Mercaptans primary

K. Potrafke, E. M. Read, R. E. et al (Exp. Stn., E. I. DuPont de Nemours and Co., Wilmington, Del.). J. Org. Chem. 1971, 36 (16), 2267-72 (Eng). Triarylimidazolyl free radicals oxidize electron-rich substances by rapid electron abstraction from tertiary amines, iodide ion, and metal ions and H atom abstraction from phenols, mercaptans, primary and secondary amines, and activated C-H compds. The rate consts. for electron abstraction from tertiary amines were related to s+ values via oxidn. potentials which were detd. by cyclic voltametry. 

Rifamycin S also undergoes conjugate addition reactions to the quinone ring by a variety of nucleophiles including ammonia, primary and secondary amines, mercaptans, carbanions, and enamines giving the C-3 substituted derivatives (38) of rifamycin SV (117,120,121). Many of the derivatives show excellent antibacterial properties (109,118,122,123). The 3-cycHc amino derivatives of rifamycin SV also inhibit the polymerase of RNA tumor vimses (123,124). 

Hydrogen Sulfide andMercaptans. Hydrogen sulfide and propylene oxide react to produce l-mercapto-2-propanol and bis(2-hydroxypropyl) sulfide (69,70). Reaction of the epoxide with mercaptans yields 1-aLkylthio- or l-arylthio-2-propanol when basic catalysis is used (71). Acid catalysts produce a mixture of primary and secondary hydroxy products, but ia low yield (72). Suitable catalysts iaclude sodium hydroxide, sodium salts of the mercaptan, tetraaLkylammonium hydroxide, acidic 2eohtes, and sodium salts of an alkoxylated alcohol or mercaptan (26,69,70,73,74). 

The primary reactions occurring during hydrotreating are (43) desulfurization of sulfides, polysulftdes, mercaptans, and thiophene as exemplified by... 

Dissociation extraction is the process of using chemical reac tion to force a solute to transfer from one liquid phase to another. One example is the use of a sodium hydroxide solution to extract phenolics, acids, or mercaptans from a hydrocarbon stream. The opposite transfer can be forced by adding an acid to a sodium phenate stream to spring the phenolic back to a free phenol that can be extrac ted into an organic solvent. Similarly, primary, secondary, and tertiary amines can be protonated with a strong acid to transfer the amine into a water solution, for example, as an amine hydrochloride salt. Conversely, a strong base can be added to convert the amine salt back to free base, which can be extracted into a solvent. This procedure is quite common in pharmaceutical production. 

Effect of Catalyst The catalysts used in hydrotreating are molybdena on alumina, cobalt molybdate on alumina, nickel molybdate on alumina or nickel tungstate. Which catalyst is used depends on the particular application. Cobalt molybdate catalyst is generally used when sulfur removal is the primary interest. The nickel catalysts find application in the treating of cracked stocks for olefin or aromatic saturation. One preferred application for molybdena catalyst is sweetening, (removal of mercaptans). The molybdena on alumina catalyst is also preferred for reducing the carbon residue of heating oils. 

The molecular weight of the continuous phase is an important parameter that affects the mechanics and the melt flow of the end product. It can be controlled by the use of a suitable chain transfer agent (e.g., /er/-dodecyl mercaptan Ct = 4.0) or their combinations (e.g., primary mercaptans Or = 26.0 and dimeric a-methyl styrene Ct = 0.1) [132]. 

Amines remove the bulk of the H2S primary amines also remove the COj. Amine treating is not effective for removal of mercaptan. In addition, it cannot remove enough H2S to meet the copper strip corrosion test. For this reason, caustic treating is the final polishing step downstream of the amine units. Table 1-3 illustrates the chemistry of some of the important caustic reactions. 

Another reagent that readily forms fluorescent derivatives with primary amines is o-phthalaldehyde (trade name "Fluoropa"). The reaction proceeds in aqueous solution in the presence of a mercaptan at a pH of 9-11 producing an isoindole. 

DMSO or other sulfoxides react with trimethylchlorosilanes (TCS) 14 or trimefhylsilyl bromide 16, via 789, to give the Sila-Pummerer product 1275. Rearrangement of 789 and further reaction with TCS 14 affords, with elimination of HMDSO 7 and via 1276 and 1277, methanesulfenyl chloride 1278, which is also accessible by chlorination of dimethyldisulfide, by treatment of DMSO with Me2SiCl2 48, with formation of silicon oil 56, or by reaction of DMSO with oxalyl chloride, whereupon CO and CO2 is evolved (cf also Section 8.2.2). On heating equimolar amounts of primary or secondary alcohols with DMSO and TCS 14 in benzene, formaldehyde acetals are formed in 76-96% yield [67]. Thus reaction of -butanol with DMSO and TCS 14 gives, via intermediate 1275 and the mixed acetal 1279, formaldehyde di-n-butyl acetal 1280 in 81% yield and methyl mercaptan (Scheme 8.26). Most importantly, use of DMSO-Dg furnishes acetals in which the 0,0 -methylene group is deuter-ated. Benzyl alcohol, however, affords, under these reaction conditions, 93% diben-zyl ether 1817 and no acetal [67]. 

Morton and Salatiello have deduced the ratio kpp/kp for radical polymerization of butadiene by applying the above described procedure, appropriately modified for the emulsion system they used. The primary molecular weight was controlled by a mercaptan acting as chain transfer agent, as in the experiments of Bardwell and Winkler cited above. Measurement of the mercaptan concentration over the course of the reaction provided the necessary information for calculating % at any stage of the process, and in particular at the critical conversion 6c for the initial appearance of gel. The velocity constant ratios which they obtained from their results through the use of Eq. 

When added to water as an aquatic herbicide, acrolein undergoes rapid decomposition, especially in sunlight. At the same time, it reacts rapidly with amines, alcohols, and mercaptans of aquatic plants, destroying cell structure and killing the plants (Parent et al. 1992). Mammals drinking acrolein-contaminated water rapidly convert acrolein to saturated alcohol compounds because of the low pH in the upper portion of their GI tracts the primary breakdown product is beta-propionaldehyde (USEPA 1980). 

This one-step procedure is a convenient and general method for the preparation of carbamates. It is substantially simpler, quicker, and safer than the multistep methods hitherto used for the preparation of carbamates of tertiary alcohols. This procedure is applicable to the preparation of carbamates of primary, secondary, and tertiary alcohols and mercaptans, polyhydric alcohols, acetylenic alcohols, phenols, and oximes. It has also been extended to the preparation of carbamyl derivatives (i.e., ureas) of inert (non-basic) amines.10... 

The primary collector used in PGM flotation is xanthate. As a choice of secondary collectors, dithiophosphates and mercaptans are used in some operating plants. 

In plant practice, lead oxide minerals are recovered using a sulphidization method with xanthate as the primary collector and mercaptans as the secondary collector. 

In the cases where CuS04 is used as an activator, mercaptan is used as a primary collector. Typical amine consumptions ranged from 80 to 150 g/t. Amine is a fast-acting collector and does not require conditioning time. 

R is the spacer group which should also terminate in an anchor e.g. a mercaptan. He report here intermediate results in which R is the methyl and ethyl moiety the case of R=H is the subject of a separate paper (K. A. B. Lee, R. Mowry, G. McLennan and H. 0. Finklea, in press). Our primary concern is whether the bipyridiniums are incorporated into the mercaptan monolayer and whether they are located at a fixed distance relative to the gold surface. 

The free radical polymerization of HPMA in the presence of mercaptans involves two different initiation mechanisms (Scheme 2) [26]. One is the initiation by RS radicals from chain transfer agent the other appears to be the direct initiation by the primary isobutyronitrile (IBN) radicals formed by the decomposition of AIBN [27]. The RS are formed by either the free radical transfer reaction of alkyl mercaptans with the IBN radicals or the chain transfer reaction of an active polymer chain with the mercaptans. The initiation by the RS radicals produces the ST polymers with a functional group at one end of the polymer chain. The initiation by IBN radicals leads to nonfunctional polymer chains with an IBN end group. The presence of the polymers with IBN end groups effects the purity and the functionality of ST polymers. As expected, the production of nonfunctionalized polymer chains is affected by reaction conditions. The polymerization is mainly terminated by chain transfer reaction with the mercaptans, but other termination mechanisms, such as disproportionation and recombination, take place depending on the reaction conditions [26]. 

Much of the methyl mercaptan and dimethyl sulfide can be oxidized to dimethylsulfoxide (DMSO), a useful side product that is a common polar, aprotic solvent in the chemical industry. This is in fact the primary method... 

Methanethiol Methyl Mercaptan under Thiols Methanol under Primary Alcohols... 

Surprisingly it was reported that when potassium cyanate is substituted for sodium cyanate the yields of carbamates are reduced to less than 5 %. The reason for this drastic effect is not known at this time. In addition, the use of other alkali or alkaline metal cyanates in this reaction has not been investigated. The Loev [28] procedure appears applicable to the synthesis of carbamates from primary, secondary, and tertiary alcohols (2 hr reaction time affords 60-90% yields), cyclic and acyclic 1,3-diols, phenols, oximes, ald-oximes, and ketoximes, and primary, secondary, and tertiary mercaptans. Carbamates could not be obtained from diphenylethylcarbinol (dehydrated to 1,1-diphenylethylene) or trichloro- and trifluoromethylcarbinols. 

Again analogous to alcohols, primary mercaptans split out H2S to give a strong M - 34 peak, the resulting ion then eliminating ethylene thus the homologous series M - H2S - (CH2=CH2) arises. 

The half-life with respect to chemical transformation of CH3I in seawater at 20°C was determined to be 20 days, as compared to about 200 days in freshwater (reaction with H20 yielding CH3OH). In a case of a groundwater contamination with several alkyl bromides, Schwarzenbach et al. (1985) reported the formation of dialkyl sulfides under sulfate-reducing conditions in an aquifer. They postulated that in an initial reaction, primary alkyl bromides reacted with HS" by an SN2 mechanism to yield the corresponding mercaptans (thiols) ... 

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