Butanone derivative

The a-acetobutyrolactone, with or without isolation, can be used in the preparation of various 5-substituted 2-butanone derivatives, presumably by decarboxylation of the acetoacetic acid obtained by ring hydrolysis. Simple hydrolysis gives 5-hydroxybutan-2-one (158) and acidolysis with hydrochloric acid gives 5-chlorobutan-2-one in good yields (159). 

The kinetics of the base-catalysed alkylation of 5-substituted 3-nitrotriazoles with methyl vinyl ketone to give the N(l)-3-butanone derivative has been studied and the reaction was shown to be first order in both mvk and the 3-nitrotriazolium anion <90JOU1170>. 

Attempts were made to epoxidise the C=C bond of diphenylcyclopropenone and thus obtain the 2-oxabicyclo[1.1.0]butanone derivative. Use of either peracetic acid or hypochlorite was not successful and the starting material was recovered. Oxidation with 25% hydrogen peroxide in a mixture of dioxane and 3M aqueous NaOH at room temperature, however, gave a 77% yield of desoxybenzoin. 

Calibration is carried out using standard calibration curves. The simplicity, repeatability, and low cost of the method have allowed its use for routine determination of trihalomethanes in tap water. SOME has also been compared with solid phase microextraction (SPME), purge and trap (P T), and direct aqueous injection (DAI) [10]. This technique offers accuracy comparable with that obtained using P T and DAI. With respect to conventional LEE, the SDME method is more accurate. In contrast to DAI and P T, it requires no special equipment. SDME has been used for extraction of chlorophenols [II], pesticides [12, 13], warfare agents [14], and butanone derivatives [15], and for control of food products [16]. The low costs of the SDME method (typical GC syringe and 2-3 pL of solvent), simplicity, and short extraction time (approximately 15 min) make it particularly suitable for preliminary analyses of organic pollutants in water samples. It can also be an effective alternative to SPME, as it does not require the use of expensive instrumentation. 

Hu, M., Chen, H., Jiang, Y., Zhu, H. Headspace single-drop microextraction coupled with gas chromatography electron capture detection of butanone derivative for determination of iodine in milk powder and urine. Chem. Pap. 67(10), 1255-1261 (2013)... 

The most widely used procedure for the preparation of benzo[a]quinolizidin-2-ones and their 3-alkyl derivatives (270) consists of the reaction between 3,4-dihydroisoquinolines and a,/3-unsaturated ketones, with iminium salt (269) as an intermediate <62CB2135>. 4-Dimethylamino-2-butanone derivatives can play the same role as unsaturated ketones, and have the advantage of allowing the reaction to be conducted in aqueous solutions, which facilitates the isolation of the product <69JCS(C)85> (Scheme 56). The yields obtained in the latter case are usually quantitative for 3-substituted benzo[a]quinolizidin-2-ones, but are considerably lower for the unsubstituted system because of the formation of a secondary product (271). Fortunately, this problem may be overcome by modifying the pH and temperature of the reaction medium <88TH822-0l>. 

Food irradiation may now be used in over 40 countries. The short chapter by Morsel describes the need to find markers which indicate that food has been irradiated (Chapter 7). The lipids which have been examined as potential markers include hydroperoxides, alkenes, alkanes, aldehydes and cyclo-butanones. Derivative formation with cyclobutanones can increase the sensitivity of detection of butanones in irradiated food. 

Reaction of the fluoroborate salt of (319) with acyclic dienes affords 3-vinylcyclo-butanone derivatives, but with cis-fixed dienes the ketenimmonium salt behaves as a dienophile and gives only [2 H- 4] adducts. Thus (319) shows a duality of behaviour, resembling both a keten and an allene depending on its cycloaddition partner. ... 

Joulain, D. and Fuganti, C. (1999) Process for preparing butanone derivatives. Patent US 5,908,770. 

While the measured values are not too different from those for the parent compound for the butanone derivatives ( (OH 2-butanone)... 

Terminal alkyne anions are popular reagents for the acyl anion synthons (RCHjCO"). If this nucleophile is added to aldehydes or ketones, the triple bond remains. This can be con verted to an alkynemercury(II) complex with mercuric salts and is hydrated with water or acids to form ketones (M.M.T. Khan, 1974). The more substituted carbon atom of the al-kynes is converted preferentially into a carbonyl group. Highly substituted a-hydroxyketones are available by this method (J.A. Katzenellenbogen, 1973). Acetylene itself can react with two molecules of an aldehyde or a ketone (V. jager, 1977). Hydration then leads to 1,4-dihydroxy-2-butanones. The 1,4-diols tend to condense to tetrahydrofuran derivatives in the presence of acids. 

Various 4-, 5-, or 4,5-disubstituted 2-aryIamino thiazoles (124), R, = QH4R with R = 0-, m-, or p-Me, HO C, Cl, Br, H N, NHAc, NR2, OH, OR, or OjN, were obtained by condensing the corresponding N-arylthiourea with chloroacetone (81, 86, 423), dichloroacetone (510, 618), phenacyichloride or its p-substituted methyl, f-butyl, n-dodecyl or undecyl (653), or 2-chlorocyclohexanone (653) (Method A) or with 2-butanone (423), acetophenone or its p-substituted derivatives (399, 439), ethyl acetate (400), ethyl acetyl propionate (621), a- or 3-unsaturated ketones (691), benzylidene acetone, furfurylidene acetone, and mesityl oxide in the presence of Btj or Ij as condensing agent (Method B) (Table 11-17). 

This adds compounds with active hydrogen such as water, alcohols, and carboxyUc acids (63), to give l,4-dihydroxy-2-butanone or its derivatives. 

Derivatives. Small amounts of alkyl quiaolines are present ia the tars resulting from the carbonization and Hquefaction of coal (111). Good yields of 4-methyl quinoline, 4,6-dimethyl quinoline [826-77-7], and 4,8-dimethyl quinoline [13362-80-6] are obtained from 4-(diethylamino)-2-butanone and the appropriate aniline. This approach is a promising addition to the traditional syntheses discussed eadier (112). Vlaylacetylene reacts with mercuric chloride and either aniline or -toluidine to yield 4-methyl- and 4,6-dimethyl quinoline, respectively (113). 

V-Acylation of oxaziridine (54) is of more importance, yielding 2-acyloxaziridines which were unaccessible otherwise until recently. Oxaziridines (54) derived from cyclohexanone, butanone or benzaldehyde are acylated readily by acetic anhydride, acid chlorides or isocyanates. Oxaziridines from aliphatic aldehydes, too unstable to be isolated, may be trapped in situ by benzoylation (67CB2593). 

Compare electrostatic potential maps of enolates derived from 2-butanone, 4,4-dimethyl-2-pentanone, 4,4,4-trifluoro-2-butanone and l-phenyl-2-propanone with those of acetone. Which substituents cause significant changes in the electronic structure of these enolates and what are the nature of these changes Justify your answers by making drawings of any important resonance contributors. 

Attempted selective displacement (96) of the primary tosylate function in 34 with sodium iodide in refluxing 2-butanone led to the 6-deoxy-6-iodo derivative 35 in 32% yield only, while the di-iodo derivative 36 was formed in 45% yield. These results are to be compared with those reported by Owen and Ragg (85) who observed no reaction with either potassium thiolacetate or potassium thiocyanate in the corresponding / -series. 

The D-gluco analog 37 reacted with sodium iodide in refluxing 2-butanone to give the crystalline 6-deoxy-6-iodo derivative 38 in 82% yield (97). Only 11% of the mixed di-iodo derivative 39 was formed in this case, which reflects on the higher order of reactivity at C-4 in 34 compared to 37. 

In contrast, highly stereoselective aldol reactions are feasible when the boron etiolates of the mandelic acid derived ketones (/ )- and (5,)-l- t,r -butyldimethylsiloxy-l-cyclohexyl-2-butanone react with aldehydes33. When these ketones are treated with dialkylboryl triflate, there is exclusive formation of the (Z)-enolates. Subsequent addition to aldehydes leads to the formation of the iyn-adducts whose ratio is 100 1 in optimized cases. 

Pinacolone (3,3-dimethyl-2-butanone) adds to aldehydes in an enantioselective manner when advantage of the induction by a C 2-symmetric boron enolate derived by addition of (2/ ,5/ )-l-chloro-2,5-diphenylborolane is taken. In this way, /i-hydroxy ketones, whose absolute configuration is unknown, arc obtained with 32- 84% cc58. 

There is also the haloform reaction (effect of a haloform on a ketone in a basic medium), already described with halogen derivatives on p.272 (the danger is more related to the interaction of the polyhalogen derivative with the base, according to the author). A large number of accidents involved the ketone as much as butanone. The accident below illustrates the danger of this reaction ... 

Figure 8.19 Two-diaenslonal separation of the components of a coal derived gasoline fraction using live switching. Column A was 121 n open tubular column coated with poly(ethelene glycol) and column B a 64 m poly(dimethylsiloxane) thick film column. Both columns were temperature programmed independently taking advantage of the two oven configuration. Peak identification 1 acetone, 2 2-butanone, 3 > benzene, 4 isopropylmethylketone, 5 isoprop-anol, 6 ethanol, 7 toluene, 8 => propionitrile, 9 acetonitrile, 10 isobutanol, 11 — 1-propanol, and 12 = 1-butanol. (Reproduced with permission from Siemens AG).

Cyclization occurred at the N-3 atom when 4-(3-bromopropylaruino)-l, 6,7,1 1 b-tctrahydro-2//-pyrimido[6,l -zz -isoquinoline was treated with NaH to give a tetracyclic derivative <2003M1271>. 9,10-Dimethoxy-2-(arylimino)-2,3,6,7-tetrahydro-4//-pyrimido[6,l- ]isoquinolin-4-ones were N-3-alkylated with iV-(ra-bromoalkyl)phthalimides in the presence of K2C03 and a catalytic amount of I2 in boiling 2-butanone in 13-67% yields <2000W020/058308>. Treatment of the 2-[(4-methoxyphenyl)methyl] derivative of 2,3,6,7-tctrahydro-l //,5//-pyrido[3,2,l-/ylqninazolinc-... 

Asymmetric ECH with [Rh(L)2(Cl)2]+ complexes containing chiral polypyridyl ligands has been attempted, in homogeneous media (L = (7)-(12)) and at carbon electrodes coated with polymer films prepared by electropolymerization of [Rh(13)2(Cl)2]+ -61 62 The latter catalytic system gave the best results in terms of turnover number (up to 4,750) and enantiomeric excess, (ee) when applied to the hydrogenation of acetophenone (ee 18%) and 2-butanone (ee 10%).62 Polymeric materials derived from the complexes [RhI(bpy)(COD)]+ 36 and [Pd(bpy)2]2+33have also been applied to the ECH reaction. 

The preparation of enantiomerically pure chemicals is also the theme of the next group of four procedures. The biopolymer polyhydroxybutyric acid, which is now produced on an industrial scale, serves as the starting material for the large scale synthesis of (R)-3-HYDROXYBUTANOIC ACID and (R)-METHYL 3-HYDROXYBUTANOATE. Esters of (-)-camphanic acid are useful derivatives for resolving and determining the enantiomeric purity of primary and secondary alcohols. An optimized preparation of (-)-(1S,4R)-CAMPHANOYL CHLORIDE is provided. The preparation of enantiomerically pure a-hydroxyketones from ethyl lactate is illustrated in the synthesis of (3HS)-[(tert)-BUTYL-DIPHENYLSILYL)OXY]-2-BUTANONE. One use of this chiral a-hydroxyketone is provided in the synthesis of (2S,3S)-3-ACETYL-8-... 

Diels and Stephan173 treated the benzoate of 3-hydroxy-2-butanone with bromine, and obtained crystalline 1-bromo- and 1,1-dibromo- derivatives. With dilute alkali, these formed 4-deoxy-DL-gZycero-tetrulose and 4-deoxy-DL-erythrosone respectively. Both compounds gave with phenylhydrazine 4-deoxy-DL-erythrose phenylosazone, which had previously been prepared from the corresponding aldotetrose.174... 

---