Dihydro isomerization

Pyrazine, 1,4-dialkyl-1,4-dihydro-isomerization, 3, 178 Pyrazine, dichloro-synthesis, 3, 187 Pyrazine, 2,3-dichloro-oxidation, 3, 169... 

The pyrrolines or dihydropyrroles can exist in three isomeric forms 1-pyrroline (3,4-dihyro-2JT-pyrrole [5724-81-2]) (16) is an unstable material that resiniftes upon exposure to air 2-pyrroline (2,3-dihydro-lJT-pyrrole [638-31-3]) (17) is even more unstable only 3-pyrroline (2,5-dihydro-lJT-pyrrole [109-96-6]) (18) is reasonably stable. 3-Pyrroline bods at 91°C and has a density of 0.9097 g/cm and a refractive index of 1.4664. 

Some 4,5-disubstituted pyridazines exhibit ring-chain isomerism involving heterospiro compounds. For example, 5-(o-aminophenylcarbamoyl)pyridazine-4-carboxylic acid exists in a zwitterionic form in the solid state, but in a solution of DMSO it is almost exclusively 3, 4 -dihydro-3 -oxospiro[pyridazine-5(2//),2 (l //)-quinoxaline]-4-carboxylic acid (134). The equilibrium is strongly influenced by the nature of the solvent, the substituents on the pyridazine ring and the nucleophilicity of the group attached to the phenyl ring (Scheme 48) <80JCS(P2)1339). 

In a series of detailed studies, Armand and coworkers have examined the electrochemical reduction of pyrazines (72CR(C)(275)279). The first step results in the formation of 1,4-dihydropyrazines (85), but the reaction is not electrochemically reproducible. The 1,4-dihydropyrazine is pH sensitive and isomerizes at a pH dependent rate to the 1,2-dihydro compound (83). The 1,2-dihydropyrazine then appears to undergo further reduction to 1,2,3,4-tetrahydropyrazine (88) which is again not electrochemically reproducible. Compound (88) then appears to undergo isomerization to another tetrahydro derivative, presumably (8, prior to complete reduction to piperazine (89). These results have been confirmed (72JA7295). 

The fusion of a benzene ring to pyrazine results in a considerable increase in the resistance to reduction and it is usually difficult to reduce quinoxalines beyond the tetrahydroquinoxa-line state (91). Two possible dihydroquinoxalines, viz. the 1,2- (92) and the 1,4- (93), are known, and 1,4-dihydroquinoxaline appears to be appreciably more stable than 1,4-dihydropyrazine (63JOC2488). Electrochemical reduction appears to follow a course anzdogous to the reduction of pyrazine, giving the 1,4-dihydro derivative which isomerizes to the 1,2- or 3,4-dihydroquinoxaline before subsequent reduction to 1,2,3,4-tetra-hydroquinoxaline (91). Quinoxaline itself is reduced directly to (91) with LiAlH4 and direct synthesis of (91) is also possible. Tetrahydroquinoxalines in which the benzenoid ring is reduced are well known but these are usually prepared from cyclohexane derivatives (Scheme 30). 

Following the classification of Chapter 4.01, three classes will be considered, (a) Compounds isomeric with aromatic compounds (6), (7) and (8). The quaternary, non-aromatic salts (Scheme 7, Chapter 4.01) will be discussed only in connection with protonation studies which lead to the conclusion of their non-existence. The carbonyl derivatives (9), (10), (13) and (14) will also be included here because it is possible to write an aromatic tautomer for each one, (9 )-(14 ), even if it is energetically unfavoured, (b) Dihydro compounds. In this class not only pyrazolines (15), (16) and (17) but also pyrazolidinones (18) and pyrazolinediones like (1) are included, (c) Tetrahydro compounds. Besides the pyrazolidines (19), the pyrazolidinetriones (2) are included here. 

H-Azepine, 2-(o-hydroxyphenyl)-synthesis, 7, 538 3 H-Azepine, methyl- H NMR, 7, 495 3H-Azepine, 3-methylring inversion barrier, 7, 14 3 H-Azepine, 2-methylene-isomerization, 7, 505 3H-Azepine, 7-(N-phthalimido) synthesis, 7, 538 4H-Azepine, 4,5-dihydro-cyclization, 7, 524... 

Cesium fluonde in dimethylformamide catalyzes the isomerization offluori-nated cyclobutenes, perfluorobipyntmdines, and their oligomers to products with expanded rings [30, 31, 32] The product distribution in cobalt tnfluonde fluorina-tion depends strongly on the temperature of the reaction [33] Fluorinated 1-dimethylamino-5,6,7,8-tetrafluoro-l,4-dihydro-l,4-ethenonaphthalene rearranges in protic media to a biphenyl derivative [34] (equation 8)... 

Azides can use enamines as dipolarophiles for ],3 cycloadditions to form triazolines. These azides can be formate ester azides (186), phenyl azides (187-195), arylsulfony] azides (191-193,196), or benzoylazides (197,198). For example, the reaction between phenyl azide (138) and the piperidine enamine of propionaldehyde (139) gives 1 -phenyl-4-methy l-5-( 1 -piperidino)-4,5-dihydro-l,2,3-triazole (140), exclusively, in a 53% yield (190). None of the isomeric l-phenyl-5-methyl product was formed. This indicates that the... 

Finally, there is a series of publications by Prinzbach and co-workers on 4,7-dihydro-l//-l,4,7-triazonine 42b (80CB3127, 80CB3161, 88CB757, 89AG1386). Tliis compound, obtained by a 3valence isomer) is a nonaromatic, nonplanar 127r-electron system, better represented as 42c. 

Isomeric 4,5-dihydro[4,5-/]derivative 76 has been prepared from 7,8-dihydro-5(6//)-quinolinone via a semicarbazone and its subsequent reaction with thionyl chloride (95JHC177). 

The ring-chain isomerism was studied in a series of 4-hydroxy-3,4-dihydro-1,2,4-triazines 87, which are models for cr -adducts at the 3 position of the... 

Ethyl 9-ethoxycarbonyl- and 9-hydroxymethyl-3-methyl-6-oxo-2/f,6//-pyrido[2,l-Z>][l,3]thiazine-4-carboxylates were isomerized into 4H,6H-pyrido[2,l-b][l,3]thiazine-4-carboxylates by treatment with KOH overnight at room temperature and by treatment with NaOEt at 0 °C for 1 h and room temperature for 3h in EtOH, respectively. In another experiment, when the 9-hydroxymethyl derivative was treated with NaOEt in EtOH at — 10°C for 3h, a 2.5 1 mixture of ethyl 3,4-cw-H-9-ethoxymethyl-3-methyl-6-oxo-3,4-dihydro-2//,6//-pyrido[2,l-Z)][l,3]thiazine-4-carboxylate and the aforementioned 4//,6//-isomer were obtained (00JCS(P1)4373). 

No annular tautomeric equilibrium transformations in compounds of the diox-ane series have been reported yet recently (97JCC1392), however, the optimized geometries and total energies of unsubstituted isomeric 3,4-dihydro-1,2-dioxin 22 and 3,6-dihydro-1,2-dioxin 23 were calculated using ab initio 3-21G, 6-31G, and MP2/6-31G //6-31G methods. All the methods applied revealed that the total energies for half-chair conformations of 22 and 23 are approximately the same. 

Interestingly, a reverse isomerization (1,4-dihydro 1,2-dihydro) was observed when a 1,4-dihydroquinoline derivative was obtained by the reaction of lithiated l-ethoxycarbonyl-l,2-dihydroquinoline-2-phosphonate 36 with benzyl bromide... 

N-Substituted 5,6-dihydro-2//-1,2-oxazines were found to be significantly more stable than their N-unsubstituted analogs and could be distinguished from the corresponding 4H isomers using H NMR spectroscopy. Thus, it was shown that oxazinium salt 80 isomerizes on treatment with sodium carbonate to tricyclic... 

Calculated Relative Energies oe Isomeric Dihydro-1,2,4-triazines Compared TO 2,5-Dihydro-1,2,4-triazine 98... 

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