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CrystEngComm
Page 6 of 9
DOI: 10.1039/C7CE00971B
ARTICLE
Journal Name
CuCl in 500 µL of 36% HCl). The mixed was stirred for 1 h at 0 purified by silica gel column chromatography (25% EtOAc/n-
oC and an additional 2 h at room temperature. The resultant Hexane), and the desired compound, dimethy-2,3-
was extracted with EtOAc, and the organic layer was dried dinitroterephthalate (798 mg, 37%) was obtained as an ivory
using MgSO4, and evaporated of ethyl acetate under reduced solid.
pressure. The obtained solid mixture was separated by silica
2,5-Dinitroterephthalic acid (BDC-2,5-(NO2)2) and 2,3-
Dinitroterephthalic acid (BDC-2,3-(NO2)2)
gel column chromatography (10% EtOAc/n-Hexane) and the
desired compound, dimethyl-2,5-dichloroterephthalate (90
mg, 34 %), was obtained as a colorless solid.
Dimethyl-2,5-dinitroterephthalate (284 mg,
1 mmol) was
Dimethyl-2,3-dichloroterephthalate
was
obtained
in
dissolved in 5 mL of THF. A 4% KOH aqueous solution (5 mL)
was slowly added to the THF solution. The mixture was stirred
at room temperature for 2 h. Once conversion was complete
(monitored by TLC), THF was removed by evaporation and the
mixture was acidified with a 1.0 M HCl aqueous solution. The
solution was stored overnight in a refrigerator. The precipitate
comparable yield from a similar procedure using dimethyl-2-
amino-3-chloroterephthalate as the starting material.
2,5-Dichloroterephthalic acid (BDC-2,5-Cl2) and 2,3-
Dichloroterephthalic acid (BDC-2,3-Cl2)
Dimethyl-2,5-dichloroterephthalate (263 mg, 1 mmol) was was collected by filtration, and washed with water. The
dissolved in 5 mL of THF, and 5 mL of a 4% KOH aqueous desired compound was obtained by air drying (249 mg, 98%)
solution was slowly added to the THF solution. The mixture as a yellow solid.
was stirred overnight under reflux (66 oC). Once conversion 2,3-Dinitroterephthalic acid was obtained in comparable yield
was complete (monitored by TLC), THF was removed by from
a
similar
procedure
using
dimethyl-2,3-
evaporation and the mixture was acidified with a 1.0 M HCl dinitroroterephthalate as the starting material.
aqueous solution. The precipitate was collected by filtration,
Diethyl-2,5-dimethoxyterephthalate (BDCE-2,5-(OMe)2) and
Dimethyl-2,3-dimethoxyterephthalate (BDCE-2,3-(OMe)2)
and washed with water. The desired compound was obtained
by air drying (161 mg, 69%) as a colorless solid.
2,3-Dichloroterephthalic acid was obtained in comparable
Diethyl-2,5-dihydroxyterephthalate (1.27 g,
5
mmol),
yield from
a
similar procedure using dimethyl-2,3-
potassium carbonate (830 mg, 16 mmol), and iodomethane (1
mL, 16 mmol) were dissolved in acetone (15 mL). The mixture
was stirred overnight under reflux (60oC). Once conversion was
complete (monitored by TLC), the solvent was evaporated.
Water was added to dissolve all of the inorganic salts. The
solution was extracted with ethyl acetate three times, the
organic layer was dried using MgSO4, filtered, and evaporated
in vaccuo. Then the desired compound, dimethyl 2,5-
dimethoxyterephthalate (1.11 g, 79%), was obtained as a
colorless solid.
dichloroterephthalate as the starting material.
Dimethyl-2,5-dinitroterephthalate (BDCE-2,5-(NO2)2)
Trifluoroacetic anhydride (4.3 mL, 31.1 mmol) was slowly
added to a solution mixture of 30% H2O2 (2.7 mL, 26.6mmol)
o
and CH2Cl2 (15 mL) at 0 C. The solution was warmed to room
temperature, and
a dimethyl-2-amino-5-nitroterephthalate
solution (428 mg, 1.68 mmol in CH2Cl2 4.5 mL) was slowly
added to the mixture. After stirring for 3 h at 45 oC, the
o
mixture was cooled to 0 C and Na2SO3 was slowly added to
Dimethyl-2,3-dimethoxyterephthalate was obtained in
comparable yield from a similar procedure using dimethyl-2,3-
dihydroxyterephthalate as the starting material.
quench the reaction. The resulting mixture was extracted with
CH2Cl2. The organic phase was washed with brine. The solution
was then dried using MgSO4, filtered, and the CH2Cl2 was
evaporated. The solid mixture was recrystallized from EtOAc,
and the desired compound, dimethyl-2,5-dinitroterephthalate
(267 mg, 23%), was obtained as a green solid.
2,5-Dimethoxyterephthalic acid (BDC-2,5-(OMe)2) and 2,3-
Dimethoxyterephthalic acid (BDC-2,5-(OMe)2)
Diethyl-2,5-dihydroxyterephthalate (1.11 g, 3.94 mmol) was
dissolved in 20 mL of THF. To this, 20 mL of a 4% KOH aqueous
solution was added. The mixture was stirred overnight under
reflux (66 oC). Once conversion was complete (monitored by
TLC), THF was removed by evaporation and the mixture was
acidified with a 1.0 M HCl aqueous solution. The precipitate
was collected by filtration, and washed with water. The
desired compound was obtained by air drying (840 mg, 94%)
as a colorless solid.
Dimethyl-2,3-dinitroterephthalate (BDCE-2,3-(NO2)2)
2,3-Dinitro-p-xylene (1,5 g, 7.65 mmol) was dissolved in conc.
sulfuric acid (45 mL) and the mixture was cooled to 0 oC.
Sodium dichromate (13.7 g, 46 mmol) was added in small
quantities (1 g) to the mixture every 0.5 h. After addition the
mixture was warmed to room temperature and stirred
overnight. Crushed ice was added to the reaction flask, and the
reaction was quenched with sodium sulfide. After extraction
with EtOAc (30 mL X 8), the organic phase was dried using
MgSO4, filtered, and evaporated in vaccuo. Methanol (80 mL)
and conc. sulfuric acid (8 mL) was added to the resulting solid
2,3-Dimethoxyterephthalic acid was obtained in comparable
yield from
a
similar procedure using Dimethyl-2,3-
dihydroxyterephthalate as the starting material.
and the mixture was stirred for 2 d at 70 oC. The methanol was Diethyl 2,5-dimethoxy-3-nitroterephthalate (BDCE-2,5-(OMe)2-3-
evaporated in vaccuo and the solid was extracted with
EtOAc/water. The organic solution was dried with MgSO4,
filtered, and evaporated in vaccuo. The resulting solid was
NO2)
6 | J. Name., 2012, 00, 1-3
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