1- Benzoyl-2-hydroxy

O -Benzoyloximcs are nicely reduced to <9-benzoyl hydroxy lamincs with EtsSiH/TFA (Eq. 328) 550,551 <9-Acetyl oximes arc reduced with Et3SiH/TMSOTf in moderate to high yields.552 The diethylphosphatoimine 88 is reduced to the hydroxylamine derivative.553... 

RJVH RjNOH,1 This reaction has generally been conducted by reaction of the amine with dibenzoyl peroxide followed by saponification of the intermediate O-benzoyl-hydroxy lamine. Yields can be markedly improved by addition of Na2HP04 to trap the benzoic acid formed and by debenzoylation with KOCH3/CH3OH (equation I). 

The mechanism for the a-keto acid formation was proposed as shown in Scheme 4, which is reminiscent of those for a-keto amide and ester formation.Benzoyl(hydroxy-carbonyOpalladium complex was assumed as a key intermediate, which undergoes reductive elimination to form a-keto acid. Decarboxylation of this intermediate giving a benzoylpalladium hydride species followed by reductive elimination was proposed to give benzaldehyde as by-product. 

In general, benzoylation of aromatic amines finds less application than acetylation in preparative work, but the process is often employed for the identification and characterisation of aromatic amines (and also of hydroxy compounds). Benzoyl chloride (Section IV, 185) is the reagent commonly used. This reagent is so slowly hydrolysed by water that benzoylation can be carried out in an aqueous medium. In the Schotten-Baumann method of benzoylation the amino compound or its salt is dissolved or suspended in a slight excess of 8-15 per cent, sodium hydroxide solution, a small excess (about 10-15 per cent, more than the theoretical quantity) of benzoyl chloride is then added and the mixture vigorously shaken in a stoppered vessel (or else the mixture is stirred mechanically). Benzoylation proceeds smoothly and the sparingly soluble benzoyl derivative usually separates as a solid. The sodium hydroxide hydrolyses the excess of benzoyl chloride, yielding sodium benzoate and sodium chloride, which remain in solution ... 

Hydroxy-4-methylthiazole failed to react when submitted to Friedel-Crafts benzoylation conditions (349) on the other hand, it reacted normally in Gattermann and in Reimer-Tiemann formylation reactions, affording the 5-formyl derivative (348). 4-Methylthiazole is insufficiently activated and fails to react under the same conditions. 2,4-Dimethylthiazole undergoes perfluoroalkylation when heated at 200° for 8 hr in a sealed tube with perfluoropropyl iodide and sodium acetate (116) (358). 

Multifunctional Hydroxy, Mercapto, and Amino Compounds. These are used to cross-link halogenated polymers. Depending on the labihty of the halogen, the cross-linking agents can be capped to reduce reactivity or used in combination with accelerators to increase the rate of reaction. Benzoyl capping is common with hydroxy and mercapto compounds forming the carbamate by reaction with one equivalent of carbon dioxide is used with diamines. 

Indole, 3-hydroxymethyl-2-phenyl-stability, 4, 272 Indole, I-hydroxy-2-phenyl-synthesis, 4, 363 Indole, 2-iodo-synthesis, 4, 216 Indole, 3-iodo-reaetions, 4, 307 synthesis, 4, 216 Indole, 2-iodo-l-methyl-reaetions, 4, 307 Indole, 2-lithio-synthesis, 4, 308 Indole, 3-lithio-synthesis, 4, 308 Indole, 2-mereapto-tautomerism, 4, 38, 199 Indole, 3-mercapto-tautomerism, 4, 38, 199 Indole, 3-methoxy-synthesis, 4, 367 Indole, 5-methoxy-oxidation, 4, 248 Indole, 7-methoxy-2,3-dimethyl-aeetylation, 4, 219 benzoylation, 4, 219 Indole, 5-methoxy-l-methyl-reduetion, 4, 256 Indole, 5-methoxy-l-methyl-3-(2-dimethylaminoethyl)-reaetions... 

Indolizidine, 1 -hydroxy-2-methyl-synthesis, 4, 471 Indolizidine, 1-hydroxy-3-oxo-benzoylation, 4, 461 Indolizidine, 3-methyl-synthesis... 

Isoxazolidine, 3-benzoyl-2-phenyl-reactions with bases, 6, 47 Isoxazolidine, 2-t-butyl-conformation, 6, 10 Isoxazolidine, 2-carbamoyl-3-hydroxy-... 

Pyrimidin-2( 1H) -one, 5-fluoro-1 -methyl-4-methylthio-alcoholysis, 3, 96 Pyrimidin-2(lH)-one, 5-hydroxy-benzoylation, 3, 89... 

Thiophene, 3-amino-2-benzoyl-4-cyano-5-hydroxy synthesis, 4, 927... 

The benzoylformate ester can be prepared from the 3 -hydroxy group in a deoxy-ribonucleotide by reaction with benzoyl chloroformate (anh. Pyr, 20°, 12 h, 86% yield) it is cleaved by aqueous pyridine (20°, 12 h, 31% yield), conditions that do not cleave an acetate ester. ... 

A-Hydroxy-5-norbornene-2,3-dicarboxylic acid imide [21715-90-2] M 179.2, m 165-166", 166-169", pKesi-6 Dissolve in CHCI3, filter, evaporate and recrystallise from EtOAc. IR (nujol) 1695, 1710 and 1770 (C=0), and 3100 (OH) cm. 0-Acetyl derivative has m 113-114° (from EtOH) with IR bands at 1730, 1770 and 1815 cm only, and the 0-benzoyl derivative has m 143-144° (from propan-2-ol or C6H6). [Bauer and Miarka J Org Chem 24 1293 1959 Fujino et al. Chem Pharm Bull Jpn 22 1857 1974],... 

P-Acetoxy-5-hydroxy-B-mrcholestan-6-carboxylic Acid 5,6-Lactone (TO)."" A solution of 5 g (0.011 mole) of keto acid (69), 4.4 g of benzoyl chloride and 10 ml of anhydrous pyridine is allowed to stand for 3 days at room temperature. After a short period the mixture turns red-brown and at the end of the reaction the dark semi-solid mass is poured into 200 ml of water and extracted with two 100 ml portions of ether. The ethereal extracts are washed twice with equal portions of 5 % sodium hydroxide and water, dried and the ether evaporated. The red sirupy residue is mixed with 10 ml of methanol and a brown solid separates immediately. After standing for 1 hr the solid is removed by filtration and washed with methanol. A second crop is obtained upon concentration of the filtrate. The combined crops are recrystallized twice from methanol to give (70) as white needles mp 124-125° yield 2.8 g (58 %). 

In a typical Knof procedure, 3jS-hydroxyandrost-5-en-17-one acetate is epoxidized with perbenzoic acid (or m-chloroperbenzoic acid ) to a mixture of 5a,6a- and 5)5,6)5-epoxides (75) in 99 % yield. Subsequent oxidation with aqueous chromium trioxide in methyl ethyl ketone affords the 5a-hydroxy-6-ketone (76) in 89% yield. Baeyer-Villiger oxidation of the hydroxy ketone (76) with perbenzoic acid (or w-chloroperbenzoic acid ) gives keto acid (77) in 96% yield as a complex with benzoic acid. The benzoic acid can be removed by sublimation or, more conveniently, by treating the complex with benzoyl chloride and pyridine to give the easily isolated )5-lactone (70) in 40% yield. As described in section III-A, pyrolysis of j5-lactone (70) affords A -B-norsteroid (71). Knof used this reaction sequence to prepare 3)5-hydroxy-B-norandrost-5-en-17-one acetate, B-noran-... 

The benzoylformate ester can be prepared from the 3 -hydroxy group in a deoxyribonucleotide by reaction with benzoyl chloroformate (anhyd. Pyr, 20°,... 

A/-o-(Benzoyloxymethyl)benzoyl, 562 A/-(2-Acetoxymethyl)benzoyl, 562 A/-2-[(t-Butyldiphenylsiloxy)methyl]benzoyl, 562 A/-3-(3, 6 -Dioxo-2, 4, 5 -trimethylcyclohexa-1, 4 -diene)-3,3-dimethylpropionyl, 562 AZ-o-Hydroxy-frans-cinnamoyl, 562... 

The mercaptals obtained by the acid catalyzed reaction of J3-ketoesters, e.g., ethyl acetoacetate, with methyl thioglycolate (73) undergo the Dieckmann cyclization with alcoholic potassium hydroxide at lower temperatures to give ethyl 3-hydroxy-5-methyl-2-thiophenecarboxylate (74) in 75% yield. ° Besides ethyl acetoacetate, ethyl a-ethylacetoacetate, ethyl benzoyl acetate, and ethyl cyclopentanonecarboxylate were also used in this reaction/ It is claimed that /8-diketones, hydroxy- or alkoxy-methyleneketones, or /8-ketoaldehyde acetals also can be used in this reaction. From acetylacetone and thioglycolic acid, 3,5-dimethyl-2-thiophenecarboxyl-ic acid is obtained. ... 

The hydroxy group undergoes 0-acylation and deacylation (79JHC689). These reactions of functionalized hydroxyfurazans are valuable methods for modification of these compounds. Thus, hydroxybifurazan 248 was aroylated with benzoyl chloride in the presence of pyridine with concomitant cleavage of the unsubstituted furazan ring to give nitrile 262 (Scheme 170) (75LA1029). 

The reaction of 1,2,4-triazine 4-oxides 55 with water in the presence of benzoyl chloride affords 3-hydroxy-1,2,4-triazines 78. The mechanism suggested for this reaction includes acylation of the substrate at the oxygen of the iV-oxide group, followed by the addition of water to the 1,2,4-tiiazinium cation and the autoaromatization of the (T -adducts with the elimination of benzoic acid. 

In a 25% aqueous solution of potassium bromide. The resultant solution is acidified with a 20% solution of sodium bisulfite, centrifuged, washed with water and then dried under vacuum. The product Is then recrystallized in acetic acid and 13.6 g of 2-(4 -hydroxy-3, 5 -di-bromo-benzoyl)-3-athyl coumarone obtained. MP 151°C. 

A mixture of 750 grams of 1-methyl-3-benzoyl-4-hydroxy-4-phenylpiperidine and 2,500 cc of 48% hydrobromic acid is refluxed for about 20 minutes. It is then poured into 8 liters of water. An oily precipitate appears which on standing crystallizes. It is filtered and crystallized from about 3.5 liters of alcohol. 2-Methyl-9-phenyl-2,3-dihydro-1-pyridindene hydrobromide, MP 201°-203°C, is obtained. 

Chemical Name 5-Benzoyl 4-hydroxy-2-methoxybenzenesulfonic acid Common Name —... 

To support a polystyrene onto the upper rim of ca-lix[4]arene (phenolic-O- of calix[4]arene) and 25,26,27-tribenzoyloxy-28-hydroxy, calix[4]arene was treated with chloromethylated polystyrene in the presence of K2CO3 (Scheme 7). Polymeric calix[4]arene (3a) thus obtained was hydrolyzed in the benzoyl groups prior to use for the extraction process. 

---