Compound(52287-51-1)Reference of 6-Bromo-2,3-dihydrobenzo[b][1,4]dioxine received a lot of attention, and I have introduced some compounds in other articles, similar to this compound(6-Bromo-2,3-dihydrobenzo[b][1,4]dioxine), if you are interested, you can check out my other related articles.
The reaction of an aromatic heterocycle with a proton is called a protonation. One of articles about this theory is 《Derivatives of 1,4-benzodioxan. I. Some halogenated 1,4-benzodioxans and amino and nitro derivatives thereof》. Authors are Heertjes, P. M.; Knape, A. A.; Talsma, H.; Andriesse, P..The article about the compound:6-Bromo-2,3-dihydrobenzo[b][1,4]dioxinecas:52287-51-1,SMILESS:BrC1=CC=C2OCCOC2=C1).Reference of 6-Bromo-2,3-dihydrobenzo[b][1,4]dioxine. Through the article, more information about this compound (cas:52287-51-1) is conveyed.
6-Bromo-1,4-benzodioxan (I), b23 153-4°, was obtained in 60% yield by the method of Ghosh (C.A. 10, 455). I (18.35 g.) in 25 ml. H2O treated dropwise at 60° with 5.5 ml. HNO3 (d. 1.52) gave 60% 6-bromo-7-nitro-1,4-benzodioxan (II), m. 171.9-2.1°. 6-Amino-7-nitro-1,4-benzodioxan (III) (5 g.) in 10 ml. concentrated H2SO4 and 25 ml. H2O diazotized at 20° with 1.75 g. NaNO2 in 3 ml. H2O, then refluxed 3 hrs. with 1.6 g. CuSO4, 0.5 g. Cu turnings, 4 g. NaBr.2H2O, 2 ml. concentrated H2SO4, and 25 ml. H2O gave 60% II. II (2.85 g.) treated at 0° with 12 ml. HNO3 and left 2 hrs. at room temperature yielded 3 g. (80%) crude 6-bromo-5(?),7,8(?)-trinitro-1,4-benzodioxan (IV), m. 248.2-8.6° after crystallization from EtOH-HOAc (1:1) and iso-BuOH. II (5 g.) subjected to cathodic reduction yielded 24% 6-amino-7-bromo-1,4-benzodioxan (V) as the HCl salt (1.25 g.). 6-Acetamido-7-bromo-1,4-benzodioxan (VI) (1.02 g., 80%), m. 179.1-9.4°, was prepared from V.HCl by acetylation for 15 min. with NaOAc and Ac2O in a small amount of H2O. 6-Acetamido-1,4-benzodioxan (VIA) (11.2 g.) was brominated to 14 g. (89%) VI. II (10 g.) reduced, extracted, refluxed 15 min. with concentrated HCl and EtOH, diluted, made alk. with NaOH, extracted with C6H6, and HCl, gas passed into the extract precipitated 6.4 g. (70%) V.HCl. 1,4-Benzodioxan (VII) (300 g.) brominated overnight with Br in HOAc yielded 518 g. (80%) 6,7-dibromo-1,4-benzodioxan (VIII), m. 139.6-40.0°. V.HCl (5 g.) diazotized and treated with refluxing Cu2Br2 gave 3.5 g. (63%) crude VIII. The mother liquor after separation of VIII from VII gave 5(?),6,7,8(?)tetrabromo-1,4-benzodioxan (IX), m. 212.8-13.4°. VIII (297 g.) on nitration gave 361 g. (93%) crude 6,7-dibromo-5,8-dinitro-1,4-benzodioxan (X); recrystallized, it m. 318-19°. When 80 g. X was heated with 600 g. SnCl2.2H2O in 600 ml. concentrated HCl and 600 ml. EtOH, a rapid endothermic reaction occurred at 60°, and when the temperature was kept at 60-70° the reaction was complete in 30 min.; working up gave 41.5 g. (84%) 5,8-diamino-1,4-benzodioxan (XI) as the HCl salt; alternatively, the free XI m. 99.1-9.7° was isolated, XI with excess Ac2O gave 64% di-Ac derivative (XII), m. 287-9°; 1 mole Ac2O gave the mono-Ac derivative (XIII), m. 141.2-1.9°. XIII yields azo dyes. VII (76 g.) in 200 ml. HOAc treated with Cl at 10-20° yielded 80.7 g. (71%) 6,7-dichloro-1,4-benzodioxan (XIV), m. 150.6-1.1°. 4,5-Dichloropyrocatechol (7.5 g.) and 75 g. (CH2Br)2 in 50 ml. (CH2OH)2, heated at 140° and treated with anhydrous K2CO3 until the mixture no longer gave a blue color with FeCl3 (3-4 hrs.), afforded 6.8 g. (70%) XIV. Nitration of XIV gave 84% 6,7-dichloro-5,8-dinitro-1,4-benzodioxan (XV), m. 287.78.6°, which, reduced with SnCl2 and HCl in EtOH and acetylated in C6H6 at 50°, gave 5,8-diacetamido-6,7-dichloro-1,4-benzodioxan (XVI), m. 299.0-300.3° (decomposition). Alternatively, HCl was passed into a mixture of 50 g. SnCl2.2H2O in 100 ml. HOAc and heated with 5 g. XV; at 60° reaction set in with a rise in temperature to 90°, and was complete in 1 hr., yielding 5,8-diamino-6,7-dichloro-1,4-benzodioxan (XVII), decompose 137-40°, slowly oxidizes in air. The HCl salt of 6-amino-1,4-benzodioxan (XVIII) (39 g.) in 65 ml. H2O and 65 ml. concentrated HCl diazotized at 0° with 18 g. NaNO2 in 40 ml. H2O and the solution added to 30 g. Cu2Cl2 in 100 ml. concentrated HCl and heated at 70°, gave 26 g. (76%) 6-chloro-1,4-benzodioxan (XIX), b3 98-100°. XIX (5 g.) nitrated with HNO3-H2SO4 at 15° and the product crystallized from Me2CO-HOAc (1:1) gave 4.5 g. (73%) 6-chloro-7-nitro-1,4-benzodioxan (XX), m. 161.7-2.1°, also prepared by diazotization of III and then treatment with Cu2Cl2. VIA (20.4 g.) in 100 ml. HOAc, treated with 1.9 g. Cl in 50 ml. HOAc, the solution added to H2O and the product crystallized from 50% aqueous Me2CO gave 6-acetamido-7-chloro-1,4-benzodioxan (XXI), m. 171.7-2.4°. Hydrogenation of 4 g. XX in EtOH in the presence of Raney Ni at room temperature, filtration, and acidification with HCl gave 4 g. (97%) of the HCl salt of 6-amino-7-chloro-1,4-benzodioxan (XXII); acetylation gave a crude yield of 86% crude XXI, converted into the HCl salt of XXII.HCl by refluxing with 1:1 EtOH-concentrated HCl.
Compound(52287-51-1)Reference of 6-Bromo-2,3-dihydrobenzo[b][1,4]dioxine received a lot of attention, and I have introduced some compounds in other articles, similar to this compound(6-Bromo-2,3-dihydrobenzo[b][1,4]dioxine), if you are interested, you can check out my other related articles.
Reference:
Pyrazole – Wikipedia,
Pyrazoles – an overview | ScienceDirect Topics