Alcohols ceric ammonium

Alcohols Ceric ammonium sulfate (or nitrate) Yellow/green spots on red background 1, 3... 

Alcohols Ceric ammonium nitrate Dichromate test Iodoform test Lucas test Positive for all alcohols Positive for 1° and 2° alcohols negative for 3° alcohols Positive for all alcohols of the general formula CH3CH(OH)R Immediate reaction for 3°, allylic or benzylic alcohols slower reaction (2-5 min) for 2° no reaction for 1° alcohols... 

Alcohols Ceric ammonium sulfate Brown spots on yellow background... 

Dimethoxybenzyl esters prepared from the acid chloride and the benzyl alcohol are readily cleaved oxidatively by DDQ (CH2CI2, H2O, rt, 18 h, 90-95% yield). A 4-methoxybenzyl ester was found not to be cleaved by DDQ. The authors have also explored the oxidative cleavage (ceric ammonium nitrate, CH3CN, H2O, 0°, 4 h, 65-97% yield) of a variety of 4-hydroxy- and 4-amino-substituted phenolic esters. ... 

Unlike benzylic groups, they cannot be made directly from the alcohol. Instead, the phenoxy group must be introduced by a nucleophilic substitution.30 Mitsunobu conditions are frequently used.31 The PMP group can be cleaved by oxidation with ceric ammonium nitrate (CAN). 

Materials. Chemically pure solvents and reagent grade ceric ammonium nitrate were used as received. Cumene hydroperoxide was purified via the sodium salt. Lucidol tert-butyl hydroperoxide was purified by low temperature crystallization. Tetralin hydroperoxide, cyclohexenyl hydroperoxide, and 2-phenylbutyl-2-hydroperoxide were prepared by hydrocarbon oxidation and purified by the usual means. 1,1-Diphenyl-ethyl hydroperoxide and triphenylmethyl hydroperoxide were prepared from the alcohols by the acid-catalyzed reaction with hydrogen peroxide (10). 

In the same book, on p 462 is described "Colorimetric Method for Determining Trace Quantities of Hydroxy Compounds . This method developed by V.W. Reid R.K. Trulove and described in Analyst 77, 325(1952) uses ceric ammonium reagent and is applicable to determination of small quantities of alcohol in aqueous or water miscible systems [Compare with J. Lamond, Analyst 74, 560—61 (1949), listed here as Ref 5, under "Ethanol, Etber, Acetone and Water Determinations in Solvents Used in Manufacture of Smokeless Propellants, as Described in the Literature ]... 

J. Lamond, Analyst 74, 560—61(1949) [Small quantities of alcohol in ether may be detd after extracting it from ether by water, followed by testing the aqueous extract by means of ceric ammonium nitrate. The following reaction takes place, producing the red coordination product ... 

The oxidative cyclization of the alcohol (214) with ceric ammonium nitrate gave a mixture of the two naphthopyrans (215) and (216) in a ratio of 3 1 (81CC534). The reaction is of interest because of the natural occurrence of quinones containing the naphtho[2,3-c]pyran ring system. 

Ceric ammonium nitrate To 1 to 2 ml of 5% ceric ammonium nitrate add 10 drops of the compound to be tested. A change to an orange/red color is indicative of an alcohol (detection limit, 100 mg compounds tested, C, to C10). 

Ceric ammonium nitrate (2.85 mmol) dissolved in 10 ml water was added in portions over 15 minutes to the product of Step 1 (1.14 mmol) dissolved in 30 ml acetonitrile. The solution was stirred at ambient temperature 1 hour, extracted 3 times with chloroform, dried, filtered, and evaporated. The mixture was purified by chromatography using methyl alcohol/chloroform, 6 94, and the product isolated in 81% yield as a yellow solid, Rf = 0.45, mp = 105-107 °C. H- and P-NMR, IR, and elemental analysis data supplied. 

Similarly, the A -tosylaziridine 14 is smoothly cleaved by aniline in the presence of bismuth trichloride acting as the Lewis acid to give the diamine 15 <2003SC547>. Ceric ammonium nitrate (CAN) catalyzes the ring opening of 14 with water to afford the amino alcohol 16 in 88% yield (Scheme 6) <2003CL82>. 

The ring-opening reaction is not limited to conventional nucleophiles. Ceric ammonium nitrate in the presence of excess nitrate ion converts oxiranes to / -nitrato alcohols <1995T909>. The reaction is believed to proceed via a one-electron transfer to form an oxiranium radical cation that is subsequently captured by a nitrate ion. Nitric oxide adds to 2,3-epoxy phenyl ketones <2004TL1565>. 

A number of studies to determine the mechanisms of grafting onto collagen initiated by CAN, including characterization of the reaction products, have been reported (5, 8, 9, 53, 62). Ceric ammonium nitrate forms an effective redox system with alcohols, aldehydes, amines, and thiols. Alcohols form a ceric ion-alcohol complex, and the dissociation of this complex is the rate-determining step 63) ... 

Conjugate addition of alcohols to conjugated esters, using ceric ammonium nitrate and LiBr, gave the corresponding a-bromo-p-alkoxy ester. ... 

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