Propenes dimethylamino

Methylisoxazole (297 R = Me) and its homologs can be synthesized by reaction of hydroxylamine hydrochloride with 1-alkyl-3-dimethylamino-2-propen-l-one (296) (54IZV47), the anilino derivatives of acetoacetaldehyde (47G556), 3-dimethyl-aminomethylene-l-propyne (equation 7) (69ZOR1179) and the /3-ketoaldehyde (293) (66JOC3193). 

Isoxazole-3-carbaldehyde has been obtained as a minor product from the reaction of acetylene with a mixture of nitric oxide and nitrogen dioxide (61JOC2976). Although 3-aryl-4-formylisoxazoles have been synthesized in good yields from the reaction of benzonitrile Af-oxides with 3-(dimethylamino)-2-propen-l-one (71S433), the parent member of the series, isoxazole-4-carbaldehyde, has never been reported. It may possibly be obtained by the addition of fulminic acid to 3-(dimethylamino)-2-propen-l-one. 

The combination of the enantiomerically pure 7V-methylephedrine derived silylketene acetal l-[(l/ ,2S)-2-dimethylamino-1-phenylpropoxy]-l-triniethylsilyloxy-l-propene with the chiral aldehyde (,R)-3-benzyloxy-2-methylpropanal leads, after reduction with lithium aluminum hydride, to the formation of a single 1,3-pentanediol 9 ( matched pair ). 

Ein weiteres, auch in bezug auf die Stereochemie gut untersuchtes Beispiel dieser Art ist die Reaktion von 3-Acetoxy-3-aryl-3-(3-pyridyl)-propenen mit Dimethylamin unter Palla-dium(ll)-Katalyse, die zu (Z/ -Gemischen von l-Aryl-3-dimethylamino-l-(3-py-ridinyl)-propenen fuhren, z.B. zu (Z)- + (E)-l-(4-Brom-phenyl)-3-dimethylamino-l-(3-pyridyl)-propen im Verhaltnis 1,2 1. Die gleichen Produkte, jedoch in anderem (Zj Ey-Verhaltnis, erhalt man unter den gleichen Reaktionsbedingungen auch aus den iso-meren 3-Acetoxy-1 -aryl-1 -(3-pyridyl)-propenen3 ... 

Reaction of rra s-Ar,A -dimethyl-2-phenylcyclopropylamine with di-methylamine in methanol to give the open-chain enamine 1-dimethylamino-3-phenyl-l-propene [178]. 

The 12-step synthesis of imatinib mesylate (1) in the manufacturing process was accomplished by Novartis in an astonishingly short time. The synthesis began with a condensation reaction between 6 and ethyl formate. Deprotonation of the methyl group on 3-acetylpyndine (6) using freshly prepared sodium methoxide afforded an enolate. Condensation of the enolate with ethyl formate was followed by exchange with to produce 3-dimethylamino-l-(3-pyridyl)-2-propen-l-one (7). could be prepared from the condensation of 6 and N,N-... 

Dimethylamino-2-propen-l-yl idene -N,N-dimethylimmonium perchlorate, AL29... 

The equilibration of allylamines like 176, which have an isolated C=C double bond, to conjugated enamines under basic conditions has been studied extensively139,292 297. With only one exception298, that of l-(indol-3-ylethyl)-3-pyrroline (181), which is only partially transformed into its enamine 182 (equation 15), the equilibrium generally lies far on the side of the enamine l-JV,JV-dimethylamino-2-propene (183) is isomerized292 with potassium terf-butoxide in DMSO, first to the Z-enamine (184) and then to the thermodynamically more stable is-enamine293,294 (185, see equation 16) as was shown by XH-NMR spectroscopy. 

We can further amplify our tale of woe by deriving (from the thermochemical numbers in our archive) the enthalpy of hydrogenation of the cyclic, unconjugated, 1,2,3,6-tetrahydropyr-idine which is almost identical to its corresponding hydrocarbon, cyclohexene, 119.9 + 2.4 and 117.9 1.0 kJ mol-1, respectively. And, as if to add insult to injury, while the enthalpy of reaction of dimethylamine with allyl chloride to give 3-(V,V-dimethylamino)propene has been measured [C. Beldie, A. Nicholae, A. Onu and G. Nemtoi, Rev. Chim. (Bucharest), 33, 917... 

Table 6-2. and chemical shifts [77], /hh coupling constants [73], and C=0 stretching vibrations [20] of 3-(dimethylamino)propenal in solvents of increasing polarity. 

That the electronic ground-state structure of a dipolar solute is indeed affected by solvent polarity has been independently shown by NMR [20, 50, 73, 75, 78], NMR [77], and IR measurements [20] of merocyanines. Some of these results observed with the positively solvatochromic 3-(dimethylamino)propenal are presented in Table 6-2. 

When changes do occur, b often increases as the polarity of the solvent increases. An example of this behaviour, f 3-(dimethylamino)propenal [20, 73], has been... 

Propen 1-Dimethylamino-l-methoxy- VII/4, 429 (H5C2 - CO - NR2 + R2Oe) Pyran 2-Aminomethyl-tetra-hydro- VI/4, 45 Pyrrolidin... 

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