* 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.
With ferric sulfate nonahydrate In water at 80℃; for 24 h;
General procedure: To model the chemical environment on the outer side of thetubular structures, NH2CHO (200 μL) was mixed with thesodium silicate solution (2.0 mL) in the presence of preformedMSH [ZnCl2, FeCl2·4H2O, CuCl2·2H2O, Fe2(SO4)3·9H2O,and MgSO4] (2.0percent w/w) at 80 °C for 24 h. In two selectedcases [FeCl2 and Fe2(SO4)3·9H2O], NH2CHO (200 μL) wasmixed with the sodium silicate solution (2.0 mL) in the presence of selected growing MSH (starting from 2.0percent w/w ofthe corresponding salt’s pellet) at 80 °C for 24 h. For the innerenvironment, NH2CHO (200 μL) was mixed with distilledwater (2.0 mL) in the presence of selected MSH (2.0percent w/w) at80 °C for 24 h. The reaction of NH2CHO (10percent v/v) with thesodium silicate solution (pH 12) without MSH membranes wasalso analyzed under similar experimental conditions. Theproducts were analyzed by gas chromatography associatedwith mass spectrometry (GC-MS) after treatment with N,Nbis-trimethylsilyl trifluoroacetamide in pyridine (620 μL) at 60°C for 4 h in the presence of betulinol (CAS Registry Number473-98-3) as the internal standard (0.2 mg). Mass spectrometrywas performed by the following program: injection temperature280 °C, detector temperature 280 °C, gradient 100 °C for 2min, and 10 °C/min for 60 min. To identify the structure of theproducts, two strategies were followed. First, the spectra werecompared with commercially available electron mass spectrumlibraries such as NIST (Fison, Manchester, U.K.). Second, GCMSanalysis was repeated with standard compounds. Allproducts have been recognized with a similarity index (SI)greater than 98percent compared to that of the reference standards.The analysis was limited to products of ≥1 ng/mL, and theyield was calculated as micrograms of product per startingformamide. For further experimental details, see the SupportingInformation.
General procedure: To model the chemical environment on the outer side of thetubular structures, NH2CHO (200 μL) was mixed with thesodium silicate solution (2.0 mL) in the presence of preformedMSH [ZnCl2, FeCl2·4H2O, CuCl2·2H2O, Fe2(SO4)3·9H2O,and MgSO4] (2.0percent w/w) at 80 °C for 24 h. In two selectedcases [FeCl2 and Fe2(SO4)3·9H2O], NH2CHO (200 μL) wasmixed with the sodium silicate solution (2.0 mL) in the presence of selected growing MSH (starting from 2.0percent w/w ofthe corresponding salt’s pellet) at 80 °C for 24 h. For the innerenvironment, NH2CHO (200 μL) was mixed with distilledwater (2.0 mL) in the presence of selected MSH (2.0percent w/w) at80 °C for 24 h. The reaction of NH2CHO (10percent v/v) with thesodium silicate solution (pH 12) without MSH membranes wasalso analyzed under similar experimental conditions. Theproducts were analyzed by gas chromatography associatedwith mass spectrometry (GC-MS) after treatment with N,Nbis-trimethylsilyl trifluoroacetamide in pyridine (620 μL) at 60°C for 4 h in the presence of betulinol (CAS Registry Number473-98-3) as the internal standard (0.2 mg). Mass spectrometrywas performed by the following program: injection temperature280 °C, detector temperature 280 °C, gradient 100 °C for 2min, and 10 °C/min for 60 min. To identify the structure of theproducts, two strategies were followed. First, the spectra werecompared with commercially available electron mass spectrumlibraries such as NIST (Fison, Manchester, U.K.). Second, GCMSanalysis was repeated with standard compounds. Allproducts have been recognized with a similarity index (SI)greater than 98percent compared to that of the reference standards.The analysis was limited to products of ≥1 ng/mL, and theyield was calculated as micrograms of product per startingformamide. For further experimental details, see the SupportingInformation.
Reference：
[1] Chemistry - A European Journal, 2018, vol. 24, # 32, p. 8126 - 8132
4
[ 77287-34-4 ]
[ 51953-18-5 ]
[ 1455-77-2 ]
[ 120-89-8 ]
[ 73-40-5 ]
[ 328-42-7 ]
[ 2491-15-8 ]
[ 110-15-6 ]
[ 71-30-7 ]
[ 120-73-0 ]
[ 144-62-7 ]
[ 113-00-8 ]
[ 127-17-3 ]
[ 66-22-8 ]
[ 66224-66-6 ]
[ 57-13-6 ]
[ 56-40-6 ]
[ 302-72-7 ]
Reference：
[1] Chemistry - A European Journal, 2018, vol. 24, # 32, p. 8126 - 8132
5
[ 77287-34-4 ]
[ 51953-18-5 ]
[ 1455-77-2 ]
[ 120-89-8 ]
[ 849585-22-4 ]
[ 73-40-5 ]
[ 328-42-7 ]
[ 2491-15-8 ]
[ 110-15-6 ]
[ 71-30-7 ]
[ 120-73-0 ]
[ 144-62-7 ]
[ 113-00-8 ]
[ 127-17-3 ]
[ 66-22-8 ]
[ 56-06-4 ]
[ 66224-66-6 ]
[ 57-13-6 ]
[ 56-40-6 ]
[ 302-72-7 ]
[ 18588-61-9 ]
Reference：
[1] Chemistry - A European Journal, 2018, vol. 24, # 32, p. 8126 - 8132
6
[ 64-18-6 ]
[ 56-40-6 ]
[ 2491-15-8 ]
Yield
Reaction Conditions
Operation in experiment
74%
Stage #1: at 45℃; for 1 h; Stage #2: at 20℃; for 24 h;
General procedure: Formic acid (140mL, 3.71mol) and acetic anhydride (47mL, 0.50mol) were stirred at 45°C for 1h. After the addition of the appropriate amino acid (0.05mol), the mixture was left stirring at room temperature for 24h, and evaporated until dryness.
67%
at 20℃; for 24 h;
Glycine (5.20 g, 69.23 mmol) was dissolved in formic acid (25 mL), was added acetic anhydride (3.0 eq, 21.3 mL), was stirred for 24 hours at room temperature the reaction. After completion of the reaction, the reaction mixture was concentrated under reduced pressure, recrystallized by adding methanol and ethyl acetate, the corresponding formamide (1a) was obtained (4.81 g, 46.66 mmol, 67percent).Compound 1a (0.95 g, 9.18 mmol) and, DMF (20 mL) inAt, benzyl bromide (1.5 eq, 1.64 mL) and potassium carbonate (3.2 eq, 3.99 g) and, at room temperatureIt was stirred for 48 hours. After completion of the reaction, water is added to inactivate the reaction mixture, with ethyl acetateExtracted. The organic layer was washed with saturated brine, dried with magnesium sulfate, filtered, concentrated under reduced pressureIt was carried out. The residue was purified by silica gel chromatography (hexane: ethyl acetate = 1: 1 → 1: 9) To give the corresponding benzyl ester (1b) (400 mg, was obtained 2.02 mmol, 22percent).Compound 1b (514.8 mg, 2.66 mmol) was added in DCM (10 mL), the mixture obtained (PhO) 2POCl (1.5 eq, 582 μL) and pyridine (5.0 eq, 1.88 mL) was added, and 2.5 hours with stirring to line the reactionWas Tsu. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer, hydrochloric acid, carbonSodium acid hydrogen, water, and successively washed with saturated brine, and dried over magnesium sulfate,After filtration, it was concentrated under reduced pressure.
Reference：
[1] Organic and Biomolecular Chemistry, 2015, vol. 14, # 1, p. 93 - 96
[2] Synthetic Communications, 1983, vol. 13, # 9, p. 745 - 752
[3] Organic Letters, 2018, vol. 20, # 18, p. 5877 - 5880
[4] Chemical Communications, 2012, vol. 48, # 31, p. 3775 - 3777
[5] Tetrahedron, 2013, vol. 69, # 43, p. 9161 - 9165
[6] Patent: JP2015/42622, 2015, A, . Location in patent: Paragraph 0124
[7] Chemische Berichte, 1905, vol. 38, p. 3999
[8] Chemische Berichte, 1905, vol. 38, p. 3999
[9] Journal of Organic Chemistry, 1961, vol. 26, p. 4698 - 4701
[10] Journal of the American Chemical Society, 1984, vol. 106, # 11, p. 3344 - 3353
[11] Journal of the American Chemical Society, 1999, vol. 121, # 7, p. 1434 - 1443
[12] Patent: CN106831628, 2017, A, . Location in patent: Paragraph 0011; 0030; 0034; 0036; 0041; 0046
7
[ 77287-34-4 ]
[ 2491-15-8 ]
[ 113-00-8 ]
[ 127-17-3 ]
[ 56-40-6 ]
Yield
Reaction Conditions
Operation in experiment
0.0034 mg
With iron(II) chloride tetrahydrate In water at 80℃; for 24 h;
General procedure: To model the chemical environment on the outer side of thetubular structures, NH2CHO (200 μL) was mixed with thesodium silicate solution (2.0 mL) in the presence of preformedMSH [ZnCl2, FeCl2·4H2O, CuCl2·2H2O, Fe2(SO4)3·9H2O,and MgSO4] (2.0percent w/w) at 80 °C for 24 h. In two selectedcases [FeCl2 and Fe2(SO4)3·9H2O], NH2CHO (200 μL) wasmixed with the sodium silicate solution (2.0 mL) in the presence of selected growing MSH (starting from 2.0percent w/w ofthe corresponding salt’s pellet) at 80 °C for 24 h. For the innerenvironment, NH2CHO (200 μL) was mixed with distilledwater (2.0 mL) in the presence of selected MSH (2.0percent w/w) at80 °C for 24 h. The reaction of NH2CHO (10percent v/v) with thesodium silicate solution (pH 12) without MSH membranes wasalso analyzed under similar experimental conditions. Theproducts were analyzed by gas chromatography associatedwith mass spectrometry (GC-MS) after treatment with N,Nbis-trimethylsilyl trifluoroacetamide in pyridine (620 μL) at 60°C for 4 h in the presence of betulinol (CAS Registry Number473-98-3) as the internal standard (0.2 mg). Mass spectrometrywas performed by the following program: injection temperature280 °C, detector temperature 280 °C, gradient 100 °C for 2min, and 10 °C/min for 60 min. To identify the structure of theproducts, two strategies were followed. First, the spectra werecompared with commercially available electron mass spectrumlibraries such as NIST (Fison, Manchester, U.K.). Second, GCMSanalysis was repeated with standard compounds. Allproducts have been recognized with a similarity index (SI)greater than 98percent compared to that of the reference standards.The analysis was limited to products of ≥1 ng/mL, and theyield was calculated as micrograms of product per startingformamide. For further experimental details, see the SupportingInformation.
0.0052 mg
With zinc(II) chloride In water at 80℃; for 24 h;
General procedure: To model the chemical environment on the outer side of thetubular structures, NH2CHO (200 μL) was mixed with thesodium silicate solution (2.0 mL) in the presence of preformedMSH [ZnCl2, FeCl2·4H2O, CuCl2·2H2O, Fe2(SO4)3·9H2O,and MgSO4] (2.0percent w/w) at 80 °C for 24 h. In two selectedcases [FeCl2 and Fe2(SO4)3·9H2O], NH2CHO (200 μL) wasmixed with the sodium silicate solution (2.0 mL) in the presence of selected growing MSH (starting from 2.0percent w/w ofthe corresponding salt’s pellet) at 80 °C for 24 h. For the innerenvironment, NH2CHO (200 μL) was mixed with distilledwater (2.0 mL) in the presence of selected MSH (2.0percent w/w) at80 °C for 24 h. The reaction of NH2CHO (10percent v/v) with thesodium silicate solution (pH 12) without MSH membranes wasalso analyzed under similar experimental conditions. Theproducts were analyzed by gas chromatography associatedwith mass spectrometry (GC-MS) after treatment with N,Nbis-trimethylsilyl trifluoroacetamide in pyridine (620 μL) at 60°C for 4 h in the presence of betulinol (CAS Registry Number473-98-3) as the internal standard (0.2 mg). Mass spectrometrywas performed by the following program: injection temperature280 °C, detector temperature 280 °C, gradient 100 °C for 2min, and 10 °C/min for 60 min. To identify the structure of theproducts, two strategies were followed. First, the spectra werecompared with commercially available electron mass spectrumlibraries such as NIST (Fison, Manchester, U.K.). Second, GCMSanalysis was repeated with standard compounds. Allproducts have been recognized with a similarity index (SI)greater than 98percent compared to that of the reference standards.The analysis was limited to products of ≥1 ng/mL, and theyield was calculated as micrograms of product per startingformamide. For further experimental details, see the SupportingInformation.
Reference：
[1] Journal of Chemical Research, 2013, vol. 37, # 3, p. 181 - 185
9
[ 128038-38-0 ]
[ 2491-15-8 ]
Reference：
[1] Synthesis, 1990, # 2, p. 122 - 124
10
[ 77287-34-4 ]
[ 156-81-0 ]
[ 849585-22-4 ]
[ 617-48-1 ]
[ 2491-15-8 ]
[ 110-15-6 ]
[ 108-53-2 ]
[ 71-30-7 ]
[ 113-00-8 ]
[ 127-17-3 ]
[ 66-22-8 ]
[ 66224-66-6 ]
[ 56-40-6 ]
[ 302-72-7 ]
[ 18514-52-8 ]
Yield
Reaction Conditions
Operation in experiment
0.18 mg
With ferric sulfate nonahydrate In water at 80℃; for 24 h;
General procedure: To model the chemical environment on the outer side of thetubular structures, NH2CHO (200 μL) was mixed with thesodium silicate solution (2.0 mL) in the presence of preformedMSH [ZnCl2, FeCl2·4H2O, CuCl2·2H2O, Fe2(SO4)3·9H2O,and MgSO4] (2.0percent w/w) at 80 °C for 24 h. In two selectedcases [FeCl2 and Fe2(SO4)3·9H2O], NH2CHO (200 μL) wasmixed with the sodium silicate solution (2.0 mL) in the presence of selected growing MSH (starting from 2.0percent w/w ofthe corresponding salt’s pellet) at 80 °C for 24 h. For the innerenvironment, NH2CHO (200 μL) was mixed with distilledwater (2.0 mL) in the presence of selected MSH (2.0percent w/w) at80 °C for 24 h. The reaction of NH2CHO (10percent v/v) with thesodium silicate solution (pH 12) without MSH membranes wasalso analyzed under similar experimental conditions. Theproducts were analyzed by gas chromatography associatedwith mass spectrometry (GC-MS) after treatment with N,Nbis-trimethylsilyl trifluoroacetamide in pyridine (620 μL) at 60°C for 4 h in the presence of betulinol (CAS Registry Number473-98-3) as the internal standard (0.2 mg). Mass spectrometrywas performed by the following program: injection temperature280 °C, detector temperature 280 °C, gradient 100 °C for 2min, and 10 °C/min for 60 min. To identify the structure of theproducts, two strategies were followed. First, the spectra werecompared with commercially available electron mass spectrumlibraries such as NIST (Fison, Manchester, U.K.). Second, GCMSanalysis was repeated with standard compounds. Allproducts have been recognized with a similarity index (SI)greater than 98percent compared to that of the reference standards.The analysis was limited to products of ≥1 ng/mL, and theyield was calculated as micrograms of product per startingformamide. For further experimental details, see the SupportingInformation.
General procedure: To model the chemical environment on the outer side of thetubular structures, NH2CHO (200 μL) was mixed with thesodium silicate solution (2.0 mL) in the presence of preformedMSH [ZnCl2, FeCl2·4H2O, CuCl2·2H2O, Fe2(SO4)3·9H2O,and MgSO4] (2.0percent w/w) at 80 °C for 24 h. In two selectedcases [FeCl2 and Fe2(SO4)3·9H2O], NH2CHO (200 μL) wasmixed with the sodium silicate solution (2.0 mL) in the presence of selected growing MSH (starting from 2.0percent w/w ofthe corresponding salt’s pellet) at 80 °C for 24 h. For the innerenvironment, NH2CHO (200 μL) was mixed with distilledwater (2.0 mL) in the presence of selected MSH (2.0percent w/w) at80 °C for 24 h. The reaction of NH2CHO (10percent v/v) with thesodium silicate solution (pH 12) without MSH membranes wasalso analyzed under similar experimental conditions. Theproducts were analyzed by gas chromatography associatedwith mass spectrometry (GC-MS) after treatment with N,Nbis-trimethylsilyl trifluoroacetamide in pyridine (620 μL) at 60°C for 4 h in the presence of betulinol (CAS Registry Number473-98-3) as the internal standard (0.2 mg). Mass spectrometrywas performed by the following program: injection temperature280 °C, detector temperature 280 °C, gradient 100 °C for 2min, and 10 °C/min for 60 min. To identify the structure of theproducts, two strategies were followed. First, the spectra werecompared with commercially available electron mass spectrumlibraries such as NIST (Fison, Manchester, U.K.). Second, GCMSanalysis was repeated with standard compounds. Allproducts have been recognized with a similarity index (SI)greater than 98percent compared to that of the reference standards.The analysis was limited to products of ≥1 ng/mL, and theyield was calculated as micrograms of product per startingformamide. For further experimental details, see the SupportingInformation.
General procedure: To model the chemical environment on the outer side of thetubular structures, NH2CHO (200 μL) was mixed with thesodium silicate solution (2.0 mL) in the presence of preformedMSH [ZnCl2, FeCl2·4H2O, CuCl2·2H2O, Fe2(SO4)3·9H2O,and MgSO4] (2.0percent w/w) at 80 °C for 24 h. In two selectedcases [FeCl2 and Fe2(SO4)3·9H2O], NH2CHO (200 μL) wasmixed with the sodium silicate solution (2.0 mL) in the presence of selected growing MSH (starting from 2.0percent w/w ofthe corresponding salt’s pellet) at 80 °C for 24 h. For the innerenvironment, NH2CHO (200 μL) was mixed with distilledwater (2.0 mL) in the presence of selected MSH (2.0percent w/w) at80 °C for 24 h. The reaction of NH2CHO (10percent v/v) with thesodium silicate solution (pH 12) without MSH membranes wasalso analyzed under similar experimental conditions. Theproducts were analyzed by gas chromatography associatedwith mass spectrometry (GC-MS) after treatment with N,Nbis-trimethylsilyl trifluoroacetamide in pyridine (620 μL) at 60°C for 4 h in the presence of betulinol (CAS Registry Number473-98-3) as the internal standard (0.2 mg). Mass spectrometrywas performed by the following program: injection temperature280 °C, detector temperature 280 °C, gradient 100 °C for 2min, and 10 °C/min for 60 min. To identify the structure of theproducts, two strategies were followed. First, the spectra werecompared with commercially available electron mass spectrumlibraries such as NIST (Fison, Manchester, U.K.). Second, GCMSanalysis was repeated with standard compounds. Allproducts have been recognized with a similarity index (SI)greater than 98percent compared to that of the reference standards.The analysis was limited to products of ≥1 ng/mL, and theyield was calculated as micrograms of product per startingformamide. For further experimental details, see the SupportingInformation.
General procedure: To model the chemical environment on the outer side of thetubular structures, NH2CHO (200 μL) was mixed with thesodium silicate solution (2.0 mL) in the presence of preformedMSH [ZnCl2, FeCl2·4H2O, CuCl2·2H2O, Fe2(SO4)3·9H2O,and MgSO4] (2.0percent w/w) at 80 °C for 24 h. In two selectedcases [FeCl2 and Fe2(SO4)3·9H2O], NH2CHO (200 μL) wasmixed with the sodium silicate solution (2.0 mL) in the presence of selected growing MSH (starting from 2.0percent w/w ofthe corresponding salt’s pellet) at 80 °C for 24 h. For the innerenvironment, NH2CHO (200 μL) was mixed with distilledwater (2.0 mL) in the presence of selected MSH (2.0percent w/w) at80 °C for 24 h. The reaction of NH2CHO (10percent v/v) with thesodium silicate solution (pH 12) without MSH membranes wasalso analyzed under similar experimental conditions. Theproducts were analyzed by gas chromatography associatedwith mass spectrometry (GC-MS) after treatment with N,Nbis-trimethylsilyl trifluoroacetamide in pyridine (620 μL) at 60°C for 4 h in the presence of betulinol (CAS Registry Number473-98-3) as the internal standard (0.2 mg). Mass spectrometrywas performed by the following program: injection temperature280 °C, detector temperature 280 °C, gradient 100 °C for 2min, and 10 °C/min for 60 min. To identify the structure of theproducts, two strategies were followed. First, the spectra werecompared with commercially available electron mass spectrumlibraries such as NIST (Fison, Manchester, U.K.). Second, GCMSanalysis was repeated with standard compounds. Allproducts have been recognized with a similarity index (SI)greater than 98percent compared to that of the reference standards.The analysis was limited to products of ≥1 ng/mL, and theyield was calculated as micrograms of product per startingformamide. For further experimental details, see the SupportingInformation.
Reference：
[1] Chemical Communications, 2008, # 26, p. 3001 - 3003
15
[ 77287-34-4 ]
[ 849585-22-4 ]
[ 617-48-1 ]
[ 2491-15-8 ]
[ 110-15-6 ]
[ 144-62-7 ]
[ 113-00-8 ]
[ 127-17-3 ]
[ 57-13-6 ]
[ 18514-52-8 ]
Yield
Reaction Conditions
Operation in experiment
0.9 mg
at 80℃; for 24 h;
General procedure: To model the chemical environment on the outer side of thetubular structures, NH2CHO (200 μL) was mixed with thesodium silicate solution (2.0 mL) in the presence of preformedMSH [ZnCl2, FeCl2·4H2O, CuCl2·2H2O, Fe2(SO4)3·9H2O,and MgSO4] (2.0percent w/w) at 80 °C for 24 h. In two selectedcases [FeCl2 and Fe2(SO4)3·9H2O], NH2CHO (200 μL) wasmixed with the sodium silicate solution (2.0 mL) in the presence of selected growing MSH (starting from 2.0percent w/w ofthe corresponding salt’s pellet) at 80 °C for 24 h. For the innerenvironment, NH2CHO (200 μL) was mixed with distilledwater (2.0 mL) in the presence of selected MSH (2.0percent w/w) at80 °C for 24 h. The reaction of NH2CHO (10percent v/v) with thesodium silicate solution (pH 12) without MSH membranes wasalso analyzed under similar experimental conditions. Theproducts were analyzed by gas chromatography associatedwith mass spectrometry (GC-MS) after treatment with N,Nbis-trimethylsilyl trifluoroacetamide in pyridine (620 μL) at 60°C for 4 h in the presence of betulinol (CAS Registry Number473-98-3) as the internal standard (0.2 mg). Mass spectrometrywas performed by the following program: injection temperature280 °C, detector temperature 280 °C, gradient 100 °C for 2min, and 10 °C/min for 60 min. To identify the structure of theproducts, two strategies were followed. First, the spectra werecompared with commercially available electron mass spectrumlibraries such as NIST (Fison, Manchester, U.K.). Second, GCMSanalysis was repeated with standard compounds. Allproducts have been recognized with a similarity index (SI)greater than 98percent compared to that of the reference standards.The analysis was limited to products of ≥1 ng/mL, and theyield was calculated as micrograms of product per startingformamide. For further experimental details, see the SupportingInformation.
Reference：
[1] Journal of the Chemical Society, Chemical Communications, 1982, # 16, p. 927 - 929
17
[ 56-40-6 ]
[ 2258-42-6 ]
[ 2491-15-8 ]
Reference：
[1] Bulletin de la Societe Chimique de France, 1934, vol. <5> 1, p. 1665
[2] Bulletin of the Chemical Society of Japan, 1965, vol. 38, p. 244 - 246
[3] The Journal of organic chemistry, 1976, vol. 41, # 7, p. 1112 - 1117
18
[ 77287-34-4 ]
[ 2491-15-8 ]
Reference：
[1] Chemistry - A European Journal, 2013, vol. 19, # 50, p. 16916 - 16922
19
[ 7750-46-1 ]
[ 2491-15-8 ]
Reference：
[1] Australian Journal of Chemistry, 1966, vol. 19, p. 1511 - 1518
20
[ 93033-02-4 ]
[ 2491-15-8 ]
Reference：
[1] Journal of Organic Chemistry USSR (English Translation), 1984, p. 908 - 910[2] Zhurnal Organicheskoi Khimii, 1984, vol. 20, # 5, p. 998 - 1000
21
[ 77287-34-4 ]
[ 51953-18-5 ]
[ 1455-77-2 ]
[ 120-89-8 ]
[ 849585-22-4 ]
[ 73-40-5 ]
[ 328-42-7 ]
[ 2491-15-8 ]
[ 110-15-6 ]
[ 71-30-7 ]
[ 120-73-0 ]
[ 144-62-7 ]
[ 113-00-8 ]
[ 127-17-3 ]
[ 66-22-8 ]
[ 56-06-4 ]
[ 66224-66-6 ]
[ 57-13-6 ]
[ 56-40-6 ]
[ 302-72-7 ]
[ 18588-61-9 ]
Reference：
[1] Chemistry - A European Journal, 2018, vol. 24, # 32, p. 8126 - 8132
22
[ 77287-34-4 ]
[ 51953-18-5 ]
[ 120-89-8 ]
[ 849585-22-4 ]
[ 73-40-5 ]
[ 328-42-7 ]
[ 2491-15-8 ]
[ 110-15-6 ]
[ 71-30-7 ]
[ 144-62-7 ]
[ 113-00-8 ]
[ 127-17-3 ]
[ 66-22-8 ]
[ 66224-66-6 ]
[ 56-40-6 ]
[ 18588-61-9 ]
[ 18514-52-8 ]
Reference：
[1] Chemistry - A European Journal, 2018, vol. 24, # 32, p. 8126 - 8132
23
[ 77287-34-4 ]
[ 51953-18-5 ]
[ 1455-77-2 ]
[ 120-89-8 ]
[ 73-40-5 ]
[ 328-42-7 ]
[ 2491-15-8 ]
[ 110-15-6 ]
[ 71-30-7 ]
[ 120-73-0 ]
[ 144-62-7 ]
[ 113-00-8 ]
[ 127-17-3 ]
[ 66-22-8 ]
[ 66224-66-6 ]
[ 57-13-6 ]
[ 56-40-6 ]
[ 302-72-7 ]
Reference：
[1] Chemistry - A European Journal, 2018, vol. 24, # 32, p. 8126 - 8132
24
[ 77287-34-4 ]
[ 56-40-6 ]
[ 2491-15-8 ]
Reference：
[1] Chemische Berichte, 1947, vol. 80, p. 38
25
[ 64-18-6 ]
[ 77287-34-4 ]
[ 56-40-6 ]
[ 2491-15-8 ]
Reference：
[1] Chemische Berichte, 1947, vol. 80, p. 38
26
[ 2491-15-8 ]
[ 2999-46-4 ]
Reference：
[1] Chemical Communications, 2008, # 26, p. 3001 - 3003
With potassium carbonate; In N,N-dimethyl-formamide; at 20℃; for 48h;
Glycine (5.20 g, 69.23 mmol) was dissolved in formic acid (25 mL), was added acetic anhydride (3.0 eq, 21.3 mL), was stirred for 24 hours at room temperature the reaction. After completion of the reaction, the reaction mixture was concentrated under reduced pressure, recrystallized by adding methanol and ethyl acetate, the corresponding formamide (1a) was obtained (4.81 g, 46.66 mmol, 67%).Compound 1a (0.95 g, 9.18 mmol) and, DMF (20 mL) inAt, benzyl bromide (1.5 eq, 1.64 mL) and potassium carbonate (3.2 eq, 3.99 g) and, at room temperatureIt was stirred for 48 hours. After completion of the reaction, water is added to inactivate the reaction mixture, with ethyl acetateExtracted. The organic layer was washed with saturated brine, dried with magnesium sulfate, filtered, concentrated under reduced pressureIt was carried out. The residue was purified by silica gel chromatography (hexane: ethyl acetate = 1: 1 ? 1: 9) To give the corresponding benzyl ester (1b) (400 mg, was obtained 2.02 mmol, 22%).Compound 1b (514.8 mg, 2.66 mmol) was added in DCM (10 mL), the mixture obtained (PhO) 2POCl (1.5 eq, 582 muL) and pyridine (5.0 eq, 1.88 mL) was added, and 2.5 hours with stirring to line the reactionWas Tsu. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer, hydrochloric acid, carbonSodium acid hydrogen, water, and successively washed with saturated brine, and dried over magnesium sulfate,After filtration, it was concentrated under reduced pressure.
(3R,4S)-N-{2-methoxy-5-[5-(trifluoromethyl)-1H-tetrazol-1-yl]benzyl}-3-phenylpiperidine-4-amine monohydrochloride[ No CAS ]
[ 2491-15-8 ]
{2-[(3R,4S)-4-({2-methoxy-5-[5-(trifluoromethyl)-1H-tetrazol-1-yl]benzyl}amino)-3-phenylpiperidin-1-yl]-2-oxoethyl}formamide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
97%
With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; triethylamine; In N,N-dimethyl-formamide; at 10 - 35℃; for 14h;
Example 5 {2-[(3R,4S)-4-({2-methoxy-5-[5-(trifluoromethyl)-1H-tetrazol-1-yl]benzyl}amino)-3-phenylpiperidin-1-yl]-2-oxoethyl}formamide To a solution of the compound (0.20 g) obtained in Example 4, Et3N (0.081 g) and N-<strong>[2491-15-8]formylglycine</strong> (0.062 g) in DMF (6 mL) were added WSC·HCl (0.12 g) and HOBt·H2O (0.092 g), and the mixture was stirred at room temperature for 14 hrs. The reaction mixture was poured into water, and the product was extracted with ethyl acetate. The organic layer was washed with a saturated solution of sodium hydrogencarbonate and brine, and dried, and the solvent was evaporated under reduced pressure. The obtained residue was purified by silica gel column chromatography (solvent gradient; 50?100% ethyl acetate/hexane) to give the title compound as a white amorphous solid (0.20 g, 97%). MS(ESI+): 518(M+H)
The title process was carried out as shown by the reaction scheme below. The yields for specific compounds are shown in Table 5, below.; The title compound was synthesized according to the reaction scheme shown below. To a solution of hydroxy beta-lactone 13f (11.0 mg, 0.0369 mmol), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (9.20 mg, 0.048 mmol), 4-dimethylaminopyridine (5.45 mg, 0.044 mmol), 0.5 mL of xylene were added and the mixture was azeotroped in vacuo for 1.0 h. The residue was then dissolved in CH2Cl2 (1 mL) and <strong>[2491-15-8]N-formyl glycine</strong> (5.71 mg, 0.055 mmol) was then added. The clear reaction mixture turned orange-red. After twelve hours the mixture was extracted with water (3×1 mL) and dichloromethane. The organic phase then dried over Na2SO4, filtered and concentrated in vacuo. The residue was purified by chromatography (SiO2, 20% EtOAc:hexanes) to afford beta-lactone 17a (17.4 mg, 99%).Rf=0.22 (50% EtOAc/hexanes); [alpha]22D=-9.4 (c 0.4, CHCl3); IR (thin film) 2926, 2855, 1823, 1738, 1651; 1H NMR (500 MHz, CDCl3) delta 8.25 (br s, 1H), 6.22 (br s, 1H), 5.05-5.09 (m, 1H), 4.30-4.27 (m, 1H), 4.08 (d, J=5.5 Hz, 2H), 3.21 (dq, J=1.0, 4.5 Hz, 1H), 2.05-2.09 (m, 2H), 1.75-1.87 (m, 2H), 1.59-1.68 (m, 2H), 1.25-1.33 (m, 19H), 1.04 (app t, J=7.0 Hz, 3H), 0.88 (app t, J=6.5 Hz, 3H); 13C (125 MHz, CDCl3) delta 171.0, 169.4, 161.3, 74.1, 73.2, 58.3, 40.4, 39.1, 34.5, 32.2, 30.0 (2), 29.9, 29.8, 29.7, 29.6, 25.4, 23.0, 21.2 (2), 14.5, 11.4; LRMS (ESI) Calcd for C22H38O5N [M+Li] 404.0, Found 401.29.
Tetrahydrocannabinol (134 mg, 0.00043 mol), N-<strong>[2491-15-8]formylglycine</strong> (56 mg, 0.00054 mol), DMAP (5.3 mg, 0.00004 mol) were combined in 10 mL dichloromethane. The solution was stirred for 20 minutes at ambient temperature. DCC (124 mg, 0.00060 mol) was added to the mixture. The mixture was allowed to stir overnight at ambient temperature.The solution was reduced to a small volume under nitrogen and hexane was added. The precipitate that formed was removed by filtration. The filtrate was taken to dryness under vacuum. The crude product was reconstituted in 1:1 hexane:methylene chloride.A silica column was used to purify the crude material using 1:1 hexane:ethyl acetate as an eluent. The purified product appeared as a transparent, viscous oil with light amber color (136.8 mg, 80%).For ALL00120, the 1H NMR (400 MHz, CDCl3) was as follows: delta=8.29-8.31 (1H, m, CHO); 6.58 (1H, d, J=1.8, H-4); 6.43 (1H, d, J=1.8, H-2); 6.15 (1H, s br, NH); 5.85-5.88 (1H, m, H-10); 4.37 (2H, AB system split by two additional coupling constants J=0.7 and J=5.1, OCOCH2N); 2.99-3.06 (1H, m, H-10a); 2.50 (2H, t, J=7.8, ArCH2); 2.11-2.18 (2H, m); 1.86-1.94 (1H, m); 1.62-1.70 (4H, m); 1.52-1.62 (2H, m); 1.41 (3H, s, 6beta-Me); 1.23-1.40 (5H, m); 1.08 (3H, s, 6alpha-Me); 0.88 (3H, t, J=7.0, CH2CH3).
With N-ethylmorpholine;; benzotriazol-1-ol; dicyclohexyl-carbodiimide; In tetrahydrofuran; at 20℃; for 4h;
A mixture of <strong>[2491-15-8]formylaminoacetic acid</strong> (3.1 g), the product of example 15c (6.3 g), N- ethylmorpholine (4 ml), DCC (6.6 g) and HOBT (4.5 g) in THF (35 ml) was stirred at room temperature for 4 h. The reaction mixture was diluted with diethyl ether (30 ml) and filtered over Celite. The filtrate was concentrated in vacuo. The residue was purified by chromatography on silica gel in dichloromethane/acetone [3/1 ? 1 :1 (v/v)] as eluent. The fractions containing product were combined and concentrated in vacuo. The residue was triturated with tert-butyl-methyl ether. The solids were collected and dried in vacuo (50 0C).Yield: 8 g. TLC Rf = 0.30 (dichloromethane/acetone 1 :1); Mp: 75-82 0C; 1H-NMR (DMSO-de) delta 1.22 (d, 6, isoprop.), 2.65 (t, 2H, CH2), 3.25 (t, 2H, CH2N), 3.68 (d, 2H, CH2), 3.72 (s, 3H, OCH3), 6.67 (d, 1, ArH), 6.80 (br s, 1, ArH), 6.84 (d, 1, ArH), 7.97 (t, 1, NH, 8.07 (s, 1, CHO), 8.22 (br t, 1, NH)
With N-ethylmorpholine;; benzotriazol-1-ol; dicyclohexyl-carbodiimide; In tetrahydrofuran; at 20℃; for 4h;
(a). 2-Formylamino-N-[2-(4-isopropoxy-3-methoxy-phenyl)-ethyl]-acetamide A mixture of <strong>[2491-15-8]formylaminoacetic acid</strong> (3.1 g), the product of example 15c (6.3 g), N-ethylmorpholine (4 ml), DCC (6.6 g) and HOBT (4.5 g) in THF (35 ml) was stirred at room temperature for 4 h. The reaction mixture was diluted with diethyl ether (30 ml) and filtered over Celite. The filtrate was concentrated in vacuo. The residue was purified by chromatography on silica gel in dichloromethane/acetone [3/1?1:1 (v/v)] as eluent. The fractions containing product were combined and concentrated in vacuo. The residue was triturated with tert-butyl-methyl ether. The solids were collected and dried in vacuo (50 C.). Yield: 8 g. TLC Rf=0.30 (dichloromethane/acetone 1:1); Mp: 75-82 C.; 1H-NMR (DMSO-d6) delta 1.22 (d, 6, isoprop.), 2.65 (t, 2H, CH2), 3.25 (t, 2H, CH2N), 3.68 (d, 2H, CH2), 3.72 (s, 3H, OCH3), 6.67 (d, 1, ArH), 6.80 (br s, 1, ArH), 6.84 (d, 1, ArH), 7.97 (t, 1, NH, 8.07 (s, 1, CHO), 8.22 (br t, 1, NH).
650 mg
With 4-methyl-morpholine; benzotriazol-1-ol; dicyclohexyl-carbodiimide; In tetrahydrofuran; at 20℃; for 3h;
2-(4-lsopropoxy-3-methoxyphenyl)ethanamine hydrochloride (487 mg, 2.33 mmol) was15 taken up in MeOH and loaded onto an SCX column. The crude material was washed with methanolthen eluted with 2 N ammonia in methanol. The product-containing fractions were concentrated toafford the free base 2-(4-isopropoxy-3-methoxyphenyl)ethanamine. This material was dissolved inTHF (23.3 ml) and <strong>[2491-15-8]2-formamidoacetic acid</strong> (360 mg, 3.49 mmol), DCC (528 mg, 2.56 mmol), HOBt(392 mg, 2.56 mmol), and NMM (1.02 ml, 9.31 mmol) were added. The resulting suspension was20 stirred at RT for 3 hours, diluted with ether and filtered through celite. The filtrate was purified bysilica gel chromoatorgraphy (25%-50% AcOH in DCM) to afford 2-formamido-N-(4-isopropoxy-3-methoxyphenethyl)acetamide (650 mg) MS [M+W] = 295.3.
With diisopropyl-carbodiimide; In N,N-dimethyl-formamide; for 24h;
General procedure: Aminomethylated polystyrene resin (2g, 1.12mmol/g of resin) was swollen in dry dimethylformamide (DMF, 10mL) for 10min. The solvent was removed and a mixture of formic acid (5equiv, 0.17mL) and N,N?-diisopropylcarbodiimide (DIC) (5equiv, 0.69mL) in DMF (20mL) was added. The mixture was left stirring for 24h. After washing the resin with DMF (3×5mL) the 2,4,6-trinitrobenzenesulphonic acid (TNBS) test was performed to evaluate if there were still some free NH2 groups in the resin. If the resin turned red the above procedure was repeated until no free NH2 groups were detected.
With ferric sulfate nonahydrate; In water; at 80℃; for 24h;pH 7.57;
General procedure: To model the chemical environment on the outer side of thetubular structures, NH2CHO (200 muL) was mixed with thesodium silicate solution (2.0 mL) in the presence of preformedMSH [ZnCl2, FeCl2·4H2O, CuCl2·2H2O, Fe2(SO4)3·9H2O,and MgSO4] (2.0% w/w) at 80 C for 24 h. In two selectedcases [FeCl2 and Fe2(SO4)3·9H2O], NH2CHO (200 muL) wasmixed with the sodium silicate solution (2.0 mL) in the presence of selected growing MSH (starting from 2.0% w/w ofthe corresponding salt?s pellet) at 80 C for 24 h. For the innerenvironment, NH2CHO (200 muL) was mixed with distilledwater (2.0 mL) in the presence of selected MSH (2.0% w/w) at80 C for 24 h. The reaction of NH2CHO (10% v/v) with thesodium silicate solution (pH 12) without MSH membranes wasalso analyzed under similar experimental conditions. Theproducts were analyzed by gas chromatography associatedwith mass spectrometry (GC-MS) after treatment with N,Nbis-trimethylsilyl trifluoroacetamide in pyridine (620 muL) at 60C for 4 h in the presence of betulinol (CAS Registry Number473-98-3) as the internal standard (0.2 mg). Mass spectrometrywas performed by the following program: injection temperature280 C, detector temperature 280 C, gradient 100 C for 2min, and 10 C/min for 60 min. To identify the structure of theproducts, two strategies were followed. First, the spectra werecompared with commercially available electron mass spectrumlibraries such as NIST (Fison, Manchester, U.K.). Second, GCMSanalysis was repeated with standard compounds. Allproducts have been recognized with a similarity index (SI)greater than 98% compared to that of the reference standards.The analysis was limited to products of ?1 ng/mL, and theyield was calculated as micrograms of product per startingformamide. For further experimental details, see the SupportingInformation.
With ferric sulfate nonahydrate; at 80℃; for 24h;pH 12.0;
General procedure: To model the chemical environment on the outer side of thetubular structures, NH2CHO (200 muL) was mixed with thesodium silicate solution (2.0 mL) in the presence of preformedMSH [ZnCl2, FeCl2·4H2O, CuCl2·2H2O, Fe2(SO4)3·9H2O,and MgSO4] (2.0% w/w) at 80 C for 24 h. In two selectedcases [FeCl2 and Fe2(SO4)3·9H2O], NH2CHO (200 muL) wasmixed with the sodium silicate solution (2.0 mL) in the presence of selected growing MSH (starting from 2.0% w/w ofthe corresponding salt?s pellet) at 80 C for 24 h. For the innerenvironment, NH2CHO (200 muL) was mixed with distilledwater (2.0 mL) in the presence of selected MSH (2.0% w/w) at80 C for 24 h. The reaction of NH2CHO (10% v/v) with thesodium silicate solution (pH 12) without MSH membranes wasalso analyzed under similar experimental conditions. Theproducts were analyzed by gas chromatography associatedwith mass spectrometry (GC-MS) after treatment with N,Nbis-trimethylsilyl trifluoroacetamide in pyridine (620 muL) at 60C for 4 h in the presence of betulinol (CAS Registry Number473-98-3) as the internal standard (0.2 mg). Mass spectrometrywas performed by the following program: injection temperature280 C, detector temperature 280 C, gradient 100 C for 2min, and 10 C/min for 60 min. To identify the structure of theproducts, two strategies were followed. First, the spectra werecompared with commercially available electron mass spectrumlibraries such as NIST (Fison, Manchester, U.K.). Second, GCMSanalysis was repeated with standard compounds. Allproducts have been recognized with a similarity index (SI)greater than 98% compared to that of the reference standards.The analysis was limited to products of ?1 ng/mL, and theyield was calculated as micrograms of product per startingformamide. For further experimental details, see the SupportingInformation.
General procedure: To model the chemical environment on the outer side of thetubular structures, NH2CHO (200 muL) was mixed with thesodium silicate solution (2.0 mL) in the presence of preformedMSH [ZnCl2, FeCl2·4H2O, CuCl2·2H2O, Fe2(SO4)3·9H2O,and MgSO4] (2.0% w/w) at 80 C for 24 h. In two selectedcases [FeCl2 and Fe2(SO4)3·9H2O], NH2CHO (200 muL) wasmixed with the sodium silicate solution (2.0 mL) in the presence of selected growing MSH (starting from 2.0% w/w ofthe corresponding salt?s pellet) at 80 C for 24 h. For the innerenvironment, NH2CHO (200 muL) was mixed with distilledwater (2.0 mL) in the presence of selected MSH (2.0% w/w) at80 C for 24 h. The reaction of NH2CHO (10% v/v) with thesodium silicate solution (pH 12) without MSH membranes wasalso analyzed under similar experimental conditions. Theproducts were analyzed by gas chromatography associatedwith mass spectrometry (GC-MS) after treatment with N,Nbis-trimethylsilyl trifluoroacetamide in pyridine (620 muL) at 60C for 4 h in the presence of betulinol (CAS Registry Number473-98-3) as the internal standard (0.2 mg). Mass spectrometrywas performed by the following program: injection temperature280 C, detector temperature 280 C, gradient 100 C for 2min, and 10 C/min for 60 min. To identify the structure of theproducts, two strategies were followed. First, the spectra werecompared with commercially available electron mass spectrumlibraries such as NIST (Fison, Manchester, U.K.). Second, GCMSanalysis was repeated with standard compounds. Allproducts have been recognized with a similarity index (SI)greater than 98% compared to that of the reference standards.The analysis was limited to products of ?1 ng/mL, and theyield was calculated as micrograms of product per startingformamide. For further experimental details, see the SupportingInformation.
With magnesium sulfate; In water; at 80℃; for 24h;pH 7.57;
General procedure: To model the chemical environment on the outer side of thetubular structures, NH2CHO (200 muL) was mixed with thesodium silicate solution (2.0 mL) in the presence of preformedMSH [ZnCl2, FeCl2·4H2O, CuCl2·2H2O, Fe2(SO4)3·9H2O,and MgSO4] (2.0% w/w) at 80 C for 24 h. In two selectedcases [FeCl2 and Fe2(SO4)3·9H2O], NH2CHO (200 muL) wasmixed with the sodium silicate solution (2.0 mL) in the presence of selected growing MSH (starting from 2.0% w/w ofthe corresponding salt?s pellet) at 80 C for 24 h. For the innerenvironment, NH2CHO (200 muL) was mixed with distilledwater (2.0 mL) in the presence of selected MSH (2.0% w/w) at80 C for 24 h. The reaction of NH2CHO (10% v/v) with thesodium silicate solution (pH 12) without MSH membranes wasalso analyzed under similar experimental conditions. Theproducts were analyzed by gas chromatography associatedwith mass spectrometry (GC-MS) after treatment with N,Nbis-trimethylsilyl trifluoroacetamide in pyridine (620 muL) at 60C for 4 h in the presence of betulinol (CAS Registry Number473-98-3) as the internal standard (0.2 mg). Mass spectrometrywas performed by the following program: injection temperature280 C, detector temperature 280 C, gradient 100 C for 2min, and 10 C/min for 60 min. To identify the structure of theproducts, two strategies were followed. First, the spectra werecompared with commercially available electron mass spectrumlibraries such as NIST (Fison, Manchester, U.K.). Second, GCMSanalysis was repeated with standard compounds. Allproducts have been recognized with a similarity index (SI)greater than 98% compared to that of the reference standards.The analysis was limited to products of ?1 ng/mL, and theyield was calculated as micrograms of product per startingformamide. For further experimental details, see the SupportingInformation.
With iron(II) chloride tetrahydrate; In water; at 80℃; for 24h;pH 7.57;
General procedure: To model the chemical environment on the outer side of thetubular structures, NH2CHO (200 muL) was mixed with thesodium silicate solution (2.0 mL) in the presence of preformedMSH [ZnCl2, FeCl2·4H2O, CuCl2·2H2O, Fe2(SO4)3·9H2O,and MgSO4] (2.0% w/w) at 80 C for 24 h. In two selectedcases [FeCl2 and Fe2(SO4)3·9H2O], NH2CHO (200 muL) wasmixed with the sodium silicate solution (2.0 mL) in the presence of selected growing MSH (starting from 2.0% w/w ofthe corresponding salt?s pellet) at 80 C for 24 h. For the innerenvironment, NH2CHO (200 muL) was mixed with distilledwater (2.0 mL) in the presence of selected MSH (2.0% w/w) at80 C for 24 h. The reaction of NH2CHO (10% v/v) with thesodium silicate solution (pH 12) without MSH membranes wasalso analyzed under similar experimental conditions. Theproducts were analyzed by gas chromatography associatedwith mass spectrometry (GC-MS) after treatment with N,Nbis-trimethylsilyl trifluoroacetamide in pyridine (620 muL) at 60C for 4 h in the presence of betulinol (CAS Registry Number473-98-3) as the internal standard (0.2 mg). Mass spectrometrywas performed by the following program: injection temperature280 C, detector temperature 280 C, gradient 100 C for 2min, and 10 C/min for 60 min. To identify the structure of theproducts, two strategies were followed. First, the spectra werecompared with commercially available electron mass spectrumlibraries such as NIST (Fison, Manchester, U.K.). Second, GCMSanalysis was repeated with standard compounds. Allproducts have been recognized with a similarity index (SI)greater than 98% compared to that of the reference standards.The analysis was limited to products of ?1 ng/mL, and theyield was calculated as micrograms of product per startingformamide. For further experimental details, see the SupportingInformation.
2.5 mg; 0.0052 mg; 0.0041 mg; 0.03 mg
With zinc(II) chloride; In water; at 80℃; for 24h;pH 7.57;
General procedure: To model the chemical environment on the outer side of thetubular structures, NH2CHO (200 muL) was mixed with thesodium silicate solution (2.0 mL) in the presence of preformedMSH [ZnCl2, FeCl2·4H2O, CuCl2·2H2O, Fe2(SO4)3·9H2O,and MgSO4] (2.0% w/w) at 80 C for 24 h. In two selectedcases [FeCl2 and Fe2(SO4)3·9H2O], NH2CHO (200 muL) wasmixed with the sodium silicate solution (2.0 mL) in the presence of selected growing MSH (starting from 2.0% w/w ofthe corresponding salt?s pellet) at 80 C for 24 h. For the innerenvironment, NH2CHO (200 muL) was mixed with distilledwater (2.0 mL) in the presence of selected MSH (2.0% w/w) at80 C for 24 h. The reaction of NH2CHO (10% v/v) with thesodium silicate solution (pH 12) without MSH membranes wasalso analyzed under similar experimental conditions. Theproducts were analyzed by gas chromatography associatedwith mass spectrometry (GC-MS) after treatment with N,Nbis-trimethylsilyl trifluoroacetamide in pyridine (620 muL) at 60C for 4 h in the presence of betulinol (CAS Registry Number473-98-3) as the internal standard (0.2 mg). Mass spectrometrywas performed by the following program: injection temperature280 C, detector temperature 280 C, gradient 100 C for 2min, and 10 C/min for 60 min. To identify the structure of theproducts, two strategies were followed. First, the spectra werecompared with commercially available electron mass spectrumlibraries such as NIST (Fison, Manchester, U.K.). Second, GCMSanalysis was repeated with standard compounds. Allproducts have been recognized with a similarity index (SI)greater than 98% compared to that of the reference standards.The analysis was limited to products of ?1 ng/mL, and theyield was calculated as micrograms of product per startingformamide. For further experimental details, see the SupportingInformation.
General procedure: To model the chemical environment on the outer side of thetubular structures, NH2CHO (200 muL) was mixed with thesodium silicate solution (2.0 mL) in the presence of preformedMSH [ZnCl2, FeCl2·4H2O, CuCl2·2H2O, Fe2(SO4)3·9H2O,and MgSO4] (2.0% w/w) at 80 C for 24 h. In two selectedcases [FeCl2 and Fe2(SO4)3·9H2O], NH2CHO (200 muL) wasmixed with the sodium silicate solution (2.0 mL) in the presence of selected growing MSH (starting from 2.0% w/w ofthe corresponding salt?s pellet) at 80 C for 24 h. For the innerenvironment, NH2CHO (200 muL) was mixed with distilledwater (2.0 mL) in the presence of selected MSH (2.0% w/w) at80 C for 24 h. The reaction of NH2CHO (10% v/v) with thesodium silicate solution (pH 12) without MSH membranes wasalso analyzed under similar experimental conditions. Theproducts were analyzed by gas chromatography associatedwith mass spectrometry (GC-MS) after treatment with N,Nbis-trimethylsilyl trifluoroacetamide in pyridine (620 muL) at 60C for 4 h in the presence of betulinol (CAS Registry Number473-98-3) as the internal standard (0.2 mg). Mass spectrometrywas performed by the following program: injection temperature280 C, detector temperature 280 C, gradient 100 C for 2min, and 10 C/min for 60 min. To identify the structure of theproducts, two strategies were followed. First, the spectra werecompared with commercially available electron mass spectrumlibraries such as NIST (Fison, Manchester, U.K.). Second, GCMSanalysis was repeated with standard compounds. Allproducts have been recognized with a similarity index (SI)greater than 98% compared to that of the reference standards.The analysis was limited to products of ?1 ng/mL, and theyield was calculated as micrograms of product per startingformamide. For further experimental details, see the SupportingInformation.
5-(4-((4-(4-(oxetan-3-yl)piperazin-1-yl)phenyl)amino)-1,3,5-triazin-2-yl)-2-(piperidin-4-yloxy)benzonitrile[ No CAS ]
N-(2-(4-(2-cyano-4-(4-((4-(4-(oxetan-3-yl)piperazin-1-yl)phenyl)amino)-1,3,5-triazin-2-yl)phenoxy)piperidin-1-yl)-2-oxoethyl)formamide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With N-ethyl-N,N-diisopropylamine; N-[(dimethylamino)-3-oxo-1H-1,2,3-triazolo[4,5-b]pyridin-1-yl-methylene]-N-methylmethanaminium hexafluorophosphate; In dichloromethane; at 20℃; for 72h;
Example 51 N-(2-(4-(2-cyano-4-(4-((4-(4-(oxetan-3-yl)piperazin-1-yl)phenyl)amino)-1,3,5-triazin-2-yl)phenoxy)piperidin-1-yl)-2-oxoethyl)formamide 5-(4-((4-(4-(oxetan-3-yl)piperazin-1-yl)phenyl)amino)-1,3,5-triazin-2-yl)-2-(piperidin-4-yloxy)benzonitrile (60 mg, 0.12 mmol), and N-<strong>[2491-15-8]formylglycine</strong> (Sigma Aldrich, 18 mg, 0.18 mmol) were taken up as suspension in dichloromethane (3 mL). The mixture was treated successively with N,N-diisopropylethylamine (41 muL, 0.23 mmol) and N-[(dimethylamino)-1H-1,2,3-triazolo-[4,5-b]pyridin-1-ylmethylene]-N-methylmethanaminiumhexafluorophosphate N-oxide (HATU, 67 mg, 0.18 mmol). The mixture was stirred for three days at room temperature and then purified by flash chromatography (silica gel) to provide N-(2-(4-(2-cyano-4-(4-((4-(4-(oxetan-3-yl)piperazin-1-yl)phenyl)amino)-1,3,5-triazin-2-yl)phenoxy)piperidin-1-yl)-2-oxoethyl)formamide. LCMS-ESI+ (m/z): [M+H]+ calcd for C31H36N9O4: 598.3. found: 598.3 1H NMR (400 MHz, DMSO-d6) delta 10.16 (m, 1H), 8.78 (s, 1H), 8.60 (m, 2H), 8.20 (m, 1H), 8.14 (s, 1H), 7.61 (m, 2H), 7.02 (m, 2H), 5.12-5.00 (m, 2H), 4.61 (m, 3H), 4.52 (m, 2H), 4.10 (t, J=4.8 Hz, 2H), 3.79 (m, 1H), 3.74-3.42 (m, 3H), 3.18 (m, 4H), 2.46 (m, 4H), 2.05 (m, 2H), 1.76 (m, 2H).
With acetic anhydride; acetic acid; at 50℃; for 6h;Green chemistry;
(2)We received 198 g (1·92 muM)) of N-<strong>[2491-15-8]formylglycine</strong> obtained in step (1) to 520 g (8.48muM) ) of glacial acetic acid, And 235 g (2.30mo 1) of acetic anhydride was added thereto, heated to 50 C and stirred for 6 h, Get a yellow solution
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