Heterocyclic studies. 45. Thermal isomerization of a 1,2-diazepine to a 1,3-diazepine

Moore, James A.; Freeman, Walter; Gearhart, Richard C.; Yokelson, Howard B.

doi:10.1021/jo00398a079

Cited by 5 publications

(6 citation statements)

References 6 publications

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“…, 109 (10), 108 (7), 95 (9), 94 (13), 93 (17), 92 (5), 83 (7), 82 (8), 81 (43), 80 (7), 72 (35), 71 (5), 69 (10), 68 (28), 67 (100), 66 (11), 56 (17), 55 (12), 54 (12), 53 (10), 44 (11), 42 (10), 41 (12), 39 (18). HRMS, calcd.…”

Section: 6-bis(trifluoromethyl)-2-methoxy-1h-13-diazepine 4kunclassified

“…1 H NMR (400 MHz, CDCl 3 ) δ 6.27 (t, 1 H, 4-H, J 4,5 = 5.2 Hz), 4.90 (t, 1 H, 6-H, J 5,6 = 6.7 Hz), 3.95 (br, 2 H, iPr 2 ), 1.65 (br, 2 H, 5-H), 1.11 (br, 12 H, iPr); the assignments were confirmed by homonuclear decoupling experiments; 13 C NMR (100 MHz, CDCl 3 ) δ 158.0 (2-C), 157.6 (4-C), 147.7 (4-C), 141.7 (q, 7-C, J C,F = 31.6 Hz), 123.0 (q, CF 3 , J C,F = 273 Hz), 95.9 (q, 6-C, J C,F = 3.4 Hz), 46.0 (iPr 2 ), 31.5 (5-C), 20.6 (iPr); IR (neat) 2974 m, 2956 w, 2935 w, 1622 m, 1595 vs, 1542 w, 1520 w, 1511 w, 1487 w, 1472 w, 1398 w, 1370 m, 1322 w, 1301 s, 1206 m, 1164 s, 1118 s, 1071 w, 1021 w, 1008 w, 956 w, 839 w, 757 w, 697 w, 672 w cm Ϫ1 . MS (EI) m/z 261 (M ϩ , 49%), 242 (11), 218 (100), 203 (12), 201 (8), 175 (64), 161 (14), 150 (10), 149 (38), 148 (6), 126 (33), 117 (10), 107 (12), 83 (11), 69 (7), 58 (12)…”

Section: -Diisopropylamino-7-trifluoromethyl-5h-13-diazepine 16ementioning

confidence: 99%

“…Yield: 61%, mp 118-119 ЊC. (8), 153 (9), 152 (13), 139 (6), 138 (7), 125 (10), 110 (14), 109 (54), 97 (17), 90 (12), 83 (15), 82 (23), 72 (36), 70 (31), 69 (17), 65 (59), 64 ( 22), 63 (17), 58 (25) 56 (17), 55 (14), 54 (18), 45 (20), 44 (17), 32 (17), 30 (18). HRMS, calcd.…”

Section: 2-dihydro-4-diethylamino-5h-13-diazepin-2-one 22bbmentioning

confidence: 99%

“…13 C NMR (100 MHz, acetone-d 6 ), 163.5 (3-C), 125.3 (q, CF 3 , J C,F = 275 Hz), 124.9 (q, CF 3 , J C,F = 275 Hz), 50.4 (q, 1-or 5-C, J C,F = 3 Hz), 48.7 (q, 5-or 1-C, J C,F = 4 Hz), 46.2 (q, 6-or 7-C, J C,F = 26 Hz), 39.8 (q, 7-or 6-C, J C,F = 27 Hz), DEPT-135 indicated protonated carbons at 50.4, 48.7, 46.2 and 39.8 ppm. IR (KBr) 3265 br (N-H ), 1710 vs, 1661 vs, 1455 m, 1413 m, 1361 s, 1319 s, 1300 w, 1265 m, 1249 vs, 1235 m, 1211 vs, 1202 s, 1166 s, 1135 s, 1124 m, 1094 vs, 953 w, 928 w, 845 w, 798 w, 738 w cm Ϫ1 ; MS (EI) m/z 249 (M ϩ ϩ 1, < 1%), 229 (1), 111 (6), 95 (4), 91 (3), 84 (100), 69 (10), 56 (20), 28 (17), MS (CI) m/z 249 (M ϩ ϩ 1, 100%), 85 (3) A solution of 2-azido-6-trifluoromethylpyridine 7A (100 mg; 0.47 mmol) in 100 ml of dioxan and 5 ml of diisopropylamine was photolysed for 12 h. Evaporation of the solvent gave a yellow oil, purified by distillation at 45-50 ЊC/0.5 mbar.…”

Section: 2-dihydro-4-diethylamino-5h-13-diazepin-2-one 22bbmentioning

confidence: 99%

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1H-1,3-Diazepines, 5H-1,3-diazepines, 1,3-diazepinones, and 2,4-diazabicyclo[3.2.0]heptenes,

Reisinger

Koch²,

Bernhardt

et al. 2004

Org. Biomol. Chem.

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Tetrazolo[1,5-a]pyridines/2-azidopyridines 1 undergo photochemical nitrogen elimination and ring expansion to 1,3-diazacyclohepta-1,2,4,6-tetraenes 3, which react with alcohols to afford 2-alkoxy-1H-1,3-diazepines 4 (5), with secondary amines to 2-dialkylamino-5H-1,3-diazepines 16, sometimes via isolable 2-dialkylamino-1H-1,3-diazepines 15, and with water to 1,3-diazepin-2-ones 19. The latter are also obtained by elimination of isobutene or propene from 2-tert-butoxy- or 2-isopropoxy-1H-1,3-diazepines 4 or 5. 1,3-Diazepin-2-one 22B and 1,3-diazepin-4-one 24 were obtained from hydrolysis of the corresponding 4-chlorodiazepines. Diazepinones 19 undergo photochemical ring closure to diazabicycloheptenones 25 in high yields. The 2-alkoxy-1H-1,3-diazepines 4 and 5 interconvert by rapid proton exchange between positions N1 and N3. The free energies of activation for the proton exchange were measured by the Forsén-Hoffman method as DeltaG([double dagger])298= 16.2 +/- 0.6 kcal mol(-1) as an average for 4a-c in CD2Cl2, acetone-d6, and methanol-d4, and 14.1 +/- 0.6 kcal mol(-1) for in 4c acetone/D2O. The structures of 2-methoxy-5,6-bis(trifluoromethyl)-1H-1,3-diazepine 4k, 1,2-dihydro-4-diethylamino-5H-1,3-diazepin-2-one 22bB, and diazabicycloheptanone were 26 determined by X-ray crystallography. The former represents the first reported X-ray crystal structure of any monocyclic N-unsubstituted 1H-azepine.

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Section: 6-bis(trifluoromethyl)-2-methoxy-1h-13-diazepine 4kunclassified

Section: -Diisopropylamino-7-trifluoromethyl-5h-13-diazepine 16ementioning

confidence: 99%

Section: 2-dihydro-4-diethylamino-5h-13-diazepin-2-one 22bbmentioning

confidence: 99%

Section: 2-dihydro-4-diethylamino-5h-13-diazepin-2-one 22bbmentioning

confidence: 99%

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1H-1,3-Diazepines, 5H-1,3-diazepines, 1,3-diazepinones, and 2,4-diazabicyclo[3.2.0]heptenes,

Reisinger

Koch²,

Bernhardt

et al. 2004

Org. Biomol. Chem.

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“…This intermediate 142 may also be the precursor of 2aminopyridine derivatives 144 isolated with certain Nheterocycles. A similar type of intermediate 146 and an aminimide (170) are considered to be intermediates in the thermal conversion of a 1,2-diazepine (145) (147) (114).…”

Section: Rc6h4ch=nn(ch3)3mentioning

confidence: 99%

Chemistry of Aminimides

Wawzonek¹

1980

Ind. Eng. Chem. Prod. Res. Dev.

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The period 1972-1979 saw considerable activity in research of the chemistry and utilization of aminimides. Studies have extended investigation to aminimides in which the acyl group is derived from imino acids, cyanuric acid, phosphonic acids, and picric acid and to vinylogues of aminimides. Work continued with aminimides derived from nitrogen heterocycles and their conversion to diazepines and bridged nitrogen bicyclic compounds. Commercial utilization of aminimides based on 1,1dimethylhydrazine has been hampered in this country by the loss of the sole commercial source of this compound.

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ChemInform Abstract: HETEROCYCLIC STUDIES. 45. THERMAL ISOMERIZATION OF A 1,2‐DIAZEPINE TO A 1,3‐DIAZEPINE

Moore¹,

Freeman²,

Gearhart³

et al. 1978

Chemischer Informationsdienst

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Heterocyclic studies. 45. Thermal isomerization of a 1,2-diazepine to a 1,3-diazepine

Cited by 5 publications

References 6 publications

1H-1,3-Diazepines, 5H-1,3-diazepines, 1,3-diazepinones, and 2,4-diazabicyclo[3.2.0]heptenes,

1H-1,3-Diazepines, 5H-1,3-diazepines, 1,3-diazepinones, and 2,4-diazabicyclo[3.2.0]heptenes,

Chemistry of Aminimides

ChemInform Abstract: HETEROCYCLIC STUDIES. 45. THERMAL ISOMERIZATION OF A 1,2‐DIAZEPINE TO A 1,3‐DIAZEPINE

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