Atmosphere ketones

Not as much work has been reported on atmospheric ketone concentrations. Acetone was present at 0.001 ppm in the air at Point Barrow, Alaska (Cavanagh et al., 1969) and also, at half that concentration or less, in air over the Atlantic (Penkett, 1982 Zhou and Mopper, 1990) it is also present at higher elevations (Arnold et al., 1986). Phenyl and higher cyclic ketones, a few Cg-Cig aliphatic ketones, butanone, biacetyl and 4-methyl-2-pentanone have also been identified in ambient air (Kawamura and Kaplan, 1983 Ramdahl, 1983 Zhou and Mopper,... 

Introduce a solution of 100 g. of sodium bisulphite in 200 ml. of water and continue the stirring, preferably for 10 hours with exclusion of air. A thick precipitate separates after a few minutes. Collect the bisulphite compound by suction filtration, wash it with ether until colourless, and then decompose it in a flask with a lukewarm solution of 125 g. of sodium carbonate in 150 ml. of water. Separate the ketone layer, extract the aqueous layer with four 30 ml. portions of ether, dry the combined organic layers over anhydrous magnesium sulphate, remove the ether at atmospheric pressure, and distil the residual oil under reduced pressure from a Qaisen flask with fractionating side arm (Fig. II, 24, 5). Collect the cyclo-heptanone at 64r-65°/12 mm. the yield is 23 g. 

Various organotin reagents react with acyl and aroyl halides under mild conditions without decarbonylation to give carbonyl compounds[390,39l]. Alkyl- or alkenyltin reagents react with acyl and aroyl chlorides to give ketones[548.733,734]. One example is the preparation of the a,/3-dnsaturated 7-keto esters 860 and 861, carried out under a CO atmosphere[735]. The reaction has been applied intramolecularly to the synthesis of the macrocyclic keto... 

Similarly to alkenes. alkynes also insert. In the reaction of 775 carried out under a CO atmosphere in AcOH, sequential insertions of alkyne, CO. alkene. and CO take place in this order, yielding the keto ester 776[483]. However, the same reaction carried out in THF in the presence of LiCl affords the ketone 777, but not the keto ester[484]. The tricyclic terpenoid hirsutene (779) has been synthesized via the Pd-catalyzed metallo-ene carbonylation reaction of 778 with 85% diastereoselectivity as the key reaction[485], Kainic acid and allo-kainic acid (783) have been synthesized by the intramolecular insertion ol an alkene in 780, followed by carbonylation to give 781 and 782[486],... 

A sensitive method for the flow injection analysis of Cu + is based on its ability to catalyze the oxidation of di-2-pyridyl ketone hydrazone (DPKH) by atmospheric oxygen. The product of the reaction is fluorescent and can be used to generate a signal when using a fluorometer as a detector. The yield of the reaction is at a maximum when the solution is made basic with NaOH. The fluorescence, however, is greatest in the presence of HCl. Sketch an FIA manifold that will be appropriate for this analysis. 

In the early 1920s Badische Arulin- und Soda-Fabrik aimounced the specific catalytic conversion of carbon monoxide and hydrogen at 20—30 MPa (200—300 atm) and 300—400°C to methanol (12,13), a process subsequendy widely industrialized. At the same time Fischer and Tropsch aimounced the Synth in e process (14,15), in which an iron catalyst effects the reaction of carbon monoxide and hydrogen to produce a mixture of alcohols, aldehydes (qv), ketones (qv), and fatty acids at atmospheric pressure. 

Peroxide-Ketazine Process. Elf Atochem in France operates a process patented by Produits Chimiques Ugine Kuhhnaim (PCUK). Hydrogen peroxide (qv), rather than chlorine or hypochlorite, is used to oxidize ammonia. The reaction is carried out in the presence of methyl ethyl ketone (MEK) at atmospheric pressure and 50°C. The ratio of H202 MEK NH2 used is 1 2 4. Hydrogen peroxide is activated by acetamide and disodium hydrogen phosphate (117). Eigure 6 is a simplified flow sheet of this process. The overall reaction results in the formation of methyl ethyl ketazine [5921-54-0] (39) and water ... 

With the exception of neopentyl alcohol (mp 53°C), the amyl alcohols are clear, colorless Hquids under atmospheric conditions, with characteristic, slightly pungent and penetrating odors. They have relatively higher boiling poiats than ketonic or hydrocarbon counterparts and are considered iatermediate boiling solvents for coating systems (Table 1) (1—16). 

Diethyl pyrocarbonate (DEP) [1609-47-8] M 162.1, b 38-40°/12mm, 160-163 /atm, d 1.119, Op 1.398. Dissolve in Et20, wash with dilute HCl, H2O, dry over Na2S04. filter, evaporate and distil the residue first in vacuo then at atmospheric pressure. It is soluble in alcohols, esters, ketones and hydrocarbon solvents. A 50% w/w soln is usually prepared for general use. Treat with great CAUTION as DEP irritates the eyes, mucous membranes and skin. [Boehm and Mehta Chem Ber 71 1797 1938 Thoma and Rinke Justus Liebigs Ann Chem 624 30 1959.]... 

Steroid ketones Apply the sample solution followed by Girard s reagent (0 1% tnmethylacetyl hydrazide in 10% acetic acid) and allow to react for 15 h in an atmosphere of acetic acid Then dry at 80 °C for 10 mm and after cooling chromatograph the hydrazones that have been formed [81]... 

Ergometrine crystallises, with solvent, from benzene in needles or from methyl ethyl ketone in prisms both forms have m.p. 162-3° (dec.). From ethyl acetate it crystallises at — 4° in thin, solvent-free plates, m.p. 160-1° (dec.), and at atmospheric temperature on concentration in vacuo in diamond-shaped plates, B.0-5EtAc, m.p. 130-2° (dec.), from which the combined solvent is not removed at 100° in vacuo. By crystallisation from acetone, Grant and Smith obtained a second form in long needles, m.p. 212° (dec.), which appears to be the more stable, since the form, m.p. 162-3°, tends to pass into it on keeping. Ergometrine has [o]d — 44° (CHCI3) - - 42-2° or + 62-6° (c = 1-7, EtOH) or... 

A solution of ketone (85) in t-butanol and excess potassium -butoxide and potassium hydroxide is heated at refluxjinder an atmosphere of oxygen for 8 hr to give the C-norpregnane acid (87), in about 46% yield. Yields tend... 

In a German patent issued in 1929, Bergs described a synthesis of some 5-substituted hydantoins by treatment of aldehydes or ketones (1) with potassium cyanide, ammonium carbonate, and carbon dioxide under several atmospheres of pressure at 80°C. In 1934, Bucherer et al. isolated a hydantoin derivative as a by-product in their preparation of cyanohydrin from cyclohexanone. They subsequently discovered that hydantoins could also be formed from the reaction of cyanohydrins (e.g. 3) and ammonium carbonate at room temperature or 60-70°C either in water or in benzene. The use of carbon dioxide under pressure was not necessary for the reaction to take place. Bucherer and Lieb later found that the reaction proceeded in 50% aqueous ethanol in excellent yields for ketones and good yields for aldehydes. ... 

An interesting feature is the sometimes observed pressure dependence of the reaction. The Michael addition of dimethyl methylmalonate 12 to the bicyclic ketone 13 does not occur under atmospheric pressure, but can be achieved at 15 Kbar in 77% yield ... 

The reaction is sensitive to the presence of water, which inhibits the migration of the third alkyl group and leads to dialkyl ketones (see Chapter 12, Section II). The convenience of the hydroboration reaction combined with the use of carbon monoxide at atmospheric pressure provides the most accessible route to many trialkylcarbinols. 

An antipolymerization agent such as hydroquinone may be added to the reaction mixture to inhibit the polymerization of the maleate or fumarate compound under the reaction conditions. This reaction is preferably carried out at a temperature within the range of 20°C to 150°C. This reaction is preferably carried out at atmospheric pressure. Reaction time of 16 to 24 hours have bean specified for this reaction by J.T. Cassaday. The reaction is preferably carried out in a solvent such as the low molecular weight aliphatic monohydric alcohols, ketones, aliphatic esters, aromatic hydrocarbons or trialkyl phosphates. 

The residue is the hydrochloride of m-hydroxyphenyl-a-aminoethyl ketone. This is purified by recrystallization from absolute alcohol. It is then dissolved in 200 parts of water and agitated with a further quantity of the palladium catalyst in an atmosphere of hydrogen until saturated. The product thus recovered from the solution is the hydrochloride... 

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