Alcohols, aromatic halogen derivatives

Diocetone Diacetone Alcohol 4-Hydroxy-4-methyl-pentonone-2 or 4-Hydroxy-2-keto-4-methylpentone [called Diacetonalkohol Dimethyl-acetonyl-carbinol 2-Methyl-pentanol-(2)-on-(4) or Methyl-(j8-oxy-isobutyl)-keton in Ger], CH3C0CH2C(CH3)20H mwll6,l6, col, pleasant-odored liq fr p -42.8°, bp 169° at 760mm, flash p 170°F, d 0.9406 at 20°, vapor pressure 1,1mm at 20°, viscosity 0,032 poise at 20°, n 1.42416 at 20°, coeff of expansion 0,00097 at 20. Diacetone is derived by condensation of acetone. It is miscible with alcohols, aromatic halogenated hydrocarbons, esters water. A const boiling mixt with water has a bp 99 6° and contains approx 13% diacetone (Refs 1, 3, 4 5)... 

Reaction with Organic Compounds. Aluminum is not attacked by saturated or unsaturated, aUphatic or aromatic hydrocarbons. Halogenated derivatives of hydrocarbons do not generally react with aluminum except in the presence of water, which leads to the forma tion of halogen acids. The chemical stabiUty of aluminum in the presence of alcohols is very good and stabiUty is excellent in the presence of aldehydes, ketones, and quinones. 

Hydriodic acid is a reagent of choice for reduction of alcohols [225], some phenols [225], some ketones [227, 228], quinones [222], halogen derivatives [22S, 229], sulfonyl chlorides [230], diazo ketones [231], azides [232], and even some carbon-carbon double bonds [233]. Under very drastic conditions at high temperatmes even polynuclear aromatics and carboxylic acids can be reduced to saturated hydrocarbons but such reactions are hardly ever used nowadays. 

The lower members of the homologous series of 1. Alcohols 2. Aldehydes 3. Ketones 4. Acids 5. Esters 6. Phenols 7. Anhydrides 8. Amines 9. Nitriles 10. Polyhydroxy phenols 1. Polybasic acids and hydro-oxy acids. 2. Glycols, poly-hydric alcohols, polyhydroxy aldehydes and ketones (sugars) 3. Some amides, ammo acids, di-and polyamino compounds, amino alcohols 4. Sulphonic acids 5. Sulphinic acids 6. Salts 1. Acids 2. Phenols 3. Imides 4. Some primary and secondary nitro compounds oximes 5. Mercaptans and thiophenols 6. Sulphonic acids, sulphinic acids, sulphuric acids, and sul-phonamides 7. Some diketones and (3-keto esters 1. Primary amines 2. Secondary aliphatic and aryl-alkyl amines 3. Aliphatic and some aryl-alkyl tertiary amines 4. Hydrazines 1. Unsaturated hydrocarbons 2. Some poly-alkylated aromatic hydrocarbons 3. Alcohols 4. Aldehydes 5. Ketones 6. Esters 7. Anhydrides 8. Ethers and acetals 9. Lactones 10. Acyl halides 1. Saturated aliphatic hydrocarbons Cyclic paraffin hydrocarbons 3. Aromatic hydrocarbons 4. Halogen derivatives of 1, 2 and 3 5. Diaryl ethers 1. Nitro compounds (tertiary) 2. Amides and derivatives of aldehydes and ketones 3. Nitriles 4. Negatively substituted amines 5. Nitroso, azo, hy-drazo, and other intermediate reduction products of nitro com-pounds 6. Sulphones, sul-phonamides of secondary amines, sulphides, sulphates and other Sulphur compounds... 

With benzaldehyde 144 or halogenated derivatives (Cl, F) as acceptors the yeast-PDC-catalyzed addition proceeds with almost complete stereoselectivity to furnish the corresponding (R)-configurated 1-hydroxy-1-phenylpropanones 145 [447]. For practical reasons, whole yeast cells are most often used as the catalyst, with only small loss of enantioselectivity [423,424]. The conversion of benzaldehyde in particular has gained industrial importance because the acyloin is an important precursor for the synthesis of L-(-)-ephedrine [448]. Otherwise, the substrate tolerance is remarkably broad for aromatic aldehydes on the laboratory scale, however, yields of acyloins are usually low because of the prior or consequent reductive metabolism of aldehyde substrate and product, giving rise to considerable quantities of alcohol 146 and vicinol diols 147, respectively [423,424,449], The range of structural variability covers both higher a-oxo-acids (e.g. -butyrate, -valerate) as the donor component, as well as a,/J-un-saturated aldehydes (e.g. cinnamaldehyde 148) as the acceptor [450]. 

The features of Red-Al are the following It easily reduces halogenated derivatives even if acetylenic (Section 2.1) tertiary amides lead to aldehydes (Section 3.2.8) and propargylic alcohols and amines are reduced to corresponding allylic alcohols and amines (Section 4.1). Epoxides remain intact unless they carry an alcohol functional group at the a position The reduction is then regioselective (Section 2.3). Aromatic nitriles are reduced, but aliphatic nitriles are not affected (Section 4.3). 

Add the add to the substance, not vice versa. Retain the liquor for test 9.) Unsaturated and hi y alkylated hydrocarbons. Some aldehydes, ketones, esters, anhy des, alcohols, ethers, acetals and Aeir halogen derivatives. Some iV-substituted amides nitriles aromatic nitrohydrocarbons iV,iV-disubstituted sulphonamides thiourea derivatives some polynitro- and polyhalogeno-aryl-amines di-arylamines. 

Most of the secondary metaboUtes of green algae consist of terpenes and aromatic derivatives, often associated with the first in meroterpenes. This category of secondary metabolites represents nearly 50% of pubUshed results. Halogenated derivatives are uncommon, representing less than 10% of the structures, which are almost exclusively brominated derivatives. Among sulfur derivatives, some triterpenic alcohols related to cycloartenol have been isolated, of which some are sulfated. 

Aqueous mineral acids react with BF to yield the hydrates of BF or the hydroxyfluoroboric acids, fluoroboric acid, or boric acid. Solution in aqueous alkali gives the soluble salts of the hydroxyfluoroboric acids, fluoroboric acids, or boric acid. Boron trifluoride, slightly soluble in many organic solvents including saturated hydrocarbons (qv), halogenated hydrocarbons, and aromatic compounds, easily polymerizes unsaturated compounds such as butylenes (qv), styrene (qv), or vinyl esters, as well as easily cleaved cycHc molecules such as tetrahydrofuran (see Furan derivatives). Other molecules containing electron-donating atoms such as O, S, N, P, etc, eg, alcohols, acids, amines, phosphines, and ethers, may dissolve BF to produce soluble adducts. 

PMVEMA, supphed as a white, fluffy powder, is soluble in ketones, esters, pyridine, lactams, and aldehydes, and insoluble in aUphatic, aromatic, or halogenated hydrocarbons, as well as in ethyl ether and nitroparaffins. When the copolymer dissolves in water or alcohols, the anhydride group is cleaved, forming the polymers in free acid form or the half-esters of the corresponding alcohol, respectively. Table 7 illustrates the commercially available alternating copolymers and derivatives. 

Solvents can be classified into three categories according to their polarity namely, polar protic, dipolar aprotic and non-polar. Most of the common solvents fall under one of following chemical classes Aliphatic hydrocarbons, aromatic hydrocarbons, alcohols, phenols, ethers, aldehydes, ketones, carboxylic acids, esters, halogen-substituted hydrocarbons, amines, nitriles, nitro-derivatives, amides and sulfur-containing solvents (Marcus, 1998). In certain cases a mixture of two or more solvents would perform better than a single solvent. 

When electronegative substituents are present, oxadiazoles undergo nucleophilic reactions on the carbon atoms, both in position 3 or 5- The substitution of halogen, alkoxy and trichloromethyl derivatives has. been studied. 5-Halogeno-oxadiazoles react with ahphatic and aromatic primary and secondary amines, to give the corresponding amino-derivatives. With sodium hydroxide and -alcoholate, hydroxy and alkoxy oxadiazoles are obtained 25 a, 55 b). 

The excellent enantioselectivity and wide scope of the CBS reduction have motivated researchers to make new chiral auxiliaries [3]. Figure 1 depicts examples of in situ prepared and preformed catalyst systems reported since 1997. Most of these amino-alcohol-derived catalysts were used for the reduction of a-halogenated ketones and/or for the double reduction of diketones [16-28]. Sulfonamides [29,30], phosphinamides [31], phosphoramides [32], and amine oxides [33] derived from chiral amino alcohols were also applied. The reduction of aromatic ketones with a chiral 1,2-diamine [34] and an a-hydroxythiol [35] gave good optical yields. Acetophenone was reduced with borane-THF in the presence of a chiral phosphoramidite with an optical yield of 96% [36]. 

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