewhat larger than those of POE. 

Using standard anaerobic techniques, a 100-mL Schlenk flask equipped with a stir bar is charged with 50 mL dry benzene and 2 mL (1.96 g, 0.0172 mol) distilled free amine. If crude daco is used, the product will be less pure and of lower yields. The mixture is warmed to 50-60°C under N2. Three 1-mL (0.05 mol) portions of ethylene sulfide are added, allowing 20 min reaction time between additions. The mixture is then heated under N2 for 1 h. Complete reaction is indicated by the formation of a finely divided white precipitate after the final addition. The reaction mixture is filtered anaerobically through a bed of celite in a glass-fritted funnel. Solvent is removed under vacuum while continuing to heat at 50-60°C. The H2-bme-daco is obtained as a colorless to pale yellow oil. Irrespective of color, this material is of suitable quality to be converted to the nickel complex. If distilled daco is used, the product is quite pure. Attempts at vacuum distillation (bpo.immHg = 135°C) resulted in partial decomposition. Yield 3.21 g (80%). 

N,N-Bis(2-mercaptoethyl)2-methylthioethylamine. In a flame-dried and argon-flushed tube (15 x 3.75 cm) fitted with a teflon needle valve, a solution of ethylene sulfide (4.40 g, 73 mmole) in toluene (13 mL) is added to a solution of 2-methylmercaptoethylamine (2.65 g, 29 mmole) in toluene (10 mL). The valve is then closed to seal the tube and the mixture is allowed to stand for 8 h at room temperature. The sealed tube containing the reaction mixture is then heated to 110-130°C for 30-40 h. After cooling to room temperature, the tube is attached to a Schlenk line and opened under N2. The product mixture is filtered to remove a white precipitate (ethylene sulfide polymer), and the solvent is removed under vacuum. The residual liquid is fractionally distilled at reduced pressure (1I4-II6°C 0.03 mm) to yield N,N-bis(2-mercaptoethyl)2-methylthioethylamine as a colorless liquid. Yield = 3.56 g (58%). 

Thiocyanate salts. The earliest publication describing additii m of a thiocyanate aalt to an epoxide appeared in 1046 from the Culvenor laboratory.3 7 Since then a number of papers have dealt will Ihr useful reaction, which may be utilized to transform ethylene oxides into ethylene sulfides conveniently in a single operation. It is general h agreed117- 1177 that the course of events may be depicted as slu>wn in Eq. (673) for the general case. 

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