Journal of the American Chemical Society published new progress about 4543-95-7. 4543-95-7 belongs to alcohols-buliding-blocks, auxiliary class Amine,Aliphatic hydrocarbon chain,Alcohol, name is 4-(Butylamino)butan-1-ol, and the molecular formula is C8H19NO, Recommanded Product: 4-(Butylamino)butan-1-ol.
Corey, E. J. published the artcileA study of the formation of halo amines and cyclic amines by the free radical chain decomposition of N-haloammonium ions (Hofmann-Löffler reaction), Recommanded Product: 4-(Butylamino)butan-1-ol, the publication is Journal of the American Chemical Society (1960), 1657-68, database is CAplus.
cf. Wawzonek and Thelen, CA 44, 9444g; W., et al., CA 46, 2058a. Cyclization of N-halo amines to pyrrolidines by heating in H2SO4 was a free-radical chain reaction which was initiated by ultraviolet light or by persulfate and (or) ferrous ions and was inhibited by O. The reaction was acid-catalyzed; the acid most likely accelerated chain-propagation or retarded chain-termination. Five-membered rings were formed almost exclusively. The ease of removal of H from the δ-C involved was tertiary > secondary > primary; there was virtually no competition when different types were present. No pyrrolidines were obtained when the δ-H was tertiary; solvolysis of the intermediate δ-Cl amine apparently predominated. Irradiation of dibutylchloramine in H2SO4 did not liberate Cl ion, indicating that a δ-Cl amine was an intermediate. The exptl. data support the Wawzonek mechanism (loc. cit.). For isotope effect and stereochem. studies, some deuteriated amines were synthesized. Valerolactone [66.2% L-(-)isomer, 33.8% D(+)-isomer] (26 g.) and liquid MeNH2 under N for 7 days in a sealed tube gave 100% crude N-methyl-4-hydroxyvaleramide (I), which with LiAlH4 gave 39% N-methyl-4-hydroxyamylamine (II), b8 97-8°, n25D 1.4460, [α]22D 4.23° (c 10, EtOH). II and p-MeC6H4SO2Cl in pyridine gave 82% (-)-N-methyl-N-(4-p-toluenesulfonoxyamyl)-p-toluenesulfonamide (III), [α]20D -2.73° (c 10, CHCl3). Reduction of III with LiAlD4 gave 73% (-)-methylamylamine-4-d (IV), n25D 1.4068, α20D -0.135 ± 0.03° (1 dm.). Cyclization of IV (Coleman, et al., Organic Syntheses Collective volume III, 159(1955)) gave 43% optically inactive 1,2-dimethylpyrrolidine; analysis of the picrate showed 4.88 atom-% D, corresponding to an isotope effect (kH/kD) of 3.54 ± 0.5. As a check on the anal. data, 1,2-dimethylpyrrolidine-2-d (V) was synthesized and the isotope effect determined from infrared absorption. 1,2-Dimethyl-2-pyrroline (30 g.), neutralized with 3N HCl and treated with aqueous KCN gave 79% 1,2-dimethyl-2-cyanopyrrolidine (VI), b36 83-4°, n22.5D 1.4447; picrate m. 154.5-6.5° (C6H6EtOH). Reduction of VI with LiAlD4 gave 72% V, b. 94-5°, n25D 1.4203. From the absorption band at 2040 cm.-1, the amount of V present in the product from cyclization of IV was determined, giving an isotope effect of 3.42 ± 0.5. N-Butyl-2-pyrrolidone was hydrolyzed with Ba(OH)2 to 4-butylaminobutyric acid, m. 145-6° (MeOH-Et2O), which on reduction with LiAlD4 gave 36% 4-butylaminobutanol-1,1-d2 (VII), b16 131-2°, n24.5D 1.4508. VII was converted to N-butyl-N-(4-p-toluenesulfonoxybutyl)-p-toluenesulfonamide-4,4-d2 (oil), which on reduction with LiAlD4 gave 66% dibutylamine-4,4-d3 (VIII), b46 76-7°; HCl salt m. 292-6° (decomposition). Cyclization of VIII after chlorination gave N-butylpyrrolidine, b55 75°; the infrared absorption showed bands corresponding to N-CD2– and C-CD3 groups. The isotope effect for this cyclization, calculated from infrared absorption, was approx. 2.6. Other amine derivatives synthesized for study were as follows. Isocaproyl chloride and amylamine gave 78% N-amylisocaproamide, b0.35 103-5°, n22D 1.4481, which on reduction with LiAlH4 gave amylisohexylamine, b16 99-102°, n22D 1.4295, yield 81%; HBr salt m. 291-2.5° (decomposition) (dioxane-EtOH). Attempted cyclization of the N-Cl derivative gave no tertiary amines. Similar failure was experienced with butyl-sohexylamine, although HCl was evolved during heating. The product amounted to 0.147 g., b14 about 75°, n21.8D 1.4378; HBr salt (IX) m. 162-4° (dioxane). IX was not identical with N-butyl-2,2-dimethylpyrrolidine-HBr nor with N-isohexylpyrrolidine-HBr, which was prepared for comparison by LiAlH4 reduction of N-isocaproylpyrrolidine [N-isohexylpyrrolidine b15 79-82°, n25D 1.4428; HBr salt m. 179-80° (dioxane)].
Journal of the American Chemical Society published new progress about 4543-95-7. 4543-95-7 belongs to alcohols-buliding-blocks, auxiliary class Amine,Aliphatic hydrocarbon chain,Alcohol, name is 4-(Butylamino)butan-1-ol, and the molecular formula is C8H19NO, Recommanded Product: 4-(Butylamino)butan-1-ol.
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