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CAS No. : | 10602-00-3 | MDL No. : | MFCD00168819 |
Formula : | C9H6O2 | Boiling Point : | - |
Linear Structure Formula : | HCCC6H4C(O)OH | InChI Key : | SJXHLZCPDZPBPW-UHFFFAOYSA-N |
M.W : | 146.14 | Pubchem ID : | 589706 |
Synonyms : |
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Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H302-H319 | Packing Group: | N/A |
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 |
---|---|---|
With triethylamine; In tetrahydrofuran; methanol; dichloromethane; | EXAMPLE 7 Diethyl N-(4-ethynylbenzoyl)-L-glutamate To a solution of 0.55 g of 4-ethynylbenzoic acid (obtained from <strong>[111291-97-5]tert.-butyl 4-ethynylbenzoate</strong> in 84% yield by hydrolysis with trifluoroacetic acid) in 50 ml of anhydrous ether and 25 ml of anhydrous tetrahydrofuran is added 1.58 ml of triethylamine. This is followed by 1.00 g of phenyl N-phenylphosphoramidochloridate. After stirring the reaction mixture at room temperature under nitrogen for 0.5 hour, 0.90 g of diethyl L-glutamate is added in one portion. The mixture is allowed to stir for another 8 hrs. After a workup, the residue is subjected to column chromatography using a 1% methanol:methylene chloride mixture as the eluent. The major fraction isolated from the column contained 0.68 g (54%) of diethyl N-(ethynylbenzoyl)-L-glutamate as an oil which slowly solidified: NMR (CDCl3, 300 MHz) delta 1.25 (t, 3H, J=6.9 Hz), 1.33 (t, 3H, J=6.9 Hz), 2.11-2.60 (m, 4H), 3.23 (s, 1H), 4.09 (q, 2H, J=6.9 Hz), 4.27 (1, 2H, J=6.9 Hz), 4.80 (m, 1H), 7.12 (d, 1H, J=7.2 Hz), 7.59 (d, 2H, J=8.4 Hz), 7.81 (d, 2H, J=8.4 Hz); IR (KBr) 3330, 3280, 2990, 1735, 1640, 1520, 1380, 1200, 1105, 1020, 855, and 770 cm -1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; In tetrahydrofuran; at 20℃; for 20h;Inert atmosphere; | Following a literature procedure [10] with slight modification, amixture of 2 (167 mg, 0.268 mmol) and 1 [9] (33 mg, 0.22 mmol) inTHF (7 mL) was stirred under nitrogen atmosphere until a homogeneoussolution was obtained. After that bis(triphenylphosphine)palladium(II) dichloride (2 mg, 0.003 mmol) and copper(I) iodide(2 mg, 0.01 mmol) were added and the reaction mixturewas stirredunder nitrogen atmosphere at room temperature. After 20 h, thereaction mixturewas redissolved in CH2Cl2 andwashed withwater.The organic phase was combined and dried over anhydrous MgSO4.After the removal of solvent under reduced pressure, the crudeproduct was precipitated in MeOH/CH2Cl2 to obtain 3 as a brownsolid (69 mg, 48percent). 1H NMR (DMSO-d6) d 6.78e6.94 (m, 6H), 7.24e7.46 (m, 4 H), 7.56e7.74 (m, 6H); MALDI-TOF-MS m/z obsd 388.508[(M 2I)] calcd avg mass 641.238 (M C27H17I2NO2). Due tothe change in colour observed during storage, compound 3 wasdirectly used in the next step without further purification andcharacterization. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
15% | A mixture of DPP-Br2 (100mg, 0.146mmoles), Ethynyl benzoic acid (20.3mg, 0.138mmoles) and N-(4-ethynylphenyl)-N-phenylbenzenamine (35.6mg, 0.138mmoles) in dry THF (15mL) and NEt3 (3mL) was degassed with dinitrogen for 20min, Then Pd2(dba)3 (80.10mg, 0.087mmol) and AsPh3 (178mg, 0.584mmole) were added to the mixture. The solution was refluxed for 12h under dinitrogen. The solvent was removed in vacuum. The residue was purified on a column chromatograph (silica gel) using CHCl3 /methanol=95/05as eluent to afford DPP1 Yield: 15.0%. 1H NMR (400MHz, CD2Cl2) delta 8.53-8.52 (d, J=7.2Hz, 2H), 7.24-7.23 (d, J=2.1Hz, 4H), 7.22 (t, J=2.3Hz, 4H), 7.20 (d, J=1.4Hz, 2H), 7.18 (d, J=4.0Hz 2H), 7.01 (d, J=2.0Hz, 4H), 7.00 (d, J=6.3, 4H), 3.84 (t, J=7.5Hz, 4H), 1.26-1.14 (m, 16H), 0.82-0.76 (m, 14H). MALDI-TOF MS Calcd. for936.2; Found 937.51. HRMS C59H57N3O4S2 calcd. for 936.03889 found 936.3823. Anal. Calcd. For C59H57N3O4S2% (936.23): C, 75.69; H, 6.14; N, 4.49. Found: C, 75.65; H, 6.13; N, 4.50. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | A mixture of DPP-Br2 (100mg, 0.146mmol), Ethynyl benzoic acid (135mg, 0.96mmol), in dry THF (15mL) and NEt3 (3mL) was degassed with dinitrogen for 10min. Then Pd2(dba)3 (83mg, 0.09mmol) and AsPh3 (190mg, 0.60mmol) were added to the mixture. The solution was refluxed for 12h under dinitrogen. The solvent was removed in vacuum. The residue was purified on a column chromatograph (silica gel) using CHCl3/methanol=85/15 as eluent to afford DPP2 Yield: 65.0%. 1H NMR (500MHz, CDCl3+CD3OD) delta 8.64 (d, J=4.2Hz, 2H), delta 7.93-7.92 (d, J=8.4Hz, 4H), 7.86 (d, J=8.3Hz, 4H) 7.23 (d, J=4.2Hz, 2H), 3.95-3.90 (t, 4H), 1.41-1.18 (m, 16H), 0.93-0.79 (m, 14H). MALDI-TOF MS Calcd. for 813.0; Found 814.12. HRMS C48H48N2O6S2 calcd for 816.06766 found 813.06778. Anal. Calcd. For C48H48N2O6S2% (813.03): C, 70.09; H, 5.95; N, 3.45. Found: C, 70.11; H, 5.93; N, 3.42. |
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