[ CAS No. 70260-17-2 ]

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CAS No. 70260-17-2, is a thiophenes compound, that is a thiophenes bioactive compound, with a molecular weight of 193.06, molecular formula C5H5BrOS, Ambeed provides batches of quality inspection (such as NMR, HPLC/GC) and other test reports.

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Product Details

CAS No. :70260-17-2MDL No. :MFCD06202660
Formula :C5H5BrOSInChI Key :IXULCOYQSDIBFO-UHFFFAOYSA-N
M.W :193.06Pubchem ID :12479011
Boiling Point :264.983буC at 760 mmHg
Synonyms :

Computed Properties

TPSA : 48.5 H-Bond Acceptor Count : 2
XLogP3 : 1.4 H-Bond Donor Count : 1
SP3 : 0.20 Rotatable Bond Count : 1

Safety

Signal Word:WarningClassN/A
Precautionary Statements:P280-P305+P351+P338UN#:N/A
Hazard Statements:H302Packing Group:N/A
GHS Pictogram:

Application In Synthesis

[ 70260-17-2 ] Synthesis Path-Downstream   1~2

  • 1
  • [ 70260-17-2 ]
  • [ 7353-88-0 ]
YieldReaction ConditionsOperation in experiment
84% With thionyl chloride In dichloromethane for 4.00 h; Reflux (3-Bromo-thiophen-2- yl)-methanol (505 mg, 2.62 mmol) was dissolved in dichloromethane (20 mL) and thionyl chloride (357 μ, 4.89 mmol) was added. The mixture was heated at reflux for 4 firs, then evaporated. The crude product was purified by column chromatography on silica, eluting with dichloromethane. The title compound (466 mg, 2.20 mmol, 84percent) was obtained as a pale yellow oil.
84% With thionyl chloride In dichloromethane for 4.00 h; Reflux [00474] (3-Bromo-thiophen-2-yl)-methanol (7) (505 mg, 2.62 mmol) was dissolved in dichloromethane (20 mL) and thionyl chloride (357 μ, 4.89 mmol) was added. The mixture was heated at reflux for 4 hrs, then evaporated. The crude product was purified by column chromatography on silica, eluting with dichloromethane. The title compound (466 mg, 2.20 mmol, 84percent>) was obtained as a pale yellow oil.
Reference: [1] Patent: WO2011/156640, 2011, A2. Location in patent: Page/Page column 134
[2] Patent: WO2013/86451, 2013, A2. Location in patent: Paragraph 00474
[3] Chemical Communications, 2015, vol. 51, # 18, p. 3842 - 3845
  • 2
  • [ 4798-45-2 ]
  • [ 70260-17-2 ]
  • [ 261711-41-5 ]
Reference: [1] Journal of Medicinal Chemistry, 2001, vol. 44, # 14, p. 2319 - 2332

[ 70260-17-2 ] Synthesis Path-Upstream   1~8

  • 1
  • [ 930-96-1 ]
  • [ 70260-17-2 ]
YieldReaction ConditionsOperation in experiment
100%
Stage #1: With sodium tetrahydroborate In methanol at 0℃; for 2.00 h;
Stage #2: With ammonium chloride In ethyl acetate
To a solution of 3- bromothiophene-2-carbaldehyde (500 mg, 2.62 mmol) in methanol (10 mL) was added sodium borohydride (169 mg, 4.47 mmol) in small portions at 0 °C and the reaction was stirred for 2 firs. The solvent was evaporated and the residue partitioned between ethyl acetate (20 mL) and 10percent ammonium chloride solution (10 mL). The organic layer was washed with water (10 mL), dried over sodium sulfate and evaporated. The title compound (505 mg, 2.62 mmol, 100percent) was obtained as a yellow oil.
100% With sodium tetrahydroborate In methanol at 0℃; for 2.00 h; [00473] To a solution of 3-bromothiophene-2-carbaldehyde (6) (500 mg, 2.62 mmol) in methanol (10 mL) was added sodium borohydride (169 mg, 4.47 mmol) in small portions at 0 °C and the reaction was stirred for 2 hrs. The solvent was evaporated and the residue partitioned between ethyl acetate (20 mL) and 10percent ammonium chloride solution (10 mL). The organic layer was washed with water (10 mL), dried over sodium sulfate and evaporated. The title compound (505 mg, 2.62 mmol, 100percent) was obtained as a yellow oil.
Reference: [1] Patent: WO2011/156640, 2011, A2. Location in patent: Page/Page column 134
[2] Patent: WO2013/86451, 2013, A2. Location in patent: Paragraph 00473
[3] Journal of the American Chemical Society, 2014, vol. 136, # 19, p. 7132 - 7139
[4] Chemical Communications, 2015, vol. 51, # 18, p. 3842 - 3845
  • 2
  • [ 7311-64-0 ]
  • [ 70260-17-2 ]
YieldReaction ConditionsOperation in experiment
95% With hydrogenchloride; sodium chloride In tetrahydrofuran; water A/Preparation of 3-Bromo-2-hydroxymethyl-thiophene:
2-(3-Bromothienyl)carboxylic acid (7 g; 34 mmoles) is dissolved in 25 ml of anhydrous THF. A solution of aluminium hydride AlH3 in anhydrous THF (2 M; 42 ml; 84 mmoles) is added slowly at a temperature of 0° C.
At the end of the addition, the reaction mixture is refluxed for 3 hours.
After cooling to 0° C., water (200 ml) and hydrochloric acid (1N, 150 ml) are added.
The mixture is decanted and the aqueous phase extracted with 3*150 ml of tert-butyl methyl ether.
The organic phases are combined and then washed with 150 ml of a saturated solution of sodium chloride, dried over magnesium sulphate and filtered.
The solvent is evaporated under reduced pressure.
The desired product is obtained as a brown oil and is used as such in the next step.
Yield: 95percent; Physical characteristics: * NMR1H: (CD3OD) 4.69 ppm (s; 2H); 6.95 ppm (d; 1H, J=5.2 Hz); 7.39 ppm (d; 1H, J=5.2 Hz).
* NMR13C: (DMSO-d6) 57.80 ppm; 106.28 ppm; 126.11 ppm; 129.80 ppm; 141.15 ppm. * MS: (EI, 70 eV); 194/192 (M+*; 80percent); 177/175 (30percent); 113 (50percent); 98 (60percent); 85 (100percent).
73% With sodium hydroxide; borane In tetrahydrofuran; methanol; (2S)-N-methyl-1-phenylpropan-2-amine hydrate b.
3-Bromo-2-thiophenemethanol
A stirred, ice-water chilled solution of 90.0 g of 3-bromo-2-thiophenecarboxylic acid and 600 ml of sieve dried tetrahydrofuran was treated at 5° C. with 962 ml of borane in tetrahydrofuran (1.04M solution) over 2 hours (nitrogen atmosphere), with exclusion of moisture.
The stirred solution and cooling bath were allowed to equilibrate to ambient temperature overnight.
The stirred, chilled (10° C.) solution was treated dropwise with 150 ml methanol over 2 hours and then with 100 ml of 10percent sodium hydroxide.
After concentration, the residue was diluted with water, adjusted to pH=8 with 10percent sodium hydroxide solution and extracted with ether (2*300 ml).
The combined dried (over anhydrous sodium sulfate) ethereal phase was concentrated.
Distillation gave 61 g (73percent) of product, b.p. 79°-82° C. (0.38 mm).
Analysis:
Calculated for C5 H5 BrOS: 31.11percentC; 2.61percentH. Found: 31.30L percentC; 2.70percentH.
Reference: [1] Patent: US6525040, 2003, B1
[2] Patent: US4560701, 1985, A
  • 3
  • [ 26137-08-6 ]
  • [ 70260-17-2 ]
Reference: [1] Journal of Medicinal Chemistry, 2001, vol. 44, # 14, p. 2319 - 2332
[2] Patent: US6528510, 2003, B1
  • 4
  • [ 872-31-1 ]
  • [ 67-56-1 ]
  • [ 70260-17-2 ]
Reference: [1] European Journal of Organic Chemistry, 2017, vol. 2017, # 18, p. 2661 - 2668
  • 5
  • [ 62224-14-0 ]
  • [ 70260-17-2 ]
Reference: [1] Patent: US6340759, 2002, B1. Location in patent: Example 259
  • 6
  • [ 930-96-1 ]
  • [ 70260-17-2 ]
YieldReaction ConditionsOperation in experiment
100%
Stage #1: With sodium tetrahydroborate In methanol at 0℃; for 2.00 h;
Stage #2: With ammonium chloride In ethyl acetate
To a solution of 3- bromothiophene-2-carbaldehyde (500 mg, 2.62 mmol) in methanol (10 mL) was added sodium borohydride (169 mg, 4.47 mmol) in small portions at 0 °C and the reaction was stirred for 2 firs. The solvent was evaporated and the residue partitioned between ethyl acetate (20 mL) and 10percent ammonium chloride solution (10 mL). The organic layer was washed with water (10 mL), dried over sodium sulfate and evaporated. The title compound (505 mg, 2.62 mmol, 100percent) was obtained as a yellow oil.
100% With sodium tetrahydroborate In methanol at 0℃; for 2.00 h; [00473] To a solution of 3-bromothiophene-2-carbaldehyde (6) (500 mg, 2.62 mmol) in methanol (10 mL) was added sodium borohydride (169 mg, 4.47 mmol) in small portions at 0 °C and the reaction was stirred for 2 hrs. The solvent was evaporated and the residue partitioned between ethyl acetate (20 mL) and 10percent ammonium chloride solution (10 mL). The organic layer was washed with water (10 mL), dried over sodium sulfate and evaporated. The title compound (505 mg, 2.62 mmol, 100percent) was obtained as a yellow oil.
92% With sodium tetrahydroborate In ethanol at 0 - 20℃; for 24.00 h; Inert atmosphere Stirring of 3-bromothiophene-2-carboxaldehyde (compound (2-1), 10 g, 52.3 mmol) / ethanol (EtOH, 200 mL) at 0 ° C under argon, and adding sodium borohydride (NaBH 4 , 3.4 g, 90.1 mmol) and stirred at room temperature for 24 hours. An aqueous solution of ammonium chloride was added to the oily solid obtained by concentration of the reaction mixture under reduced pressure, and the organic layer was extracted with ethyl acetate. After the extract was dried over magnesium sulfate and filtered, the filtrate was concentrated under reduced pressure to give a crude material. The crude product was purified by a silica gel column chromatography (ethyl acetate / hexane (volume ratio) = 2 / 8) to thereby obtain 3-bromothiophene-2-methanol (the compound (3-1), The yield was 9.3 g, and the yield was 92percent)
92% at 0 - 20℃; for 24.00 h; Inert atmosphere A solution of 3-bromothiophene-2-carboxaldehyde (compound (2-1), 10 g, 52.3 mmol) / ethanol (EtOH, 200 mL) was stirred at 0 ° C under an argon atmosphere, and sodium borohydride (NaBH 4 , 3.4 g, 90.1 mmol) and stirred at room temperature for 24 hours. An aqueous solution of ammonium chloride was added to the obtained oily solid, and the organic layer was extracted with ethyl acetate. After the extract was dried over magnesium sulfate and filtered, the filtrate was concentrated under reduced pressure to give a crude material. The crude product was purified by silica gel column chromatography (ethyl acetate / hexane (volume ratio) = 2/8), whereby 3-bromothiophene-2-methanol (the compound (3) -1), yield 9.3 g, yield 92percent).
92% With sodium tetrahydroborate In ethanol at 0 - 20℃; for 24.00 h; Inert atmosphere In an argon environment,A solution of 3-bromothiophene-2-carbaldehyde (compound (2-1), 10 g, 52.3 mmol) / ethanol (EtOH, 200 mL) was stirred at 0 ° C.Sodium borohydride (NaBH4, 3.4 g, 90.1 mmol) was added on one side.Stir at room temperature for 24 hours.The oily solid obtained by concentrating the reaction liquid under reduced pressure is added to an aqueous solution of ammonium chloride.The organic layer was extracted with ethyl acetate.Drying the extract with magnesium sulfate,After filtering,The filtrate was concentrated under reduced pressure to give a crude product.The crude product was purified by column chromatography (ethyl acetate/hexane (volume ratio) = 2/8).And the target compound 3-bromothiophene-2-methanol was obtained.(Compound (3-1), yield 9.3 g, yield 92percent).

Reference: [1] Patent: WO2011/156640, 2011, A2. Location in patent: Page/Page column 134
[2] Patent: WO2013/86451, 2013, A2. Location in patent: Paragraph 00473
[3] Patent: TW2018/43157, 2018, A. Location in patent: Paragraph 0229-0232
[4] Patent: TW2018/41922, 2018, A. Location in patent: Paragraph 0239; 0240; 0241; 0242
[5] Patent: TW2018/41923, 2018, A. Location in patent: Paragraph 0213; 0214; 0215; 0216
[6] Journal of the American Chemical Society, 2014, vol. 136, # 19, p. 7132 - 7139
[7] Chemical Communications, 2015, vol. 51, # 18, p. 3842 - 3845
  • 7
  • [ 7311-64-0 ]
  • [ 70260-17-2 ]
YieldReaction ConditionsOperation in experiment
95% With hydrogenchloride; sodium chloride In tetrahydrofuran; water A/Preparation of 3-Bromo-2-hydroxymethyl-thiophene:
2-(3-Bromothienyl)carboxylic acid (7 g; 34 mmoles) is dissolved in 25 ml of anhydrous THF. A solution of aluminium hydride AlH3 in anhydrous THF (2 M; 42 ml; 84 mmoles) is added slowly at a temperature of 0° C.
At the end of the addition, the reaction mixture is refluxed for 3 hours.
After cooling to 0° C., water (200 ml) and hydrochloric acid (1N, 150 ml) are added.
The mixture is decanted and the aqueous phase extracted with 3*150 ml of tert-butyl methyl ether.
The organic phases are combined and then washed with 150 ml of a saturated solution of sodium chloride, dried over magnesium sulphate and filtered.
The solvent is evaporated under reduced pressure.
The desired product is obtained as a brown oil and is used as such in the next step.
Yield: 95percent; Physical characteristics: * NMR1H: (CD3OD) 4.69 ppm (s; 2H); 6.95 ppm (d; 1H, J=5.2 Hz); 7.39 ppm (d; 1H, J=5.2 Hz).
* NMR13C: (DMSO-d6) 57.80 ppm; 106.28 ppm; 126.11 ppm; 129.80 ppm; 141.15 ppm. * MS: (EI, 70 eV); 194/192 (M+*; 80percent); 177/175 (30percent); 113 (50percent); 98 (60percent); 85 (100percent).
73% With sodium hydroxide; borane In tetrahydrofuran; methanol; (2S)-N-methyl-1-phenylpropan-2-amine hydrate b.
3-Bromo-2-thiophenemethanol
A stirred, ice-water chilled solution of 90.0 g of 3-bromo-2-thiophenecarboxylic acid and 600 ml of sieve dried tetrahydrofuran was treated at 5° C. with 962 ml of borane in tetrahydrofuran (1.04M solution) over 2 hours (nitrogen atmosphere), with exclusion of moisture.
The stirred solution and cooling bath were allowed to equilibrate to ambient temperature overnight.
The stirred, chilled (10° C.) solution was treated dropwise with 150 ml methanol over 2 hours and then with 100 ml of 10percent sodium hydroxide.
After concentration, the residue was diluted with water, adjusted to pH=8 with 10percent sodium hydroxide solution and extracted with ether (2*300 ml).
The combined dried (over anhydrous sodium sulfate) ethereal phase was concentrated.
Distillation gave 61 g (73percent) of product, b.p. 79°-82° C. (0.38 mm).
Analysis:
Calculated for C5 H5 BrOS: 31.11percentC; 2.61percentH. Found: 31.30L percentC; 2.70percentH.
Reference: [1] Patent: US6525040, 2003, B1
[2] Patent: US4560701, 1985, A
  • 8
  • [ 26137-08-6 ]
  • [ 70260-17-2 ]
Reference: [1] Journal of Medicinal Chemistry, 2001, vol. 44, # 14, p. 2319 - 2332
[2] Patent: US6528510, 2003, B1
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