1,3-Benzenediol, 4,6-diamino-, hydrochloride (1:2)

grey-brown crystalline solid

General procedure: Under the condition that the molar ratio of phosphorus pentoxide/methanesulfonic acid/hydroxylamine hydrochloride/acetic acid/resorcinol is 0/4/2/2/1 at 100 ° C, 4, 6-diaminoresorcinol hydrochloride was prepared in one pot.Resorcinol (5.50 g) and acetic acid (6.00 g) were weighed into a 100 mL three-necked flask, and 13 mL (0.2 mol) of methanesulfonic acid was added thereto, stirred and dissolved, and the temperature was raised to 100 ° C for 2 hours.Then, hydroxylamine hydrochloride (7.00 g) was gradually added thereto.Then, the reaction was continued for 4 hours, and then hydrochloric acid (6 mol/L, 40 mL) was further added thereto, and stirring was continued at 100 ° C, and the reaction was allowed to cool for 2 hours.The crystals were precipitated, suction filtered, washed with hydrochloric acid, washed with ethanol, and dried in vacuo to give 4, 6-diaminoresorcinol hydrochloride in a yield of 5.0percent.EXAMPLE 6 The 100g (0.426mol) of 2-chloro-4, 6-dinitroresorcin, 1g of 5wtpercent palladium on carbon catalyst, 1500mL of ethanol, and purified water was added 300mL hydrogenation reactor of 5L purged with nitrogen three times and then pass into the hydrogen, the hydrogen pressure was kept at 0.3 ~ 0.4MPa, temperature control in 30 ~ 40 °C, the reaction 2h, HPLC control to the disappearance of starting material. 22g was then added at a concentration of 25wtpercent (0.157mol) of concentrated aqueous ammonia, the hydrogen pressure was kept at 0.2 ~ 0.3MPa, warmed to 60 ~ 70 °C reaction 3h, HPLC control sample to the intermediate 2-chloro-4, 6- amino resorcinol disappear. the material pressure to hydrochloric acid solution, and filtered to give 4, 6-diamino dihydrochloride crude, recrystallized 69g of a white solid 4, 6-diamino resorcinol dihydrochloride boutique, purity of 99.74percent, a yield of 75.9percent.EXAMPLE 3 In a 250 mL four-necked flask, 12.0 g (0.0536 mol) of 4, 6-bis[(1Z)-N-hydroxyethylimino)benzene-1, 3-diol, 50 g of polyphosphoric acid (PPA), 32mL glacial acetic acid, stirring, slowly warming to 70 C reaction for 0.5h time, after the second hydrazine is completely dissolved, the temperature is controlled at about 90 C, after 3 hours of reaction, cooling, adding 1.35g SnCl2 · 2H2O, 10mL H2O, 20mL concentrated hydrochloric acid, heating up to 120 C, reflux for 2 h. Filter after cooling, The obtained filter cake was dissolved by heating with an appropriate amount of water, and filtered while hot to remove impurities. Concentrated hydrochloric acid was added dropwise to the filtrate until the precipitate was completely precipitated, and filtered to obtain 4, 6-diaminoresorcin hydrochloride (DAR·HCl) hydrochloride, which was dried under vacuum at 50 C for 24 hours to obtain 8.2 g (0.0387). Mol) white crystals with a yield of 69.5%.In a 250 mL four-necked flask, 14 g of KOH, 50 mL of C2H5OH and 5 mL of H2O were sequentially added, and 15 g of CS2 was added dropwise thereto, and reacted at room temperature for 1 hour to gradually precipitate a pale yellow solid, which was filtered and dried to obtain potassium ethyl xanthate (C2H5OCS2-K+). ). In a 250 mL four-necked flask, 4.26 g (0.02 mol) of DAR·HCl, 10 mL of H 2 O, and 20 mL of CH 3 OH were sequentially added. After the DAR·HCL was substantially dissolved, 16 g of a 15% KOH solution was further added.After magnetic stirring, the reaction was carried out for 20 min at room temperature, and a solution of potassium ethyl xanthate in methanol (3.2 g of C2H5OCS2-K+ dissolved in 20 mL of CH3OH) was added dropwise to a four-necked flask, and the mixture was refluxed for 8 hours. After the reaction is completed, the solvent is distilled off under reduced pressure.Add water to dissolve, adjust pH 2-3 with dilute hydrochloric acid, filter, dry to obtain a purple-red solid, and then purify the product by column chromatography (eluent is methanol: dichloromethane = 1:40 (volume ratio)), weigh 2.85 g ( 0.0127 mol), the yield was 63.6%.

Molecular Weight:213.06
Hydrogen Bond Donor Count:6
Hydrogen Bond Acceptor Count:4
Exact Mass:212.0119330
Monoisotopic Mass:212.0119330
Topological Polar Surface Area:92.5
Heavy Atom Count:12
Complexity:108
Covalently-Bonded Unit Count:3
Compound Is Canonicalized:Yes