The Meisenheimer rearrangement in heterocyclic synthesis. III. Derivatives of the 1H-[1,2]oxazepino[6,5-b]indole, thieno[2,3-e][1,2]oxazepine and [l]benzothieno[3,2-e][1,2]oxazepine ring systems

1980 ◽  
Vol 33 (6) ◽  
pp. 1335 ◽  
Author(s):  
JB Bremner ◽  
EJ Browne ◽  
PE Davies
Keyword(s):  
Acetic Acid ◽  
Tertiary Amine ◽  
Good Yield ◽  
Heterocyclic Synthesis ◽  
Ring Systems ◽  
Heterocyclic Derivatives ◽  
Derivatives Of

The new heterocyclic derivatives 3-methyl-1-phenyl-3,4,5,10-tetrahydro- 1H-[1,2]oxazepino[6,5-b]-indole (5c), 6-methyl-4-phenyl-4,6,7,8- tetrahydrothieno[2,3-e][1,2]oxazepine (6f), and 3-methyl-1-phenyl- 1,3,4,5-tetrahydro[1]benzothieno[3,2-e][1,2]oxazepine (7c) were prepared in good yield by thermal Meisenheimer rearrangement of the corresponding tertiary amine N-oxide precursors. No such rearrangement occurred on heating the N-oxides of the fused bicyclic systems 2,3,11,12-tetramethoxy-5,8,9,13b-tetrahydro-6H-dibenzo[a,h]quinolizine (3) and 8,9-dimethoxy-1,2,3,5,6,10b-hexahydropyrrolo[2,1-a]isoquinoline (4). The reduction of (5c), (6f) and (7c) with zinc in acetic acid is also described.

The Meisenheimer rearrangement in heterocyclic synthesis. II. Synthesis and X-ray crystal structure of a tetrahydro-1H-2,3-benzoxazocine and preparation of a hexahydro-2,3-benzoxazonine

1980 ◽  
Vol 33 (6) ◽  
pp. 1323 ◽  
Author(s):  
JB Bremner ◽  
EJ Browne ◽  
PE Davies ◽  
CLWAH Raston
Keyword(s):  
Molecular Structure ◽  
Crystal Structure ◽  
Acetic Acid ◽  
Crystal And Molecular Structure ◽  
Phosphorus Oxychloride ◽  
Crystallographic Analysis ◽  
Heterocyclic Synthesis ◽  
Reaction Conditions ◽  
X Ray ◽  
Heterocyclic Derivatives

The heterocyclic derivatives, 8,9-dimethoxy-3-methyl-1-phenyl-3,4,5,6- tetrahydro-1H-2,3-benzoxazocine(3a) and 9,10-dimethoxy-3-methyl-1- phenyl-1,3,4,5,6,7-hexahydro-2,3-benzoxazonine (3b),examples of two new ring systems, have been prepared by Meisenheimer rearrangement of the corresponding 2-benzazepine and 2-benzazocine N-oxide derivatives (2a) and (2b). The Bischler-Napieralski-type cyclization reaction was used in the preparation of the tertiary amine precursors of these N-oxides reaction conditions for the cyclization were critical and phosphorus oxychloride in refluxing butanenitrile was found to give the best yields of the seven- or eight-membered cyclic imine intermediates. Reductive cleavage of the benzoxazocine derivative (3a) with zinc in acetic acid followed by N-methylation gave the expected product, [2-{3- (dimethylamino)propyl}-4,5-di-methoxyphenyl]phenylmethanol (12). The crystal and molecular structure of (3a) has been determined by X-ray crystallographic analysis.

The Meisenheimer Rearrangement in Heterocyclic Synthesis. IV. Derivatives of the 2H,6H-1,5,4-Benzodioxazocine and 7H-1,6,5-Benzodioxazonine Ring Systems: X-Ray Crystal Structure of 10-Methoxy-5-methyl-7-phenyl-2,3,4,5-tetrahydro-7H-1,6,5-benzodioxazonine

1988 ◽  
Vol 41 (3) ◽  
pp. 293 ◽  
Author(s):  
JB Bremner ◽  
EJ Browne ◽  
LM Engelhardt ◽  
IWK Gunawardana ◽  
AH White
Keyword(s):  
Molecular Structure ◽  
Crystal Structure ◽  
Crystal And Molecular Structure ◽  
Ring System ◽  
Heterocyclic Synthesis ◽  
Rearrangement Product ◽  
Ring Systems ◽  
X Ray ◽  
Derivatives Of ◽  
Moderate Yield

Meisenheimer rearrangement of the N-oxides (4) derived from a series of 5-aryl-4-methyl-2,3,4,5-tetrahydro-1,4-benzoxazepines (3) gave rise to eight derivatives (5) of the new 2H,6H-1,5,4-benzodioxazocine ring system. Reaction of 9-methoxy-5-methyl-6-phenyl-3,4,5,6- tetrahydro-2H-1,5-benzoxazocine (6) with 3-chloroperoxybenzoic acid gave an unstable N-oxide (7). A Meisenheimer rearrangement product from (7), 10-methoxy-5-methyl-7-phenyl-2,3,4,5-tetrahydro-7 H-1,6,5- benzodioxazonine (8), the first example of this ring system, was isolated directly in moderate yield on oxidation of (6) with cooling. The crystal and molecular structure of (8) has been determined by X-ray crystallographic methods.

N,N-Dialkyl-N′-Chlorosulfonyl Chloroformamidines in Heterocyclic Synthesis. III. Pyrido- and Pyridazo-Fused [1,2,4,6]Thiatriazine Dioxides

2007 ◽  
Vol 60 (2) ◽  
pp. 105 ◽  
Author(s):  
Teresa Cablewski ◽  
Erin J. Carter ◽  
Craig L. Francis ◽  
Andris J. Liepa ◽  
Michael V. Perkins
Keyword(s):  
Heterocyclic Synthesis ◽  
Ring Systems ◽  
Derivatives Of

N,N-Dialkyl-N′-chlorosulfonylchloroformamidines 1 reacted with 2-aminopyridines 2 to give novel pyrido[1,2-b][1,2,4,6]thiatriazine dioxides 3 and pyrido[2,1-c][1,2,4,6]thiatriazine dioxides 4. Reaction of 1 with 3-aminopyridazines 5 afforded pyridazo[3,2-c][1,2,4,6]thiatriazine dioxides 6 and a pyridazo[2,3-b][1,2,4,6]thiatriazine dioxide 7. The compounds 6 and 7 are derivatives of new ring systems.

N,N-Dialkyl-N′-Chlorosulfonyl Chloroformamidines in Heterocyclic Synthesis. IV. 3-Dialkylamino-1,1,8-trioxo-1H-1λ6-pyrano[3,4-e][1,4,3]oxathiazines

2007 ◽  
Vol 60 (2) ◽  
pp. 113 ◽  
Author(s):  
Teresa Cablewski ◽  
Craig L. Francis ◽  
Andris J. Liepa
Keyword(s):  
Heterocyclic Synthesis ◽  
Ring Systems ◽  
Derivatives Of

N,N-dialkyl-N′-chlorosulfonylchloroformamidines 1 reacted regioselectively with 4-hydroxy-2-pyrone derivatives 2 to give 3-dialkylamino-1,1,8-trioxo-1H-1λ6-pyrano[3,4-e][1,4,3]oxathiazines 3. Dichloride 1b reacted regioselectively with 1,3-dimethylbarbituric acid 10 to give 3-diethylamino-5,7-dimethyl-1,1,6,8-tetraoxo-1H-1λ6-pyrimido[5,4-e][1,4,3]oxathiazine 11. The compounds 3 and 11 are derivatives of new ring systems.

N,N-Dialkyl-N'-Chlorosulfonyl Chloroformamidines in Heterocyclic Synthesis. Part VIII. Novel Pyrazolo-Fused Oxathiadiazines and Thiatriazoles

2010 ◽  
Vol 63 (4) ◽  
pp. 659 ◽  
Author(s):  
Craig M. Forsyth ◽  
Craig L. Francis ◽  
Saba Jahangiri ◽  
Andris J. Liepa ◽  
Michael V. Perkins ◽  
...  
Keyword(s):  
Recent Work ◽  
Major Product ◽  
Ring System ◽  
Heterocyclic Synthesis ◽  
Ring Systems ◽  
The Core ◽  
Derivatives Of

N,N-dialkyl-N′-chlorosulfonyl chloroformamidines 1 reacted with pyrazol-3-ones 2 under a variety of conditions to give pyrazolo[2,3-e][1,2,3,5]oxathiadiazine dioxides 3 and pyrazolo[3,2-b][1,4,3,5]oxathiadiazine dioxides 5, and frequently, one or both of pyrazolo[1,2-b][1,2,3,5]thiatriazole 1,1,5-trioxides 4 and 1,1,7-trioxides 6. In all reactions, the pyrazolo[3,2-b][1,4,3,5]oxathiadiazine 5 was the major product, with the pyrazolo[2,3-e][1,2,3,5]oxathiadiazine 3 being a significant product in the absence of base. Prior to our recent work, the core ring systems of compounds 3 and 5 had not been reported and compounds 4 and 6 are new derivatives of a rare ring system.

N,N-Dialkyl-N´-Chlorosulfonylchloroformamidines in Heterocyclic Synthesis. II. Thiazolo-, Thiadiazolo-, and Oxadiazolo-Fused [1,2,4,6]Thiatriazine Dioxides

2005 ◽  
Vol 58 (12) ◽  
pp. 891 ◽  
Author(s):  
Gary D. Fallon ◽  
Craig L. Francis ◽  
Katarina Johansson ◽  
Andris J. Liepa ◽  
Ruth C. J. Woodgate
Keyword(s):  
Heterocyclic Synthesis ◽  
Ring Systems ◽  
Derivatives Of

N,N-dialkyl-N′-chlorosulfonylchloroformamidines 1 were treated with 2-aminothiazoline, 2-aminothiazoles, 2-aminobenzothiazoles, 2-amino-1,3,4-thiadiazoles, and 2-amino-1,3,4-oxadiazoles to give a 6,7-dihydrothiazolo[3,2-b][1,2,4,6]thiatriazine dioxide 3, a 6,7-dihydrothiazolo[2,3-c][1,2,4,6]thiatriazine dioxide 4, thiazolo[3,2-b][1,2,4,6]thiatriazine dioxides 5, [1,2,4,6]thiatriazino[3,2-b]benzothiazole dioxides 7, a [1,2,4,6]thiatriazino[3,4-b]benzothiazole dioxide 8, [1,3,4]thiadiazolo[2,3-c][1,2,4,6]thiatriazine dioxides 10, [1,3,4]thiadiazolo[3,2-b][1,2,4,6]thiatriazine dioxides 11, [1,3,4]oxadiazolo[2,3-c][1,2,4,6]thiatriazine dioxides 13, and [1,3,4]thiadiazolo[3,2-b][1,2,4,6]thiatriazine dioxides 14. Compounds 3, 4, 5, 7, 8, 10, 11, 13, and 14 are derivatives of new ring systems.

scholarly journals Synthesis of new derivatives of 4-(4-methyl-5H-pyrimido[4,5-b][1,4]thiazin-2-yl)morpholine and 4-methyl-2-(piperidin-1-yl)-5H-pyrimido[4,5-b][1,4]thiazine

2017 ◽  
Vol 41 (7) ◽  
pp. 406-407 ◽  
Author(s):  
Azam Karimian ◽  
Hassan Karimian
Keyword(s):  
Acetic Acid ◽  
Glacial Acetic Acid ◽  
The Novel ◽  
Ring Systems ◽  
Thiazine Ring ◽  
Derivatives Of

Several derivatives of the novel 4-(4-methyl-5 H-pyrimido[4,5- b][1,4]thiazin-2-yl)morpholine and 4-methyl-2-(piperidin-1-yl)-5 H-pyrimido[4,5- b][1,4]thiazine ring systems have been synthesised through cyclocondensation of 5-amino-6-methylpyrimidine-4-thiols and the appropriate α-haloketone in glacial acetic acid under reflux.

Fluorinated tricyclic neuroleptics with prolonged action: 8-Methoxy, 8-ethoxy, 8-ethylthio and 8-hydroxy derivatives of 3-fluoro-10-(4-methylpiperazino)-10,11-dihydrodibenzo[b,f]thiepin

1982 ◽  
Vol 47 (5) ◽  
pp. 1382-1391 ◽  
Author(s):  
Jiří Jílek ◽  
Josef Pomykáček ◽  
Jiřina Metyšová ◽  
Miroslav Protiva
Keyword(s):  
Acetic Acid ◽  
Polyphosphoric Acid ◽  
Prolonged Action ◽  
Substitution Reactions ◽  
Methoxy Derivative ◽  
Chloro Derivatives ◽  
Boron Tribromide ◽  
Derivatives Of ◽  
Central Depressant ◽  
Boiling Toluene

Acids IIa-c were prepared by reactions of (4-fluoro-2-iodophenyl)acetic acid with 4-methoxythiophenol, 4-ethoxythiophenol and 4-(ethylthio)thiophenol and cyclized with polyphosphoric acid in boiling toluene to dibenzo[b,f]thiepin-10(11H)-ones IIIa-c. Reduction with sodium borohydride afforded the alcohols IVa-c which were treated with hydrogen chloride and gave the chloro derivatives Va-c. Substitution reactions with 1-methylpiperazine resulted in the title compounds Ia-c out of which the methoxy derivative Ia was transformed by demethylation with boron tribromide to the phenol Id. Compounds Ia-d are very potent neuroleptics exhibiting a clear prolongation of the central depressant and some prolongation of the cataleptic activity.

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