Acetone oximes

Developments in aliphatic isocyanates include the synthesis of polymeric aliphatic isocyanates and masked or blocked diisocyanates for appflcafions in which volatility or reactivity ate of concern. Polymeric aliphatic isocyanates ate made by copolymerizing methacrylic acid derivatives, such as 2-isocyanatoethyl methacrylate, and styrene [100-42-5] (100). Blocked isocyanates ate prepared via the reaction of the isocyanate with an active hydrogen compound, such as S-caprolactam, phenol [108-95-2] or acetone oxime. 

Aceton-oxim + Propansaure — N-Propyl-N-isopropyl-hydroxylamin 68°/0 d. Th. 

Aryl- und 1,3-Diaryl-aceton-oxime, Aryl-acetaldoxime, ungesattigte Oxime mit kon-jugierter C=C-Doppelbindung und deren O-Alkyl- und O-Acyl-Derivate sowie 3-Phe-... 

C21H22F3N3OS 807-57-8) see Fluphenazine Y-[4-(trifluoromethyl)phenoxyJbenzenepropanamine -(Ci HiftFjNO 83891-03-6) see Fluoxetine (3-trifluoromethylphenyl)acetone (CioHgFjO 21906-39-8) see Fenfluramine (3-trifluoromethylphenyl)acetone oxime (CiijHkjFjNO, 834-19-5) see Fenfluramine [[[2-(trifiuoromethyl)phenyl]amino]methylene]propane-dioic acid diethyl ester (C 3Hi(,F3N04 23779-94-4) see Floctafenine... 

Eastman grade acetone oxime was used as obtained from Eastman Organic Chemicals. 

Ethyl isocyanide, 46, 76, 77 Ethyl a-(isopropylideneaminooxy)pro-pionate, from acetone oxime and ethyl a-bromopropionate, 48,120 hydrolysis of, 48,121 Ethylmagnesium bromide, use with ferric chloride in cyclization of di-chloroacetone /J-Lolylmagncsium bromide adduct to l-f>-tolyicy-clopropanol, 47,108 Ethyl a-methyl-/3-phenylcinnamate, 48, 79... 

Figure 2. The contour energy map for the reaction ofprotonated acetone oxime (1) calculated by HF/6-31G. Numbers on contour lines are relative energies with respect to TS in kcal mot1.

Individually indexed compounds are f Acetaldehyde oxime, 0865 Acetone oxime, 1258 Azoformaldoxime, 0815 Benzaldehyde oxime, 2760 Bromoacetone oxime, 1201 Butane-2,3-dione dioxime, 1595... 

Acetohydrazide, 0912 Acetone oxime, 1258 Acetylenedicarboxylic acid, 1405 Acrylaldehyde, 1145 f Allyl acetate, 1912 A-Ally lthiourca. 1600 4-Aminophenylazobenzene, 3487 Ammonium dichromate, 4246 Ammonium peroxodisulfate, 4576 4-Azidobenzaldehyde, 2697 2-Azido-2-phenylpropane, 3159 f Aziridine, 0863 Azobenzene, 3483 Azoformamide, 0816 Azoisobutyronitrile, 3011 Azoxybenzene, 3485 Benzaldehyde oxime, 2760... 

Fluoro- and chloroarenes activated by complexation with chromium tricarbonyl react readily with primary and secondary alcohols under basic conditions in the presence of a quaternary ammonium catalyst [46, 47]. Reaction of the chromium complexes with acetone oxime produces O-aryloximes in good yields (55-80%) [48]. 

Vinyl chloroformate (50 mmol) acetone oxime (35 mmol) anhydrous pyridine (10 mL) dichloromethane (3 x 20 mL) brine... 

In a 25 mL Schlenk with magnetic stirrer and addition funnel, vinyl chloroformate (4.25 mL, 50 mmol) was added dropwise to a solution of acetone oxime (2.56 g, 35 mmol) in anhydrous pyridine (10 mL) at 0 °C. The reaction was stirred overnight at room temperature. 

For the two aldehydes discussed in the previous section (R, R = H R = Me, R = Hep), the reaction is thermoneutral in the gas phase. Thermoneutrality would also be expected for ketones, but which ketone/oxime should be the standard for comparison In the gas phase there are two possibilities acetone/acetone oxime and cyclohexanone/cyclohexanone oxime. The latter pair may be assumed to be essentially strainless, or at least that their strain energies are very much the same. The assumption is borne out by substituting these two pairs into equation 23 (R, R = Me R R = — (CH2)5—) and finding that the enthalpy of reaction is only 1.2 kJ moE, essentially thermoneutral. Comparing the Cg species with the cyclohexyl species (RR = —(CH2)s- R /R = Me/Hex, Et/Pen, Pr/Bu), the enthalpies... 

In this case, the enthalpies of reaction are 52.1, 45.7 and 44.6kJmoD where the enthalpies of formation of solid and gaseous acetone oxime are from References 1 and 4, respectively, and the enthalpies of oximation in aqueous media are from References 49a and 49c. In both cases, the values are comfortably similar for the three phases. Perhaps we should not be too surprised that the values are close—after all, the number of hydrogen bonds are the same on the two sides of the reaction. However, nothing prepares us for the observation that the aqueous phase oximation enthalpy of propionaldehyde is 73.2 kJmoD, even though we recall problems with the enthalpy of formation of EtCH=NOH. 

The carbon-13 NMR spectrum of acetone oxime has three resonances, the deriva-tized carbonyl carbon at 154.5 ppm and the two nonequivalent CH3 groups at 21.5 and 14.7 ppm. The difference between the chemical shifts of the two methyl groups, 6.8 ppm, is primarily a steric compression shift. This is clearly indicated in the carbon NMR spectrum of methyl ethyl ketoximes (Scheme 1), where the two oxime substituents are not sterically identical and thus the two isomers are not present in equal amounts. In methyl... 

Imines, Oximes, Hydrazones A -Me1hylbenzaldimine A -Phenylbenzaldimine Acetone oxime Benzaldehyde oxime Benzaldehyde A -phenylhydrazone... 

Substituted 5-alkylisoxazoles 203 are successfully obtained from oxime dianions, prepared from acetone oxime 202 and BuLi, and then by interaction with Af-methoxyamides of type RCON(OMe)Me (equation 88) . ... 

Alvernhe and Laurent first developed a procedure for conversion of Grignard reagents to primary amines using acetone oxime 6c and butanone oxime 6d (Scheme 55) 22 23 However, the yields were low. They expanded their study to investigate how well organo-lithiums perform in their reaction with 6c or 6d 23. Phenyllithium gave a 1 4 mixture of aniline and the addition product of phenyllithium to the imine (Scheme 53, path e product) in the reaction with 6c while aziridine was obtained in the reaction with 6d (Scheme 56). 

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