Reaction with diethyl sulfide

Reactions with Sulfur Compounds. Thiosuccinic anhydride [3194-60-3] is obtained by reaction of diethyl or diphenyl succinate [621-14-7] with potassium hydrogen sulfide followed by acidification (eq. 10). Thiosuccinic anhydride is also obtained from succinic anhydride and hydrogen sulfide under pressure (121). 

Diphenylimidazole with palladium acetate forms the cyclometallated complex 80 (X = OAc) (97AOC491). The acetate group is replaced by chloride or bromide when 80 (X = OAc) reacts with sodium chloride or lithium bromide, respectively, to give 80 (X = C1, Br). Bromide with diethyl sulfide forms the mononuclear complex 81. Similar reactions are known for 1 -acetyl-2-phenylimidazole (96JOM(522)97). 1,5-Bis(A -methylimidazol-2-yl)pen-tane with palladium(II) acetate gives the cyclometallated complex 82 (OOJOM (607)194). 

Preparation of (diethyl phosphonomethyl) acetyl sulfide — Reaction of a trialkyl phosphite with a 1-halosulfide... 

Swern oxidations have been performed using the PEG2000 bound sulfoxide 34 as a dimethylsulfoxide (DMSO) substitute (reaction 13).49-50 Several alcohols were efficiently oxidized to their aldehydes or ketones using this reagent, oxalyl chloride, and triethylamine. Precipitation of the polymer with cold diethyl ether and filtration through a pad of silica afforded the desired oxidized products in very good yields and purities. The reduced sulfide polymer could be reoxidized to sulfoxide 34 with sodium metaperiodate and used again in reactions with no appreciable loss in oxidation capacity. 

In anticipation of the intrinsic luminescence properties of these polymeric materials incorporating polymetallic CuX substructures, we resynthesized the Cul and CuBr adducts with Et2S under similar reaction conditions to study the luminescence properties of these diethyl sulfide compounds. The presence of CU4I4 cubane clusters in the polymer could be easily detected by the very strong... 

A solution of 4.15 g. (0.01 mol) of potassium tetrachloro-platinate(II) in 50 ml. of water is placed in a 250-ml., glass-stoppered Erlenmeyer flask. Two and one-tenth milliliters (1.76 g. = slightly less than 0.02 mol) of diethyl sulfide (density, 0.837) is addedf to this solution in small portions, the mixture being shaken vigorously after each addition to ensure complete reaction. J The bright yellow precipitate is immediately separated from the reddish solution by suction filtration, washed at once with several 5-ml. portions of ice-cold alcohol, and then washed with several 5-ml. portions of cold water to remove the potassium chloride. The crystals are dissolved in a minimum amount (ca. 6 ml.) of hot ethanol and the solution cooled in an ice-salt bath. The bright yellow needles are separated by suction filtration and air-dried. The yield is 2.3 g. (51.5%). Anal. Calcd. 

It is not necessary to start with the protonated Fe(II) complex to isolate these substituted products, however. Reaction of a slurry of the unsubstituted Fe(III) complex with anhydrous HC1 in diethyl sulfide produced a mixture of substitution products, including the species shown in Eq. (12). Although no evidence has been found for a protonated cobalt metallo-carborane analog, boron-substituted complexes of cobalt (III) may also be obtained by reaction of the (1,2-C2B9Hn)2Co- ion with R2S and HC1 52). 

In a series of publications (75JOC2600, 70JOC1965, 73JOC3087), Potts and coworkers have reported that cyclic amidines (290) readily condense with trichloromethylsulfenyl chloride (329) to yield the sulfenamides (330 Scheme 119). Treatment of the latter compounds with aromatic amines in the presence of triethylamine results in cyclization, possibly via an intermediate such as (331), to produce bicyclic products of type (332). Heterocycles (290) which have been used successfully in this reaction include 2-amino-l,3,4-thiadiazoles, 3-aminopyridazines, 2-aminopyrimidines, 2-aminopyrazines, 2-aminopyridines, 3-aminoisoxazoles and 5-amino-1,2,4-thiadiazoles. The sulfenamide derivative (330) of 2-aminopyridine also was found to react with sodium sulfide and with diethyl malonate to produce (333) and (334) respectively. Attempts to hydrolyze (332) to (295) under acidic conditions failed. 

Dodecylbenzyldiethylsulfonium Chloride. Into a 500 ml flask was added 76.6 g (0.200 moles) of- practical grade p-dodecylbenzyl chloride, 26.5 g (0.294 moles) diethyl sulfide (Eastman White label), 200 gof methanol and 2 g deionized water. Stirring was started and after 218.5 hrs the reaction was terminated by extracting it 3 times with 125 ml portions of a 50/50 (vol/vol) n-hexane/ether mixture. The aqueous fraction was separated and concentrated under vacuum to give 429 g of solution which was 19.8% active. The conversion was 85%. 

Ignition or explosive reaction with metals (e.g., aluminum, antimony powder, bismuth powder, brass, calcium powder, copper, germanium, iron, manganese, potassium, tin, vanadium powder). Reaction with some metals requires moist CI2 or heat. Ignites with diethyl zinc (on contact), polyisobutylene (at 130°), metal acetylides, metal carbides, metal hydrides (e.g., potassium hydride, sodium hydride, copper hydride), metal phosphides (e.g., copper(II) phosphide), methane + oxygen, hydrazine, hydroxylamine, calcium nitride, nonmetals (e.g., boron, active carbon, silicon, phosphoms), nonmetal hydrides (e.g., arsine, phosphine, silane), steel (above 200° or as low as 50° when impurities are present), sulfides (e.g., arsenic disulfide, boron trisulfide, mercuric sulfide), trialkyl boranes. 

A powerful oxidizer. Explosive reaction with acetaldehyde, acetic acid + heat, acetic anhydride + heat, benzaldehyde, benzene, benzylthylaniUne, butyraldehyde, 1,3-dimethylhexahydropyrimidone, diethyl ether, ethylacetate, isopropylacetate, methyl dioxane, pelargonic acid, pentyl acetate, phosphoms + heat, propionaldehyde, and other organic materials or solvents. Forms a friction- and heat-sensitive explosive mixture with potassium hexacyanoferrate. Ignites on contact with alcohols, acetic anhydride + tetrahydronaphthalene, acetone, butanol, chromium(II) sulfide, cyclohexanol, dimethyl formamide, ethanol, ethylene glycol, methanol, 2-propanol, pyridine. Violent reaction with acetic anhydride + 3-methylphenol (above 75°C), acetylene, bromine pentafluoride, glycerol, hexamethylphosphoramide, peroxyformic acid, selenium, sodium amide. Incandescent reaction with alkali metals (e.g., sodium, potassium), ammonia, arsenic, butyric acid (above 100°C), chlorine trifluoride, hydrogen sulfide + heat, sodium + heat, and sulfur. Incompatible with N,N-dimethylformamide. 

If alkyldichloroboranes are specifically required, dichloroborane-dimethyl sulfide is the reagent of choice. It is more stable and more convenient than the dichloroborane-diethyl ether complex, but its hydroborating properties are very similar." Dichloroborane complexes ethers even more strongly than monochloroborane, and its reactions with alkenes in this solvent are slow and lead to mixtures. Therefore, it is generally used in pentane and trichloroborane is added to liberate uncomplexed dichloroborane. Under these conditions it readily gives alkyldichloroboranes on reaction with alkenes or alkenyldichloro-boranes on reaction with alkynes. " " The latter reaction has been applied to alkynylsilanes (equation 44)." ... 

Calculate the enthalpy of adduct formation predicted by Drago s E, C equation for the reactions of I2 with diethyl ether and diethyl sulfide. 

---