18643-86-2|Dimethyl 2-bromoterephthalate| Ambeed

Structure of 18643-86-2

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Quality Control of [ 18643-86-2 ] Purity: 98% SDS Specification

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Product Details of [ 18643-86-2 ]

CAS No. :	18643-86-2
Formula :	C₁₀H₉BrO₄
M.W :	273.08
SMILES Code :	O=C(OC)C1=CC=C(C(OC)=O)C=C1Br
MDL No. :	MFCD00060638
InChI Key :	VUMPFOPENBVFOF-UHFFFAOYSA-N
Pubchem ID :	87741

Safety of [ 18643-86-2 ]

GHS Pictogram:
Signal Word:	Warning
Hazard Statements:	H302-H315-H317-H319-H335
Precautionary Statements:	P261-P305+P351+P338

Application In Synthesis of [ 18643-86-2 ]

* 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.

Downstream synthetic route of [ 18643-86-2 ]

[ 18643-86-2 ] Synthesis Path-Downstream 1~35

1
[ 67-56-1 ]
[ 586-35-6 ]
[ 18643-86-2 ]

Yield	Reaction Conditions	Operation in experiment
98%	With sulfuric acid; for 5h;Reflux;	2-Bromo terephthalic acid (204 mmol,Methanol (MeOH) 0.4M and20 mmol of sulfuric acid (H2SO4) was added to a round flask, and the mixture was refluxed for 5 hours. Next, the reaction solution was filtered and washed to obtain a reaction product in a yield of 98%
93%	With thionyl chloride; at 0 - 20℃;	Example 13Dimethyl 2-bromoterephthalate; Intermediate-4 To a round bottom flask was added 2-bromoterephthalic acid (10.0 g, 40.8 mmol) in methanol (120 mL). The suspension was cooled to 0 C. and thionyl chloride (11.9 mL, 163 mmol) was added dropwise. The reaction mixture was allowed to warm to rt and was stirred overnight. The mixture was concentrated, sat. NaHCO3 was added and extracted with DCM (3×). The combined organic phases were then washed with water, and brine, dried over anhydrous Na2SO4, filtered and concentrated to afford dimethyl 2-bromoterephthalate (10.4 g, 93%). LC-MS: (FA) ES+274; 1H NMR (400 MHz, CDCl3) δ 8.31 (d, J=1.6 Hz, 1H), 8.00 (dd, J=8.1, 1.6 Hz, 1H), 7.81 (d, J=8.1 Hz, 1H), 3.96 (s, 3H), 3.95 (s, 3H).
93%	With thionyl chloride; at 0 - 20℃; for 16h;	To a stirred solution of 2-bromoterephthalic acid (15.0 g, 61.2 mmol) in methanol (150.0 mL) was added dropwise thionyl chloride (4.91 mL, 67.3 mmol) at 0C. The reaction mixture was allowed to warm to room temperature and stirred further for 16 h. The rection was monitored by TLC, the reaction mixture was concentrated. Added saturated solution of sodium bicarbonate to the residue and extracted using dichloromethane (3 x 150.0 mL). The combined organic phase was washed with water (200.0 mL), brine (100.0 mL) and dried over anhydrous sodium sulphate. Concentrate this reaction mixture to afford 26.7 g crude, which was purified by column chromatography using eluent 0-30% of ethyl acetate in n-hexane to afford the titled compound dimethyl 2-bromoterephthalate (15.5 g, 93 % yield) as off white solid. MS (ES+) m/z = 274.04 (M+1). 1H NMR (400 MHz, Chloroform-d) δ 8.33 (d, J = 1.6 Hz, 1H), 8.02 (dd, J = 8.1, 1.6 Hz, 1H), 7.83 (d, J = 8.2 Hz, 1H), 3.98 (s, 3H), 3.97 (s, 3H).

92%	With sulfuric acid; at 60℃; for 6h;Inert atmosphere; Large scale;	In nitrogen atmosphere, 2-bromoterephthalic acid (30.0 kg, 122.4mol) was suspened in methanol (95 kg), cooled to about 5 C, and 98 weight % sulfuric acid (33.0 kg) was added and the mixture was stirred at 60 C for 6 hours. TLC is confirmed for the end of reaction, the reaction mixture is then cooled to the room temperature, methyl tert-butyl ether (220.0 kg) was added and the organic layer was washed with water (180.0 kg), and NaHCO3 aqueous solution (8 weight %, 180.0 kg) and salt water (24 weight %, 180.0 kg) , dried using anhydrous magnesium sulfate (6.0 kg) , concentrated under reduced pressure to obtain the title compound as pale yellow crystals (30.40 kg, yield 92.0%).
92.2%	With sulfuric acid; In water; at 65℃;	As shown in Scheme 1, MOF-ligand (see the Fig.S5 for the 1H and 13CNMR spectra of the MOF-ligand) and UiO-66-C≡CH could be synthesized by following a similar published procedure [28].Compound 1 to a solution of 2-bromoterephthalic acid (7.5 g,40 mmol) in 250 mL methanol, conc. H2SO4 (15 mL) was added slowly.Then being stirred at 65C overnight. After methanol was removed by evaporation, 300 mL ethyl acetate (EA) was added. The mixture was washed with K2CO3 solution (1 M) and dried with Na2SO4. Finally, the crude product 1 was purified by flask silica gel column chromatography(white solid 7.7 g, yield 92.2 %). 1H NMR (400 MHz, CDCl3) δ 8.30 (d, J=1.8 Hz, 1 H), 8.12 - 7.93 (m, 1 H), 7.81 (t, J =6.7 Hz, 1 H), 4.00 3.93(m, 6 H). 13C NMR (600 MHz, CDCl3) δ 167.96, 164.36, 137.47, 134.56,132.18, 129.76, 126.96, 122.04, 47.07.
83%	With thionyl chloride; at 0 - 20℃;Inert atmosphere;	To a solution of 2-bromoterephthalic acid (2.0 g, 8.2 mmol) in MeOH (20 mL) at 0 00 underN2was added thionyl chloride (5.8 g, 49 mmol) dropwise. The resulting mixture was stirred atroom temperature overnight. The mixture was concentrated and the residue partitioned between DCM (20 mL) and saturated aqueous NaHCO3 (15 mL). The aqueous phase was extracted with DCM (3 x 10 mL). The combined organic fractions were washed with saturated aqueous NaHCO3 (3 x 10 mL), brine (3 x 10 mL), dried (Na2SO4), filtered and concentrated to give the title compound (1.85 g, 83%) as a white solid. 1H NMR (400 MHz,ODd3) 6 8.30 (d, J = 1.6 Hz, 1 H), 7.99 (dd, J = 8.0, 1.2 Hz, 1 H), 7.80 (d, J = 8.0 Hz, 1 H),3.95 (s, 3H), 3.94 (s, 3H); LCMS RT 2.63 mm; m/z 273,275 [M+H]+
44%	With thionyl chloride; for 4h;Reflux;	2-Bromoterephthalic acid (2.0 g, 8.2 mmol) was dissolved in 50.0 mL of methanol and 7.0 mL SOCl2. The mixture was heated to reflux for 4.0 h. After cooling to room temperature, MeOH was removed by evaporation and then 60 mL (20.0 mL * 3) of CH2Cl2 was added. The solution was washed water. Then the organic solution was dried with MgSO4. After solution was removed by evaporation, raw solid was obtained. Vacuum thermal sublimation and deposition was performed for a further purity (1.0 g, 0.44%).
		To a mixture of 2-bromoterephthalic acid (2.0 g, 8.2 mmol) and DMF (0.3 mL) in DCM (20 mL) was added oxalyl chloride (15.6 g, 123 mmol) and the mixture stirred at room (0570) temperature overnight. The reaction was then concentrated and the residue diluted with MeOH (50 mL) at 0 C and stirred for 10 min. The solvent was removed under reduced pressure to give the title product as a yellow oil that was used for the next step directly. LCMS: RT 2.61 min; m/z 273.0, 275.0 [M+H] +.

References: [1]Patent: KR2015/33493,2015,A .Location in patent: Paragraph 0067; 0068; 0069.
[2]Patent: US2012/94997,2012,A1 .Location in patent: Page/Page column 79-80.
[3]Patent: WO2021/130731,2021,A1 .Location in patent: Page/Page column 171; 172.
[4]Patent: CN102656177,2016,B .Location in patent: Paragraph 0310-0314.
[5]Chemistry - A European Journal,2016,vol. 22,p. 12800 - 12807.
[6]Applied Catalysis A: General,2021,vol. 623.
[7]Chemical Communications,2019,vol. 55,p. 11844 - 11847.
[8]Chemical Communications,2011,vol. 47,p. 12089 - 12091.
[9]Patent: WO2017/153518,2017,A1 .Location in patent: Page/Page column 61; 62.
[10]Journal of Materials Chemistry A,2018,vol. 6,p. 21961 - 21968.
[11]Chinese Chemical Letters,2021,vol. 32,p. 1669 - 1674.
[12]Gazzetta Chimica Italiana,1886,vol. 16,p. 282.
[13]Monatshefte fur Chemie,1900,vol. 21,p. 639.
[14]Journal of medicinal chemistry,1970,vol. 13,p. 1235 - 1237.
[15]Bioorganic and Medicinal Chemistry Letters,2016,vol. 26,p. 5797 - 5801.
[16]Patent: WO2017/153515,2017,A1 .Location in patent: Page/Page column 67.

2
[ 67-56-1 ]
[ 13815-89-9 ]
[ 18643-86-2 ]

Yield	Reaction Conditions	Operation in experiment
5.5 g	With triethylamine; at 0 - 20℃; for 2h;Inert atmosphere;	A solution of 2-bromoterephthalic acid (5.000 g, 20.41 mmol) in thionyl chloride (20.00 mL, 273 mmol) was heated at 100C for 5 h. The dark colored reaction mass was cooled to room temperature and solvent was evaporated off under reduced pressure. The residual mass was cooled to OoC and methanol (20 ml) and triethylamine (5 ml, 35.5 mmol) were added slowly under nitrogen. The reaction mixture was then stirred for 2 h at ambient temperature. The solution was evaporated to dryness under reduced pressure. The residual mass was dissolved in ethylacetate (100 ml) and washed with water (2X 25ml), followed by 2N HCI (2X 25 ml) and finally with saturated sodium bicarbonate solution. Combined organic layers were dried over sodium sulfate and evaporated under reduced pressure to obtain dimethyl 2-bromobenzene-1 ,4-dicarboxylate (5.5 g, 99% of theoretical yield) as a white solid. H NMR (400 MHz, CHLOROFORM-c/) δ ppm 3.95 (d, J=1 .25 Hz, 3 H) 3.96 (d, J=1 .25 Hz, 3 H) 7.81 (dd, J=8.03, 1.25 Hz, 1 H) 8.00 (d, J=8.03 Hz, 1 H) 8.31 (s, 1 H) MS [M-H] " : 272.9/ 273.9 (rt 1.90-1.97 min)

References: [1]Chemische Berichte,1879,vol. 12,p. 616.
[2]Tetrahedron,2009,vol. 65,p. 8738 - 8744.
[3]Journal of Medicinal Chemistry,2012,vol. 55,p. 3553 - 3557.
[4]Patent: WO2015/97276,2015,A1 .Location in patent: Page/Page column 47; 48.

3
[ 18643-86-2 ]
[ 264272-63-1 ]

Yield	Reaction Conditions	Operation in experiment
24%	With potassium hydroxide; acetic acid; In methanol; ethyl acetate; toluene; Petroleum ether;	Example 76 Preparation of 3-bromo-4-(methoxycarbonyl)benzoic Acid Potassium hydroxide (2.87 g, 51 mmol) was added to a solution of 2-bromo-1,4-benzenedicarboxylic acid, dimethyl ester (14 g, 51 mmol) in methanol (50 mL) at 25 C. The reaction mixture was stirred at 25 C. for 24 h and then at 50 C. for 3 h. The solvent was concentrated under reduced pressure and the residue was diluted with water (100 mL) and extracted with ethyl acetate (2200 mL). The water layer was acidified to pH 2 with 2N hydrochloric acid solution and extracted with ethyl acetate (2200 mL). The combined organic layers were washed with brine (100 mL), dried (MgSO4), filtered and concentrated in vacuo. The resulting solid was boiled in toluene (100 mL) and the insolubles were removed by filtration. The filtrate was concentrated to dryness under reduced pressure and the resulting solid was flash chromatographed (silica gel, 50% ethyl acetate in petroleum ether with 1% acetic acid) to give 3-bromo-4-(methoxycarbonyl)benzoic acid (3.28 g, 24% yield) as a colorless solid.
24%	With potassium hydroxide; acetic acid; In methanol; ethyl acetate; toluene; Petroleum ether;	Example 2 Preparation of 2-bromo-1,4-benzenedicarboxylic acid, 1-methyl ester Potassium hydroxide (2.87 g, 51 mmol) was added to a solution of 2-bromo-1,4-benzenedicarboxylic acid, dimethyl ester (14 g, 51 mmol) in methanol (50 mL) at 25 C. The reaction mixture was stirred at 25 C. for 24 h, and then at 50 C. for 3 h. The solvent was concentrated under reduced pressure and the residue was diluted with water (100 mL) and extracted with ethyl acetate (2200 mL). The water layer was acidified to pH 2 with 2 M HCl and extracted with ethyl acetate (2200 mL). The combined organic layers were washed with brine (100 mL), dried (MgSO4), filtered, and concentrated. The resulting solid was boiled in toluene (100 mL) and the insolubles were filtered. The filtrate was concentrated and the resulting solid was flash chromatographed (silica, 50% ethyl acetate in petroleum ether with 1% acetic acid) to give 2-bromo-1,4-benzenedicarboxylic acid, 1-methyl ester (3.28 g, 24%) as a white solid.
	With sodium hydroxide; water; In methanol; at 20℃; for 1.5h;	To a solution of <strong>[18643-86-2]dimethyl 2-bromoterephthalate</strong> (1.04 g) in methanol (10 mL) was added 1 N sodium hydroxide (5.71 mL) at room temperature. After stirring for 1.5 hour, the reaction was quenched by adding 1 N hydrochloric acid (7 mL). White crystals were formed. Water (10 mL) was added to aid crystalyzation. The crystals were collected by filtration, washed with water, and dried in the air.3-Bromo-4- (methoxycarbonyl) benzoic acid was obtained as white crystals (532 mg). 3-bromo-4- (methoxycarbonyl) benzoic acid 'H-NMR (DMSO-d6) δ 3.89 (3H, s), 7.87 (1H, d, J = 8 Hz), 8.01 (1H, d, J = 8 Hz), 8.17 (1H, s).

References: [1]Patent: US2002/161237,2002,A1 .
[2]Patent: US6331640,2001,B1 .
[3]Monatshefte fur Chemie,1900,vol. 21,p. 639.
[4]Patent: WO2004/63197,2004,A1 .Location in patent: Page 255.

4
[ 18643-86-2 ]
[ 30240-01-8 ]

References: [1]Journal of medicinal chemistry,1970,vol. 13,p. 1235 - 1237.

5
[ 120-61-6 ]
[ 18643-86-2 ]

References: [1]Journal of Organic Chemistry,1993,vol. 58,p. 239 - 240.

6
[ 18643-86-2 ]
[ 13052-77-2 ]
[ 893415-43-5 ]

References: [1]Journal of Medicinal Chemistry,1986,vol. 29,p. 1436 - 1441.

7
[ 577-19-5 ]
[ 18643-86-2 ]
2'-nitro-biphenyl-2,5-dicarboxylic acid dimethyl ester [ No CAS ]

References: [1]Organic Letters,2004,vol. 6,p. 2741 - 2744.

8
[ 592-31-4 ]
[ 18643-86-2 ]
methyl 3-butyl-2,4-dioxo-1,2,3,4-tetrahydroquinazoline-7-carboxylate [ No CAS ]

References: [1]Organic Letters,2006,vol. 8,p. 5089 - 5091.

9
[ 110-85-0 ]
[ 18643-86-2 ]
[ 898547-76-7 ]

Yield	Reaction Conditions	Operation in experiment
	With caesium carbonate;palladium diacetate; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene; In 1,4-dioxane; at 100℃; for 24h;	1.80 g of piperazine, 1.0 g of <strong>[18643-86-2]dimethyl 2-bromoterephthalate</strong>, 720 mg of 9,9-diemthyl-4,5-bis(diphenylphosphino)xanthene, 280 mg of palladium(II) acetate and 2.20 g of cesium carbonate are dissolved in 40 ml of 1,4-dioxane and stirred at 100 C. under an argon atmosphere for 24 hours. The reaction mixture is diluted with 100 ml of dichloromethane and extracted with 50 ml of saturated sodium bicarbonate solution and 50 ml of saturated sodium chloride solution. The organic phases is dried over MgSO4 and then the solvent is removed in vacuo. 330 mg of dimethyl 2-piperazin-1-yl terephthalate are obtained as an oil. C14H18N204 (278.31), LCMS (ESI): 279.3 (M+H+).

References: [1]Patent: US2008/45540,2008,A1 .Location in patent: Page/Page column 30-31.

10
[ 18643-86-2 ]
[ 62-53-3 ]
[ 566155-74-6 ]