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CAS No. : | 273749-25-0 | MDL No. : | MFCD04038587 |
Formula : | C7H10N2O | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | FYUDUZRLZITSTF-UHFFFAOYSA-N |
M.W : | 138.17 | Pubchem ID : | 1514188 |
Synonyms : |
|
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H302-H319 | Packing Group: | N/A |
GHS Pictogram: |
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* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With hydrogenchloride; acetic acid; In methanol; ethanol; water; | 4-Hydroxymethyl-2-(2-nitrophenyl)-benzimidazole (3) 2,3-Diaminobenzyl alcohol 2 (3.45 g, 25 mmol) was dissolved in a MeOH/H2O mixture (200 mL, v/v=1:1). Acetic acid (3 mL), 2-nitro-benzaldehyde (5.3 g, 35 mmol) in MeOH (50 mL) and Cu(OAc)2.H2O (7.0 g, 35 mmol) in water (100 mL), were added sequentially to the stirring solution. It was then heated to reflux under vigorous stirring for 3 hr, after which a pale yellow precipitate was formed. The mixture was filtered hot and then washed with water to afford a gray-yellow solid. The precipitate was redissolved in EtOH (150 mL) and concentrated HCl (24 mL), and then a solution of Na2S.9H2O (12.8 g, 50 mmol) in water (100 mL) was added. The mixture was heated at reflux for 1 hour resulting in a black slurry. It was then allowed to cool to room temperature, and filtered through a pad of celite to remove the resulting CuS. The filtrate was neutralized with ammonium hydroxide to pH=8-9 and then concentrated by rotary evaporation to yield a green-yellow precipitate. After filtration and vacuum evaporation, 4-hydroxymethyl-2-(2-nitrophenyl)-benzimidazole (5.55 g, 82%) was obtained as a green-yellow solid. Rf=0.28 (hexane/ethyl acetate=1:2); 1H NMR (200 MHz, DMSO) delta 4.84 (broad s, 2H), 5.22 (broad s, 1H), 7.28 (m, 2H), 7.49 (d, J=6.8 Hz, 1H), 7.71-8.06 (m, 4H), 12.93 (broad s, 1H); HRMS: Calcd. for C14H11N3O3 269.0800, found 269.0845. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | aluminum nickel; In tetrahydrofuran; | 2,3-Diaminobenzyl alcohol (2) Raney nickel (~5 g) was placed in a hydrogenation bottle and washed with THF three times before being slurried in 50 mL of THF. 4-Hydroxymethyl-2,1,3-benzothiadiazole56 (5.0 g, 30 mmol) was then added. It was hydrogenated under 10 psi pressure at room temperature for 6 hours. TLC was used to confirm that all starting material had been consumed. The reaction mixture was then filtered carefully through a pad of celite and washed with THF. After removal of the solvent, 2,3-diaminobenzyl alcohol (4.0 g, 96%) was obtained as a colorless crystalline solid. Rf=0.18 (hexane/ethyl acetate/MeOH=5:5:1); 1H NMR (200 MHz, DMSO) delta 4.33 (broad s, 2H), 4.36 (d, J=5.4 Hz, 2H), 4.43 (broad s, 2H), 4.96 (t, J=5.4 Hz, 1H), 6.43 (m, 3H); HRMS: Calcd. for C7H10N2O 138.0793, found 138.0830. |
1.6 g | With hydrogen; In methanol; at 20.0℃; for 16.0h; | To a stirred solution of 2,l,3-benzothiadiazol-4-ylmethanol (2.5 g, 15 mmol) (from step 4) in methanol (150 mL) was added Raney nickel (100% w/w, washed five times with methanol) and it was hydrogenated under balloon pressure of hydrogen gas at ambient temperature. After 16 h, the reaction mixture was filtered through a celite bed and the residue was washed with methanol (3 x 250 mL). The combined filtrate was concentrated to afford (2, 3-diaminophenyl) methanol (1.6 g) as blue gum. NMR (400 MHz, DMSO-de) delta 6.48 (d, 1H, J = 7.20 Hz), 6.42 (d, 1H, J = 7.20 Hz), 6.36 (t, 1H, J = 7.20 Hz), 4.92 (bs, 1H), 4.43 (s, 2H), 4.35 (d, 4H, J = 14.80 Hz); |
1.6 g | With hydrogen; In methanol; at 20.0℃; for 16.0h; | To a stirred solution of 2,l,3-benzothiadiazol-4-ylmethanol (2.5 g, 15 mmol) (from step 4) in methanol (150 mL) was added raney nickel (100% w/w, washed five times with methanol) and it was hydrogenated (under balloon pressure) at ambient temperature. After 16 h, the above reaction mass was filtered through a celite bed, the residue was washed with methanol (3 x 250 mL). The combined filtrate was concentrated to afford (2,3-diaminophenyl)methanol (1.6 g) as a gum. NMR (400 MHz, DMSO-de) delta 6.48 (d, IH, J=7.20 Hz), 6.42 (d, IH, J=7.20 Hz), 6.36 (t, IH, J = 7.20 Hz), 4.92 (br.s, IH), 4.43 (s, 2H), 4.35 (d, 4H, J = 14.80 Hz);MS: m/z 139 (M+l). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1.3 g | In dichloromethane; at 20.0℃; for 12.0h; | A mixture of methyl 3-isothiocyanato-3- {3- [(trifluoromethyl)sulfanyl]phenyl}propanoate (from step 3) (1.3 g, 4 mmol) and (2,3- diaminophenyl)methanol (step 5) (0.48 g, 3.47 mmol) in dichloromethane (50 mL) was stirred at ambient temperature for 12 h. The reaction mixture was concentrated to afford a crude product (1.8 g) as a brownish gum, which was purified by silica gel (230-400 mesh) column chromatography eluting with 7% methanol in chloroform to afford methyl 3-(3-(2-amino-6-(hydroxymethyl)phenyl)thioureido)-3-(3- ((trifluoromethyl)thio)phenyl)propanoate (1.3 g) as a brownish solid. MS: m/z 460.0 (M+l). |
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