Ketones cychc

As a class of compounds, nitriles have broad commercial utility that includes their use as solvents, feedstocks, pharmaceuticals, catalysts, and pesticides. The versatile reactivity of organonitnles arises both from the reactivity of the C=N bond, and from the abiHty of the cyano substituent to activate adjacent bonds, especially C—H bonds. Nitriles can be used to prepare amines, amides, amidines, carboxyHc acids and esters, aldehydes, ketones, large-ring cycHc ketones, imines, heterocycles, orthoesters, and other compounds. Some of the more common transformations involve hydrolysis or alcoholysis to produce amides, acids and esters, and hydrogenation to produce amines, which are intermediates for the production of polyurethanes and polyamides. An extensive review on hydrogenation of nitriles has been recendy pubHshed (10). 

A varnish is often appHed on top of the paint layers. A varnish serves two purposes as a protective coating and also for an optical effect that enriches the colors of the painting. A traditional varnish consists of a natural plant resin dissolved or fused in a Hquid for appHcation to the surface (see Resins, natural). There are two types of varnish resins hard ones, the most important of which is copal, and soft ones, notably dammar and mastic. The hard resins are fossil, and to convert these to a fluid state, they are fused in oil at high temperature. The soft resins dissolve in organic solvents, eg, turpentine. The natural resin varnishes discolor over time and also become less soluble, making removal in case of failure more difficult (see Paint and FINNISH removers). Thus the use of more stable synthetic resins, such as certain methacrylates and cycHc ketone resins, has become quite common, especially in conservation practice. 

Stereoselective Acylations. Intramolecular Ftiedel-Crafts acylation reaction of A/-ataLkyl a-amino acid detivatives gives cycHc ketones with high enantioselectivity (100). This methodology has been used for the enantiospeciftc syntheses of tylophorine [482-20-2] and cryptopleutine [87302-53-2] the ptincipal representatives of phenanthroiadolizidine and phenanthroquiaolizidine alkaloids (qv) (101). 

Intramolecular Friedel-Crafts acylations of olefins also give cycHc a,P-unsaturated cycHc ketones. Cyclopropane fused bicyclo[5.3.0]octenones, thus obtained, were used in the preparation of the marine sesquiterpenes, africanol [53823-07-7] and dactjlol [58542-75-9] (174). 

Ketones and aldehydes react with ethylene glycol under acidic conditions to form 1,3-dioxolanes (cychc ketals and acetals) (eq. 7). 

A convenient annulation procedure based on cycHc hydroboration—carbonylation of 1-vinyl- and l-aHylcycloalkenes with thexylborane provides trans-fused bicychc ketones (312). 

Ketones are an important class of industrial chemicals that have found widespread use as solvents and chemical intermediates. Acetone (qv) is the simplest and most important ketone and finds ubiquitous use as a solvent. Higher members of the aUphatic methyl ketone series (eg, methyl ethyl ketone, methyl isobutyl ketone, and methyl amyl ketone) are also industrially significant solvents. Cyclohexanone is the most important cycHc ketone and is primarily used in the manufacture of y-caprolactam for nylon-6 (see Cyclohexanoland cyclohexanone). Other ketones find appHcation in fields as diverse as fragrance formulation and metals extraction. Although the industrially important ketones are reviewed herein, the laboratory preparation of ketones is covered elsewhere (1). 

In contrast, aromatic ketones are high boiling, colorless Hquids that generally have a fragrant odor and are almost insoluble in water. They are useful as intermediates in chemical manufacture. Functionalized and cycHc ketones are also good solvents. Ring size and the type and location of functional groups affect odor, color, and reactivity of these ketones. 

Preparation of Amines. Amines are prepared by heating aUphatic, aromatic, or cycHc ketones with ammonium formate, formamide, or an A/-substituted ammonium formate at 165—190°C (Leuckart reaction). For example, cx-methylbenzylamine is prepared by the reaction of acetophenone with ammonium formate. 

Isophorone. Isophorone (3,5,5-trimethyl-2-cyclohexen-l-one) is a cycHc a,P-unsaturated ketone derived from the trimeri2ation of acetone. It has a light yellow color and a disagreeable camphoraceous odor. It has the tendency to discolor and form residues on prolonged storage. Isophorone is completely miscible with organic solvents, and other physical properties are Hsted ia Table 1. 

Diketones are readily transformed to cycHc derivatives, such as cyclopentanones and furans. In this manner, the fragrance dihydrojasmone (3-meth5l-2-pentyl-2-cyclopenten-l-one) is prepared by the base-catalyzed aldol condensation of 2,5-undecanedione. 2,5-Undecanedione is itself prepared from heptanal and methyl vinyl ketone in the presence of thiazoHum salts (329). i7j -Jasmone can be similarly prepared (330,331). 

Many cycHc ketones occur in natural oils. Jasmone [488-10-8] (3-meth5l-2-(2-pentyl)-2-cyclopenten-l-one) (4) is an odoriferous component of the oil obtained from jasmine flowers. /-Menthone [14073-97-3] (5) is the most frequently occurring of four optically active isomers, and is a colorless Hquid with a minty odor obtained from Mentha species of plants. Muscone [541-91-3] (6) and civetone [542-46-1] (7) are expensive animal products. 

The chemical properties of cycHc ketones also vary with ring size. Lower members (addition reactions, than corresponding acycHc ketones. The Cg—C 2 ketones are unreactive, reflecting the strain and high enol content of medium-sized ring systems. Lactones are prepared from cycHc ketones by the Bayer-ViUiger oxidation reaction with peracids. S-Caprolactone is manufactured from cyclohexane by this process ... 

Cyclohexanone is by far the most important industrial cycHc ketone (see Cyclohexanoland cyclohexanone). 

Commercially, pure ozonides generally are not isolated or handled because of the explosive nature of lower molecular weight species. Ozonides can be hydrolyzed or reduced (eg, by Zn/CH COOH) to aldehydes and/or ketones. Hydrolysis of the cycHc bisperoxide (8) gives similar products. Catalytic (Pt/excess H2) or hydride (eg, LiAlH reduction of (7) provides alcohols. Oxidation (O2, H2O2, peracids) leads to ketones and/or carboxyUc acids. Ozonides also can be catalyticaHy converted to amines by NH and H2. Reaction with an alcohol and anhydrous HCl gives carboxyUc esters. 

Hydroxyalkyl hydroperoxides from cycHc ketones (1), where X = OH, R =, H and R, R = alkylene, apparentiy exist in solution as equihbrium mixtures of the cycHc ketone, hydrogen peroxide, and other peroxides, eg, the dihydroperoxide (1) in which X = OOH, and dialkyl peroxides (2) where X = OH and Y = OH or OOH. Due to the existence of this equihbrium, the latter two dialkyl peroxides react as mixtures of monomeric hydroperoxides in solution. 

Acidic hydrolysis of these hydroxyaLkyl hydroperoxides yields carboxyUc acids, whereas basic hydrolysis regenerates the parent aldehyde, hydrogen peroxide, and often other products. When derived from either aldehydes or cycHc ketones, peroxides (1, X = OH, = H, R, = alkylene or... 

As with other hydroperoxides, hydroxyaLkyl hydroperoxides are decomposed by transition-metal ions in an electron-transfer process. This is tme even for those hydroxyaLkyl hydroperoxides that only exist in equiUbrium. For example, those hydroperoxides from cycHc ketones (R, R = alkylene) form an oxygen-centered radical initially which then undergoes ring-opening -scission forming an intermediate carboxyalkyl radical (124) ... 

When derived from cycHc ketones, dihydroperoxides (1, X = OOH R = H, R and R = alkylene) react with vinyl monomers in the presence of Cr, V, or Ti salts to form difimctional compounds (145) ... 

Hydroxyall l Hydroperoxyall l Peroxides. There is evidence that hydroxyalkyl hydroperoxyalkyl peroxides (2, X = OH, Y = OOH) exist in equihbrium with their corresponding carbonyl compounds and other a-oxygen-substituted peroxides. For example, reaction with acyl haUdes yields diperoxyesters. Dilute acid hydrolysis yields the corresponding ketone (44). Reduction with phosphines yields di(hydroxyalkyl) peroxides and dehydration results in formation of cycHc diperoxides (4). 

R = cyl), eg, with -nitrobenzoyl chloride. Upon reaction with lead tetraacetate, di(hydroperoxyalkyl) peroxides can also be converted to cycHc diperoxides (4). They are also converted to symmetrical or unsymmetrical cycHc triperoxides (5) in the presence of a second ketone and a catalyst, eg, CuSO -HCl (44,119). 

Acid hydrolysis of peroxides (4) and (5) generates carbonyl compounds (parent ketones or aldehydes) and hydrogen peroxide. Basic hydrolysis of cycHc diperoxides with a-hydrogen (those from aldehydes) yields carboxyHc acids (44) ... 

Cycloahphatic amine synthesis routes may be described as distinct synthetic methods, though practice often combines, or hybridi2es, the steps that occur amination of cycloalkanols, reductive amination of cycHc ketones, ring reduction of cycloalkenylarnines, nitrile addition to ahcycHc carbocations, reduction of cyanocycloalkanes to aminomethylcycloalkanes, and reduction of nitrocycloalkanes or cycHc ketoximes. 

Carbonyl Compounds. Cychc ketals and acetals (dioxolanes) are produced from reaction of propylene oxide with ketones and aldehydes, respectively. Suitable catalysts iaclude stannic chloride, quaternary ammonium salts, glycol sulphites, and molybdenum acetyl acetonate or naphthenate (89—91). Lactones come from Ph4Sbl-cataly2ed reaction with ketenes (92). 

PUtzing erReaction. Quinoline-4-carboxyhc acids are easily prepared by the condensation of isatin [91-56-5] (16) with carbonyl compounds (50). The products may be decarboxylated to the corresponding quinolines. The reaction of isatin with cycHc ketones has been reported, eg, the addition of cyclohexanone gives the tricycHc intermediate (17) [38186-54-8] which upon oxidation produces quinoline-2,3,4-tricarboxyhc acid [16880-83-4] (51). 

Alkaline Degradation. At high pH, sucrose is relatively stable however, prolonged exposure to strong alkaU and heat converts sucrose to a mixture of organic acids (mainly lactate), ketones, and cycHc condensation products. The mechanism of alkaline degradation is uncertain however, initial formation of glucose and fructose apparendy does not occur (31). In aqueous solutions, sucrose is most stable at —pH 9.0. 

Poly(vinyhdene chloride) also dissolves readily in certain solvent mixtures (82). One component must be a sulfoxide or A/,Al-diaIk5lamide. Effective cosolvents are less polar and have cycHc stmctures. They include aUphatic and aromatic hydrocarbons, ethers, sulfides, and ketones. Acidic or hydrogen-bonding solvents have an opposite effect, rendering the polar aprotic component less effective. Both hydrocarbons and strong hydrogen-bonding solvents are nonsolvents for PVDC. 

Acetalation. As polyhydroxy compounds, carbohydrates react with aldehydes and ketones to form cycHc acetals (1,13). Examples are the reaction of D-glucose with acetone and a protic or Lewis acid catalyst to form l,2 5,6-di-0-isoprop5lidene-a-D-glucofuranose [582-52-5] and its reaction with benzaldehyde to form 4,6-0-benzyhdene-D-glucopyranose [25152-90-3]. The 4,6-0-(l-carboxyethyhdine) group (related to pymvic acid) occurs naturally in some polysaccharides. 

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