Hydroxy methyl phenyl ketone

The compound formed is a mixed aromatic alcohol and ketone, i.e. (hydroxy-methyl-phenyl) phenyl ketone, and is known as benzoin. This compound should properly be considered in the class of hydroxy ketones, which we shall take up a little later, but, because of its relation to benzaldehyde, it may also be mentioned here. 

Hydroxy Alkyl Phenyl Ketones The basic structures, 2-hydroxy-2-methyl-l-phenyl-1-propanone HAP and 1-hydroxy-cyclohexyl-1-phenyl ketone HCAP, are also well known [17] and still largely used (10.10) and studied [2i,f,18]. The para substitution of the benzoyl group (with an amino, an ether, or a thioether group) drastically changes the electronic transitions but does not significantly affect the reactivity of the derived benzoyl initiating radical. 

Acetone cyanohydrin 2-Hydroxy-2-methylpropanenitrile 77-76-9 Acetone dimethyl acetal see 2,2-Dimethoxypropane 75-05-8 Acetonitrile Ethanenitiile 98-86-2 Acetophenone see Methyl phenyl ketone 79-34-5 Acetylene tetrachloride 1,1,2,2-Tetrachloroethane... 

In 1979, Johnson reported the enantioselective reduction of ketones with stoichiometric amounts of optically active (1-hydroxy sulfoximine-borane complexes.131 Prochiral alkyl phenyl ketones (RCOPh) undergo enantioselective reduction with enantiomerically pure p-hydroxy sulfoximine borane complexes (301 and 302). These complexes are prepared by reaction of the corresponding P-hydroxy sulfoximine with borane at -78 °C. The structures 301 and 302 have been suggested for these complexes. In the case of the borane complex 301, the enantioselectivity increased as the steric bulk of the R substituent of the ketone (RCOPh) was decreased from IV to Me. The analogous reductions of methyl alkyl ketones (MeCOR) with these borane complexes were less enantioselective (3-27% ee).131... 

Ell, 790 [DMSO + LiRCS(SR)2] (l-tert.-Butyloxycarbonyl-2-hydroxy-alkyl)-(4-methyl-phenyl)- Ell, 773f. (R-SO-CH2-COOR + R —MgX/Keton) (tu-Chlor-alkyl)-phenyl- Ell, 704 (S-Oxygenier.)... 

N-Phenyl- -S-tert.-butylester E4, 307 (R-SH + NaOCN) Thiokohlensaurc -imid-0-(2-methyl-propylester)-S-phenylester (Hydrochlorid) E4, 572 (R-S-CN + R-OH) Thiopropansaure 2-Hydroxy-2-phenyl- -dimethylamid VI/la,2, 1044 (DMF + Keton/LiNR2), E19d, 663 (H Li + Keton)... 

Syn 3-(Ethylth(oniethyl)-4-hydroxy-6-phenyl>2-hexanone (4) and amt (5) 3 To emanethwi (to 0 mg 0 17 mmol) in the (2 mL) was added 1 54 M n butyliithwm in hexane (0 11 mU at 0°C under Ar Stannous Inflate (69 0 mg 0 17 mmol) was added and alter 20 mm the mixture was cooled to 45°C Methyl vinyl Ketone 1 (118 mg 1 98 mmol) m THE 1 5 mL) was added followed by 3 phenylpropanal 3 (350 mg 2 61 mmol) in THE (1 5 mL) Alter 12 h aq cilnc acid was added and the organic material extracted with CHjCia The resxlue after evaporation was dissolved in MeOH and treated with citric acid After 30 mm stimng. the mixture was quenched with pH 7 phosphate buffer extracted with CH2CI2, the solvent evaporated and the residue chromatographed to afford 336 mg of 4 (75%), syn anti (90 10)... 

Subsequent work has shown that the presence of an alkyl substituent a to the ketone carbonyl is crucial for the intramolecular five-membered-ring cyclization to occur. Thus, jS-hydroxy cyclopentanones can be synthesized from ketones containing both methyl and cyclopropanol moieties a to the carbonyl by treatment with sodium hydride at 0-25 °C. In the case of phenyl ketone, further retro-aldol ring scission leads to the 1,4-diketone as the only product. A retro-aldol/re-aldol sequence occurs when the methyl substituent is replaced by a longer alkyl substituent, such as an allyl group. In this case, the allyl substituent is located 7 to the carbonyl of the final product. ... 

This type of reaction was first used by Dilthey and Fischer69 in connection with the mechanism of the type in Section II, D, 2. By analogy with the well-known formation of benzopyrylium salts from methyl(ene) ketones and o-hydroxybenzaldehyde or o-hydroxy-acetophenone,340 benzoylacetone (84, R = Me, R = H, R" = Ph) and acetophenone (85, RIV = Ph, R" = H) afforded in the presence of acetic anhydride and sulfuric acid, 2-methyl-4,6-diphenylpyrylium sulfoacetate. The interesting feature of this reaction is that a unique product is obtained (i.e., only the carbonyl group of the diketone adjacent to the phenyl enters the condensation, although two such groups are available) R and R" could be reversed, but they are not.69-69 Similarly, dibenzoylmethane (84, R = R" = Ph, R =H) afforded 2,4,6-triphenylpyrylium with acetophenone in 80% yield.69... 

Scholl reactions generally lead to six-membered rings but a few cases have been reported where five-membered rings were formed, particularly from ketones that carried a hydroxyl or an alkoxyl group para to the carbonyl group, such a case was reported by Fierz-David and Jaccard275 who found that 4-hydroxy-1-naphthyl phenyl ketone (and its methyl ether) gave 5-hydroxy-benzo[a]fluoren-l 1-one and not 4-hydroxybenz[de]anthrone ... 

Thus, a short-range strategy for the synthesis of 4-hydroxy-l-phenyl-pentanone-2 (I) will lead to the two carbonyl compounds methyl benzyl ketone and acetaldehyde as synthesis precursors (Figure 1). Having reached this conclusion it is absolutely necessary to consider whether those two precursors will react by the anticipated aldol condensation to the target compound (I). A closer inspection based on insight into chemical reactivity has to decide that this reaction will not proceed unequivocally to the desired product (I). Rather, a mixture of compounds will be obtained including the... 

Synonyms 4-(2-Hydroxyethoxy) phenyl-(2-hydroxy-2-propyl) ketone 2-Hydroxy-1-[4-(2-hydroxyethoxy) phenyl]-2-methyl-1 -propanone... 

Propionitrile, 2,2 -azobis (2-methyl). See 2,2 -Azobisisobutyronitrile Propionitrile, 2-hydroxy-. See Lactonitrile Propionitrile, 3-methoxy-. See3-Methoxypropionitrile Propionitrile, 3-(triethoxysilyl)-. See2-Cyanoethyltriethoxysilane P-Propionolactone. See p-Propiolactone Propionphenone. See Propiophenone Propionylbenzene. See Ethyl phenyl ketone Propiophenone... 

Propiophenone. See Ethyl phenyl ketone Propiophenone, 2-hydroxy-2-methyl-. See 2-Hydroxy 2-methyl 1-phenyl 1-propanone Propomeen 2HT-11. See Bis hydrogenated tallowalkyl-2-hydroxypropyl amine Propomeen C/12. See PPG-2 cocam I ne Propomeen HT/12. See PPG-2 hydrogenated tallowamine... 

Benzophenone p-Chlorobenzophenone 1-Hydroxycyclohexyl phenyl ketone 2-Hydroxy 2-methyl 1-phenyl 1-propanone photoinitiator, radiation-cured lacquers Anisoin Benzoin 2-Hydroxy 2-methyl 1-phenyl 1-propanone p-Phenylbenzophenone photoinitiator, resins o-Methyl benzoyl benzoate photoinitiator, resist inks Tribromomethyl phenylsulfone photoinitiator, screen inks... 

Though the attempts to synthesize ethyl 2-hydroxy-2-phenyl-3-methylene-4 oxopentanoate via DABCO-catalyzed coupling of methyl vinyl ketone with ethyl phenylglyoxylate (a-keto ester) were unsuccessful, the chalcogeno-MBH reaction between a-keto esters and alkyl vinyl ketones proceeded smoothly under the catalytic influence of dimethyl sulfide in the presence of TiCU, affording 2-aryl-2-hydroxy-3-methylene-4-oxoalkanoates 297 in moderate to good yields (Scheme 2.163). ... 

---