Reaction with 1-hexanethiol

Chan et al. studied bulk reaction of hexanethiol (5 mmol) with hexyl acrylate (5 mmol) in the presence of 0.43 M hexylamine (p/C = 10.56), -dipropylamine (p/C3 = ll), and NEtj (pfC = 10.75) under ambient condition for 500 s. After 500 s, reaction with hexylamine showed approximately 95% conversion, n-dipropylamine showed approximately 60% conversion, and NEtj showed less than 1% conversion. These amines have almost the same p/T, but there is a huge difference in their kinetic profiles. Apart from these amines, they also studied various weak nucleophiles, which have varying basicity, such as pyridine (p/C3 = 5.14), aniline (pA3 = 9.34), and l,8-bis(dimethylamino)naphthalene (a proton sponge with pA = 12.1), and found that they yield less than 1% conversion. Based on these observations, the catalysis was attributed to the kinetic... 

Related sulfur-containing derivatives are formed from the reaction of 49 with 2-methyl-2-propanethiol, cyclo-hexanethiol, and 2-propanethiol in toluene at ambient temperature. The resulting tetrameric cyclopentadienyl thiolato complexes [(if-Cp)Mg(/.t3-SR) ]4 (R = Bu, CgFIn, Pr1) are colorless crystalline solids. Treatment of... 

Other modifications to the reaction conditions of the Brust-Schiffrin method, such as a reduction temperature of — 78 °C and the use of a hyperexcess of hexanethiol, results in an Au38(thiolate)24, based on observations, LDI-TOF mass spectrometry, TGA analysis and elemental analysis [69]. The influence of preparation temperature on the size and monodispersity of dodecylthiol monolayer protected gold clusters has also been reported. Both and SAXS measurements show that higher temperatures increase polydispersity. This modification of poly-dispersity may be related to the existence of a dynamic exchange of thiols at the particle surface with thiols in the solvent [70]. 

The redox reaction of the ferrocene moiety in a 6-(ferrocenyl)hexanethiol-hexanethiol (FcCgSH Q,SH, 1 20) mixed monolayer has been studied in the presence of potassium ferrocyanide as reducing agent. Thus, the ferrocenium formed at anodic potentials is reduced to ferrocene by the ferrocyanide in solution and the whole process becomes a surface catalytic reaction, in agreement with the following reaction scheme ... 

Graft Polymerization. Ceric Initiation. A stirred slurry of 10 g of starch in 200 ml of water was sparged with a slow stream of nitrogen for 1 hr at room temperature 15 g of acrylonitrile was then added, followed after 5 min by a solution of 0.338 g of ceric ammonium nitrate in 3 ml of IN nitric acid. In the reaction run with 1-hexanethiol, ceric ammonium nitrate solution was added first, followed after 5 min by a solution of 1.0 g of mercaptan in 15 g of acrylonitrile. The resulting mixture was allowed to stir for 2 hr at 25-27°C (temperature maintained with ice-water) and then was diluted with 200 ml of ethanol. The pH was adjusted to 6-7 with sodium hydroxide solution, and the polymer was isolated by filtration, washed with water and ethanol, and vacuum dried at 60°C. Ungrafted PAN was removed by repeated extraction of the polymer with dimethylformamide (DMF) at room temperature. 

In reactions run with mercaptans, either 1.0 g of 1-hexanethiol or 0.1 g of 2-mercaptoethanol was dissolved in 15 g of acrylonitrile. The reaction mixture was stirred magnetically and irradiated with cobalt-60 to a total dose of 0.1 Mrad. 

Other Systems. Alkyl Thiols. The reduction of hemin with ethane-thiol has been suggested to occur by a free radical mechanism on the basis of product analysis (II). The reaction of n-hexanethiol with TPPFeCl in DMSO carried out in the ESR cavity gives rise to the signal illustrated in Figure 7. These are preliminary results, and the spectrum is of poor quality and probably reflects some saturation from the low steady-state concentration of the radical. Nevertheless the signal only appears during the autoreduction of the iron porphyrin and again indicates that the autoreduction occurs by a free radical pathway. 

NPCl2)n reacts with 1-hexanethiol to give the fully substituted thio polymer utilizing 4-picoline as base in thf solutions. Only degradation products are obtained when the reaction is carried out with sodium hexanethiolate as... 

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