Origin preparation

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The residue in the flask may be mixed with the aqueous layer of the first distillate, 40 g. of isopropyl alcohol added, and the slow distillation repeated. The yield of crude isopropyl bromide in the second distillation is only slightly less than that obtained in the original preparation. Subsequently most of the residual hydrobromic acid may be recovered by distillation as the constant boiling point acid (126°). 

Reduction of the ethylenic compound gives a ketone, propiophenone (III), with one more methylene group than the ketone used in the original preparation ... 

Olah s original preparative nitrations were carried out with mixtures of the aromatic compound and nitronium salt alone or in ether, and later with sulpholan as the solvent. High yields of nitro-compounds were obtained from a wide range of aromatic compounds, and the anhydrous conditions have obvious advantages when functional groups such as cyano, alkoxycarbonyl, or halogenocarbonyl are present. The presence of basic fimctions raises difficulties with pyridine no C-nitration occurs, i-nitropyridinium being formed. ... 

Syntheses, crystallization, structural identification, and chemical characterization of high nuclearity clusters can be exceedingly difficult. Usually, several different clusters are formed in any given synthetic procedure, and each compound must be extracted and identified. The problem may be compounded by the instabiUty of a particular molecule. In 1962 the stmcture of the first high nuclearity carbide complex formulated as Fe (CO) C [11087-47-1] was characterized (40,41) see stmcture (12). This complex was originally prepared in an extremely low yield of 0.5%. This molecule was the first carbide complex isolated and became the foremnner of a whole family of carbide complexes of square pyramidal stmcture and a total of 74-valence electrons (see also Carbides, survey). 

These were originally prepared by Khorana as selective protective groups for the 5 -OH of nucleosides and nucleotides. They were designed to be more acid-labile than the trityl group because depurination is often a problem in the acid-catalyzed removal of the trityl group. Introduction of p-methoxy groups increases the rate of hydrolysis by about one order of magnitude for each p-methoxy substituent. For 5 -protected uridine derivatives in 80% AcOH, 20°, the time for hydrolysis was... 

Vinyl acetate was originally prepared industrially by the reaction of acetylene with acetic acid or by oxidation of ethylene. 

The properties of halogen(I) perchlorates are in Table 17.25. FOCIO3 was originally prepared... 

Finally, the borohydrides An(BFl4)4 must be mentioned.Those of Th and U were originally prepared as part of the Manhattan Project and those of Pa, Np and Pu have been prepared more recently, all by the general reaction... 

Dihydro-j8-carboline itself, the parent compound of the group, whose original preparation from A -formyltryptamine was doubtful, has now been describedand characterized. Its 9-methyl and 6-methoxy derivatives have also been prepared. 

Methylisoquinolinium 2-carboxylate (230), originally prepared by Quast (70LA64), was recently identified as a defensive betaine from Photuris versicolor fireflies (99JNP378). It is a pseudo-cross-conjugated mesomeric betaine isoconjugate to the odd alternant hydrocarbon 2-isopropenyl-naphthalene anion which is an odd alternant hydrocarbon anion. This compound therefore is a member of class 13, which is very rare. The UV absorption maxima Imax (methanol) were found at 235 (4.35), 320 (shoulder, 3.97), and 326 (3.99) nm. This compound undergoes similar reactions as Homarine 19 (Scheme 75). The NMR data are presented in Table VIII. 

Replacement of the ketone by an amide leads to Increased potency. Hydrolysis of nitrile, 133 (obtained by alkylation of diphenylacetonitrile with the morpholine analog of the chloro-amine used in the original preparation of methadone), affords acid, 134. Conversion to the acid chloride followed by reaction with pyrrolidine affords racemoramide (135) Separation of the (+) isomer by optical resolution gives dextromoramide, an analgesic an order of magnitude more potent than methadone. 

Most of these compounds were originally prepared by liquid-phase epitaxy. That process is now largely replaced by MOCVD, particularly in the case of gallium arsenide, gallium arsenic phosphide, and gallium aluminum phosphide. 

Our group has exploited 4-phenylthio-l,3-dioxanes as convenient precursors to 4-lithio-l,3-dioxanes [45,65-69]. 4-Phenylthio-l,3-dioxanes 184 were originally prepared from -silyloxy aldehydes 183 [65] (Eq. 28). Lewis acid-promoted addition of phenylthiotrimethylsilane gave an unstable thioacetal intermediate, which could be converted in situ to the corresponding 1,3-dioxane. Yields for this process are variable, as the product is unstable under the conditions of its formation. The reaction slowly evolves to a mixture of the desired product, the phenylthio acetal of 183, the phenylthio acetal of acetone, and a variety of other unidentified products. 

A series of alkyl esters (Fig. 10.1) of/ (4)-hydroxybenzoic acid was originally prepared to overcome the marked pH-dependence on activity of the acids. 

The Baeyer-Villiger reaction has found considerable application in the synthesis of prostaglandins. One common pattern involves the use of bicyclo[2.2.1]heptan-2-one derivatives, which are generally obtained by Diels-Alder reactions. For example, compound 10 is known as the Corey lactone and has played a prominent role in the synthesis of prostaglandins.237 This compound was originally prepared by a Baeyer-Villiger oxidation of 7-(methoxymethyl)bicyclo[2.2.1]hept-5-en-2-one.238... 

In analogy to the original preparation of Malachite Green lactone, pyromellitic anhydride has also been reacted with N, Ar-di me thy laniline in a zinc chloride melt to yield mixtures of the bisphthalides 29 and 30.109 However, far superior yields were obtained if reaction was carried out in two steps, as described in Scheme 12. The initial condensation was carried out... 

The first NNTRI drug candidate 2 was selected for development in 1992. Compound 2 exhibits very potent antivirus activity of IC50 = 12nM (inhibition HIV-1 RT using rC-dG template/primer). The Medicinal Chemistry original preparation route is depicted in Scheme 1.1 [2]. 

Scheme 6.10 The original preparation of potassium salt of oxadiazolyl acid.

C10Hlo)o.01 C8H8 0.57 (c8H7Br)o.42 (Bromo)polystyrene (20.00 g, 60 meq), originally prepared from commercial 1% crosslinked polystyrene resin (37), was suspended in 500 ml dry benzene under nitrogen. Into this pale orange suspension was injected 2.2 M nBuLi/hexane (60 ml,... 

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