Alcohols indirect

Alcohol indirectly affects hematopoiesis through metabolic and nutritional effects and may also directly inhibit the proliferation of all cellular elements in bone marrow. The most common hematologic disorder seen in chronic drinkers is mild anemia resulting from alcohol-related folic acid deficiency. Iron deficiency anemia may result from gastrointestinal bleeding. Alcohol has also been implicated as a cause of several hemolytic syndromes, some of which are associated with hyperlipidemia and severe liver disease. 

Molecular ion Mostly weak, often missing, especially in tertiary and long-chain alcohols. Indirect determination of M+ is often possible from the fragments at [M-15], [M-18]+ and [M-33]+. [M+l] is often significant. In primary and secondary alcohols also [M-1] can usually be seen. Sometimes, [M-2]+ is formed because of oxidation to carbonyl compounds during sample introduction. 

The carbonyiation of o-diiodobenzene with a primary amine affords the phthalimide 501 [355,356]. Carbonyiation of iodobenzene in the presence of (9-diaminobenzene (502) and DBU or 2,6-lutidine affords 2-phenylbenzimida-zole (503)[357, The carbonyiation of aryl iodides in the presence of pentaflnor-oaniline affords 2-arylbenzoxazoles directly, 2-Arylbenzoxazole is prepared indirectly by the carbonyiation of (9-aminophenol[358j. The optically active aryl or alkenyl oxazolinc 505 is prepared by the carbonyiation of the aryl or enol triflates in the presence of the opticaly active amino alcohol 504, followed by treatment with thionyl chloride[359]. 

Indirect Hydration. Indirect hydration is based on a two-step reaction of propylene and sulfuric acid. In the first step, mixed sulfate esters, primarily isopropyl hydrogen sulfate, but also diisopropyl sulfate, form. These are then hydrolyzed, forming the alcohol and sulfuric acid. 

Process. A typical indirect hydration process is presented in Eigure 1. In the process, propylene reacts with sulfuric acid (>60 wt%) in agitated reactors or absorbers at moderate (0.7—2.8 MPa (100—400 psig)) pressure. The isopropyl sulfate esters form and are maintained in the Hquid state at 20—80°C. Low propylene concentrations, ie, 50 wt %, can be tolerated, but concentrations of 65 wt % or higher are preferred to achieve high alcohol yields. Because the reaction is exothermic, internal cooling coils or external heat exchangers are used to control the temperature. 

Fig. 1. Indirect hydration process for the manufacture of isopropyl alcohol CBM = constant boiling mixture (61,62).

Isopropyl Alcohol. Propylene may be easily hydrolyzed to isopropyl alcohol. Eady commercial processes involved the use of sulfuric acid in an indirect process (100). The disadvantage was the need to reconcentrate the sulfuric acid after hydrolysis. Direct catalytic hydration of propylene to 2-propanol followed commercialization of the sulfuric acid process and eliniinated the need for acid reconcentration, thus reducing corrosion problems, energy use, and air pollution by SO2 and organic sulfur compounds. Gas-phase hydration takes place over supported oxides of tungsten at 540 K and 25... 

Mass spectral analysis of quaternary ammonium compounds can be achieved by fast-atom bombardment (fab) ms (189,190). This technique rehes on bombarding a solution of the molecule, usually in glycerol [56-81-5] or y -nitroben2yl alcohol [619-25-0], with argon and detecting the parent cation plus a proton (MH ). A more recent technique has been reported (191), in which information on the stmcture of the quaternary compounds is obtained indirectly through cluster-ion formation detected via Hquid secondary ion mass spectrometry (Isims) experiments. 

Steam is introduced at the base of the whiskey column through a sparger. Where economy is an important factor, as in a fuel alcohol plant, a calandtia is employed as the source of indirect heat. The diameter of the stiU, number of perforated and bubble cap plates, capacity of the doubler, and proof of distiUation are the critical factors that largely determine the characteristics of a whiskey. 

There are two main processes for the synthesis of ethyl alcohol from ethylene. The eadiest to be developed (in 1930 by Union Carbide Corp.) was the indirect hydration process, variously called the strong sulfuric acid—ethylene process, the ethyl sulfate process, the esterification—hydrolysis process, or the sulfation—hydrolysis process. This process is stiU in use in Russia. The other synthesis process, designed to eliminate the use of sulfuric acid and which, since the early 1970s, has completely supplanted the old sulfuric acid process in the United States, is the direct hydration process. This process, the catalytic vapor-phase hydration of ethylene, is now practiced by only three U.S. companies Union Carbide Corp. (UCC), Quantum Chemical Corp., and Eastman Chemical Co. (a Division of Eastman Kodak Co.). UCC imports cmde industrial ethanol, CIE, from SADAF (the joint venture of SABIC and Pecten [Shell]) in Saudi Arabia, and refines it to industrial grade. 

Other carbon electrophiles which are frequently employed include aldehydes, ketones, esters, nitriles and amides of the type RCONMei. An indirect method of acylation involves the initial reaction of a lithio compound with an aldehyde followed by oxidation of the resulting secondary alcohol to the corresponding acyl derivative. 

The landmark report by Winstein et al. (Scheme 3.6) on the powerful accelerating and directing effect of a proximal hydroxyl group would become one of the most critical in the development of the Simmons-Smith cyclopropanation reactions [11]. A clear syw directing effect is observed, implying coordination of the reagent to the alcohol before methylene transfer. This characteristic served as the basis of subsequent developments for stereocontrolled reactions with many classes of chiral allylic cycloalkenols and indirectly for chiral auxiliaries and catalysts. A full understanding of this phenomenon would not only be informative, but it would have practical applications in the rationalization of asymmetric catalytic reactions. 

Synthetic ethyl alcohol (known as ethanol to differentiate it from fermentation alcohol) was originally produced hy the indirect hydration of ethylene in the presence of concentrated sulfuric acid. The formed mono-and diethyl sulfates are hydrolyzed with water to ethanol and sulfuric acid, which is regenerated ... 

Yet another example of an electrophilic addition is the reaction of alkenes with the hypohalous acids HO—Cl or HO-Br to yield 1,2-halo alcohols, called halohydrins. Halohydrin formation doesn t take place by direct reaction of an alkene with HOBr or HOC1, however. Rather, the addition is done indirectly by reaction of the alkene with either Br2 or Cl2 in the presence of water. 

Alcohols can be prepared by hydration of alkenes. Because the direct hydration of alkenes with aqueous acid is generally a poor reaction in the laboratory, two indirect methods are commonly used. Hydroboration/oxiclation yields the product of syn, non-Markovnikov hydration (Section 7.5), whereas... 

Alcohol sulfates can be characterized by HPLC. Their molecular structure does not permit a direct UV detection but an indirect UV detection of the alcohol sulfate is possible [285]. The detection can be made by the change in UV absorbance of the mobile phase, either by using an ion exchange column contain-... 

Indirect UV absorbance detection in capillary zone electrophoresis has been used to analyze sodium alcohol sulfates. Excellent reproducibility was obtained when veronal buffer was used as UV-absorbing background electrolyte [302],... 

Acquired disease of muscle is more common than is generally appreciated. It may result from the use of drugs—prescription or nonprescription—that have a recognized capacity to compromise the structure or function of skeletal muscle. Drugs particularly well recognized as myotoxic include clofibrate and its derivatives, anabolic steroids, penicillamine, and emetine. Many nonprescription drugs, including alcohol and laxatives, are directly or indirectly myotoxic. Other forms of acquired myopathies include the acute myopathic conditions caused by the bites of many snakes. 

An alcohol is an example of a compound which does not react with a 2-bromoamide, in the absence of a promoter. Representative reactions (Fig. 3), with methanol in the presence of Ag20, gave an (S)-O-methyllactamide 4 rapidly and with retention of configuration. To explore if an alternative stereochemistry was available and to have indirect information on the role of Ag20, reactions were also run between methanol and a 2-bromoamide, in the presence of Ag+CF3S03 . The inversion product (R)-0-methyllactamide was obtained rapidly, with high yield (ref. 10). 

Alcohols can be converted to amines in an indirect manner. The alcohols are converted to alkyloxyphosphonium perchlorates which in DMF successfully monoalkylate not only secondary but also primary amines. ... 

Alcohols can also be reduced indirectly by conversion to a sulfonate and reduction of that compound (10-80). The two reactions can be carried out without isolation of the sulfonate if the alcohol is treated with pyiidine-S03 in THF, and then LiAlH4 added. Another indirect reduction that can be done in one step involves treatment of the alcohol (primary, secondary, orbenzylic) with Nal, Zn, and Me3SiCl. In this case the alcohol is first converted to the iodide, which is reduced. For other indirect reductions of OH, see 10-86. 

No matter which of the electrophilic methods of double-bond shifting is employed, the thermodynamically most stable alkene is usually formed in the largest amount in most cases, though a few anomalies are known. However, there is another, indirect, method of double-bond isomerization, by means of which migration in the other direction can often be carried out. This involves conversion of the alkene to a borane (15-16), rearrangement of the borane (18-11), oxidation and hydrolysis of the newly formed borane to the alcohol (12-28), and dehydration of the alcohol (17-1) ... 

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