Category: 102236-19-1

Essery, J. M. published the artcileDerivatives of 4-amino- and 4-nitropyridine, HPLC of Formula: 102236-19-1, the publication is Journal of the Chemical Society (1960), 4953-9, database is CAplus.

The following were prepared by conventional procedures. A series of substituted pyridine 1-oxides (substituent given): 3-Et (I), hygroscopic oil, b₁₂ 123-5°, picrate, m. 95°; 3-iso-Pr, b_0.8 120-2°, picrate, m. 125-6°; 3-tert-Bu (Ia), b₁ 132-4°, picrate, m. 143-4°; 3,5-Me₂, b_0.1 116-18°, picrate, m. 135-6°; 2,3,5,6-Me₄, needles, m. 139-40°, picrate, m. 144-5°; and 3-Br, -, picrate, m. 144.5-5.5°. I (24.5 g.), 65 ml. concentrated H₂SO₄ and 34 ml. concentrated HNO₃ were warmed to 50° to initiate reaction, then heated 3.5 hrs. at 90-100°, the whole cooled, neutralized with solid K₂CO₃, filtered, the filtrate extracted with CHCl₃ and the CHCl₃ concentrated gave 19 g. 3-ethyl-4-nitropyridine 1-oxide (II), yellow needles, m. 68-9°. In similar fashion were prepared the following substd. 4-nitropyridine 1-oxides: 3-iso-Pr, m. 138-9°; 3,5-Me₂ (IIa), m. 174-5° (picrate m. 137.5-8.5°); 2,3, 5,6-Me₄ (IIb), m. 115-16° (picrate m. 160-1°); 3-Br, m. 156-7° [small amount of 3,4-Br(O₂N)C₅H₃N also formed]. 3-tert-Butyl-2(or 6-)nitropyridine (IIc) m. 104.5-5.5°. To 5 g. II in 100 ml. dry CHCl₃ at 0-10° was added 25 ml. PCl₃, the whole kept 0.67 hr. at 10° poured on ice, treated with excess NaOH, extracted with CHCl₃, and the CHCl₃ extracts concentrated to give 3.8 g. 3,4-Et(O₂N)C₅H₃N, b_0.25 56-8°. Similarly were prepared 3,4-iso-Pr(O₂N)C₅H₃N, b_0.85 82-4° (picrate m. 106-7°); 3,5,4-Me₂(O₂N)C₅H₂N.0.5.H₂O, m. 38-9° (picrate m. 169-70°); and 2,3,5,6,4-Me₄(O₂N)C₅N.2H₂O, m. 198-200° (picrate m. 174-6°). To 13 g. II was added 60 ml. AcCl; a vigorous reaction occurred. Subsequently, the mixture was poured on ice, the whole treated with excess NaOH and the product isolated via CHCl₃ extraction to give 8.2 g. 4-chloro-3-ethylpyridine 1-oxide (IId), m. 86° (picrate m. 137-8°). The following substituted 4-chloropyridine 1-oxides were similarly prepared: 3-iso-Pr, hygroscopic, m. 87-8° (picrate m. 130-1°); 3,5-Me₂ (III), m. 201-2° (picrate m. 142-3°); 2,3,5,6-Me₄, m. 153-4° (picrate m. 154-5°); 3-Br, m. 153.5-4.5° (picrate m. 120-1°). III (2.5 g.) and 18 ml. concentrated aqueous NH₃ heated 18 hrs. at 140°, the whole cooled, treated with 2.5 g. K₂CO₃, evaporated to dryness and the residue extracted with AcEt gave 1.6 g. 4-amino-3,5-dimethylpyridine 1-oxide-2H₂O (IV), m. 227-9°, picrate m. 221-3°. 3,4-Me(O₂N)C₅H₃N (2.5 g.), 50 ml. EtOH, 4 ml. 90% H₂NNH₂.H₂O, and a small amount of Raney Ni (V) were heated 0.5 hr. on the steam bath, more V added, the whole filtered, and the filtrate concentrated to give 1.2 g. 3,4-Me(H₂N)C₅H₃N, m. 108-9°. This procedure also gave 3,4-Et(H₂N)C₅H₃N.0.5.H₂O, m. 52-3° (picrate m. 196-7°); 3,4-iso-Pr(H₂N)C₅H₃N.0.5.H₂O, m. 69-70° (picrate m. 156-7°). To 0.5 g. IV in 5 ml. AcOH was added 0.3 g. Fe dust, the whole heated 1.5 hrs. on the steam bath, cooled, treated with excess NaOH and the product isolated via Et₂O extraction to give 0.2 g. 3,5,4-Me₂(H₂N)C₅H₂N.2H₂O (VI), m. 83-4° (picrate m. 226-7°). Alternately, 2 g. IIa, 25 ml. MeOH, 2 g. Raney Ni, and H gave 1.1 g. VI; the same procedure with IIb gave the amino derivative hemihydrate m. 196-7° (picrate m. 225-6°). Both reduction procedures with IIc gave the amino derivatives, m. 128-9°, λ 292, 228 mμ (log ε 3.56, 4.9) (picrate m. 242°). IId (3 g.) and 18 ml. 30% aqueous MeNH₂ heated 18 hrs. at 140° gave, as above with IV, 2.1 g. 3-methyl-4-methylaminopyridine 1-oxide (VII), m. 106-7° (picrate m. 184-5°). Similarly were prepared the following substituted 4-methylaminopyridine 1-oxides: 3-Et, b_0.5 120-2°, m. 117-18° (picrate m. 182-3°); 3-iso-Pr (VIII) (no m.p. given) (picrate m. 164-5°); 3,5-Me₂, m. 94.5-5.5° (picrate m. 172-3°); 3-Br, hygroscopic solid (picrate m. 189-91°) and 2,3,5,6-Me₄, hygroscopic solid (picrate m. 140-1°). VII reduced by Fe in AcOH gave 3,4-Me(MeNH)C₅H₃N, m. 125-6° (picrate m. 199-200°). VIII hydrogenated as above gave 3,3-iso-Pr-(MeNH)C₅H₃N, m. 95-6° (picrate m. 159-60°) and this procedure gave the following 3-substituted 4-(MeNH)C₅H₃N derivatives): 3,5-Me₂, m. 119.5-20.5° (picrate m. 194.5-5.5°); 2,3,5,6-Me₄, m. 118-19° (picrate m. 160-1°); 3-Br, 92-3°. The following were prepared by the above procedures: 3,4-Me(Me₂N)C₅H₃N (IX), b₁ 73-5° (picrate m. 172-3°) and IX 1-oxide, b_0.15 142-4° (picrate m. 130-1°); 3,4-Et(Me₂N)C₅H₃N (X), b_0.6 82-3° (picrate m. 118-19°) and X 1-oxide, b₁ 178-80° (picrate m. 139-40°); 3,4-iso-Pr-(Me₂N)C₅H₃N (XI), b_0.45 79-80° (picrate m. 138-9°) and XI 1-oxide, – (picrate m. 151-2°); 3,5,4-Me₂(Me₂N)C₅H₂N (XII), b_0.4 69-7° (picrate m. 172-3°) and XII 1-oxide m. 83-4° (picrate m. 115-16°); and 3,4-Br(Me₂N)C₅H₃N (XIII), b_0.5 82-4° (picrate m. 182-3°) and XIII 1-oxide, – (picrate m. 160-1°). Ia (3.5 g.) and SO₂Cl₂ heated 2 hrs. at 110-20° gave 2 products, C₉H₁₂ClN, giving picrates, m. 152-3° and 149-50°.

Journal of the Chemical Society published new progress about 102236-19-1. 102236-19-1 belongs to pyridine-derivatives, auxiliary class Pyridine,Chloride, name is 5-(tert-Butyl)-2-chloropyridine, and the molecular formula is C9H12ClN, HPLC of Formula: 102236-19-1.

Referemce:
https://en.wikipedia.org/wiki/Pyridine,
Pyridine | C5H5N – PubChem

Pelchowicz, Zvi published the artcileSubstituted tryptamines and their derivatives, HPLC of Formula: 102236-19-1, the publication is Journal of the Chemical Society (1960), 4699-701, database is CAplus.

o-MeC₆H₄NH₂ (21.3 g.), 54 ml. concentrated HCl, and 236 ml. H₂O diazotized with 15 g. NaNO₂, 10% aqueous Na₂CO₃ added at 0° to bring the pH to 5-6, the whole filtered, added to 34 g. Et 2-oxopiperidine-3-carboxylate (I), 400 ml. H₂O, and 12 g. KOH (kept 24 hrs. at room temperature before use), the pH adjusted to 34 with AcOH, and the whole kept 48 hrs. at 0° gave 35 g. 3-(o-tolyl)hydrazone of 2,3-dioxopiperidine (II), m. 140.0-40.5° (aqueous alc.). 3-(p-Tolyl)hydrazone of 2,3-dioxopiperidine (III) was similarly obtained, 81%, m. 209-9.5°. Crude II (45 g.), 200 ml. AcOH, and 100 ml. concentrated HCl refluxed 1 hr., cooled, and diluted with H₂O gave 28.8 g. 1,2,3,4-tetrahydro-8-methyl-1-oxo-β-carboline (IV), m. 228.5-29° (aqueous alc.); III similarly gave 83% 6-Me analog of IV, m. 187.5-8.5° (aqueous alc.). III (28 g.), 260 ml. alc., and 260 ml. 4N aqueous KOH refluxed 1 hr., concentrated to half volume, diluted with 250 ml. H₂O, and neutralized with AcOH gave 24 g. 7-methyltryptamine-2-carboxylic acid (V), m. 278-81°; the 5-Me analog (VI) of V was obtained similarly, 83%, m. 267-7.5° (decomposition). V (10.5 g.) and 400 ml. 5% HCl refluxed until CO₂ evolution ceased, the whole cooled, and neutralized with NaOH gave 7.2 g. 7-methyltryptamine (VII), purified by sublimation, m. 130-1°; 5-methyltryptamine, obtained in 76% yield from VI, m. 99-9.5° (Et₂O-petr. ether). Diazotized 5,2-FMeC₆H₃NH₂ and I as above gave 72% 5-F derivative (VIII) of II, m. 204.5-5.0°, and VIII was used as above to obtain 73% 5-F derivative of IV, m. 204.5-5.0° (aqueous alc.), 80% 4-F derivative of V, m. 273° (decomposition) (H₂O), and 4-F derivative of VII, m. 141-2° (after sublimation). VIII (5 g.), 100 ml. 10% aqueous AcH, 16 ml. 2N H₂SO₄, and 100 ml. H₂O heated 0.33 hr. at 110°, cooled, and treated with excess alkali gave 4.9 g. 6-fluoro-1,2,3,4-tetrahydroharmaline, m. 201-2° (by sublimation) (L.D.₅₀ 600 mg./kg. in mice). VIII (5.74 g.), 1 g. NaHCO₃, and 25 ml. Ac₂O refluxed 0.25 hr., poured into H₂O, the whole treated with excess Na₂CO₃, and extracted with Et₂O gave 5.5 g. N^α-Ac derivative (IX), m. 127.5-8.0° (Et₂O-petr. ether). To 5 g. IX in 200 ml. hot xylene was added in small portions 50 g. P₂O₅; the whole refluxed 2 hrs., the solid filtered off and added in small portions to 500 ml. 5% HCl, the whole heated at 80°, filtered, the filtrate cooled, treated with excess alkali and extracted with Et₂O gave 6-fluoro-3,4-dihydroharmaline, m. 206-7° (aqueous alc.).

Journal of the Chemical Society published new progress about 102236-19-1. 102236-19-1 belongs to pyridine-derivatives, auxiliary class Pyridine,Chloride, name is 5-(tert-Butyl)-2-chloropyridine, and the molecular formula is C9H12ClN, HPLC of Formula: 102236-19-1.

Referemce:
https://en.wikipedia.org/wiki/Pyridine,
Pyridine | C5H5N – PubChem