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CAS No. : | 166599-84-4 | MDL No. : | MFCD10000600 |
Formula : | C9H6O3 | Boiling Point : | No data available |
Linear Structure Formula : | - | InChI Key : | WFAPIZKLEVLUMX-UHFFFAOYSA-N |
M.W : | 162.14 | Pubchem ID : | 22324117 |
Synonyms : |
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Signal Word: | Warning | Class: | |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | |
Hazard Statements: | H302-H315-H319-H335 | Packing Group: | |
GHS Pictogram: |
* 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.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With water; lithium hydroxide; In tetrahydrofuran; methanol; at 20℃; for 16h; | A solution of LiOH (1.44 g, 34.3 mmol) in water (20 mL) was added to a solution of 131 (2.02 g, 11.4 mmol) in THF (20mL) and MeOH (20 mL) and the solution was stirred at r.t. for 16 h and then evaporated. The residue was dissolved in water (50 mL) and acidified with cone. HC1 and the precipitate was filtered and dried to give 132 (1.83 g, 99%). 1H NMR (DMSO-d6) δ 13.10 (s, 1H), 8.14 (d, J = 2.1 Hz, 1H), 7.85-7.91 (m, 2H), 7.43 (t, J = 7.9 Hz, 1H), 7.33 (dd, J = 2.1, 1.0 Hz, 1H). Found: [M-H] = 161.1. |
99% | A solution of LiOH (1.44 g, 34.3 mmol) in water (20 mL) wasadded to a solution of the above ester (2.02 g, 11.4 mmol) in THF(20 mL) and MeOH (20 mL) and the solution was stirred at 20 Cfor 16 h and then evaporated. The residue was dissolved in water(50 mL) and acidified with conc. HCl and the precipitate was filteredand dried to give benzofuran-4-carboxylic acid (1.83 g,99%). 1H NMR (DMSO d6) d 13.10 (s, 1H), 8.14 (d, J = 2.1 Hz, 1H),7.85-7.91 (m, 2H), 7.43 (t, J = 7.9 Hz, 1H), 7.33 (dd, J = 2.1, 1.0 Hz,1H). Found: [MH] = 161.1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With oxalyl dichloride;N,N-dimethyl-formamide; In dichloromethane; at 19 - 20℃; for 2.5h; | All volumes and weights refer to the weight of Intermediate 12. The reactor was charged with Intermediate 1 1 (1.0 eq) and DMF (0.025 vol, 0.14 eq) in dichloromethane (1.9 vol) at 20 0C. A solution of oxalyl chloride (0.20 vol, 1.0 eq) in dichloromethane (2.1 vol) was added at 20-19 0C over 30 minutes. The mixture was stirred 2 hours at 19-20 0C. Solvent (2.8 vol) was removed at a maximum jacket temperature of 45 0C under reduced pressure. The solution was stored under nitrogen in a feed tank. The reactor was cleaned, dried under vacuum and charged with Intermediate 12 (1.0 eq, 1 wt) and dichloromethane (7.0 vol). Trifluoroacetic acid (3.05 wt, 12 eq) was added at 19-20 0C over 18 minutes. The mixture was stirred overnight at 20-21 0C. The mixture was split in 2 equal portions. Each portion was washed with half saturated aqueous Na2CO3 (8.6 vol) at 20 0C. The combined organic phases were dried over MgSO4 (0.45 wt). After filtration the filtrate was transferred into the cleaned and dried reactor. Dichloromethane (1.3 vol) and triethylamine (0.96 vol, 3eq) were added.The acid chloride solution was added at 1-5 0C over 25 minutes and the mixture was stirred at 19-22 0C overnight. The mixture was split in 2 equal portions. Each portion was washed with saturated aqueous NaHCO3 (7.3 vol) at 20 0C. The combined organic phases were concentrated in the cleaned reactor. The mixture was filtered through a plug of silica gel (0.78 wt) conditioned with ethyl acetate and eluted with ethyl acetate (8.8 vol). The filtrate was concentrated in the cleaned reactor and a solvent change to iPrOAc was performed. The resulting suspension was heated to obtain a clear solution. The solution was cooled and seed crystals (obtained by cooling of about 1 vol% of the clear solution) was added at 57C. The resulting suspension was concentrated, cooled to 100C, stirred overnight and filtered. The filter cake was washed with iPrOAc and IPA and dried at a max. jacket temperature of 50 0C and reduced pressure at the rotavap to give intermediate grade title compound. Yield (% theory): 48% | |
With thionyl chloride; for 2h;Heating / reflux; | A mixture of <strong>[166599-84-4]benzofuran-4-carboxylic acid</strong> [Eissenstat, et al., J. Medicinal Chemistry, 38 (16) 3094-3105 (1995)] (2.8 g, 17.4 mmol) and thionyl chloride (25 mL) was heated to reflux for 2 h and then concentrated in vacuo. The solid residue was dissolved in ethyl acetate (50 mL) and a solution of N,O-dimethylhydroxylamine hydrochloride (2.8 g) in saturated NaHCO3 (60 mL) was added with stirring. After stirring for 1.5 h, the ethyl acetate layer was separated. The aqueous layer was extracted with ethyl acetate. The ethyl acetate extracts were combined, washed with saturated NaHCO3 and concentrated in vacuo to give an oil (3.2 g, 95.4%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate; N-ethyl-N,N-diisopropylamine; In N,N-dimethyl-formamide; for 0.166667h; | A.9 Synthesis of N-substituted (IR ,2S ,5S )-2-(amino-methyl)-3-aza- bicyclo [3.1.0] -hexane derivativesA.9.1 Synthesis of (lR*,2S*,5S*)-2-(aroylamino-methyl)-3-aza-bicyclo[3.1.0]- hexane-3-carboxylic acid tert-butyl ester derivatives (general procedure); To a solution of the respective carboxylic acid (3.2 mmol, l.lOeq) in DMF (5.0 mL) is added successively DIPEA (8.8 mmol, 3.0eq) and a solution of TBTU (3.7 mmol,1.25eq) in DMF (5.0 mL). The obtained mixture is added to a solution of(IR ,2S ,5S )-2-aminomethyl-3-aza-bicyclo[3.1.0]hexane-3-carboxylic acid tert-butyl ester (2.9 mmol, l.Oeq) in DMF (5.0 mL). After 10 min sat. aq. NaHCO3 solution and ether are added, the layers are separated and the organic layer is washed with sat. NaHCO3 solution, citric acid (5% in water) and water. After drying over Na2SO4 and removal of solvents in vacuo the desired amides are obtained which are used without further purification. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62% | A solution of Intermediate 10 in toluene (1 wt in 6.6 vol) was added to a refluxing mixture of p-toluenesulfonic acid (0.03 eq., 0.03 wt) in toluene (3.8 vol) over 43 minutes. The mixture was stirred under reflux for 33 minutes then solvent (1.1 vol) was withdrawn at 130 0C jacket temperature under slightly reduced pressure (1000- 880 mbar). The mixture was further stirred at reflux. 4.25 hours after the addition of Intermediate 10 the mixture was cooled to 25 0C. The mixture was filtered over silica gel (1.1 wt) that had been conditioned with toluene (4.1 vol). The silica plug was further washed with toluene (8.2 vol). The product containing fractions were combined (total volume 10.8 vol). Solvent (8.6 vol) was withdrawn at 80 0C jacket temperature under reduced pressure. Toluene (0.6 vol) and 1.0 M NaOH (1.5 eq., 7.7 vol) was added and the two-phase mixture was stirred at 60 0C for 9 hours. After cooling to 20 0C the phases were separated and 32% HCI (1.7 vol) was added at 2- 14C to the aqueous phase. After addition of 9.4 vol toluene the mixture was stirred under reflux for 14.5 hours. The suspension was cooled to 20 0C and THF (5.3 vol) was added. The phases were separated and the organic layer was washed two times with a mixture of 5.6 vol water and 0.6 vol THF. 10.3 vol of solvent was distilled off at 80 0C jacket temperature and reduced pressure before 3.2 vol toluene was added. The mixture was refluxed for 33 minutes (ambient pressure), cooled to 0 0C over 3 hours and stirred at that temperature for 2.5 days. The precipitate was filtered, dried for 2 hours in a stream of nitrogen and dried in a rotavap at 50 0C to give the title compound as an off-white solid. Yield (% theory): 62% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With hydrogen;palladium 10% on activated carbon; In acetic acid; under 3102.97 Torr; for 12h; | Benzofuran-4-carboxylic acid [] [Eissenstat, et al, J. Medicinal Chemistry, 38 (16) 3094-3105 (1995)] (10.0 g, 61.7 mmol) was hydrogenated (60 psi) in acetic acid (100 mL) over 10% Pd/C (2 g) for 12 hr. The mixture was filtered and the filtrate was diluted with water (500 mL) to give 2,3-dihydro<strong>[166599-84-4]benzofuran-4-carboxylic acid</strong> as a white powder (8.4 g, 83%). A sample was recrystallized from isopropanol to give fine white needles (mp: 185.5-185.5C). |
With hydrogen;palladium 10% on activated carbon; In ethanol; at 20℃; under 3000.3 Torr; for 16h; | Benzofuran-4-carboxylic acid (30.8 mmol, M.A. Eissenstat et al. J. Med. Chem. 1995, 38, 3094-3105) is added to a suspension of Pd/C (10%, 2.00 g) in EtOH (25 mL). Additional EtOH (75 mL) is added and the mixture is stirred at RT under a hydrogen atmosphere (4 bar) for 16 h. After filtration through celite and removal of the solvents the desired product is obtained which is used without further purification. 1H-NMR (DMSO-dβ): δ = 3.45 (t, J = 8.79 Hz, 2H); 4.55 (t, J = 8.79 Hz, 2H); 6.99 (d, J = 7.78 Hz, IH); 7.21 (t, J = 7.91 Hz, IH); 7.39 (d, J = 7.78 Hz, IH); 12.9 (bs, IH). | |
With hydrogen;palladium 10% on activated carbon; In ethanol; at 20℃; under 3000.3 Torr; for 16h; | Benzofuran-4-carboxylic acid (30.8 mmol, M.A. Eissenstat et al. J. Med. Chem. 1995, 38, 3094-3105) is added to a suspension of Pd/C (10%, 2.00 g) in EtOH (25 mL). Additional EtOH (75 mL) is added and the mixture is stirred at RT under a hydrogen atmosphere (4 bar) for 16 h. After filtration through celite and removal of the solvents the desired product is obtained which is used without further purification. 1H-NMR (DMSO-d6): δ = 3.45 (t, J = 8.79 Hz, 2H); 4.55 (t, J = 8.79 Hz, 2H); 6.99 (d, J = 7.78 Hz, IH); 7.21 (t, J = 7.91 Hz, IH); 7.39 (d, J = 7.78 Hz, IH); 12.9 (bs, IH). |
With hydrogen;palladium 10% on activated carbon; In ethanol; at 20℃; under 3000.3 Torr; for 16h; | Benzofuran-4-carboxylic acid (30.8 mmol, M.A. Eissenstat et al. J. Med. Chem. 1995, 38, 3094-3105) is added to a suspension of Pd/C (10%, 2.00 g) in EtOH (25 mL). Additional EtOH (75 mL) is added and the mixture is stirred at RT under a hydrogen atmosphere (4 bar) for 16 h. After filtration through celite and removal of the solvents the desired product is obtained which is used without further purification. 1H-NMR (DMSO-de): δ = 3.45 (t, J = 8.79 Hz, 2H); 4.55 (t, J = 8.79 Hz, 2H); 6.99 (d, J = 7.78 Hz, IH); 7.21 (t, J = 7.91 Hz, IH); 7.39 (d, J = 7.78 Hz, IH); 12.9 (bs, IH). | |
With hydrogen;palladium 10% on activated carbon; In ethanol; at 20℃; under 3000.3 Torr; for 16h; | Benzofuran-4-carboxylic acid (30.8 mmol, M. A. Eissenstat et al. J. Med. Chem. 1995, 38, 3094-3105) is added to a suspension of Pd/C (10%, 2.00 g) in EtOH (25 mL). Additional EtOH (75 mL) is added and the mixture is stirred at RT under a hydrogen atmosphere (4 bar) for 16 h. After filtration through celite and removal of the solvents the desired product is obtained which is used without further purification. 1H-NMR (DMSO-d6): δ=3.45 (t, J=8.79 Hz, 2H); 4.55 (t, J=8.79 Hz, 2H); 6.99 (d, J=7.78 Hz, 1H); 7.21 (t, J=7.91 Hz, 1H); 7.39 (d, J=7.78 Hz, 1H); 12.9 (bs, 1H). | |
With hydrogen;palladium 10% on activated carbon; In ethanol; at 20℃; under 3000.3 Torr; for 16h; | A.2 Synthesis of 2,3-dihydro-<strong>[166599-84-4]benzofuran-4-carboxylic acid</strong> Benzofuran-4-carboxylic acid (30.8 mmol, M. A. Eissenstat et al. J. Med. Chem. 1995, 38, 3094-3105) is added to a suspension of Pd/C (10%, 2.00 g) in EtOH (25 mL). Additional EtOH (75 mL) is added and the mixture is stirred at RT under a hydrogen atmosphere (4 bar) for 16 h. After filtration through celite and removal of the solvents the desired product is obtained which is used without further purification. 1H-NMR (DMSO-d6): δ=3.45 (t, J=8.79 Hz, 2H); 4.55 (t, J=8.79 Hz, 2H); 6.99 (d, J=7.78 Hz, 1H); 7.21 (t, J=7.91 Hz, 1H); 7.39 (d, J=7.78 Hz, 1H); 12.9 (bs, 1H). | |
With hydrogen;palladium 10% on activated carbon; In acetic acid; under 3102.97 Torr; for 12h; | Benzofuran-4-carboxylic acid (10.0 g, 61.7 mmol) was hydrogenated (60 psi) in acetic acid (100 mL) over 10% Pd/C (2 g) for 12 hr. The mixture was filtered and the filtrate was diluted with water (500 mL) to give 2,3-dihydro<strong>[166599-84-4]benzofuran-4-carboxylic acid</strong> as a white powder (8.4 g, 83%). A sample was recrystallized from isopropanol to give fine white needles (mp: 185.5-187.5C). | |
With palladium 10% on activated carbon; hydrogen; In methanol; at 25℃; under 2585.81 Torr; for 12h; | A third exemplary Intermediate B, Intermediate B-3, may be used to synthesize compounds of formula I wherein Z is O, n is one, X is C(R5)2, - is a single bond and one R3 is chlorine. To a solution of <strong>[166599-84-4]benzofuran-4-carboxylic acid</strong> (900 mg, 5.55 mmol, 1 equiv) in MeOH (9.00 mL) was added palladium on activated carbon (20.0 mg, 555 pmol, 10.0 wt %, 0.10 equiv) under nitrogen. The vessel was evacuated and purged with hydrogen several times. The mixture was stirred at 25 C for 12 h under hydrogen (50.0 psi). The reaction mixture was filtered and the filtrate was concentrated in vacuo to afford 2, 3-dihydro<strong>[166599-84-4]benzofuran-4-carboxylic acid</strong> (750 mg, 3.66 mmol, 65.9% yield, 80.0% purity) as a white solid. 1H NMR (400MHz, DMSO-d6) d = 7.38 (d, J=8.0 Hz, 1H), 7.20 (t, =8.0 Hz, 1H), 6.97 (d, =8.0 Hz, 1H), 4.54 (t, =8.8 Hz, 2H), 3.45 (br t, =8.8 Hz, 2H). | |
With palladium 10% on activated carbon; hydrogen; In methanol; at 25℃; under 2585.81 Torr; for 12h; | To a solution of <strong>[166599-84-4]benzofuran-4-carboxylic acid</strong> (900 mg, 5.55 mmol, 1 equiv) in MeOH (9.00 mL) was added palladium on activated carbon (20.0 mg, 555 μmol, 10.0 wt %, 0.10 equiv) under nitrogen. The vessel was evacuated and purged with hydrogen several times. The mixture was stirred at 25 C for 12 h under hydrogen (50.0 psi). The reaction mixture was filtered and the filtrate was concentrated in vacuo to afford 2,3-dihydrobenzofuran-4- carboxylic acid (750 mg, 3.66 mmol, 65.9% yield, 80.0% purity) as a white solid. [0271] 1H NMR (400MHz, DMSO-d6) d = 7.38 (d, J = 8.0 Hz, 1H), 7.20 (t, J = 8.0 Hz, 1H), 6.97 (d, J = 8.0 Hz, 1H), 4.54 (t, J = 8.8 Hz, 2H), 3.45 (br t, J = 8.8 Hz, 2H). | |
With palladium 10% on activated carbon; hydrogen; In methanol; at 25℃; under 2585.81 Torr; for 12h; | To a solution of <strong>[166599-84-4]benzofuran-4-carboxylic acid</strong> (900 mg, 5.55 mmol, 1 equiv) in MeOH (9.00 mL) was added palladium on activated carbon (20.0 mg, 555 mol, 10.0 wt %, 0.10 equiv) under nitrogen. The vessel was evacuated and purged with hydrogen several times. The mixture was stirred at 25 C for 12 h under hydrogen (50.0 psi). The reaction mixture was filtered and the filtrate was concentrated in vacuo to afford 2,3-dihydro<strong>[166599-84-4]benzofuran-4-carboxylic acid</strong> (750 mg, 3.66 mmol, 65.9 % yield, 80.0% purity) as a white solid. [0186] 1H NMR (400MHz, DMSO-d6) d = 7.38 (d, J=8.0 Hz, 1H), 7.20 (t, J=8.0 Hz, 1H), 6.97 (d, J=8.0 Hz, 1H), 4.54 (t, J=8.8 Hz, 2H), 3.45 (br t, J=8.8 Hz, 2H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With diphenylphosphoranyl azide; triethylamine; In tert-butyl alcohol; | Using analogous procedures to those described in J. Med. Chem., 1995, 38, 3102-3103, methyl 2-allyl-3-hydroxybenzoate was converted in three steps via methyl 2-hydroxy-2,3-dihydrobenzofuran-4-carboxylate and methyl benzofuran-4-carboxylate into <strong>[166599-84-4]benzofuran-4-carboxylic acid</strong>. A mixture of benzofuran-4carboxylic acid (0.5 g), diphenylphosphoryl azide (1.2 ml), triethylamine (0.79 ml) and tert-butanol (1.5 ml) were stirred and heated to reflux for 18 hours. The mixture was cooled to ambient temperature and partitioned between ethyl acetate and water. The organic phase was washed in turn with water and brine, dried over magnesium sulphate and evaporated. The residue was purified by column chromatography using methylene chloride as eluent. There was thus obtained tert-butyl benzofuran-4-carbamate (0.8 g) as an oil; Mass Spectrum: M+Na+ 256. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With benzotriazol-1-yloxyl-tris-(pyrrolidino)-phosphonium hexafluorophosphate; N-ethyl-N,N-diisopropylamine; In N,N-dimethyl-formamide; at 20℃; for 20h; | A.2.4 Synthesis of (R)-3-[(benzofuran-4-carbonyl)-amino]-piperidine-l- carboxylic acid tert-buty ester; A mixture of (R)-3-amino-l-N-Boc-piperidine (1 g), <strong>[166599-84-4]benzofuran-4-carboxylic acid</strong> (809 mg), PyBOP (2.6g), DIEA (1.96 mL) in dry DMF (10 mL) was stirred at RT under nitrogen for 20 h. The reaction mixture was diluted with EA, washed with water. The aqueous phase was extracted twice with EA, the combined organic extracts were washed with brine, dried (MgSO4), filtered and concentrated to yield a crude light brown oil. FC (EA/ n-heptane: 1/1 to EA) gave 1.41 g (82%) of the title compound as an oil. LC-MS: tR = 0.93 min; [M+H]+ = 345. |
82% | With benzotriazol-1-yloxyl-tris-(pyrrolidino)-phosphonium hexafluorophosphate; N-ethyl-N,N-diisopropylamine; In N,N-dimethyl-formamide; at 20℃; for 20h; | A mixture of (R)-3-amino-1-N-Boc-piperidine (1 g), <strong>[166599-84-4]benzofuran-4-carboxylic acid</strong> (809 mg), PyBOP (2.6 g), DIEA (1.96 mL) in dry DMF (10 mL) was stirred at RT under nitrogen for 20 h. The reaction mixture was diluted with EA, washed with water. The aqueous phase was extracted twice with EA, the combined organic extracts were washed with brine, dried (MgSO4), filtered and concentrated to yield a crude light brown oil. FC (EA/n-heptane: 1/1 to EA) gave 1.41 g (82%) of the title compound as an oil.LC-MS: tR=0.93 min; [M+H]+=345. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate; N-ethyl-N,N-diisopropylamine; for 2h; | TBTU (1.24 mmol, 1.05eq) is added to a solution of the respective carboxylic acid (1.18 mmol, l.Oeq), (lS,3S,5S)-3-aminomethyl-2-aza-bicyclo[3.1.0]hexane-2-carboxylic acid tert-butyl ester (1.18 mmol, l.Oeq) and DIPEA (1.77 mmol, 1.5eq) in DCM, DMF or acetonitrile (10 mL). After 2h the mixture is washed with water, hydrochloric acid (0.5 M) and water. The organic layer is dried over Na2SO4, the solvents are removed in vacuo and the residue is purified by prep. HPLC or by flash chromatography (EtO Ac/heptane).(lS,3S,5S)-3-[(benzofuran-4-carbonyl)-amino]-methyl}-2-aza-bicyclo[3.1.0]hexane-2- carboxylic acid tert-butyl ester prepared by reaction of (lS,3S,5S)-3-aminomethyl-2-aza-bicyclo[3.1.0]hexane-2- carboxylic acid tert-butyl ester with <strong>[166599-84-4]benzofuran-4-carboxylic acid</strong> (M.A. Eissenstat et al. J. Med. Chem. 1995, 38, 3094-3105). LC-MS (acidic): tR = 1.00 min; [M+H]+ = 357.1. 1H- NMR (CDCl3): δ = 0.58 (bs, IH); 0.80-0.86 (m, IH); 1.52 (s, 9H); 1.52-1.59 (m, IH); 1.79 (bd, J = 13.3 Hz, IH); 2.51-2.60 (m, IH); 3.24-3.30 (m, IH); 3.60-3.64 (m, 2H); 4.45-4.52 (m, IH); 7.32 (t, J = 7.9 Hz, IH); 7.47 (bs, IH); 7.61 (d, J = 8.2 Hz, IH); 7.65 (d, J = 7.5 Hz, IH); 7.70 (bs, IH); 8.43 (bs, IH). |
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