2- ethyl sulfides reaction products

Examples of the behavior of other substituted vinyl substrates upon exposure to the action of trifluoroacetic acid and triethylsilane are known. For example, -butyl vinyl ether, when reacted at 50° for 10 hours, gives -butyl ethyl ether in 80% yield (Eq. 65).234 In contrast, -butyl vinyl thioether gives only a 5% yield of n-butyl ethyl sulfide product after 2 hours and 15% after 20 horns of reaction.234 It is suggested that this low reactvity is the result of the formation of a very stable sulfur-bridged carbocation intermediate that resists attack by the organosilicon hydride (Eq. 66). 

Grosjean, D. Atmospheric reactions of ortho cresol gas phase and aerosol products, Atmos. Environ., 19(8) 1641-1652,1984. Grosjean, D. Photooxidation of methyl sulfide, ethyl sulfide, and methanethiol, Environ. Sci. Technol, 18(6) 460-468,1984a. Grosjean, D. Atmospheric reactions of styrenes and peroxybenzoyl nitrate, ScL Total Environ., 50 41-59, 1985. 

Moreover, product formation was not the same. Dibenzyl ethylsulfonium salt 72 gave only benzyl ethyl sulfide (73) and benzyl thiocyanate 74, but no dibenzyl sulfide or ethyl thiocyanate. By contrast, the cyclic sulfonium salt 75 gave a mixture containing chiefly (80%) dihydroisothianaphthene (76) with an equivalent amount of ethyl thiocyanate (77) and a minor amount (20%) of the sulfide-thiocyanate 78. This work represents the first direct experimental information on the rate of bimolecular nucleophilic substitution and relative orientation of the benzene ring and the leaving group and it demonstrates clearly the importance of stereoelectronic effects in these reactions. 

Reaction of the sandwich-type POM [(Fc(0H2)2)j(A-a-PW9034)2 9 with a colloidal suspension of silica/alumina nanopartides ((Si/A102)Cl) resulted in the production of a novel supported POM catalyst [146-148]. In this case, about 58 POM molecules per cationic silica/alumina nanoparticle were electrostatically stabilized on the surface. The aerobic oxidation of 2-chloroethyl ethyl sulfide (mustard simulant) to the corresponding harmless sulfoxide proceeded efficiently in the presence of the heterogeneous catalyst and the catalytic activity of the heterogeneous catalyst was much higher than that of the parent POM. In addition, this catalytic activity was much enhanced when binary cupric triflate and nitrate [Cu(OTf)2/Cu(N03)2 = 1.5] were also present [148],... 

Hart and coworkers tried two methods to prepare [9]N2S compounds. The first method was the reaction of the ditosylate derivative of thiodiethylene glycol with the disodium salt of A,N -ditosylethylenediamine. This method did not give [9]N2S. The second method from A,A -ditosylbis(2-amino-ethyl)sulfide gave a 10% yield of the macrocycle (method Z-11) (Hart et al., 1983) Others reported the same product but without details (Gahan et al.,... 

The quaternary phosphonium iodide, R P+I", can be isolated after treatment of the reaction product with aqueous hydrogen sulfide. Thus, white phosphorus heated with excess ethyl iodide at 180° for 22 hr. gave a product from which tetraethylphosphonium iodide was obtained in 49% yield (4). The remainder of the phosphorus was said to be converted to triethylphosphine oxide, although this product was not isolated. When the reaction product is refluxed with ethanol and then distilled over potassium hydroxide, the major product is the trialkyl phosphine oxide (3). Both trialkyldiiodophosphoranes and quaternary phosphonium iodides would be converted to the tertiary phosphine oxide under these conditions. Table III summarizes the... 

The tandem ylide generation/[2,3]-sigmatropic rearrangement can also be performed with sulfur and iodonium ylides and in these cases the reaction can proceed in intermolecular fashion.For example, up to 78% ee has been obtained in the reaction of allyl-2-methylphenyl sulfide (9.129) with aryl diazoacetates such as (9.130) in the presence of the copper catalyst generated with bis-oxazoline (9.07), while the reaction of aUyl iodide (9.132) with ethyl diazoacetate yields product (9.133) with 69% ee using this complex. ... 

Benzyl ethyl sulfide allowed to react with 1,4-diazabicyclo [2.2.2] octane bromine complex in aq. 70%-acetic acid benzyl ethyl sulfoxide. Y 95%. — The reaction is very rapid. The products are completely free from sulfones. Neither cleavage of aliphatic G-S-bonds, which may occur when N-bromosuccinimide is used, nor ar. bromination, when bromine is used, has been observed. F. e., also O-labeled sulfoxides with 0-enriched water, and use of bromine complexes with pyridine and quinoline, s. S. Oae et al.. Bull. Ghem. Soc. Japan 39, 364 (1966). 

Typical procedure. N,N -Bis(2-hydroxyethyl)urea 1024 [577] Excess ethanolamine and DMDTC were mixed and heated at 60 °C for 15 h. The released malodorous methyl sulfide by-product was absorbed and oxidized by NaOCl solution. When the reaction was complete, the unreacted ethanolamine was removed under reduced pressure by simple distillation, leaving a crude mixture of oxazolidinone 1025 and bis(2-hydroxyethyl)urea 1024, which was further purified by recrystallization from methanol/ethyl acetate (1 4.5) to give N,N -bis(2-hydroxyethyl)urea as colorless crystals. 

As shown in Scheme 14.1, guanidine hydrochloride [H2NC(NH2)NH2 Cl ] was converted to the free base with sodium ethoxide in ethanol. After the precipitated sodium chloride was removed, the solution was treated with ethyl cyanoacetate.The product of the condensation reaction, on heating (and also on treatment with aqueous base), underwent cychzation to produce 2,4-diamino-6-oxypyrimidine. On nitrosation, followed by reduction (with ammonium sulfide, (NH4)2S), the corresponding 2,4,5-triamino-8-oxopyrimidine resulted and the reaction of the pyrimidine with sodium formate and formic acid yielded guanine (G), indistinguishable from the authentic material. 

Distribution of Products in the Reaction of 2-(o-lodophenyl)ethyl Sulfides (1) with Tri-n-Butyltrn Hydride... 

The reaction of pyrrole-l-carbodithioate with ethyl propynoate and benzoylacet-ylene (aqueous DMSO, KOH, room temperature, 2 h) leads to normal adducts, S-vinylpyrrole-l-carbodithioates in a low yield (10%-18%, Scheme 2.81, Table 2.9) [549,554]. Among the major reaction products are substituted divinyl sulfides as a mixture of E,E-, Z,E-, and Z,Z-isomers. 

Miscellaneous Reactions. Sodium bisulfite adds to acetaldehyde to form a white crystalline addition compound, insoluble in ethyl alcohol and ether. This bisulfite addition compound is frequendy used to isolate and purify acetaldehyde, which may be regenerated with dilute acid. Hydrocyanic acid adds to acetaldehyde in the presence of an alkaU catalyst to form cyanohydrin the cyanohydrin may also be prepared from sodium cyanide and the bisulfite addition compound. Acrylonittile [107-13-1] (qv) can be made from acetaldehyde and hydrocyanic acid by heating the cyanohydrin that is formed to 600—700°C (77). Alanine [302-72-7] can be prepared by the reaction of an ammonium salt and an alkaU metal cyanide with acetaldehyde this is a general method for the preparation of a-amino acids called the Strecker amino acids synthesis. Grignard reagents add readily to acetaldehyde, the final product being a secondary alcohol. Thioacetaldehyde [2765-04-0] is formed by reaction of acetaldehyde with hydrogen sulfide thioacetaldehyde polymerizes readily to the trimer. 

The zinc. salts of these acids are extensively used as additives to lubricating oils to improve their extreme-pressure properties. The compounds also act as antioxidants, corrosion inhibitors and detergents. Short-chain dialkyl dithiophosphates and their sodium and ammonium salts are used as flotation agents for zinc and lead sulfide ores. The methyl and ethyl derivatives (RO)2P(S)SH and (RO)2P(S)CI are of particular interest in the large-scale manufacture of pesticides such as parathion, malathion, dimethylparathion, etc. For example parathion. which first went into production as an insecticide in Germany in 1947. is made by the following reaction sequence ... 

It is well known that palladium on carbon catalysts are poisoned by hydrogen cyanide and thiol products or hydrogen sulfide (6). Therefore, it was of interest to investigate the reduction of perfluoroalkyl thiocyanates as a function of tin concentration, keeping the concentration of palladium and reaction conditions constant. Figure 15.1 delineates the % conversion vs. Sn/Pd ratio, under the same reaction conditions of 175°C, 700 psig H2 for 2 hours with 5% Pd on carbon catalysts in ethyl acetate solvent at a 1000 1 substrate catalyst molar ratio. The increase in... 

Powerful evidence for the intermediacy of a metaphosphorimidate of type 189 nevertheless comes from the product spectrum obtained on reaction of 202 with KOH in ethanol or propanol. The principal products dimethyl sulfide and potassium O-ethyl (or propyl) phosphoramidate can be readily rationalized in terms of the reaction sequence presented in the Scheme 138). 

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