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Methyl 5-broMothiophene-3-carboxylate

Product Name
Methyl 5-broMothiophene-3-carboxylate
CAS No.
88770-19-8
Chemical Name
Methyl 5-broMothiophene-3-carboxylate
Synonyms
EA458;Methyl 2-bromothiophene-4-carboxylate;Methyl 5-broMothiophene-3-carboxylate;Methyl 5-bromo-3-thiophenecarboxylate;Methyl 5-bromothiophene-3-carboxylate 98%;5-Bromothiophene-3-carboxylic acid methyl ester;3-Thiophenecarboxylic acid, 5-bromo-, methyl ester
CBNumber
CB72652875
Molecular Formula
C6H5BrO2S
Formula Weight
221.07
MOL File
88770-19-8.mol
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Methyl 5-broMothiophene-3-carboxylate Property

Melting point:
43-44 °C
Boiling point:
244.6±20.0 °C(Predicted)
Density 
1.662±0.06 g/cm3(Predicted)
storage temp. 
under inert gas (nitrogen or Argon) at 2–8 °C
Appearance
Off-white to light brown Solid
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Safety

HS Code 
2934999090
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Hazard and Precautionary Statements (GHS)

Symbol(GHS)
Signal word
Warning
Hazard statements

H302Harmful if swallowed

H315Causes skin irritation

H319Causes serious eye irritation

H335May cause respiratory irritation

Precautionary statements

P261Avoid breathing dust/fume/gas/mist/vapours/spray.

P280Wear protective gloves/protective clothing/eye protection/face protection.

P301+P312IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell.

P302+P352IF ON SKIN: wash with plenty of soap and water.

P305+P351+P338IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continuerinsing.

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N-Bromosuccinimide Price

TRC
Product number
M224648
Product name
Methyl5-Bromothiophene-3-carboxylate
Packaging
100mg
Price
$65
Updated
2021/12/16
Apolloscientific
Product number
OR17258
Product name
Methyl5-bromothiophene-3-carboxylate
Purity
99%
Packaging
1g
Price
$73
Updated
2021/12/16
SynQuest Laboratories
Product number
6H66-9-09
Product name
Methyl 5-bromothiophene-3-carboxylate
Purity
98%
Packaging
1g
Price
$87
Updated
2021/12/16
AK Scientific
Product number
9704AF
Product name
Methyl5-bromo-3-thiophenecarboxylate
Packaging
250mg
Price
$108
Updated
2021/12/16
Apolloscientific
Product number
OR17258
Product name
Methyl5-bromothiophene-3-carboxylate
Purity
99%
Packaging
5g
Price
$193
Updated
2021/12/16
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Methyl 5-broMothiophene-3-carboxylate Chemical Properties,Usage,Production

Synthesis

67-56-1

100523-84-0

88770-19-8

1. Add a solution of bromine (2 mL, 39.06 mmol) in glacial acetic acid (64 mL) slowly dropwise to a stirred solution of 5-bromothiophene-3-carboxylic acid (5 g, 39.06 mmol) in glacial acetic acid (37 mL) at 0 °C. Stirring was done for 20 minutes at room temperature. The reaction mixture was poured into ice water with vigorous stirring. The white solid precipitate was collected by filtration, washed with water and recrystallized from hot water to give pure 5-bromothiophene-3-carboxylic acid bromide (Int-2) as a white solid (3.68 g, 46%).1H NMR (200 MHz, DMSO-d6): δ 7.55 (s, 1H), 8.17 (s, 1H). 2. Int-2 (3.4 g, 16.42 mmol) was dissolved in methanol (40 mL), H2SO4 (321 mg, 3.28 mmol) was added, and stirred at reflux for 12 hours. Volatiles were removed by distillation under reduced pressure and the residue was extracted with DCM (75 mL). The organic phase was washed sequentially with water (40 mL), saturated aqueous NaHCO3 (40 mL), brine (40 mL), dried over Na2SO4, filtered and concentrated under reduced pressure to give pure methyl 5-bromothiophene-3-carboxylate (Int-3) as a colorless viscous oil (3.3 g, 91%).1H NMR (200 MHz, DMSO-d6): δ 7.98 (s, 1H), 7.44 (s, 1H), 3.87 (s, 3H). 3. Int-3 (0.5 g, 2.26 mmol) was dissolved in dioxane (25 mL), and Int-4 (0.51 g, 2.26 mmol), Pd(OAc)2 (105 mg, 0.45 mmol), xanthic acid (265 mg, 0.497 mmol) and Cs2CO3 (1.18 g, 3.62 mmol) were added. After vacuum degassing, the reaction was stirred at reflux for 20 h under N2 protection. The reaction mixture was concentrated under reduced pressure and purified by column chromatography with the product eluting with EtOAc. The mixture was further purified by preparative HPLC (140 mg) to give pure Int-5 as a yellow solid (80 mg, 10%). Mass spectrum (m/z): 366.0 [M++1]. 1H NMR (200 MHz, DMSO-d6): δ 9.50 (d, J=7 Hz, 1H), 8.51 (d, J=7 Hz, 1H), 8.56 (d, J=5.2 Hz, 1H), 7.74 (brs, 1H), 7.66 (d, J=11.8 Hz, 1H). 7.35 (d, J=7.4 Hz, 1H), 7.11 (s, 1H), 7.02 (d, J=5.6 Hz, 1H), 6.87 (t, J=6.8 Hz, 1H), 3.86 (s, 3H), 2.73 (s, 3H). 4. Int-5 (0.7 g, 1.91 mmol) was dissolved in THF:MeOH:H2O (2:1:2, 50 mL), LiOH (0.24 g, 5.74 mmol) was added, and heated and stirred at 50 °C for 16 hours. Volatiles were removed by distillation under reduced pressure and the reaction mixture was acidified to pH 5-6 with 2N HCl. The precipitated solid was filtered and dried under vacuum to give pure Int-6 (0.51 g, 76%). Mass spectrum (m/z): 352.0 [M++1]. 1H NMR (200 MHz, DMSO-d6): δ 12.45 (brs, 1H), 10.87 (s, 1H), 9.70 (brs, 1H), 8.60 (d, J=4.68 Hz, 1H), 7.67-7.59 (m, 2H), 7.45 (t, J=8.4 Hz, 1H), 7.13 (d, J=5.2 Hz, 1H), 7.04 (s, 2H), 2.65 (s, 3H).

References

[1] Patent: US2010/29638, 2010, A1. Location in patent: Page/Page column 110
[2] Tetrahedron Letters, 2013, vol. 54, # 11, p. 1460 - 1462
[3] Journal of Materials Chemistry C, 2018, vol. 6, # 14, p. 3731 - 3742
[4] Patent: WO2005/9941, 2005, A1. Location in patent: Page 43-44
[5] Patent: WO2011/33255, 2011, A1. Location in patent: Page/Page column 72

Methyl 5-broMothiophene-3-carboxylate Preparation Products And Raw materials

Raw materials

Preparation Products

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Methyl 5-broMothiophene-3-carboxylate Suppliers

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View Lastest Price from Methyl 5-broMothiophene-3-carboxylate manufacturers

Career Henan Chemical Co
Product
Methyl 5-broMothiophene-3-carboxylate 88770-19-8
Price
US $1.00/g
Min. Order
1g
Purity
99.0%
Supply Ability
100kg
Release date
2020-01-07