Carbon Tetrachloride → Dimethyl 2-amino-3,5-dichloroterephthalate

HRID 449894

Reaction equation

[NH2:1][C:2]1[CH:11]=[C:10]([C:12]([O:14][CH3:15])=[O:13])C=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5].C1C(=O)N([Cl:23])C(=O)C1.[C:24]([Cl:28])(Cl)(Cl)Cl>>[NH2:1][C:2]1[C:11]([Cl:23])=[C:10]([C:12]([O:14][CH3:15])=[O:13])[C:24]([Cl:28])=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5]

Participants

Reactant 3

HCID 5943Carbon Tetrachloride

HCID 31398Chlorosuccinimide

HCID 79336Dimethyl aminoterephthalate

Product 1

HCID 20714731Dimethyl 2-amino-3,5-dichloroterephthalateYield 97%

Conditions

Temperature: 80 °C

Procedure

To a solution of dimethyl 2-aminoterephthalate (500 g, 2.39 mol) in CCl4 (4 L) at 60° C. was slowly added NCS (957 g, 7.17 mol). The reaction mixture was heated at 80° C. for 16 hours, cooled to room temperature and filtered. The solid was washed with dichloromethane (2×500 mL) and the combined organic solution was washed with 1 N NaOH (2×3 L), water (3 L) and brine (1 L). The mixture was dried over Na2SO4, and concentrated under reduced pressure to afford dimethyl 2-amino-3,5-dichloroterephthalate (645 g, yield: 97%) as a red oil. 1H NMR (400 MHz, DMSO-d6) δ 3.81 (s, 3H), 3.87 (s, 3H), 7.04 (s, 2H), 7.77 (s, 1H). LCMS (ESI) m/z: 210.0 [M+H+].

Workup

customat 60° C.
temperaturecooled to room temperature
filtrationfiltered
washThe solid was washed with dichloromethane (2×500 mL)
washthe combined organic solution was washed with 1 N NaOH (2×3 L), water (3 L) and brine (1 L)
dry with materialThe mixture was dried over Na2SO4
concentrationconcentrated under reduced pressure

Sources & evidence

ORD record: ord-cc7a136af5c642b5bbe208eb81abc572
Source dataset: uspto-grants-2013_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08486950B2

Linked notes

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