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With triethylamine; In N-methyl-acetamide; water; ethyl acetate;
b. Diethyl (4,6-dichloro-m-phenylene)dioxamate To a solution of 31.9 gm. (0.18 mole) of 1,3-diamino-4,6-dichlorobenzene in 75 ml. of dry dimethylformamide is added 300 ml. of dry ethyl acetate and 43.6 gm. (0.432 mole) of triethylamine. The resulting solution is cooled to 0 in an ice-bath. To the stirred solution is added dropwise 59.0 gm. (0.432 mole) of ethyl oxalyl chloride, keeping the temperature below 15. The mixture is stirred in the ice-bath for 1 hour and then allowed to stand at room temperature for 48 hours. Most of the solvents are removed by distillation under reduced pressure. The residue is poured into 1 liter of cold water. The precipitate is removed by filtration and recrystallized from ethanol. There is obtained 55.3 gm. (81%) of long colorless needles melting at 124-5. Analysis Calc'd. for: C14 H14 Cl2 N2 O6 C, 44.58; H, 3.74; Cl, 18.80; N, 7.43. Found: C, 44.67; H, 3.75; Cl, 18.90; N, 7.74.
Preparation of B-5a:A solution of 2,4-dichloro-5-amino-aniline (4.1 g, 23.2 mmol) in DMF (50 mL) is combined with potassium-ethylxanthogenate and stirred for 3 days at 150 0C. After cooling to RT the mixture is diluted with ice water and acidified with aqueous HCl. The precipitate is filtered off and dried in vacuo until a constant weight is obtained. The title compound is used in the next reaction without further purification (HPLC tRet = 3.9 min; MS [M+H]+: m/z = 261).
(c) N-(3-Amino-4,6-dichlorophenyl)-γ-chlorobutyramide 14.1 g (0.10 mol) of γ-chlorobutyryl chloride in 50 ml of chloroform are added dropwise in the course of 1 hour, at 10-15 C., to a solution of 17.7 g (0.10 mol) of 1,3-diamino-4,6-dichlorobenzene and 8.7 g (0.11 mol) of pyridine in 500 ml of chloroform. The mixture is then stirred for 2 hours at room temperature, the solution is washed with water and filtered through 40 g of silica gel and the filtrate is concentrated. The resulting product is recrystallized from hexane/toluene. Yield: 13.5 g; melting point 125-128 C.
With hydrogen;Raney nickel; In methanol; under 760.051 Torr; for 18h;
A solution of 1 ,5-dichloro-2,4-dinitrobenzene (1.08 g, 4.56 mmol) in methanol (50 ml_) was stirred with Raney nickel (-0.1 g) under hydrogen at room pressure for 18 h, then the hydrogen flushed out with nitrogen and the mixture filtered through a micropore filter. The solvent was removed under reduced pressure to give the title compound (0.810 g, 100%). 1 H NMR (400MHz, DMSOd6) delta 5.13 (br s, 4H), 6.21 (s, 1 H), 6.99 (s, 1 H).
95%
In acetonitrile;
D-2; 4,6-Dichloro-benzene-1,3-diamine 4,6-Dichloro-benzene-1,3-diamine (D-2) was synthesized following the general scheme above starting from 1,5-dichloro-2,4-dinitro-benzene. Yield (95%). HPLC ret. time 1.88 min, 10-99% CH3CN, 5 min run; ESI-MS 177.1 m/z (MH+).
95%
With tin(II) chloride dihdyrate; In ethanol;
General procedure: 4,6-Dichloro-benzene-1,3-diamine (D-2) was synthesized following the general scheme above starting from 1,5-dichloro-2,4-dinitro-benzene. Yield (95%). HPLC ret. time 1.88 min, 10-99% CH3CN, 5 min run; ESI-MS 177.1 m/z (MH+).
In 1,4-dioxane;
(b) 1,3-Dichloro-4,6-diaminobenzene 87.0 g (0.37 mol) of 1,3-dichloro-4,6-dinitrobenzene are dissolved in 1.5 liters of dioxane and, after adding a total of 100 g of Raney Ni, hydrogenated at 40 to 80 C. The catalyst is filtered off and washed with dioxane and the filtrate is concentrated. The product obtained in this way is recrystallized from hexane/toluene. Yield: 40.6 g; melting point 138-141 C.
a. 1,3-Diamino-4,6-dichlorobenzene To a solution of 399 gm. (1.77 mole) of stannous chloride dihydrate in 975 ml. of concentrated hydrochloric acid is added 60 gm. (0.258 mole) of 1,5-dichloro-2,4-dinitrobenzene. The temperature rises to 72 and a solution occurs. The mixture is allowed to cool to room temperature and then cooled in an ice-bath (to 5). A cold 50% solution of sodium hydroxide is added, with cooling, until the mixture is strongly basic. The mixture is filtered and the precipitate on the funnel washed four times with 500 ml. portions of ethyl acetate. The ethyl acetate extracts are combined, dried over anhydrous M9 SO4 and the solvent removed. The residue is recrystallized from 50% ethanol-water. There is obtained 31.9 gm. (70%) of colorless needles melting at 142-3.
2-[(5-amino-2,4-dichlorophenyl)amino]-1,3-thiazol-4(5H)-one[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
69%
In ethanol; for 5.0h;Heating / reflux;
A mixture of 4,6-dichloro-1 ,3-benzenediamine (0.684 g, 3.86 mmol) and2-(methylthio)-1,3-thiazol-4(5H)-one (0.294 g, 2.00 mmol) in ethanol (10 mL) was heated under reflux for 5 h, then cooled. The solvent was evaporated under reduced pressure and the residue chromatographed (silica gel, 1-7% methanol/dichloromethane) to give the title compound (0.380 g, 69%) as a solid. 1 H NMR (400MHz, DMSOo6) δ 4.02 (s, 2H), 5.53 (br s, 2H), 6.41 (s, 1 H), 7.31 (s,1 H), 11.93 (br s, 1 H).
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