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The BI-3802 was designed by Boehringer Ingelheim and could be obtained free of charge through the Boehringer Ingelheim open innovation portal opnMe.com, associated with its negative control.
Synonyms: MPEG3-Propyne
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Batch number can be found on the product's label following the word 'Batch'.
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CAS No. : | 89635-82-5 |
Formula : | C10H18O4 |
M.W : | 202.25 |
SMILES Code : | COCCOCCOCCOCC#C |
Synonyms : |
MPEG3-Propyne
|
MDL No. : | MFCD27977518 |
InChI Key : | TYHJQPGPBRVOJZ-UHFFFAOYSA-N |
Pubchem ID : | 58079716 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H315-H319-H335 |
Precautionary Statements: | P261-P264-P271-P280-P302+P352-P304+P340-P305+P351+P338-P312-P362-P403+P233-P501 |
* 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 |
---|---|---|
91% | General procedure: NaH (60% w/w in mineral oil, 3 equiv (for bis-propargylation) or 1.5 equiv (for mono-propargylation)) was added to a solution of appropriate diol 15ba-d or alcohol 19a-d (1 equiv) in anhydrous THF (0.2 M) at 0 C under an N2 atmosphere. A catalytic amount (spatula tip) of Bu4NI (0.05 equiv) and propargyl bromide (3 equiv (for bis-propargylation) or 1.5 equiv (for mono-propargylation)) was added sequentially. The mixture was stirred at rt overnight, before being concentrated under reduced pressure. Purification of the residue by flash column chromatography afforded diynes 16b-e and alkynes 9b-e as pale yellow oils. | |
82% | With sodium hydroxide; In tetrahydrofuran; at 20℃;Cooling with ice; | General procedure: A dry flask was charged with THF (15 mL), NaOH pellets (2.40 g, 60 mmol), and n-octanol or triethyleneglycol monomethyl ether (15 mmol). The flask was immersed in an ice-bath and the contents stirred for 10 min. before propargyl bromide (2.51 mL, 22.5 mmol) was added dropwise. The reaction mixture was then allowed to stir for 24 h, gradually warming to r.t. The reaction mixture was poured into Et2O (20 mL) and water (50 mL) and the layers were separated. The aqueous layer was further extracted with Et2O (2 × 20 mL), and the combined organic extracts were washed with 10% aq. HCl, followed by sat. NaHCO3 solution and brine, and then dried over MgSO4. Column chromatography (silica gel, Et2O/light petroleum, 10:90) followed by Kulgelrohr distillation gave the desired products. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | General procedure: Perfluoroalkylethyl iodide (1.0 mol equiv.) (3-5 mmol) and NaN3 (1.0-1.5 mol equiv.) were added to dry DMSO (4 mL), a magnetic stirring bead added, and the mixture stirred under argon in a bath at 65 C for 24 h then cooled to r.t. The methoxytriethylenoxy propargyl ether 21 (1.0 mol equiv.) added, followed by sodium ascorbate (0.1 mol equiv.) and CuSO4·5H2O (0.05 mol equiv.), and additional DMSO (2 mL). The mixture was again stirred under argon at elevated temperature for 48 h. The contents were cooled and diluted with water (50 mL). The product was then extracted into Et2O (3 × 20 mL), and the combined extracts washed in turn with brine (2 × 10 mL), H2O (2 × 10 mL) and again brine (10 mL), then dried and evaporated. The residue was chromatographed on silica gel and the product eluted with a gradient of Et2O/light petroleum and distilled or characterized directly as an oil. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | General procedure: Perfluoroalkylethyl iodide (1.0 mol equiv.) (3-5 mmol) and NaN3 (1.0-1.5 mol equiv.) were added to dry DMSO (4 mL), a magnetic stirring bead added, and the mixture stirred under argon in a bath at 65 C for 24 h then cooled to r.t. The methoxytriethylenoxy propargyl ether 21 (1.0 mol equiv.) added, followed by sodium ascorbate (0.1 mol equiv.) and CuSO4·5H2O (0.05 mol equiv.), and additional DMSO (2 mL). The mixture was again stirred under argon at elevated temperature for 48 h. The contents were cooled and diluted with water (50 mL). The product was then extracted into Et2O (3 × 20 mL), and the combined extracts washed in turn with brine (2 × 10 mL), H2O (2 × 10 mL) and again brine (10 mL), then dried and evaporated. The residue was chromatographed on silica gel and the product eluted with a gradient of Et2O/light petroleum and distilled or characterized directly as an oil. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | General procedure: Perfluoroalkylethyl iodide (1.0 mol equiv.) (3-5 mmol) and NaN3 (1.0-1.5 mol equiv.) were added to dry DMSO (4 mL), a magnetic stirring bead added, and the mixture stirred under argon in a bath at 65 C for 24 h then cooled to r.t. The methoxytriethylenoxy propargyl ether 21 (1.0 mol equiv.) added, followed by sodium ascorbate (0.1 mol equiv.) and CuSO4·5H2O (0.05 mol equiv.), and additional DMSO (2 mL). The mixture was again stirred under argon at elevated temperature for 48 h. The contents were cooled and diluted with water (50 mL). The product was then extracted into Et2O (3 × 20 mL), and the combined extracts washed in turn with brine (2 × 10 mL), H2O (2 × 10 mL) and again brine (10 mL), then dried and evaporated. The residue was chromatographed on silica gel and the product eluted with a gradient of Et2O/light petroleum and distilled or characterized directly as an oil. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | With copper(ll) sulfate pentahydrate; sodium L-ascorbate; In dimethyl sulfoxide; at 70℃; for 2h;Microwave irradiation; | General procedure: Non-fluorous triazolyl triethyleneglycol ethers 27 and 28 were synthesized under modified Meldal-Sharpless conditions from 1-azidohexane and 1-azidooctane, respectively, by treatment in equimolar amounts with methoxy(triethyleneoxy)propyne (3.00 mmol), CuSO4·5H2O (0.15 mmol) and sodium ascorbate (0.30 mmol) in DMSO (1.0 cm3) under microwave irradiation at 70 C and 150 W power for 2 h, followed by chromatography on silica gel.Triazole 27 an oil (73% yield). 1H NMR (300 MHz; CDCl3) δ: 0.87 (t, 3H), 1.31 (m, 6H), 1.92 (m, 2H), 3.37 (s, 3H), 3.65 (m, 2H), 3.60-3.72 (m, 10H), 4.34 (t, 2H), 4.71 (s, 2H), 7.62 (s, 1H). ESI-MS found m/z: 352.2197 (15%), calcd for [M+Na]+m/z: 352.2214; found m/z: 331.2407 (18) calcd for [M+2H]+m/z: 331.2472; found m/z: 330.2378 (100) calcd for [M+H]+m/z: 330.2394. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With copper(ll) sulfate pentahydrate; sodium L-ascorbate; In dimethyl sulfoxide; at 70℃; for 2h;Microwave irradiation; | General procedure: Non-fluorous triazolyl triethyleneglycol ethers 27 and 28 were synthesized under modified Meldal-Sharpless conditions from 1-azidohexane and 1-azidooctane, respectively, by treatment in equimolar amounts with methoxy(triethyleneoxy)propyne (3.00 mmol), CuSO4·5H2O (0.15 mmol) and sodium ascorbate (0.30 mmol) in DMSO (1.0 cm3) under microwave irradiation at 70 C and 150 W power for 2 h, followed by chromatography on silica gel. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With copper(II) sulfate; sodium L-ascorbate; In water; tert-butyl alcohol; at 20 - 50℃; for 10h; | General procedure: CuSO4 solution (5 μL of 0.5 M solution, 2.5 μmol) and sodium ascorbate solution (18 μL of a 1.0 M solution, 18 μmol) were added to a solution of azide 8 (20 mg, 0.023 mmol) and diyne 14a-e or 16a-c (0.011 mmol) or alkyne 9a-e or 11 (0.023 mmol) in tBuOH/H2O (1 mL, 1:1) at rt. The reaction mixture was heated for 10 h at 50 C and then diluted with CHCl3 (10 mL), and washed with brine (3 mL). The phases were separated and the aqueous layer was extracted with CHCl3 (2 × 5 mL). The combined organic layers were dried over MgSO4, filtered and concentrated under reduced pressure. Purification of the residue by flash column chromatography afforded dimers 13a-e and 14a-c and monomers 10a-e and 12. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
General procedure: To a stirred suspension of NaH (60% in mineral oil, 2.4 g, 60 mmol) in dry THF (20 mL) was added a solution of 2-methoxyethanol (3.8 g, 50 mmol) in dry THF (20 mL) dropwise at 0C un der N2. After stirring for 0.5 h, a solution of propargyl bromide (6.5 g, 55 mmol) in anhydrous THF (10 mL) was added. The reaction mixture was allowed to stir at 0C for 1 h. The reaction mixture was quenched with water (30 mL), extracted with EtOAc (3 x 30 mL). The combined organic phases were washed with brine, dried over Na2S04, concentrated, and purified by flash column chromatog raphy (silica gel, eluted with 5-10% EtOAc in heptane) to give Example 9-A (0.8 g, 14%) as a yellow oil.1HNMR (400MHz, CDC13) d 4.21 (d, 2H), 3.72-3.65 (m, 2H), 3.62 -3.51 (m, 2H), 3.39 (s, 3H), 2.43 (t, 1H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With 2,6-dimethylpyridine; tetrakis(actonitrile)copper(I) hexafluorophosphate; In dichloromethane; for 12h;Inert atmosphere; Reflux; | A mixture of 1 (150 mg, 411 pmol, 1 eq), <strong>[89635-82-5]triethylene glycol methyl propargyl ether</strong> (249 mg, 1.23 mmol, 3 eq), Cu(MeCN)4PF6(7.65 mg, 20.5 pmol, 0.05 eq) and one drop of 2,6-lutidine in DCM (10 mL) was refluxedunder argonatmosphere overnight. Solvent was removed and the residue was purified by flash column chromatography (S1O2, 0-8% MeOH in DCM) to afford 2 as a brown oil (316 mg, 99%, Rf = 0.4 in DCM/MeOH = 10/1).1HNMR (500 MHz, DMSO- e, 25 C) d (ppm): 8.60 (s, 2H), 7.79 (d, J= 1.9 Hz, 2H), 7.72 (d, J= 1.9 Hz, 2H), 7.08 (s, 2H), 5.33 (s, 4H), 4.45 (s, 4H), 3.50 - 3.39 (m, 24H), 3.20 (s, 6H), 1.50 (s, 9H).13C NMR (126 MHz, DMSO- e, 25 C) d(ppm): 164.5, 150.5, 150.4, 144.7, 143.0, 135.2, 132.4, 130.9, 129.9, 125.1, 82.1, 71.9, 70.5, 70.4, 70.3, 70.2, 69.5, 64.0, 58.7, 51.3, 28.3.HRMS(ESI-TOF) m/z: [M + H]+calcd for C38H56NVOIO+770.4083, found 770.4086. |