Crown sulfides

References concerning research studies of enyzme-like polymers conducted during the period of 1978-1982, catalytic properties of water-soluble imidazole-containing polymers during ester hydrolysis, as well as the latest achievements in the manufacture and application of high-molecular weight catalysts containing thiocrown-ethers or crown-sulfides, can be found in previous reviews [199-201]. 

It is interesting to note that Kulstad and Malmsten have utilized yet another method for introducing nitrogen into the crown precursors. They utilize sodium azide in DMSO to displace halogen from triethylene glycol dichloride. The bis-azide is then reduced using hydrogen sulfide in ethanol. ... 

Although the polysulfur macrocycles became more interesting to the scientific community after Pedersen s report of the crown compounds (see Chap. 1), examples of such structures may be found in the literature dating back some time. The first report of a macrocyclic polysulfide appears to be that by Ray who found in 1920 that when 1,2-dimercaptoethane and 1,2-dibromoethane were heated with alcoholic potassium hydrogen sulfide as shown in Eq. (6.2), triethylene trisulfide (2) and a substance presumed to be triethylene tetrasulfide (3) could be isolated. 

Early efforts to effect the photoinduced ring expansion of aryl azides to 3H-azepines in the presence of other nucleophiles met with only limited success. For example, irradiation of phenyl azide in hydrogen sulfide-diethyl ether, or in methanol, gave 17/-azepine-2(3//)-thione35 (5% mp 106—107 " O and 2-methoxy-3//-azepine (11 %),2 3 respectively. Later workers194 failed to reproduce this latter result, but found that in strongly basic media (3 M potassium hydroxide in methanol/dioxane) and in the presence of 18-crown-6, 17/-azepin-2(3//)-one was produced in 48% yield. In the absence of the crown ether the yield of azepinone falls to 35%. 

For the heavier alkaline earth elements the characterized compounds are octahedral monomers, dimers, or separated-ion species. The complexes M(SR)2 (M=Ca, Sr, Ba) have been obtained by aminolysis and proved to be soluble in solvents such as py these compounds decompose rather cleanly to their metal sulfides.86 The monomeric species include [M(EMes )2(thf)4] (M=Ca, Sr, Ba E=S, Se),87 89 [Ca(SC6F5)2(py)4],90 [Ca(SMes )2(18-crown-6)] thf,90 or [Ba(Se-Trip)2(18-crown-6)].87 Only a dimeric barium derivative, [Ba(SeTrip) (py)3(thf)]2, has been described.87 For these elements separated ion-triple species, such as [M(18-crown-6)(hmpa)2][EMes ]2 (M=Ca, Sr, Ba E=S, Se)87,88,91 or contact/separated ion-triple species as [Ba(SMes )(18-crown-6)(hmpa)][SMes ] have been reported.91... 

Dupont Durst et al. (1974) have used 18-crown-6 to solubilize NaBH3CN in a methanol/dichloromethane mixture, the solution reducing alkoxysulfonium salts to the corresponding sulfides in high yields. 

Hagglund and Enkvist (6) developed a laboratory scale method for manufacturing methyl sulfide from kraft black liquor by pressure heating after addition of sodium sulfide. This process was later taken over by Crown-Zellerbach in the United States and developed in pilot plant and full scale. However, the yield is only about 7% of the initial lignin utilized in the process. 

Symmetrical diaryl sulfides were produced in fair yield from the PTC reaction of sodium sulfide with molten aryl chlorides activated by a cyano, nitro, phthalimido or anhydrido group.193 Typical conditions require use of a 3 1 mole ratio of aryl chloride to Na2S and 10% of catalyst (crown ethers and onium salts) at 200 C for 24 h. 

Fluorodestannylation. Bu4NF is the most reactive source of F, but is difficult to obtain anhydrous. For fluorodestannylation, Harpp and Gingras1 prefer CsF with a catalytic amount of 18-crown-6. This reagent combines with diorganotin oxides, sulfides, or selenides to liberate the corresponding anion, which can be alkylated to give ethers, sulfides, or selenides. 

Metal sulfide films were also deposited by aerosol-assisted (AA)CVD, as exemplified by the results for Ca(SOCMe)2(15-crown-5) described here. 

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