* 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 bromine In methanol; chloroform at 0℃; for 12 h;
Step A: Preparation of 5-bromopyrimidin-4(3H)-one: Bromine (16.0 mL, 312 mmol) was added to a suspension of pyrimidin-4(3H)-one (30 g, 312 mmol) in chloroform (1 L) at 0° C. Methanol (10 mL) was added and the reaction mixture was stirred for 12 hours. The resulting solid was collected by filtration, washed with hexane and ether, and dried under vacuum to afford the title compound as a white solid (50 g, 91.5percent yield). 1H NMR (400 MHz, DMSO-d6) δ 11.15 (broad s, 1H), 8.42 (s, 1H), 8.40 (s, 1H).
3.1 g
at 20℃; for 0.5 h; Inert atmosphere
Step T2: 5-Bromo-3H-pyrimidin-4-one A mixture of 3H-pyrimidin-4-one (1 1 g, 114 mmol), bromine (6.5 mL, 126 mmol), and KOAc (33.7 g, 343 mmol) in AcOH (100 mL) was stirred for 30 min at rt. The resulting precipitate was collected by filtration to provide 30 g of a white solid. This solid was dissolved in CH2CI2/water, extracted with CH2CI2/MeOH (9: 1 ). The organic layer was dried (Na2S04), filtered, and concentrated to afford 3.1 g of the title compound (compound was soluble in water and stayed in the aqueous layer despite repeated extractions). tR: 0.35 min (LC-MS 2); ESI-MS: 175.0 [M+H]+ (LC-MS 2).
Reference:
[1] Patent: US2007/238726, 2007, A1, . Location in patent: Page/Page column 75
[2] Bioorganic and Medicinal Chemistry Letters, 2016, vol. 26, # 16, p. 3905 - 3912
[3] Journal of the Chemical Society, 1955, p. 3478,3481
[4] Patent: WO2013/111105, 2013, A1, . Location in patent: Page/Page column 125
2
[ 77287-34-4 ]
[ 51953-18-5 ]
[ 156-81-0 ]
[ 113-00-8 ]
[ 66-22-8 ]
[ 56-06-4 ]
[ 57-13-6 ]
Yield
Reaction Conditions
Operation in experiment
0.1 mg
With manganese(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.
With copper(II) choride dihydrate 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] Chemical and Pharmaceutical Bulletin, 1989, vol. 37, # 8, p. 1984 - 1986
[2] Chemical and Pharmaceutical Bulletin, 1989, vol. 37, # 8, p. 1984 - 1986
9
[ 694-59-7 ]
[ 51953-18-5 ]
[ 64264-15-9 ]
[ 126126-58-7 ]
[ 126126-57-6 ]
Reference:
[1] Chemical and Pharmaceutical Bulletin, 1989, vol. 37, # 8, p. 1984 - 1986
10
[ 77287-34-4 ]
[ 51953-18-5 ]
[ 156-81-0 ]
[ 113-00-8 ]
[ 66-22-8 ]
[ 56-06-4 ]
[ 57-13-6 ]
Yield
Reaction Conditions
Operation in experiment
0.1 mg
With manganese(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.
With copper(II) choride dihydrate 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] Chemistry - A European Journal, 2018, vol. 24, # 32, p. 8126 - 8132
13
[ 77287-34-4 ]
[ 51953-18-5 ]
[ 120-89-8 ]
[ 73-40-5 ]
[ 328-42-7 ]
[ 110-15-6 ]
[ 144-62-7 ]
[ 127-17-3 ]
[ 56-06-4 ]
[ 57-13-6 ]
[ 18588-61-9 ]
[ 18514-52-8 ]
Reference:
[1] Chemistry - A European Journal, 2018, vol. 24, # 32, p. 8126 - 8132
14
[ 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
15
[ 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
16
[ 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
17
[ 51953-18-5 ]
[ 4349-07-9 ]
Yield
Reaction Conditions
Operation in experiment
67%
With N-iodo-succinimide In acetic acid at 100℃; for 0.5 h;
10 g of 4(3H)-pyrimidone was dissolved in 156 mL of acetic acid, and 25.8 g of N-iodosuccinimide was added thereto at 70°C and heated to 100°C, followed by stirring for 30 minutes. After the reaction was completed, the mixture was cooled to room temperature then cooled in ice to induce the crystallization of the product, followed by filtering under a reduced pressure. The solid thus obtained was washed with water and dried under a reduced pressure to obtain the title compound (16 g, yield: 67percent).1H-NMR (300MHz, DMSO-d6) δ 12.88 (bs, 1H), 8.42 (s, 1H), 8.17 (s, 1H).
64%
With sodium hydroxide In water at 85℃; for 16 h;
To a stirred solution containing 20.2 g (0. 21 mol) of pyrimidin-4 (3H)-one and 170 mL of water was added 10.9 g (0.27 mol) of sodium hydroxide, followed by 53.3 g (0.21 mol) of iodide. The reaction mixture was heated at 85°C for 16h, then cooled to room temperature and filtered. The filter cake was washed with water, collected, and dried under reduced pressure to give 29.7g (64percent) of the TITLE COMPOUND. H-NMR (300 MHz, DMSO-d6) No. 8. 17 (s, 1H), 8.43 (s, 1H), and 12.92 (brs, 1H) ; ESIMS : 223.1 (M+H) +
44%
With iodine; sodium hydroxide In water at 85℃; for 72 h;
Pyrimidin-4(3H)-one (1 g, 10.41 mmol) was dissolved in 10 ml water. Sodium hydroxide (0.54 g, 13.50 mmol) and iodine (2.64 g, 10.40 mmol) were added and the reaction mixture heated at 85°C for 72 h. The reaction mixture was filtered and washed with water. The solid formed was dried in the vacuum oven to give 1.01 g (44percent yield) of the title compound. Purity 100percent.LRMS (m/z): 223 (M+1 )+
With bromine; In methanol; chloroform; at 0℃; for 12h;
Step A: Preparation of 5-bromopyrimidin-4(3H)-one: Bromine (16.0 mL, 312 mmol) was added to a suspension of pyrimidin-4(3H)-one (30 g, 312 mmol) in chloroform (1 L) at 0 C. Methanol (10 mL) was added and the reaction mixture was stirred for 12 hours. The resulting solid was collected by filtration, washed with hexane and ether, and dried under vacuum to afford the title compound as a white solid (50 g, 91.5% yield). 1H NMR (400 MHz, DMSO-d6) delta 11.15 (broad s, 1H), 8.42 (s, 1H), 8.40 (s, 1H).
3.1 g
With bromine; potassium acetate; acetic acid; at 20℃; for 0.5h;Inert atmosphere;
Step T2: 5-Bromo-3H-pyrimidin-4-one A mixture of 3H-pyrimidin-4-one (1 1 g, 114 mmol), bromine (6.5 mL, 126 mmol), and KOAc (33.7 g, 343 mmol) in AcOH (100 mL) was stirred for 30 min at rt. The resulting precipitate was collected by filtration to provide 30 g of a white solid. This solid was dissolved in CH2CI2/water, extracted with CH2CI2/MeOH (9: 1 ). The organic layer was dried (Na2S04), filtered, and concentrated to afford 3.1 g of the title compound (compound was soluble in water and stayed in the aqueous layer despite repeated extractions). tR: 0.35 min (LC-MS 2); ESI-MS: 175.0 [M+H]+ (LC-MS 2).
With N-iodo-succinimide; In acetic acid; at 100℃; for 0.5h;
10 g of 4(3H)-pyrimidone was dissolved in 156 mL of acetic acid, and 25.8 g of N-iodosuccinimide was added thereto at 70C and heated to 100C, followed by stirring for 30 minutes. After the reaction was completed, the mixture was cooled to room temperature then cooled in ice to induce the crystallization of the product, followed by filtering under a reduced pressure. The solid thus obtained was washed with water and dried under a reduced pressure to obtain the title compound (16 g, yield: 67%).1H-NMR (300MHz, DMSO-d6) delta 12.88 (bs, 1H), 8.42 (s, 1H), 8.17 (s, 1H).
64%
With sodium hydroxide; In water; at 85℃; for 16.0h;
To a stirred solution containing 20.2 g (0. 21 mol) of pyrimidin-4 (3H)-one and 170 mL of water was added 10.9 g (0.27 mol) of sodium hydroxide, followed by 53.3 g (0.21 mol) of iodide. The reaction mixture was heated at 85C for 16h, then cooled to room temperature and filtered. The filter cake was washed with water, collected, and dried under reduced pressure to give 29.7g (64%) of the TITLE COMPOUND. H-NMR (300 MHz, DMSO-d6) No. 8. 17 (s, 1H), 8.43 (s, 1H), and 12.92 (brs, 1H) ; ESIMS : 223.1 (M+H) +
44%
With iodine; sodium hydroxide; In water; at 85℃; for 72.0h;
Pyrimidin-4(3H)-one (1 g, 10.41 mmol) was dissolved in 10 ml water. Sodium hydroxide (0.54 g, 13.50 mmol) and iodine (2.64 g, 10.40 mmol) were added and the reaction mixture heated at 85C for 72 h. The reaction mixture was filtered and washed with water. The solid formed was dried in the vacuum oven to give 1.01 g (44% yield) of the title compound. Purity 100%.LRMS (m/z): 223 (M+1 )+
Method U Preparation of 5-Iodo-4(3H)-pyrimidinone The procedure of Sakamoto et. al. (Chem. Pharm. Bull. 1986, 34(7), 2719-2724) was used to convert 4(3H)-pyrimidinone into 5-iodo-4(3H)-pyrimidinone, which was of sufficient purity for conversion to 4-chloro-5-iodopyrimidine.
Method L Preparation of 5-Iodo-4(3H)-pyrimidinone The procedure of Sakamoto et. al. (Chem. Pharm. Bull. 1986, 34(7), 2719-2724) was used to convert 4(3H)-pyrimidinone into 5-iodo-4(3H)-pyrimidinone.
Method N Preparation of 5-Iodo-4(3H)-pyrimidinone The procedure of Sakamoto et. al. (Chem. Pharm. Bull. 1986, 34(7), 2719- 2724) was used to convert 4(3H)-pyrimidinone into 5-iodo-4(3H)-pyrimidinone, which was of sufficient purity for conversion to 4-chloro-5-iodopyrimidine.
(b) 4, [5-DICHLOROPYRIMIDINE.] A solution of the pyrimidin-4-one from step (a) above (3.5 g, 26.8 mmol) in phosphorus oxychloride (50 mL) was heated under for 3 h. The reaction mixture was cooled to room temperature, the solvent was evaporated [IN VACUO] and the residue was dissolved in EtOAc (100 mL). The organic solution was washed with saturated aqueous solution of NaHC03 (50 mL) and brine [(50] mL), dried over [NA2S04,] filtered, and concentrated in vacuo. The residue was purified by silica gel column chromatography, eluting with 10% [ETOAC/HEXANE,] to give the title compound as an orange oil. MS (ESI, pos. [ION) M/Z] : 131 [(M+1).]
With di-isopropyl azodicarboxylate; triphenylphosphine In dichloromethane at 20℃; Inert atmosphere; Cooling with ice;
69%
With di-isopropyl azodicarboxylate; triphenylphosphine In dichloromethane for 48.16h; Cooling with ice;
1
(S)-tert-Butyl 2-(pyrimidin-4-yloxymethyl)pyrrolidine-1-carboxylate (compound 19g). To a stirred solution of N-tert-butoxycarbonyl-L-prolinol (0.81 g, 4 mmol) 18 in dry DCM (10 mL) was added triphenylphosphine (5.24 g, 20 mmol) followed by 4(3H)-pyrimidone (0.77 g, 8 mmol). The solution was cooled in an ice bath and DIAD (3.24 g, 16 mmol) added dropwise over 10 min. After 48 h GC-MS indicated complete conversion of 18 and the reaction mixture was poured onto water (30 mL), the organic fraction collected and the aqueous phase washed with further DCM (2×20 mL). The combined organic fractions were washed with 1M NaOH (2×15 mL) then brine (1×15 mL) and dried over Na2SO4. Removal of bulk solvent yielded an orange gum, addition of hexanes/diethyl ether (1:1) resulted in formation of a precipitate of triphenylphosphine oxide, which was removed by filtration. Chromatography (ethyl acetate) afforded the desired product as a colorless oil (0.77 g, 69%).
methyl 3-methoxy-4-((6-oxopyrimidin-1(6H)-yl)methyl)benzoate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
A solution of pyrimidin-4(3H)-one (8.9 g, 93 mmol) in DMF (150 mL) was added to a stirring 0 °C slurry of NaH (3.9 g, 60percent dispersion in mineral oil, 96 mmol) in DMF (200 mL). The resulting mixture was stirred at 0 °C for 15 min. A solution of methyl 4- (bromomethyl)-3-methoxybenzoate (20 g, 77 mmol) in DMF (150 mL) was then added. The resulting mixture was allowed to slowly warm to ambient temperature and stirred for 1 h. The mixture was cooled to 0 °C and saturated aqueous ammonium chloride was added. The aqueous phase was extracted with EtOAc (3x). The combined organic phases were washed with saturated aqueous sodium chloride (3x), dried over MgS04, filtered, and concentrated in vacuo. Purification of the concentrate by silica gel chromatography (100? 90percent DCM/ MeOH) gave the title compound. LC-MS m/z found = 275.2 [M+l]+.
With copper(II) choride dihydrate; 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 sodium silicate solution; CuN2O6; 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 manganese(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.
With H2O8S2*2H3N; [4,4'-bis(1,1-dimethylethyl)-2,2'-bipyridine-N1,N1]bis-{3,5-difluoro-2-[5-(trifluoromethyl)-2-pyridinyl-N]phenyl-C}iridium(III) hexafluorophosphate In dimethyl sulfoxide at 40℃; for 0.5h; Flow reactor; UV-irradiation;
Trifluoromethylation; General Procedure:
General procedure: In an oven-dried vial equipped with a magnetic stirrer and a PTFE septum, [Ir{dF(CF3)ppy}2](dtbpy)]PF6 (5.6 mg, 1 mol%) was added to a mixture of the substrate (0.5 mmol, 1 equiv), CF3SO2Na (1.5 mmol, 3 equiv), and (NH4)2S2O8 (0.5 mmol, 1 equiv) in DMSO (5 mL). The solution was pumped into the Vapourtec photoreactor (fluoropolymer tube, 1.3 mm i.d., 10 mL) and the liquid flowrate was set at 0.33 mL/min (30 min residence time). The reactor was irradiated with 54 blue LEDs (450 nm, total power 24 W). The reaction mixture collected from the outlet was diluted with H2O and extracted with Et2O (3×). The combined organic layers were washed with brine, dried over MgSO4, and concentrated in vacuo. The crude was then pre-adsorbed onto silica, dried in vacuo, and purified by flash chromatography to yield the trifluoromethylated product.
13%
With C46H91N3O4; dimethylglyoxal In ethyl acetate at 20℃; for 24h; Irradiation;
4.3.2. General Procedure for Intragel Reactions and Product Analysis
General procedure: An oven-dried 5 mL vial was loaded with sodium triflate (62.4 mg, 0.4 mmol), the desired arene(0.1 mmol) and G-1 gelator (25.0 g L1). The vial was equipped with a septum through which EtOAc(0.8 mL) and diacetyl (0.2 mL) were added with a syringe. The resulting mixture was homogenizedin an ultrasonic bath (USC200TH, 45 kHz, 120 Watt, VWR, Leicestershire, England) at constanttemperature (23 2 C) for ca. 1 min and heated with a heat gun (heating level 3 of 10) until the gelatorwas completely dissolved. The gel was formed during sonication or after cooling down the mixtureto RT. Then, the vials were placed under LED (l = 400 nm or 455 nm, as indicated) light irradiationduring the specified time (vide infra). Subsequently, the vials were heated up with a heat gun (heatinglevel 3 of 10) until dissolution of the gel phase. At this point, EtOAc (1.0 mL) and hexafluorobenzene(11.6 L, 0.1 mmol, NMR internal standard) were added into the hot solution and 5 drops of the crudesolution were taken out for NMR analysis. Notes: (1) Reactions using different gelators, light source,gelator concentration and/or reactants concentration were performed following the same procedureusing the amounts given in the main text. (2) Gelator G-3 required 5 min sonication for complete dissolution in the reaction mixture, and gelation occurred during this process.
3-(4-(oxazol-2-yl)benzyl)pyrimidin-4(3H)-one[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
Stage #1: pyrimidine-4(3H)-one With caesium carbonate In N,N-dimethyl-formamide at 20℃; for 0.166667h;
Stage #2: 2-(4-(bromomethyl)phenyl)oxazole In N,N-dimethyl-formamide for 3h;
1
Pyrimidin-4(3H)-one (500mg, 5.2 mmol) and caesium carbonate (5g, 15.6 mmol) were stirred in dimethylformamide (25ml) for 10 minutes at room temperature. 2-(4- (bromomethyl)phenyl)oxazole (1.26g, 5.3 mmol) was added and the reaction was stirred for 3 hours. The reaction was diluted with water and the resulting yellow precipitate collected by filtration. The crude product was purified by column chromatography on silica, eluting with ethyl acetate/hexane (5 % to 95%) to give 3-(4-(oxazol-2- yl)benzyl)pyrimidin-4(3H)-one. m/z: 253.01 (calc 253.09) 8.69 (1H, s), 8.21 (1H, s), 7.94 (3H, m), 7.45 (2H, d), 7.37 (1H, d), 6.44 (1H, d), 5.11 (2H, s).