* 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.
Reference：
[1] Bioorganic and Medicinal Chemistry Letters, 2014, vol. 24, # 9, p. 2073 - 2078
2
[ 612-25-9 ]
[ 612-23-7 ]
Reference：
[1] Canadian Journal of Chemistry, 2006, vol. 84, # 7, p. 1006 - 1012
[2] Tetrahedron, 1996, vol. 52, # 47, p. 14929 - 14936
[3] Molecules, 2011, vol. 16, # 7, p. 5665 - 5673
[4] Chemische Berichte, 1885, vol. 18, p. 2402
[5] Chemische Berichte, 1883, vol. 16, p. 2066
[6] Journal of the Chemical Society, 1965, p. 1080 - 1087
[7] Recueil des Travaux Chimiques des Pays-Bas, 1949, vol. 68, p. 1143,1158
[8] European Journal of Organic Chemistry, 2018, vol. 2018, # 1, p. 41 - 47
3
[ 612-25-9 ]
[ 3958-60-9 ]
Reference：
[1] Canadian Journal of Chemistry, 2006, vol. 84, # 7, p. 1006 - 1012
[2] Chemical Communications, 2017, vol. 54, # 5, p. 449 - 451
[3] Australian Journal of Chemistry, 1983, vol. 36, # 10, p. 2095 - 2110
[4] Bulletin de la Societe Chimique de France, 1921, vol. <4> 29, p. 1007
[5] Journal of the Chemical Society, 1924, vol. 125, p. 1315
[6] Bulletin de la Societe Chimique de France, 1921, vol. <4> 29, p. 1007
[7] Journal of the Chemical Society, 1924, vol. 125, p. 1315
[8] Journal of the American Chemical Society, 1916, vol. 38, p. 1076
[9] Journal of the American Chemical Society, 1930, vol. 52, p. 1640,1643
[10] Tetrahedron Letters, 2011, vol. 52, # 1, p. 13 - 16
[11] Organic Process Research and Development, 2003, vol. 7, # 5, p. 655 - 662
[12] Inorganic Chemistry, 2016, vol. 55, # 17, p. 9038 - 9046
[13] Soft Matter, 2018, vol. 14, # 36, p. 7420 - 7428
4
[ 612-25-9 ]
[ 631-61-8 ]
[ 77376-01-3 ]
[ 3958-60-9 ]
Yield
Reaction Conditions
Operation in experiment
78%
With N-Bromosuccinimide; triphenylphosphine In acetonitrile at 20℃; for 12 h; Cooling with ice
General procedure: To a solution of Ph3P(OAc)2, was added 3-phenylpropanol (1 mmol, 0.137 mL). The progress of the reaction was monitored by TLC (Table 3, entry 2). After completion of the reaction (0.3 h) the reaction mixture was filtered to remove the precipitated NH4Br followed by evaporation of the solvent. Column chromatography of the crude mixture on silica gel using n-hexane/EtOAc (3:1) as the eluent gave 3-phenylpropyl acetate in 90percent yield (0.159 g).
General procedure: A mixture of the substrate (1 mmol), ionic liquid [Dsim]HSO4 (6.5 mg, ∼0.02 mmol) in methanol (2 mL) was stirred at room temperature. After completion of the reaction (monitored by TLC), solvent was evaporated, water (1 mL) was added to the mixture, and stirred vigorously. Decantation of the mixture gave almost pure product(s). The products were characterized by comparison of their IR and NMR data. The ionic liquid was dried at 65 ◦C under vacuum to remove moisture, and then reused.
91%
With poly (ethylene glycol)-sulfonated sodium montmorillonite nanocomposite In methanol at 20℃; for 0.0833333 h;
General procedure: A mixture of the substrate (1 mmol) and the PEG-SANMnanocomposite (8 mg) in methanol (2 mL) was stirred at roomtemperature. After completion of the reaction (monitored byTLC), the catalyst was filtered off and the solvent was evaporatedunder reduced pressure. The crude product was purifiedby column chromatography on silica gel to yield pure alcoholsand phenols.
77%
With nano magnetic sulfated zirconia (Fe3O4 at ZrO2/SO42−) In neat (no solvent) at 20℃; for 0.5 h; Green chemistry
General procedure: To a mixture of trimethylsilyl ether (1.0 mmol), 80.0 mgFe3O4ZrO2/SO42−was added and the mixture was stirredat room temperature for an appropriate time (Table 3). Aftercompletion of the reaction, as indicated by thin-layer chromatography (TLC), 10.0 mL CCl4 was added to the reactionmixture, the catalyst was separated by an external magnet,and the product was obtained by evaporation of the volatileportion under reduced pressure. All compounds are known and were characterized on the basis of their spectroscopic data(IR,1H NMR) and by comparison with those reported in theliterature.
Reference：
[1] Bulletin of the Chemical Society of Japan, 2000, vol. 73, # 12, p. 2775 - 2778
[2] Journal of Molecular Catalysis A: Chemical, 2012, vol. 365, p. 15 - 23
[3] Journal of Chemical Research, 2006, # 1, p. 29 - 31
[4] Phosphorus, Sulfur and Silicon and the Related Elements, 2008, vol. 183, # 1, p. 168 - 177
[5] Journal of the Chinese Chemical Society, 2008, vol. 55, # 5, p. 943 - 946
[6] RSC Advances, 2016, vol. 6, # 28, p. 23564 - 23570
[7] Phosphorus, Sulfur and Silicon and the Related Elements, 2016, vol. 191, # 6, p. 944 - 951
[8] Synthetic Communications, 1996, vol. 26, # 3, p. 423 - 432
[9] Phosphorus, Sulfur and Silicon and the Related Elements, 2004, vol. 179, # 11, p. 2189 - 2193
[10] Phosphorus, Sulfur and Silicon and the Related Elements, 2010, vol. 185, # 3, p. 641 - 646
[11] Mendeleev Communications, 2005, vol. 15, # 3, p. 113 - 116
[12] Synthetic Communications, 2005, vol. 35, # 22, p. 2913 - 2919
[13] Phosphorus, Sulfur and Silicon and the Related Elements, 2017, vol. 192, # 1, p. 129 - 135
6
[ 552-89-6 ]
[ 612-25-9 ]
Yield
Reaction Conditions
Operation in experiment
98%
With Zn(2+)*2BH4(1-)*C6H7NO In acetonitrile at 20℃;
General procedure: A Typical ProcedureIn a round-bottomed flask (10 mL),equipped with a magnetic stirrer, a solution ofbanzaldehye (0.106 g, l mmol) in CH3CN (3 mL)was prepared. The complex reducing agent (0.1 g,0.5 mmol) was then added and the mixture wasstirred at room temperature. TLC monitored theprogress of the reaction (eluent; Hexane/EtOAc: 9/1). After completion of the reaction within 1 min, asolution of 5percent HCl (5 mL) was added to the reactionmixture and stirred for 5 min. The mixture was extracted with CH2Cl2 (3 × 10 mL) and dried overthe anhydrous sodium sulfate. Evaporation of thesolvent and short column chromatography of theresulting crude material over silica gel (0.015-0.040mm) by eluent of (Hexane/EtOAc: 9/1) afforded thepure liquid benzyl alcohol (0.105 g, 98percent yield)
97%
Stage #1: With nickel boride In water; acetonitrile at 20℃; for 0.0833333 h; Green chemistry Stage #2: With sodium tetrahydroborate In water; acetonitrile at 20℃; for 0.00833333 h; Green chemistry
General procedure: In a round-bottomed flask (10 mL) equipped with a magneticstirrer, a mixture of nitrobenzene (0.123 g, 1 mmol)and H2O (2 mL) was prepared. Ni2B (0.006 g, 0.05 mmol) was then added and the mixture was stirred for 5 min.NaBH4 (0.095 g, 2.5 mmol) was also added and the resultingmixture was continued to stirring for 3 min at roomtemperature. TLC monitored the progress of the reaction(eluent, n-hexane/Et2O:5/3). After completion of the reaction,aqueous solution of KOH (2 percent, 5 mL) was addedand the mixture was stirred for 10 min. The mixture wasextracted with EtOAc (3 × 8 mL) and then dried overanhydrous Na2SO4. Evaporation of the solvent affords thepure liquid aniline in 95 percent yield (0.088 g, Table 2, entry 1).
91%
Stage #1: With Triethoxysilane; [cis-Fe(H)(SPh)(PMe3)4] In tetrahydrofuran at 50℃; for 2 h; Stage #2: With methanol; sodium hydroxide In tetrahydrofuran; water at 60℃; for 24 h;
General procedure: To a 25 mL Schlenk tube containing a solution of 1 in 2 mL of THF was added an aldehyde (1.0 mmol) and (EtO)3 SiH (0.20 g, 1.2 mmol). The reaction mixture was stirred at 50–55 °C until there was no aldehyde left (monitored by TLC and GC–MS). The reaction was then quenched byMeOH (2mL) and a 10percent aqueous solution of NaOH (5 mL) with vigorous stirring at 60 °C for about 24 h.The organic product was extracted with diethyl ether (10 mL × 3), dried over anhydrous MgSO4, and concentrated under vacuum. The alcohol product was further purified using flash column chromatography (elute with 5–10percent ethyl acetate in petroleum ether). The 1H NMR and 13C NMR spectra of the alcohol products are providedin Supporting information.
85%
With Poly(n-butyl-4-vinylpyridinium)borohydride In ethanol at 20℃; for 2.33333 h;
General procedure: To a solution of the substrate (1 mmol) in ethanol as asolvent (5 mL) in a round-bottomed flask (25 mL) equippedwith a magnetic stirrer, P(BVP)BH4 (100 mg) was addedand stirred at room temperature. The progress of thereaction was monitored by TLC. On completion of thereaction, the mixture was filtered and the used reagent waswashed successively with HCl (1.0 M, 2 10 mL) andethanol (2 5 mL). The combined filtrates were evaporatedand the pure product was obtained in moderate to excellent yields. In a few cases in which the reaction wasnot complete, the crude product was purified on silica gelwith an appropriate eluent (Scheme 1).
81.1%
With sodium tetrahydroborate In methanol at 15℃; for 2 h;
To 136 g1,2-bis (o-nitrophenyl) ethane(0.50 mol),324 g of benzoquinone (3.0 mol) was added to a 1000 ml four-necked reaction flask,After heating and melting,The reaction was carried out at 135-140 ° C for 6 hours,High performance liquid chromatography tracking detection; after the reaction, the pump decompression recovery of excess benzoquinone and by-product hydroquinone;To the residue was added 408 g of methanol dissolved,Then, 19 g of sodium borohydride (0.5 mol) was added and the reaction was stirred at 15 ° C for 2 hours.After the reduction reaction, the solvent methanol was recovered and 145.4 g of a product of 160-165 ° C / 15 mmHg was collected by distillation,As the target product o-nitrobenzyl alcohol,Liquid content of 94.9percent,Yield 90.2percent;Recrystallization from toluene gave 125.2 g of pale yellow crystals,Mp 70 ~ 72 ,Liquid content of 99.2percentThe total yield was 81.1percent.
39%
Reflux
General procedure: The carbonyl compound (1.0 mmol) and ytterbium triflate hydrate (0.1 mmol) were dissolved in iPr-OH (2 mL). The resulting mixture was stirred at reflux overnight. The solvent was removed by anhydrous N2 bubbling into the reaction medium, then the residue was dissolved in 10 mL of cold CHCl3 and let to stand for 5 h at 4 °C. The resulting solid was removed by paper filtration and the resulting solution dried by anhydrous N2 bubbling. The resulting crude mixture was purified by flash chromatography (elution CH2Cl2) affording the desired adduct.
10.45 g
With sodium tetrahydroborate In methanol at 0℃; for 0.5 h; Inert atmosphere; Schlenk technique
To a stirred solution of 2-nitrobenzaldehyde (11.0 g, 72.79 mmol) in methanol (55 ml) was added sodium borohydride (3.3 g, 88.02 mmol) at 0 °C and the reaction solution was stirred for 30 min at same temperature. The mixture was quenched with saturated aqueous ammonium chloride (150 ml) and extracted with ethyl acetate (2 x 300 ml). The combined organic layers were washed with brine (200 ml) and dried over anhydrous sodium sulphate. The organic layer was filtered and concentrated under reduced pressure. The residue obtained was purified by flash silica gel column chromatography to yield 10.45 g of product as a white solid.
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[79] Patent: CN108218800, 2018, A, . Location in patent: Paragraph 0128; 0130; 0131
[80] Journal of Materials Chemistry A, 2018, vol. 6, # 37, p. 18242 - 18251
7
[ 18483-88-0 ]
[ 612-25-9 ]
Reference：
[1] Synthetic Communications, 2002, vol. 32, # 11, p. 1633 - 1637
[2] Tetrahedron Letters, 2001, vol. 42, # 43, p. 7679 - 7681
[3] Bulletin of the Chemical Society of Japan, 2000, vol. 73, # 12, p. 2775 - 2778
[4] Phosphorus, Sulfur and Silicon and the Related Elements, 2007, vol. 182, # 9, p. 2235 - 2240
[5] Tetrahedron Letters, 2002, vol. 43, # 29, p. 5123 - 5126
8
[ 552-89-6 ]
[ 552-16-9 ]
[ 612-25-9 ]
Reference：
[1] Chemische Berichte, 1881, vol. 14, p. 2804
[2] Chemische Berichte, 1885, vol. 18, p. 2402
[3] Tetrahedron Letters, 2014, vol. 55, # 29, p. 3920 - 3922
[4] Oriental Journal of Chemistry, 2016, vol. 32, # 1, p. 359 - 365
9
[ 42854-99-9 ]
[ 612-25-9 ]
Reference：
[1] Patent: US4994568, 1991, A,
[2] Patent: US4260627, 1981, A,
[3] Patent: US4262009, 1981, A,
[4] Patent: US4341705, 1982, A,
[5] Patent: US4465632, 1984, A,
[6] Patent: US4206219, 1980, A,
10
[ 552-16-9 ]
[ 612-25-9 ]
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[1] Tetrahedron Letters, 1999, vol. 40, # 23, p. 4395 - 4396
[2] Journal of Organic Chemistry, 1996, vol. 61, # 20, p. 6994 - 6996
[3] Indian Journal of Chemistry, Section B: Organic Chemistry Including Medicinal Chemistry, 1998, vol. 37, # 9, p. 945 - 947
11
[ 3958-60-9 ]
[ 612-25-9 ]
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[1] RSC Advances, 2014, vol. 4, # 91, p. 49974 - 49978
[2] Canadian Journal of Chemistry, 1985, vol. 63, p. 2958 - 2960
[3] Patent: CN105439867, 2016, A, . Location in patent: Paragraph 0021; 0030; 0031
Reference：
[1] Canadian Journal of Chemistry, 1985, vol. 63, p. 2958 - 2960
24
[ 88-72-2 ]
[ 612-25-9 ]
Reference：
[1] Helvetica Chimica Acta, 1920, vol. 3, p. 404
[2] Bulletin de la Societe Chimique de France, 1901, vol. <3> 25, p. 853
[3] Patent: CN105439867, 2016, A,
Reference：
[1] Chemical Communications, 2016, vol. 52, # 47, p. 7501 - 7504
29
[ 3718-21-6 ]
[ 612-25-9 ]
Reference：
[1] Chemical Communications, 2016, vol. 52, # 47, p. 7501 - 7504
30
[ 2385-27-5 ]
[ 612-25-9 ]
[ 33331-19-0 ]
[ 62-53-3 ]
Reference：
[1] Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 2004, vol. 43, # 2, p. 432 - 436
31
[ 555-31-7 ]
[ 552-89-6 ]
[ 612-25-9 ]
Reference：
[1] Recueil des Travaux Chimiques des Pays-Bas, 1949, vol. 68, p. 1143,1158
[2] Chemische Berichte, 1937, vol. 70, p. 1520,1524
[3] Chemische Berichte, 1934, vol. 67, p. 1571
Reference：
[1] Chemische Berichte, 1881, vol. 14, p. 2804
34
[ 2269-22-9 ]
[ 552-89-6 ]
[ 612-25-9 ]
Reference：
[1] Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, 1945, vol. 220, p. 460
35
[ 3162-96-7 ]
[ 3958-60-9 ]
[ 612-25-9 ]
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[1] Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), 1993, # 18, p. 2161 - 2166
[2] Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), 1993, # 18, p. 2161 - 2166
Reference：
[1] Chemische Berichte, 1937, vol. 70, p. 1520,1524
[2] Chemische Berichte, 1934, vol. 67, p. 1571
40
[ 67-56-1 ]
[ 56-23-5 ]
[ 552-89-6 ]
[ 552-16-9 ]
[ 612-25-9 ]
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[1] Justus Liebigs Annalen der Chemie, 1947, vol. 558, p. 34,41
[2] Annales Academiae Scientiarum Fennicae, Series A, 1942, vol. 59, # 4, p. 3,4[3] Chem.Abstr., 1944, p. 6173
[4] Chemische Berichte, 1930, vol. 63, p. 855,865[5] Journal fuer Praktische Chemie (Leipzig), 1933, vol. <2>138, p. 51,54
41
[ 2269-22-9 ]
[ 552-89-6 ]
[ 78-92-2 ]
[ 612-25-9 ]
Reference：
[1] Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, 1945, vol. 220, p. 460
Reference：
[1] Journal of Organic Chemistry, 2016, vol. 81, # 22, p. 10688 - 10697
44
[ 612-25-9 ]
[ 67-63-0 ]
[ 18189-02-1 ]
Yield
Reaction Conditions
Operation in experiment
80%
at 100℃; for 16 h; Schlenk technique; Inert atmosphere
In the schlenk tube was added 0.5 mmol o-nitrobenzyl alcohol,0.25 mmol of cesium carbonate and 0.75 ml of isopropanol, charged with N2,After the reaction was stirred at 100 ° C for 16 hours, heating and stirring were stopped, cooled to room temperature,The reaction solution was diluted with 5 mL of ethyl acetate, filtered under atmospheric pressure, and the resulting filtrate was dried under reduced pressure,The crude product was obtained and purified by column chromatography (silica gel)Get the target product, the column eluate used is 30: 1 by volume of petroleum ether:Ethyl acetate mixed solvent, yield 80percent.
Reference：
[1] Patent: CN107353217, 2017, A, . Location in patent: Paragraph 0049; 0050; 0051; 0052; 0053; 0054; 0055-0057
[2] Organic and Biomolecular Chemistry, 2018, vol. 16, # 4, p. 531 - 535
45
[ 612-25-9 ]
[ 24835-08-3 ]
Reference：
[1] European Journal of Organic Chemistry, 2018, vol. 2018, # 1, p. 41 - 47
With dmap; In chloroform; for 24h;Reflux; Inert atmosphere; Darkness;
2.3 Synthesis of 2-nitrobenzyl succinate (NBS) Typically, <strong>[612-25-9]2-nitrobenzyl alcohol</strong> (3.83 g, 25.0 mmol), succinic anhydride (5.03 g, 50.0 mmol), and DMAP (1.53 g, 12.5 mmol) were dissolved completely in CHCl3 (86 mL). The reaction mixture was refluxed overnight (24 h) under a nitrogen atmosphere. CHCl3 was evaporated under reduced pressure. The mixture was washed three times with 10% HCl and then extracted with saturated NaHCO3 solution. The basic aqueous phase was washed with diethyl ether and acidified to pH 5.0 with 10% HCl. The white solid precipitate was collected and dried in vacuo at 40 C overnight to provide the product (NBS) (5.63 g, 89%). All above reactions were in dark place.
EXAMPLE 177 Succinic acid mono-o-nitrobenzyl ester was prepared from succinic anhydride and <strong>[612-25-9]o-nitrobenzyl alcohol</strong> by the procedure similar to that described in Example 174. m.p.: 63~65 C. IRmaxNujol (cm-1): 1726, 1693, 1528, 1333, 1152,
With toluene-4-sulfonic acid; In toluene; for 14h;Inert atmosphere; Dean-Stark; Reflux;
General procedure: The aryl hydrogen succinates (1-29) weresynthesized and characterised by following the standard protocol [19]. Briefly, 15 mmol ofcorresponding alcohol was added to succinic anhydride (15 mmol), anhydrous p-toluenesulfonicacid (0.06 mmol) and toluene (15 mL) under the atmosphere of nitrogen in a single-neckedround-bottom flask (100 mL). The flask was equipped with magnetic stirrer, Dean-Stark trapand a reflux condenser. The solution was refluxed for 14 h and allowed to cool up to 25 oC. The product was then poured into saturated aqueous solution of NaHCO3 (12.5 mL) and the organiclayer was extracted with hexane (3 × 25 mL). The organic phase was then washed with brine (10mL), dried over anhydrous Na2SO4 and the excess of the solvent was removed under vacuum togive a resinous product. It was then subjected to column chromatography to get pure monoesters(1-29). The target substrates were characterized by UV, IR, 1H-NMR and 13C-NMR and massmeasurement.
With dmap; In chloroform; for 24h;Inert atmosphere; Reflux;
Mole ratio of 1:2 ortho-nitrophenyl-methanol with succinic anhydride dissolved in chloroform, joined the raw materials material amount of 0.2 times the amount of catalyst 4 - dimethylamino pyridine (DMAP), nitrogen to protect the environment, reflux reaction 24h, after stopping the reaction, chloroform is distilled under reduced pressure to remove a portion of, the volume of the remaining reaction solution the percentage concentration of 10% (v/v) HCl solution to wash three times, then saturated sodium bicarbonate solution extraction after washing, the volume for the percentage concentration of 10% (v/v) aqueous HCl solution to adjust pH to 5, a large amount of white precipitate generated. Collecting white precipitate, for 40 degree c vacuum drying, to obtain the O-nitryl phenmethyl succinic acid monoester (NBS).
With dmap; In chloroform; for 24h;Inert atmosphere; Reflux; Darkness;
Take the light trigger molecule <strong>[612-25-9]o-nitrobenzyl alcohol</strong> (25.0mmol),Succinic anhydride (5.03 g) and DMAP (1.53 g) were dissolved in pure chloroform (90 mL).The reaction mixture was refluxed under nitrogen for 24 h.Subsequently, chloroform was distilled off under reduced pressure.The mixture was washed three times with 10% by volume hydrochloric acid to remove DMAP, and then extracted with a saturated NaHCO3 solution.The aqueous phase was washed with diethyl ether and then adjusted to pH 5.0 with a 10% by volume hydrochloric acid.Collect white precipitate andIt was dried under vacuum at 40 C to obtain o-nitrobenzyl succinic acid monoester (NBS).All of the above reactions were carried out in a dark environment.
With tetra-N-butylammonium tribromide In acetonitrile at 20℃; for 15h; Irradiation;
2.2 General experimental procedure for the photocatalytic oxidation of alcohol
General procedure: In a 50ml Pyrex round-bottom flask, a mixture of alcohol (1mmol), TBATB (10-20mg, 0.02-0.04mmol) in 10ml of CH3CN was exposed to blue or violet light LED irradiation at room temperature under an air atmosphere with stirring. The progress of the photocatalytic oxidation reaction was monitored by TLC on silica gel plates. The reaction mixture externally irradiated until the alcohol was completely consumed.
91%
With dihydrogen peroxide at 90℃; for 9h;
90%
With 2,2,6,6-tetramethyl-piperidine-N-oxyl; trichloroisocyanuric acid; sodium hydrogencarbonate In water; acetone at 20℃; for 6h;
90%
With sodium bromate; sodium hydrogen sulfate In acetonitrile for 30h; Heating;
84%
With tert.-butylhydroperoxide; ammonium cerium (IV) nitrate In water; acetonitrile at 20℃; for 49h; chemoselective reaction;
84%
With tert.-butylhydroperoxide; water; iodine; sodium hydroxide at 70℃; Green chemistry;
83%
With Cu(II)-complex of salen-H4; dihydrogen peroxide In acetonitrile at 80℃; for 8h;
82%
With tert.-butylhydroperoxide; bismuth(III) oxide In water; ethyl acetate for 50h; Reflux; chemoselective reaction;
81%
With Iron(III) nitrate nonahydrate; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; potassium chloride; oxygen In 1,2-dichloro-ethane at 25℃; for 48h; Schlenk technique;
General procedure: To a Schlenk tube were added Fe(NO3)3·9H2O (40.6 mg, 0.1 mmol), TEMPO (15.8 mg, 0.1 mmol), KCl (7.5 mg, 0.1 mmol), 1a (108.5 mg, 1.0 mmol), and DCE (4.0 mL) sequentially under an atmosphere of oxygen (gas bag, commercial size: 2 L, which could be expanded to 5 L). The mixture was then stirred at 25 °C until completion of the reaction as monitored by TLC (petroleum ether/EtOAc = 5:1) (48h). The crude reaction mixture was filtered through a short column of silica gel (height: 2 cm, diameter: 3 cm) eluting with Et2O (3 × 25 mL). After evaporation, the residue was purified by chromatography on silica gel [petroleum ether/EtOAc = 15:1 (500 mL) to 2:1 (300 mL)] to afford benzoic acid (2a)14 (69.9 mg, 57%) as a pale yellow solid. Yields of 57% of 2a and 38% of benzaldehyde (3a)15 were observed by NMR analysisof the crude product using CH2Br2 as an internal standard and by comparison with spectra reported in the literature.
75%
With superoxide; oxygen In N,N-dimethyl-formamide for 12h; electrolysis, divided electrolytic cell, mercury pool cathode, platinum foil anode, Bu4N+Br-, cyclohexene, constant potential -1.0 V vs. SCE, current 95 (initial) to 12 (final) mA;
75%
With superoxide; oxygen In N,N-dimethyl-formamide for 12h; electrolysis, divided electrolytic cell, mercury pool cathode, platinum foil anode, Bu4N+Br-, cyclohexene, constant potential -1.0 V vs. SCE, current 95 (initial) to 12 (final) mA; other primary alcohols, other times, other currents;
74%
With Oxone In water; acetonitrile for 24h; Reflux;
6.2 General procedure for oxidation of benzyl halides, alcohols, and aromatic hydrocarbons
General procedure: To 16 mL of acetonitrile/water (1:1 v/v) mixture was added 0.5-1.2 mmol of the starting compound. The contents were heated at reflux with introduction of oxone (cf. entries for each case) incrementally over the entire duration of the reaction. For secondary benzyl halides, the reactions were run at room temperature. The progress of the reaction in each case was monitored by TLC analysis. After completion of the reaction, the reaction mixture was cooled to room temperature and the organic matter was extracted with ethyl acetate. The combined organic extract was dried over anhyd Na2SO4 and concentrated in vacuo. Short pad silica gel column chromatography of the residue led to isolation of the pure product.
72%
With dihydrogen peroxide; oxygen In acetonitrile at 80℃; for 9h;
66%
With oxygen; sodium hydroxide In ethanol at 60℃; for 24h; Green chemistry; chemoselective reaction;
17%
With meta-dinitrobenzene; sodium hydroxide In water at 100℃; for 2.5h; Sealed tube;
90 %Chromat.
With dihydrogen peroxide; copper dichloride at 25℃; for 1h; Ionic liquid;
At room temperature, to a 1 L four-necked flask was added 200 g of ethyl acetate, 150 g of acetonitrile and 45.9 g of 0.3 mol of <strong>[612-25-9]o-nitrobenzyl alcohol</strong>, 44.5 g 0.42 mol sodium carbonate, stirring 10min, 50.5 g of 0.40 mol of dimethyl sulfate was slowly added dropwise at 20 to 25 C, dropping time is 1.0h, drop complete in 50 ~ 60 deg. C under the insulation 0.5h ~ 1.0h, HPLC in control, when the raw material was<1.0% the reaction was stopped, to room temperature, 100 ml of water was added, stirring was continued for 20 min, phase separation, the aqueous phase was extracted with 100 ml of ethyl acetate, phase separation, the organic phases were combined, ethyl acetate was recovered by distillation under reduced pressure, to give a yellow solid, the mixture was air-dried overnight at 30 C to give o-nitrobenzyl methyl ether: 49.0 g, yield: 97.8%, HPLC: 98.6%.
With methanol; 1,3-disulfonic acid imidazolium hydrogen sulfate; at 20℃; for 0.0833333h;Green chemistry;
General procedure: A mixture of the substrate (1 mmol), ionic liquid [Dsim]HSO4 (6.5 mg, ?0.02 mmol) in methanol (2 mL) was stirred at room temperature. After completion of the reaction (monitored by TLC), solvent was evaporated, water (1 mL) was added to the mixture, and stirred vigorously. Decantation of the mixture gave almost pure product(s). The products were characterized by comparison of their IR and NMR data. The ionic liquid was dried at 65 ?C under vacuum to remove moisture, and then reused.
92%
With Nanoporous Na+-Montmorillonite Perchloric Acid; In ethanol; at 20℃; for 0.05h;
General procedure: A mixture of the substrate (1 mmol) and MMT-HClO4(10 mg) in ethanol (2 mL) was stirred at room temperature.The progress of the reaction was monitored by TLC, ethylacetate: n-hexane (3:7). After completion of the reactionthe catalyst was filtered off and the solvent was evaporatedunder reduced pressure. The crude product was purifiedby column chromatography on silica gel (EtOAc:hexane=1:4) to gave the pure alcohol and/or phenol derivative ingood to high yields.
91%
With poly (ethylene glycol)-sulfonated sodium montmorillonite nanocomposite; In methanol; at 20℃; for 0.0833333h;
General procedure: A mixture of the substrate (1 mmol) and the PEG-SANMnanocomposite (8 mg) in methanol (2 mL) was stirred at roomtemperature. After completion of the reaction (monitored byTLC), the catalyst was filtered off and the solvent was evaporatedunder reduced pressure. The crude product was purifiedby column chromatography on silica gel to yield pure alcoholsand phenols.
77%
With nano magnetic sulfated zirconia (Fe3O4 at ZrO2/SO42-); In neat (no solvent); at 20℃; for 0.5h;Green chemistry;
General procedure: To a mixture of trimethylsilyl ether (1.0 mmol), 80.0 mgFe3O4ZrO2/SO42-was added and the mixture was stirredat room temperature for an appropriate time (Table 3). Aftercompletion of the reaction, as indicated by thin-layer chromatography (TLC), 10.0 mL CCl4 was added to the reactionmixture, the catalyst was separated by an external magnet,and the product was obtained by evaporation of the volatileportion under reduced pressure. All compounds are known and were characterized on the basis of their spectroscopic data(IR,1H NMR) and by comparison with those reported in theliterature.
Stage #1: ortho-nitrobenzoic acid With 4-methyl-morpholine; 1,3,5-trichloro-2,4,6-triazine In 1,2-dimethoxyethane at 20℃; for 3h;
Stage #2: With sodium tetrahydroborate In water at 0℃;
92%
Stage #1: ortho-nitrobenzoic acid With sodium aminodiboranate In tetrahydrofuran at 20℃;
Stage #2: With water
With triethylamine; In tetrahydrofuran; at 0 - 25℃; for 2.5h;
Diisopropylphosphoramidous dichloride (2.0 g, 9.90 mmol) was dissolved in 15 mL of THF and the resulting solution was added slowly to a solution containing 4.2 mL (29.7 mmol) of triethylamine and 3.03 g (19.8 mmol) of <strong>[612-25-9]2-nitrobenzyl alcohol</strong> in 10 mL of THF at 0 C. The reaction mixture was stirred at 0 C for 30 min and then at 25 C for another 2h. The colorless precipitate was isolated by filtration and the solid was washed with 100 mL of ethyl acetate. The organic phase was washedsuccessively with 15 mL portions of saturated NaHCOs and saturated NaCl and then dried (MgS04) and concentrated under diminished pressure at 25 C. The residue was precipitated from ethyl acetate/hexane, affording bis(2-nitrobenzyl) N,N- diisopropylphosphoramidite (3.0 g, 70%) as a colorless solid.
70%
With triethylamine; In tetrahydrofuran; at 0 - 25℃; for 2.5h;
Diisopropylphosphoramidous dichloride 5 (2.0 g, 9.90 mmol) was dissolved in 15 mL of THF and the resulting solution was added slowly to a solution containing 4.2 mL (29.7 mmol) of triethylamine and 3.03 g (19.8 mmol) of <strong>[612-25-9]2-nitrobenzyl alcohol</strong> 6 in 10 mL of THF at 0 C. The reaction mixture was stirred at 0 C for 30 min and then at 25 C for another 2h. The colorless precipitate was isolated by filtration and the solid was washed with 100 mL of ethyl acetate. The organic phase was washed successively with 15 mL portions of saturated NaHC03 and saturated NaCI and then dried (MgS04) and concentrated under reduced pressure at 25 C. The residue was precipitated from ethyl acetate/hexane, affording bis (2- nitrobenzyl)-N,N-diisopropylphosphoramidite 9 (3.0 g, 70%) as a colorless solid.5 (see Figure 3). bis-(2-nitrobenzyl)-N,N-diisopropylphosphoramidite 9. Mp 71-72 C. [lit.5 Mp 71-73 C] 1H NMR (400 MHz, CDCl3) delta 8.10 (d, J= 8.4 Hz, 2 H, H-3 and H-3'), 7.86 (d, J= 8.0 Hz, 2 H, H-6 and H-6'), 7.67 (t, J= 8.0 Hz, 2H, H-5 and H-5'), 7.44 (t, J= 8.4 Hz, 2H, H-4 and H- 4'), 5.21 (dd, J= 16.4 Hz and J= 6.8 Hz, 2H, CH2Ar), 5.12 (dd, J= 16.4 Hz and J= 6.8 Hz, 2H, CH2Ar , 3.77-3.71 (m, 2Eta, 2 x CH(CH3)2), 1.25 (d, J= 8.5 Hz, 12H, 2 x CH(CH5)2); 13 C NMR (100 MHz, CDC13) delta 146.8 (C-2 and C-2'), 136.1, 136.0 (C-I and C-Gamma), 133.7 (C-6 and C-6'), 128.5 (C-5 and C-5'), 127.8 (C-4 and C-4'), 124.6 (C-3 and C-3'), 62.5 ( H2Ar), 62.3 ( H2Ar), 43.4 ( H(CH3)2), 43.3 ( H(CH3)2), 24.7 (CH( H3)2), 24.6 (CH( H3)2); 31P NMR (162 MH, CDCl3) delta 149.0; ESI-LRMS m/z calculated for C20H26N3O6P [M+ H]+
70%
With triethylamine; In tetrahydrofuran;
Diisopropylphosphoramidous dichloride 5 (2.0 g, 9.90 mmol) was dissolved in 15 mL of THF and the resulting solution was added slowly to a solution containing 4.2 mL (29.7 mmol) of triethylamine and 3.03 g (19.8 mmol) of <strong>[612-25-9]2-nitrobenzyl alcohol</strong> 6 in 10 mL of THFat 0 C. The reaction mixture was stirred at 0 C for 30 mm and then at 25 C for another 2h. The colorless precipitate was isolated by filtration and the solid was washed with 100 mL of ethyl acetate. The organic phase was washed successively with 15 mL portions of saturated NaHCO3 and saturated NaCI and then dried (MgSO4) and concentrated under reduced pressure at 25 C. The residue was precipitated from ethyl acetate/hexane, affording bis (2-nitrobenzyl)N,N-diisopropylphosphoramidite 9 (3.0 g, 70%) as a colorless solid.5 (see Figure 3)bis-(2-nitrobenzyl)-N,N-diisopropylphosphoramidite 9. Mp 71-72 C. [lit.5 Mp 71-73 Cj ?H NMR (400 MHz, CDCI3) 8.10 (d, J= 8.4 Hz, 2 H, H-3 and H-3?), 7.86 (d, J= 8.0 Hz, 2 H, H-6 and H-6?), 7.67 (t, J= 8.0 Hz, 2H, H-S and H-S?), 7.44 (t, J= 8.4 Hz, 2H, H-4 and H-4?), 5.21 (dd,J= 16.4 Hz andJ= 6.8 Hz, 2H, CH2Ar), 5.12 (dd,J= 16.4 Hz andJ= 6.8 Hz,2H, CH2Ar), 3.77-3.71 (m, 2H, 2 x CH(CH3)2), 1.25 (d, J 8.5 Hz, 12H, 2 x CH(CH3)2); ?3C NMR (100 MHz, CDC13) oe 146.8 (C-2 and C-2?), 136.1, 136.0 (C-I and C-I?), 133.7 (C-6 and C-6?), 128.5 (C-S and C-S?), 127.8 (C-4 and C-4?), 124.6 (C-3 and C-3?), 62.5 (CH2Ar), 62.3 (CH2Ar), 43.4 (CH(CH3)2), 43.3 (CH(CH3)2), 24.7 (CH(CH3)2), 24.6 (CH(CH3)2); 3?PNMR (162 MH, CDCI3) S 149.0; ESI-LRMS m/z calculated for C20H26N306P [M+ Hj436.1; Found 436.1
With C10H10N2O6S2(2+)*2HO4S(1-); at 20℃; for 0.416667h;
General procedure: A mixture of the substrate (1 mmol), hexamethyldisilazane (0.70 mmol), and/or 3,4-dihydro-2H-pyran (1.4 mmol) and BiPy(SO3H)2(HSO4)2 (10 mg, 1.95 mol%) in CH3CN(3 mL) and/or CH2Cl2 (3 mL) was stirred at room temperature. The progress of thereaction was monitored by TLC (n-hexane: EtOAc; 10:1) and/or GC. After completion ofthe reaction, the mixture was filtered to separate the solid catalyst. Then the solution wasfiltered through a silica gel pad and washed with CH3CN (2 × 3 mL) and/or CH2Cl2 (2 ×3 mL). Evaporation of the solvent gave the desired products in high purity.
92%
With poly(4-vinylpyridine) supported copper(II) oxide nanoparticles; In dichloromethane; at 20℃; for 0.0333333h;
General procedure: A mixture of the substrate (1 mmol), 3,4-dihydro-2H-pyran (1 mmol) and PC-NPs (12 mg) in CH2Cl2 (3 drops) was stirred at room temperature. The progress of the reaction was monitored by TLC (EtOAc: n-hexane; 1:1). After completion of the reaction, the mixture was filtered to separate the solid catalyst. Then, the solution was filtered through a silica gel pad and washed with CH2Cl2 (2 × 5 mL). Evaporation of the solvent gave the desired product in high yields.
89%
With titanium tetrachloride; In dichloromethane; at 40℃; for 7h;Molecular sieve;
General procedure: A typical reaction was carried out in a 10 mL flask.Alcohol (5 mmol), 3,4-dihydro-2H-pyran (DHP,5.5 mmol), Ti4?/4A (0.5 g) and dichloromethane (3 mL)were stirred at 40 C for 7 h. The solid was filtered, andwashed with dichloromethane, then the filtrate was evaporated.The residue was subjected to GC-MS analysis andNMR spectroscopy. The crude product could be purified bycolumn chromatography (Kieselgel, hexane:acetone 4:1).
With yttrium iron garnet; In neat (no solvent); at 80℃; for 0.333333h;Green chemistry;
General procedure: Mixture of 0.005 g and glacial acetic acid was placed in a 50-mL round bottom flask, and was stirred for 5 min. Then, alcohol(1 mmol) was added to the solution, and reaction solution was stirred under reflux condition for specified time. The progress of reaction was monitored by TLC (acetone-n-hexane, 1 : 2). After completion of the reaction, catalyst was easily removed by shutting down the stirrer without using any external magnet. The product was purified by recrystallizationin hot ethanol. For the reaction times andthe structures and yields of the products, see Table 2.
78%
With poly(4-vinylpyridine) perchlorate; In neat (no solvent); at 20℃; for 0.916667h;
General procedure: The substrate (alcohol, phenol or amine; 1.0 mmol) was treated with Ac2O (2.0 mmol) in the presence of P(4-VPH)ClO4 (50 mg) at room temperature under solvent-free conditions and magnetic stirring. After completion of the reaction as indicated by TLC, the mixture was diluted with Et2O (25 ml) and the catalyst allowed to settle down. The supernatant ethereal solution was decanted off, the catalyst washed with Et2O (2 ml) and the combined ethereal solution concentrated under vacuum to afford the product, identical(mp, IR, 1H and 13C NMR, and GC-MS) to an authentic sample of acetylated product. The recovered catalyst was dried at 50 C under vacuum for 2 h. The recovered catalyst, after drying, was reused for four more consecutive acetylation reactions of benzyl alcohol (1.0 mmol) affording 96, 96, 94, and 94% yields, respectively, in 22, 23, 23, and 25 min (Scheme 2).
With hydroxyapatite supported copper(I) oxide; In acetonitrile; at 50℃; for 0.0833333h;
General procedure: A mixture of alcohol or phenol (1 mmol), acetyl chloride(1 mmol), hydroxyapatite -Cu2O (0.1 g) in acetonitrilewas taken in a round-bottom flask and stirred at 50 C foran appropriate time. On completion (monitored by TLC),the reaction mixture was cooled to room temperature andfiltered. The residue was washed with water followed byEtOAc (3 × 10 mL). The product was obtained after theremoval of solvent under reduced pressure followed bycrystallization from pet ether or EtOAc:pet ether or passingthrough column of silica and elution with EtOAc:pet ether.
With tert.-butylhydroperoxide In decane; acetonitrile at 20℃; for 2h;
1: 92%
2: 5%
With peracetic acid; C24H29INO5 In acetic acid at 30℃; for 48h;
1: 46%
2: 46%
With Iron(III) nitrate nonahydrate; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; potassium chloride; oxygen In 1,2-dichloro-ethane at 25℃; for 48h; Schlenk technique;
General procedure: To a Schlenk tube were added Fe(NO3)3·9H2O (40.6 mg, 0.1 mmol), TEMPO (15.8 mg, 0.1 mmol), KCl (7.5 mg, 0.1 mmol), 1a (108.5 mg, 1.0 mmol), and DCE (4.0 mL) sequentially under an atmosphere of oxygen (gas bag, commercial size: 2 L, which could be expanded to 5 L). The mixture was then stirred at 25 °C until completion of the reaction as monitored by TLC (petroleum ether/EtOAc = 5:1) (48h). The crude reaction mixture was filtered through a short column of silica gel (height: 2 cm, diameter: 3 cm) eluting with Et2O (3 × 25 mL). After evaporation, the residue was purified by chromatography on silica gel [petroleum ether/EtOAc = 15:1 (500 mL) to 2:1 (300 mL)] to afford benzoic acid (2a)14 (69.9 mg, 57%) as a pale yellow solid. Yields of 57% of 2a and 38% of benzaldehyde (3a)15 were observed by NMR analysisof the crude product using CH2Br2 as an internal standard and by comparison with spectra reported in the literature.
1: 31.7%
2: 5%
With dihydrogen peroxide In acetonitrile at 70℃; for 8h;
With Ti0.85V0.15O2; dihydrogen peroxide In methanol at 20℃; for 2h;
With Fe3O4/FeO; In water; at 40℃; for 1h;Green chemistry;
General procedure: In a typical reaction, a suspension of amine (1.0 mmol) and alcohol (1.0 mmol) was added to a mixture of magnetic catalyst (0.04 g) with 1.5 ml distilled water. The resulting mixture was heated to 40 C for an appropriate time under aerobic conditions. In the case of exposure by EMF, the resulting mixture was transferred to a Helmholtz cylinder permanent magnet and exposed with 362 muT intensity for an appropriate time. Progress of the reaction was monitored by TLC. After completion of the reaction, the mixture was cooled to room temperature, and the catalyst was separated from the product solution using an external magnet, washed with deoxygenated distilled water, dried in a desiccator at room temperature, and used for the next reaction cycle without any pre-treatment. Solvent of the reaction mixture was evaporated to generate the crude product. The product was concentrated and purifiedby column chromatography on silica-gel using EtOAc/heptane (1:4) as eluent.
At room temperature, to a 1 L four-necked flask, 300 g of acetonitrile and 45.9 g of 0.3 mol of <strong>[612-25-9]o-nitrobenzyl alcohol</strong> were added, 42.0 g 0.42 mol potassium bicarbonate, stirring 10min, 63.9 g of 0.45 mol of methyl iodide was slowly added dropwise at a temperature of 20 to 25 C for a time of 1.0 h, drop in 50 ~ 60 under the insulation 0.5h ~ 1.0h, HPLC control, when the raw material was <1.0% the reaction was stopped, the aqueous phase was extracted with 100 ml of ethyl acetate. The layers were separated and the organic phase was combined. The ethyl acetate was collected by distillation under reduced pressure to give a yellow solid, which was recrystallized from ethyl acetate, dried over anhydrous magnesium sulfate and evaporated to dryness. After drying overnight at 300C, o-nitrobenzyl methyl ether: 46.9 g, yield: 93.6%, HPLC: 98.2%.
86%
To a stirred solution of (2-Nitro-phenyl)-methanol (18) (500 mg, 3.268 mmol) in THF(10 mL) was added NaH (117 mg, 4.902 mmol) at room temperature and the resultant mixture was stirred for 30 min. Methyl iodide (0.607 mL, 9.804 mmol) was then added to it and the reaction mixture was stirred at ambient temperature for 16 hours. It was then quenched with water, diluted with ethyl acetate, washed with water, dried over sodium sulfate and concentrated under reduced pressure. Crude thus obtained was purified by column chromatography (silica, gradient: 20-30% EtOAc in Hexane) to afford intermediate 19 (470 mg, 86%)) as yellow gum.
With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; ammonia; oxygen; copper(II) nitrate In water; dimethyl sulfoxide at 80℃; for 7h;
68%
Stage #1: 2-Nitrobenzyl alcohol With sodium azide; 2,4,5,6‐tetra‐9H‐carbazol‐9‐yl‐1,3‐benzenedicarbonitrile; zinc trifluoromethanesulfonate In acetonitrile at 25℃; Irradiation;
Stage #2: With trifluorormethanesulfonic acid In acetonitrile for 1h;
66%
With potassium phosphate; ammonium formate In acetonitrile at 115℃; for 16h; Sealed tube; Green chemistry;
35%
With copper(II) choride dihydrate; ammonium formate; potassium carbonate In neat (no solvent) at 135℃; for 24h; Sealed tube; Schlenk technique; Green chemistry;
Multi-step reaction with 3 steps
1: potassium carbonate; fluorosulfonyl fluoride; dimethyl sulfoxide / 12 h / 20 °C
2: hydroxylamine hydrochloride; potassium carbonate / 20 °C
3: potassium carbonate; fluorosulfonyl fluoride / 12 h / 20 °C
82 %Chromat.
With ammonium hydroxide In <i>tert</i>-butyl alcohol at 120℃; for 24h; Sealed tube; Autoclave;
S7. Procedure for the synthesis of nitriles
General procedure: The magnetic stirring bar and corresponding alcohol were transferred to 8 mL glass vial then 2 mL t-butanolsolvent was added. Then, 35 mg catalyst was added followed by the addition of aq. NH3. Then the vial wasf itted with septum, cap, and needle. The reaction vials were placed into a 300 mL autoclave (8 vials containingdif ferent substrates were placed at a time in the autoclave) and the autoclave was pressurized with 10 bar air.The autoclave was placed into an aluminium block and the temperature of the aluminum block was set in orderobtain 120 °C inside the autoclave. Temperature of the aluminum block was set to 130 oC to attain 120 oCinside the autoclave, which was considered as the reaction temperature. The reactions were allowed toprogress under continuous stirring for the required time at 120 °C. Af ter completion of the reaction, the autoclave was cooled down to room temperature and the remaining air was gradually discharged. Then, thecatalyst was f iltered-off, and washed with ethyl acetate. The solvent f rom the f iltrate containing the reactionproducts was purif ied by column chromatography. Products were analyzed by GC, GC-MS, and NMRspectroscopy. In the case of yields determined the by GC, 100 μL n-hexadecane was added to the reactionvial containing the products and diluted with ethyl acetate. Then the reaction mixture containing catalyst andproducts was filtered through a plug of silica and the filtrate containing product was analyzed by GC.
With C22H24ClIrN3O(1+)*Cl(1-); potassium hydroxide In water at 120℃; for 24h; Green chemistry;
73%
With 1,1'-bis-(diphenylphosphino)ferrocene; formic acid; N-ethyl-N,N-diisopropylamine In toluene at 150℃; for 24h; Inert atmosphere;
Quinolines 3; General Procedure
General procedure: The mixture of 2-nitrobenzyl alcohol 1a-f (0.5 mmol), alcohol 2a-k (0.6 mmol), HCO2H (53 μL, 1.0 mmol), DIPEA (125 μL, 0.75 mmol), and dppf (14.1 mg, 0.025 mmol) in toluene (1.0 mL) was stirred at 150°C (screw-capped vial) for 1 d under argon, cooled to r.t., then water (5mL) was added. The two layers were separated, and the aqueous phase was extracted with EtOAc (3 × 10 mL). The combined organic extracts were washed by brine, dried (anhyd Na2SO4), filtered, and concentrated. The residue was purified by flash chromatography on silica gel (100-200 mesh) to afford the desired quinoline 3a-r. 2-Phenylquinoline (3a) White solid; yield: 74.9 mg (73%); mp 82-84 °C (Lit.5b 81.9-83.6 °C). FTIR (film): 2922, 2851, 1598, 1554, 1493, 1446, 1423, 1320, 1285,1256, 1177, 1028, 831, 813, 773 cm-1. 1H NMR (400 MHz, CDCl3): δ = 8.26-8.16 (m, 4 H), 7.88 (d, J = 8.6 Hz, 1H), 7.83 (d, J = 8.1 Hz, 1 H), 7.74 (t, J = 7.8 Hz, 1 H), 7.58-7.44 (m, 4 H). 13C NMR (100 MHz, CDCl3): δ = 157.3, 148.1, 139.4, 136.9, 129.7,129.6, 129.4, 128.8, 127.6, 127.4, 127.2, 126.3, 119.0. HRMS (ESI): m/z [M + Na]+ calcd for C15H11NNa: 228.0784; found:228.0761.
72%
With 1,1'-bis-(diphenylphosphino)ferrocene; dodecacarbonyl-triangulo-triruthenium; potassium <i>tert</i>-butylate In tert-Amyl alcohol at 150℃; for 18h; Inert atmosphere; Schlenk technique;
With CuNiFeO; potassium <i>tert</i>-butylate In toluene at 130℃; for 24h;
a) General procedure for the synthesis of Quinoline
General procedure: To a mixture of alcohols (1.0 mmol), 2-aminobenzyl alcohol (1.0 mmol), and 1-phenylethylalcohol (1.0 mmol) and t-BuOK (1.0 mmol) in toulene (2 ml), CuNiFeO (25 mg) was added. The resulting mixture was then flush with O2 two time and then sealed andthen kept on stirred for 24 h at 130 °C. After completion of the reaction,the reaction mixture was cooled to room temperature and extracted with ethyl acetate. The organic phase was dried over anhydrous Na2SO4. The crude residue was obtained after evaporation of the solvent using rotavapor, and the residue was purified by column chromatography with ethyl acetate and pet-ether as eluents to give the pure product.
With 1,1'-bis-(diphenylphosphino)ferrocene; formic acid; N-ethyl-N,N-diisopropylamine; In toluene; at 150℃; for 24h;Inert atmosphere;
General procedure: The mixture of 2-nitrobenzyl alcohol 1a-f (0.5 mmol), alcohol 2a-k (0.6 mmol), HCO2H (53 muL, 1.0 mmol), DIPEA (125 muL, 0.75 mmol), and dppf (14.1 mg, 0.025 mmol) in toluene (1.0 mL) was stirred at 150C (screw-capped vial) for 1 d under argon, cooled to r.t., then water (5mL) was added. The two layers were separated, and the aqueous phase was extracted with EtOAc (3 × 10 mL). The combined organic extracts were washed by brine, dried (anhyd Na2SO4), filtered, and concentrated. The residue was purified by flash chromatography on silica gel (100-200 mesh) to afford the desired quinoline 3a-r.
With dmap; dicyclohexyl-carbodiimide; In dichloromethane; at 20℃; for 17.0h;
General procedure: 4-Dimethylaminopyridine (DMAP, 56mg, 0.45mmol) was added to (+)-ABA solution (100mg, 0.38mmol in 10mL CH2Cl2, followed by dicyclohexylcarbodiimide (DCC, 93mg, 0.45mmol). After stirring for lh, a solution of phenol (110mg, 1.14mmol) in CH2Cl2 (5mL) was added and stirred at room temperature for 16h. The crystals were filtered through celite and washed on the filter with CH2Cl2 (15mL). The combined solution was washed successively with saturated Na2CO3(aq) and brine, then dried (Na2SO4). The solvent was then removed in vacuum to afford the crude product, which was purified by silica gel chromatography with CH2Cl2/CH3OH (50:1) to furnish the product ABA-phenol ester 0.12g,
With water; at 30℃; for 168.0h;Sealed tube; Irradiation;
General procedure: An aqueous solution (2 mL) containing test compounds(100 mM) was prepared in a glass tube for the rice growth assay.The tube was sealed with a plastic cap and incubated undercontinuous light at 30 C for 7 days. Then the solution wassubjected to HPLC analysis: reverse phase column, SHIMADZUC18VP-ODS (150 mm4.6 mm, 6 mm); mobile phase, 60% MeOH inH2O (0.5% AcOH), and 70% MeOH in H2O (0.5% AcOH);flow rate,1 mL/min; detection, 254 nm.
With triphenylphosphine; In dichloromethane; at 20℃;
<strong>[612-25-9]o-nitrobenzyl alcohol</strong> (15.3 g, 0.1 mol), propargyl alcohol (6.1 g, 0.11 mol) and triphenylphosphine (31.4 g, 0.12 mol) were added to 180 mL of dichloromethane, and after stirring, completely dissolved. A mixed solution containing diethyl azodicarboxylate (20.9 g, 1.2 eq) and 50 mL of dichloromethane was added dropwise at room temperature, and the mixture was stirred at room temperature overnight.The material disappeared by TLC, the system was cooled to -40 C, the complex solid by-product was filtered off, the filtrate was concentrated, and column chromatography was carried out to obtain 17.6 g of a yellow oily liquid 4 in a yield of 92%.
70%
With methylmagnesium bromide; In tetrahydrofuran; at -10 - 20℃;
Method 3, <strong>[612-25-9]o-nitrobenzyl alcohol</strong> 3 (15.3 g, 0.1 mol) andPropargyl bromide (14.3 g, 0.12 mol)After adding to 110 mL of anhydrous THF,After stirring evenly, the temperature of the system drops to -10 C.3M methylmagnesium chloride tetrahydrofuran solution (0.12 mol) was added dropwise.Do not exceed 0 C during the addition process,Insulation reaction for 1 hour,Then slowly increase to room temperature and stir the reaction for 4-5 hours.After the TLC detection material disappeared, it was poured into 200 g of water, and MTBE was extracted three times with 100 mL.The organic phases were combined and washed with saturated sodium bicarbonate.The organic layer was concentrated, and the column was separated by column chromatography using n-heptane/ethyl acetate from 10:1 to 6:1.13.0 g of a yellow oily liquid 4 was obtained in a yield of 68%.Using a 1 M methylmagnesium bromide tetrahydrofuran solution, the isolated yield was 70% in the same manner as in Method 3.
70%
With methylmagnesium bromide; In tetrahydrofuran; at -10 - 20℃;
Method 3, <strong>[612-25-9]o-nitrobenzyl alcohol</strong> 3 (15.3 g, 0.1 mol) andPropargyl bromide (14.3 g, 0.12 mol)After adding to 110 mL of anhydrous THF,After stirring evenly, the temperature of the system drops to -10 C.3M methylmagnesium chloride tetrahydrofuran solution (0.12 mol) was added dropwise.Do not exceed 0 C during the dropwise addition, and keep the reaction for 1 hour.Then slowly increase to room temperature and stir the reaction for 4-5 hours.After the TLC detection of the disappearance of the raw materials, the mixture was poured into 200 g of water, and the MTBE was extracted three times with 100 mL of the organic phase, washed with saturated sodium hydrogencarbonate, washed with saturated brine, and concentrated.Column chromatography using n-heptane / ethyl acetate 10:1 to 6:1 gave 13.0 g of a yellow oily liquid 4 yield 68%.Using a 1 M methylmagnesium bromide tetrahydrofuran solution, the isolated yield was 70% in the same manner as in Method 3.
70%
With methylmagnesium chloride; In tetrahydrofuran; at -10 - 20℃;
Method 3, <strong>[612-25-9]o-nitrobenzyl alcohol</strong> 3 (15.3 g, 0.1 mol) And propargyl bromide (14.3 g, 0.12 mol) After adding to 110 mL of anhydrous THF, After stirring evenly, the temperature of the system drops to -10 C. 3M methylmagnesium chloride tetrahydrofuran solution was added dropwise(0.12 mol), do not exceed 0 C during the dropwise addition, and keep the reaction for 1 hour. Then slowly increase to room temperature and stir the reaction for 4-5 hours. After TLC detects the disappearance of the raw materials,Pour into 200 g of water, extract 100 mL of MTBE three times, and combine the organic phases. saturated sodium bicarbonate was washed with water, washed with saturated brine and concentrated.Column chromatography using n-heptane/ethyl acetate 10:1 to 6:1 gave 13.0 g of a yellow oily liquid 4 yield 68%.
70%
With methylmagnesium bromide; In tetrahydrofuran; at -10 - 0℃;
General procedure: Method 3: o-Nitrobenzyl alcohol 3 (15.3 g, 0.1 mol) and propargyl bromide (14.3 g, 0.12 mol) were added to 110 mL of anhydrous THF, and after stirring uniformly, the temperature of the system was lowered to -10 C, and the solution was dropped. Add 3M methylmagnesium chloride tetrahydrofuran solution (0.12 mol), do not exceed 0 C during the dropwise addition, keep the reaction for 1 hour, then slowly increase to room temperature and stir the reaction for 4-5 hours. After TLC detection of the disappearance of the raw materials, pour into 200 g of water, MTBE 100 mL After extracting three times, the organic phase was combined, washed with saturated aqueous sodium hydrogen carbonate, and brine, and brine, and the organic phase was concentrated, and then subjected to column chromatography with n-heptane/ethyl acetate 10:1 to 6:1 to obtain 13.0 g of a yellow oily liquid 4. The yield was 68%. Using a 1 M methylmagnesium bromide tetrahydrofuran solution, the isolated yield was 70% in the same manner as in Method 3.
With barium manganate; triphenylphosphine In acetonitrile at 80℃; for 24h; Overall yield = 84 %; stereoselective reaction;
General procedure for the one-pot tandem oxidation-Wittig reaction
General procedure: General procedure for the one-pot tandem oxidation-Wittig reaction To a flask containing BaMnO4 (1.2 mmol, 300 mg)and the alcohol (1 mmol) in CH3CN (5 mL) were added PPh3(1.2 mmol, 315 mg) and ethyl bromoacetate (1.2 mmol, 0.13 mL) and the mixturewas stirred at 80 °C for 24 h. Then the obtained mixture was filtered and theresulting solution was subjected to column chromatography using n-hexane/ethylacetate to isolate the pure products in 78-93% isolated yields with highstereoselectivity.
With potassium <i>tert</i>-butylate In water at 120℃; for 24h; Inert atmosphere;
General procedure for the synthesis of quinolines
General procedure: 2-nitrobenzyl alcohol (0.5 mmol), t-BuOK (1 mmol), ketone (1 mmol) and a magnetic stir bar were placed in a pressure tube and water (3 mL) was then injected. The mixture was bubbled with argon for 15 min at r.t. then stirred at 120 oC for 24 h. The mixture was cooled to r.t., extracted with ethyl acetate (3 x 10 mL). The organic layers were combined, washed with brine, dried (Na2SO4) and concentrated. The residue was purified by flash chromatography (PE-EtOAc).
With potassium <i>tert</i>-butylate In water at 120℃; for 24h; Inert atmosphere;
General procedure for the synthesis of quinolines
General procedure: 2-nitrobenzyl alcohol (0.5 mmol), t-BuOK (1 mmol), ketone (1 mmol) and a magnetic stir bar were placed in a pressure tube and water (3 mL) was then injected. The mixture was bubbled with argon for 15 min at r.t. then stirred at 120 oC for 24 h. The mixture was cooled to r.t., extracted with ethyl acetate (3 x 10 mL). The organic layers were combined, washed with brine, dried (Na2SO4) and concentrated. The residue was purified by flash chromatography (PE-EtOAc).
With potassium <i>tert</i>-butylate In water at 120℃; for 24h; Inert atmosphere;
General procedure for the synthesis of quinolines
General procedure: 2-nitrobenzyl alcohol (0.5 mmol), t-BuOK (1 mmol), ketone (1 mmol) and a magnetic stir bar were placed in a pressure tube and water (3 mL) was then injected. The mixture was bubbled with argon for 15 min at r.t. then stirred at 120 oC for 24 h. The mixture was cooled to r.t., extracted with ethyl acetate (3 x 10 mL). The organic layers were combined, washed with brine, dried (Na2SO4) and concentrated. The residue was purified by flash chromatography (PE-EtOAc).
With potassium tert-butylate; In water; at 120℃; for 24h;Inert atmosphere;
General procedure: 2-nitrobenzyl alcohol (0.5 mmol), t-BuOK (1 mmol), ketone (1 mmol) and a magnetic stir bar were placed in a pressure tube and water (3 mL) was then injected. The mixture was bubbled with argon for 15 min at r.t. then stirred at 120 oC for 24 h. The mixture was cooled to r.t., extracted with ethyl acetate (3 x 10 mL). The organic layers were combined, washed with brine, dried (Na2SO4) and concentrated. The residue was purified by flash chromatography (PE-EtOAc).
With potassium tert-butylate; In water; at 120℃; for 24h;Inert atmosphere;
General procedure: 2-nitrobenzyl alcohol (0.5 mmol), t-BuOK (1 mmol), ketone (1 mmol) and a magnetic stir bar were placed in a pressure tube and water (3 mL) was then injected. The mixture was bubbled with argon for 15 min at r.t. then stirred at 120 oC for 24 h. The mixture was cooled to r.t., extracted with ethyl acetate (3 x 10 mL). The organic layers were combined, washed with brine, dried (Na2SO4) and concentrated. The residue was purified by flash chromatography (PE-EtOAc).
With 1,1'-bis-(diphenylphosphino)ferrocene; formic acid; N-ethyl-N,N-diisopropylamine In toluene at 150℃; for 24h; Inert atmosphere;
Quinolines 3; General Procedure
General procedure: The mixture of 2-nitrobenzyl alcohol 1a-f (0.5 mmol), alcohol 2a-k (0.6 mmol), HCO2H (53 μL, 1.0 mmol), DIPEA (125 μL, 0.75 mmol), and dppf (14.1 mg, 0.025 mmol) in toluene (1.0 mL) was stirred at 150°C (screw-capped vial) for 1 d under argon, cooled to r.t., then water (5mL) was added. The two layers were separated, and the aqueous phase was extracted with EtOAc (3 × 10 mL). The combined organic extracts were washed by brine, dried (anhyd Na2SO4), filtered, and concentrated. The residue was purified by flash chromatography on silica gel (100-200 mesh) to afford the desired quinoline 3a-r.
With 1,1'-bis-(diphenylphosphino)ferrocene; formic acid; N-ethyl-N,N-diisopropylamine; In toluene; at 150℃; for 24h;Inert atmosphere;
General procedure: The mixture of 2-nitrobenzyl alcohol 1a-f (0.5 mmol), alcohol 2a-k (0.6 mmol), HCO2H (53 muL, 1.0 mmol), DIPEA (125 muL, 0.75 mmol), and dppf (14.1 mg, 0.025 mmol) in toluene (1.0 mL) was stirred at 150C (screw-capped vial) for 1 d under argon, cooled to r.t., then water (5mL) was added. The two layers were separated, and the aqueous phase was extracted with EtOAc (3 × 10 mL). The combined organic extracts were washed by brine, dried (anhyd Na2SO4), filtered, and concentrated. The residue was purified by flash chromatography on silica gel (100-200 mesh) to afford the desired quinoline 3a-r.
Stage #1: bis(trichloromethyl) carbonate; 2-Nitrobenzyl alcohol With N-ethyl-N,N-diisopropylamine In dichloromethane at 0 - 20℃; for 3h; Inert atmosphere;
Stage #2: 2-ethyl-N-(2-ethylhexyl)-1-hexanamine In dichloromethane for 4h; Inert atmosphere;
2 Synthesis of NB-DEHC(E)
As generally depicted in the above Scheme 2, Triphosgene(1.16 g 0.3 eq.) suspended in anhydrous DCM(30 mL) under nitrogen atmosphere. The solution was cooled to 0° C. Then (2-nitrophenyl)methanol (2.0 g; 1.0 eq.) in anhydrous DCM(30 mL) and N,N-diisopropylethylamine (3.38 g; 2.0 eq.) were added. After stirring at RT for 3 h, bis(2-ethylhexyl)amine (3.15 g; 1.0 eq.) was slowly added and stirred for 4 h. The reaction mixture was washed by water and the organic phase is dried over sodium sulfate, filtered off and concentrated under reduced pressure. The crude title compound was purified by flash chromatography (EtOAc/heptane).
PhotoCM-1
o-Nitrobenzyl alcohol (153 mg, 1.0 mmol, 1.0 equiv.) was combined with p-fluorophenyl isocyanate (137 mg, 1.0 mmol, 1.0 equiv.) in anhydrous toluene (30 mL) at room temperature, followed by the addition of triethylamine (101 mg, 1.0 mmol, 1.0 equiv.). The resultant mixture was stirred at 110° C. for 20 h, after which the oil bath was removed, and the reaction solution was cooled to room temperature. The reaction mixture was quenched by adding brine (30 mL), and the aqueous solution was extracted with ethyl acetate (3×15 mL). The organic layers were combined, dried over MgSO4, and evaporated under vacuum. The crude product was purified by using column chromatography to afford pure PhotoCM-1 as white solid (220 mg, 76%).1H NMR (500 MHz, CDCl3) δ (ppm): 9.95 (s, 1H), 8.14 (d, J=10.0 Hz, 1H), 7.83 (t, J=5.0 Hz, 1H), 7.75 (t, J=10.0 Hz, 1H), 7.64 (t, J=5.0 Hz, 1H), 7.49 (m, 2H), 7.14 (t, J=10.0 Hz, 2H), 5.50 (s, 2H).19F NMR (470 MHz, CDCl3) δ (ppm): -120.6.13C{1H} NMR (125 MHz, CDCl3) δ (ppm): 159.2, 157.3, 153.5, 147.8, 135.7, 134.6, 132.7, 129.8, 125.3, 120.4, 115.9, 63.0. IR (cm-1): 3170, 3007, 1521, 1502, 1406, 1333, 1235, 1208, 1185, 1154, 1056, 846, 791, 778, 726, 703, 681, 561.HRMSm/z [M+H]+calcd. for [C14H12FN2O4]+291.0781; found 291.0786. M. P. (° C.): 146-148.
4.2.1 Alkylation with corresponding benzylic alcohols. (3-Iodo)benzyl amidinoisothiourea (1)
To the solution of guanylthiourea (500mg, 4.23mmol) in 48% aq HBr (2mL) was added the 3-iodobenzyl alcohol (894mg, 3.82mmol) and resultant mixture was heated under reflux (oil bath temp 100°C) for 12h. The reaction was cooled to 0°C and treated with 6M aq NaOH (5mL). The solid that precipitated was filtered and recrystallized in ethanol to get the final product in 90% (1.15g) yield as white solid
With carbon dioxide; In tetrahydrofuran; at 25℃; for 24h;UV-irradiation;
Add 0.2 mmol I (where R1 = H) to a 10 mL reaction flask, 0.24mmol II (where R2=nC3H7) and 4mL THF, the atmosphere is carbon dioxide atmosphere, the light was irradiated by ultraviolet light at 25 C for 24 h. After the reaction was completed, it was filtered and concentrated. Chromatographically isolated III (where R1 = H; R2 = nC3H7), yield 79%.
With carbon dioxide; In tetrahydrofuran; at 25℃; for 24h;UV-irradiation;
0.2 mmol of I (where R1 = H), 0.24 mmol of II (where R2 = CH2-C6H5) and 4 mL of THF were added to a 10 mL reaction vial. The gas atmosphere is carbon dioxide atmosphere. UV light was irradiated at 25 C for 24 h, After the reaction is completed, it is filtered and concentrated. By chromatography, III (where R1=H; R2=CH2-C6H5), The yield is 73%.
With triphenylphosphine; diethylazodicarboxylate; In dichloromethane; at 20℃;
Method 4, <strong>[612-25-9]o-nitrobenzyl alcohol</strong> (15.3 g, 0.1 mol),Propargyl alcohol (6.1 g, 0.11 mol) andTriphenylphosphine (31.4g, 0.12mol)After adding to 180 mL of dichloromethane,After the mixture is completely dissolved,Diethyl azodicarboxylate (20.9 g, 1.2 eq) was added dropwise at room temperature.50mL dichloromethane mixed solution,Continue to stir at room temperature overnight.The TLC detected the disappearance of the raw materials, and the system was cooled to -40 C to stand still.The solid by-product of the complex is filtered off, the filtrate is concentrated, and eluted by column chromatography to obtain 17.6 g of a yellow oily liquid 4,The yield was 92%.
92%
With triphenylphosphine; In dichloromethane; at 20℃;
Method four, o-Nitrobenzyl alcohol (15.3 g, 0.1 mol), propargyl alcohol (6.1 g, 0.11 mol) After adding triphenylphosphine (31.4 g, 0.12 mol) to 180 mL of dichloromethane, After the mixture is completely dissolved, A mixed solution containing diethyl azodicarboxylate (20.9 g, 1.2 eq) and 50 mL of dichloromethane was added dropwise at room temperature.After the dropwise addition, stirring was continued at room temperature overnight, and the raw materials disappeared by TLC.The system was cooled to -40 C to stand still, and the solid by-product of the complex was filtered off.The filtrate is concentrated and eluted by column chromatography.17.6 g of a yellow oily liquid 4 in a yield of 92%.
92%
With di-isopropyl azodicarboxylate; triphenylphosphine; In dichloromethane; at 20℃;
Method 4: Add <strong>[612-25-9]o-nitrobenzyl alcohol</strong> (15.3 g, 0.1 mol), propargyl alcohol (6.1 g, 0.11 mol) and triphenylphosphine (31.4 g, 0.12 mol) to 180 mL of dichloromethane, stir and dissolve completely. After clearing, a mixed solution containing diethyl azodicarboxylate (20.9 g, 1.2 eq) and 50 mL of dichloromethane was added dropwise at room temperature, and the mixture was stirred overnight at room temperature. The material disappeared by TLC, and the system was cooled to -40 C. The solid by-product of the complex was filtered off, and the filtrate was concentrated and purified by column chromatography to yield 17.6 g of a yellow oily liquid 4 with a yield of 92%.
2-[(3-phenyl-prop-2-ynyloxy)methyl]aniline[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
81%
Stage #1: 3-Phenyl-2-propyn-1-ol; 2-Nitrobenzyl alcohol With triphenylphosphine; diethylazodicarboxylate In dichloromethane at 20℃;
Stage #2: With iron; acetic acid In ethanol at 55 - 65℃; for 3h;
3
o-Nitrobenzyl alcohol 3 (15.3 g, 0.1 mol),Phenyl propargyl alcohol 11 (13.5g, 0.102mol) andTriphenylphosphine (31.4g, 0.12mol)After adding to 200 mL of dichloromethane,After the mixture is completely dissolved,Diethyl azodicarboxylate (20.9 g, 1.2 eq) was added dropwise at room temperature.50mL dichloromethane mixed solution,Continue to stir at room temperature overnight.TLC detection of raw materials disappeared,The system is cooled to -40 ° C to stand still.Filter out the complex by-products of the complex,After the filtrate was concentrated, it was added directly to 250 mL of ethanol and 3.5 eq of reduced iron powder.Control the temperature 55-65 ° C dropwise addition of acetic acid solution (2.5 eq),After the dropwise addition, the temperature was raised to reflux reaction for 3 hours.The TLC test material disappeared basically, and the temperature was lowered to 50 ° C.Filter through diatomaceous earth and filter cake with ethanol.The filtrate was concentrated to dryness under reduced pressure and dichloromethane (150 mL).The aqueous layer is adjusted with a saturated aqueous solution of sodium carbonate pH=9-10,Wash with saturated sodium chloride, dry over anhydrous sodium sulfate,Column chromatography separation using n-heptane / ethyl acetate 10:1 to 6:1,19.2 g of a yellow oily liquid was obtained in a two-step yield of 81%.
19.2 g
Stage #1: 3-Phenyl-2-propyn-1-ol; 2-Nitrobenzyl alcohol With triethylamine; diethylazodicarboxylate In dichloromethane at 20℃; for 3h;
Stage #2: With iron; acetic acid In ethanol; dichloromethane for 3h; Reflux;
3.3
o-Nitrobenzyl alcohol 3 (15.3 g, 0.1 mol), benzynpropanol 11 (13.5 g, 0.102 mol) and triphenylphosphine (31.4 g, 0.12 mol) were added to 200 mL of dichloromethane, and then completely dissolved by stirring. After clearing, a mixed solution containing diethyl azodicarboxylate (20.9 g, 1.2 eq) and 50 mL of dichloromethane was added dropwise at room temperature. After the dropwise addition, the mixture was stirred at room temperature overnight, and the raw material disappeared by TLC. The system was cooled to -40 °C to stand still, and the solid by-product of the complex was filtered off. After the filtrate was concentrated, the solution was directly added to 250 mL of ethanol and 3.5 eq of reduced iron powder to control the temperature. Add acetic acid solution (2.5 eq) at 55-65 ° C,After the dropwise addition, the temperature was raised to reflux reaction for 3 hours. The raw material disappeared by TLC, and the temperature was reduced to 50 ° C. The mixture was filtered through Celite, and the filter cake was rinsed with ethanol. The filtrate was concentrated to dryness under reduced pressure.The aqueous layer was adjusted to pH = 9-10 with a saturated aqueous solution of sodium carbonate, washed with saturated sodium chloride, dried over anhydrous sodium sulfate, filtered and evaporated. After separation, 19.2 g of a yellow oily liquid was obtained. The yield in two steps was 81%
2-(4-bromobenzyl)-1,2-dihydro-3H-indazol-3-one[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
75%
With carbon dioxide In tetrahydrofuran at 20℃; for 24h; UV-irradiation;
75%
With carbon dioxide In tetrahydrofuran at 25℃; for 24h; UV-irradiation;
4 Preparation Example 4
In a 10 mL reaction flask, 0.2 mmol of I (wherein R1 = H), 0.24 mmol of II (wherein R2 = 4-Br-C6H5) and 4 mL of THF were added, and the atmosphere was a carbon dioxide atmosphere, and the reaction was carried out by ultraviolet light at 25 °C for 24 hours. After completion, it is filtered, concentrated, and chromatographed to obtain III (wherein R1 = H; R2 = 4-br-C6H5) in a yield of 75%.
2-(3-methylbenzyl)-1,2-dihydro-3H-indazol-3-one[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
81%
With carbon dioxide; In tetrahydrofuran; at 25℃; for 24h;UV-irradiation;
0.2 mmol of I (wherein R1=H), 0.24 mmol of II (wherein R2=3-CH3-C6H5) and 4 mL of THF were added to a 10 mL reaction flask, and the atmosphere was a carbon dioxide atmosphere. The light was irradiated by ultraviolet light at 25 C for 24 h. After the reaction was completed, it was filtered and concentrated. By chromatography, III (where R1=H; R2=3-CH3-C6H5). The yield is 81%.
2-(4-(tert-butyl)benzyl)-1,2-dihydro-3H-indazol-3-one[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
83%
With carbon dioxide In tetrahydrofuran at 20℃; for 24h; UV-irradiation;
83%
With carbon dioxide In tetrahydrofuran at 25℃; for 24h; UV-irradiation;
8 Preparation Example 8
Add 0.2 mmol I (where R1 = H) to a 10 mL reaction flask, 0.24 mmol II (where R2 = 4-tBu-C6H5) and 4 mL THF, The gas atmosphere is carbon dioxide atmosphere. UV light was irradiated at 25 °C for 24 h, After the reaction, Filtration, concentration, chromatographic separation of III (where R1 = H; R2 = 4-tBu-C6H5), The yield is 83%.
2-(2-(trifluoromethyl)benzyl)-1,2-dihydro-3H-indazol-3-one[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
79%
With carbon dioxide In tetrahydrofuran at 25℃; for 24h; UV-irradiation;
10 Preparation Example 10
Add 0.2 mmol I (where R1 = H) to a 10 mL reaction flask, 0.24mmol II (where R2=2-CF3-C6H5) and 4mL THF, the atmosphere is carbon dioxide atmosphere, UV light was irradiated at 25 °C for 24 h, After the reaction is completed, it is filtered and concentrated. By chromatography, III (where R1=H; R2=2-CF3-C6H5), The yield is 79%.
43%
With carbon dioxide In tetrahydrofuran at 20℃; for 24h; UV-irradiation;
2-(3-aminobenzyl)-1,2-dihydro-3H-indazol-3-one[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
93%
With carbon dioxide; In tetrahydrofuran; at 25℃; for 24h;UV-irradiation;
In a 10 mL reaction flask, 0.2 mmol of I (wherein R1 = H), 0.24 mmol of II (wherein R2 = 3-NH2-C6H5) and 4 mL of THF were added, and the atmosphere was a carbon dioxide atmosphere, and ultraviolet light was irradiated at 25 °C for 24 hours. After completion, it is filtered, concentrated, and chromatographed to give III (wherein R1 = H; R2 = 3-NH2-C6H5), yield 93percent.
With carbon dioxide In tetrahydrofuran at 20℃; for 24h; UV-irradiation;
80%
With carbon dioxide In tetrahydrofuran at 25℃; for 24h; UV-irradiation;
34 Preparation Example 34
Add 0.2 mmol I (where R1 = H) to a 10 mL reaction flask, 0.24 mmol II (where R2 = (nC11H23) and 4 mL THF, the gas atmosphere is carbon dioxide atmosphere, and the UV lamp is illuminated at 25 °C for 24 h. After the reaction, Filtration, concentration, chromatographic separation of III (where R1 = H; R2 = (nC11H23), yield 80%.
2-((tetrahydro-2H-pyran-4-yl)methyl)-1,2-dihydro-3H-indazol-3-one[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
78%
With carbon dioxide; In tetrahydrofuran; at 25℃; for 24h;UV-irradiation;
Add 0.2 mmol I (where R1 = H) to a 10 mL reaction flask, 0.24 mmol II (where R 2 = (tetrahydro-2H-pyran-4-yl) and 4 mL THF, the gas atmosphere is carbon dioxide atmosphere, and the UV lamp is illuminated at 25 C for 24 h. After the reaction is over, filter, concentrate, by chromatography, III (where R1 = H; R2 = tetrahydro-2H-pyran-4-yl), the yield is 78%.
With carbon dioxide In tetrahydrofuran at 25℃; for 24h; UV-irradiation;
31 Preparation Example 31
Add 0.2 mmol I (where R1 = H) to a 10 mL reaction flask, 0.24mmol II (where R2= Methylcyclopropane) and 4 mL THF, the gas atmosphere is carbon dioxide atmosphere, and the UV lamp is illuminated at 25 °C for 24 h. After the reaction, Filtration, concentration, chromatographic separation of III (where R1 = H; R2-methylcyclopropane), the yield is 94%.
With [pentamethylcyclopentadienyl*Ir(N-phenyl-2-pyridinecarboxamidate)Cl] In d(4)-methanol at 37℃; for 15h; chemoselective reaction;
General Procedure for Reductive Amination of Carbonyls - Isolated Product
General procedure: A carbonyl compound (0.5 mmol) and Ir1 (1 mol%) were added to a 1.5-dram vial equippedwith a magnetic stir bar in methanol (2.5 mL). Solid HCOONH4 (5 mmol, 10 equiv.) was addedinto the vial and the solution was stirred at 37 °C for 15 h. The solvent was evaporated underreduced pressure and then aqueous HCl was added dropwise until a pH of 1-2 was obtained. Thesolution was washed with Et2O (3×5 mL), and the aqueous layer was collected. The aqueoussolution was adjusted to pH 10-12 using KOH. The product was extracted into DCM (3×5 mL)and the combined organic phase was dried over Na2SO4, filtered, and evaporated under reducedpressure to give the isolated product.
With 1,4-diaza-bicyclo[2.2.2]octane; sulfur; urea In dimethyl sulfoxide at 140℃; for 2h;
2.1. General procedure
General procedure: To a 4-mL screw-cap vial was added 2-nitrobenzyl alcohol (15.3 mg, 0.1 mmol), phenylacetic acid (34.0 mg, 0.25 mmol), base, elemental sulfur, urea, and DMSO (0.3 mL).The reaction tube was tightly capped and the resulting mixture was then stirred at a given temperature. After completion of the reaction, the mixture was cooled to room temperature and diphenyl ether (17.2 mg, 0.1 mmol) as an internal standard was added. The organic components were then extracted into ethyl acetate (3×2 mL), washed with NaHCO3 solution (10% in water, 3×1 mL), dried over anhydrous Na2SO4, filtered, and analyzed by GC with reference to diphenyl ether.
With 1,4-diaza-bicyclo[2.2.2]octane; sulfur; urea In dimethyl sulfoxide at 140℃; for 2h;
2.1. General procedure
General procedure: To a 4-mL screw-cap vial was added 2-nitrobenzyl alcohol (15.3 mg, 0.1 mmol), phenylacetic acid (34.0 mg, 0.25 mmol), base, elemental sulfur, urea, and DMSO (0.3 mL).The reaction tube was tightly capped and the resulting mixture was then stirred at a given temperature. After completion of the reaction, the mixture was cooled to room temperature and diphenyl ether (17.2 mg, 0.1 mmol) as an internal standard was added. The organic components were then extracted into ethyl acetate (3×2 mL), washed with NaHCO3 solution (10% in water, 3×1 mL), dried over anhydrous Na2SO4, filtered, and analyzed by GC with reference to diphenyl ether.
With 1,4-diaza-bicyclo[2.2.2]octane; sulfur; urea In dimethyl sulfoxide at 140℃; for 2h;
2.1. General procedure
General procedure: To a 4-mL screw-cap vial was added 2-nitrobenzyl alcohol (15.3 mg, 0.1 mmol), phenylacetic acid (34.0 mg, 0.25 mmol), base, elemental sulfur, urea, and DMSO (0.3 mL).The reaction tube was tightly capped and the resulting mixture was then stirred at a given temperature. After completion of the reaction, the mixture was cooled to room temperature and diphenyl ether (17.2 mg, 0.1 mmol) as an internal standard was added. The organic components were then extracted into ethyl acetate (3×2 mL), washed with NaHCO3 solution (10% in water, 3×1 mL), dried over anhydrous Na2SO4, filtered, and analyzed by GC with reference to diphenyl ether.
With 1,4-diaza-bicyclo[2.2.2]octane; sulfur; urea In dimethyl sulfoxide at 140℃; for 2h;
2.1. General procedure
General procedure: To a 4-mL screw-cap vial was added 2-nitrobenzyl alcohol (15.3 mg, 0.1 mmol), phenylacetic acid (34.0 mg, 0.25 mmol), base, elemental sulfur, urea, and DMSO (0.3 mL).The reaction tube was tightly capped and the resulting mixture was then stirred at a given temperature. After completion of the reaction, the mixture was cooled to room temperature and diphenyl ether (17.2 mg, 0.1 mmol) as an internal standard was added. The organic components were then extracted into ethyl acetate (3×2 mL), washed with NaHCO3 solution (10% in water, 3×1 mL), dried over anhydrous Na2SO4, filtered, and analyzed by GC with reference to diphenyl ether.
With 1,4-diaza-bicyclo[2.2.2]octane; sulfur; urea In dimethyl sulfoxide at 140℃; for 8h;
2.1. General procedure
General procedure: To a 4-mL screw-cap vial was added 2-nitrobenzyl alcohol (15.3 mg, 0.1 mmol), phenylacetic acid (34.0 mg, 0.25 mmol), base, elemental sulfur, urea, and DMSO (0.3 mL).The reaction tube was tightly capped and the resulting mixture was then stirred at a given temperature. After completion of the reaction, the mixture was cooled to room temperature and diphenyl ether (17.2 mg, 0.1 mmol) as an internal standard was added. The organic components were then extracted into ethyl acetate (3×2 mL), washed with NaHCO3 solution (10% in water, 3×1 mL), dried over anhydrous Na2SO4, filtered, and analyzed by GC with reference to diphenyl ether.
With 1,4-diaza-bicyclo[2.2.2]octane; sulfur; urea In dimethyl sulfoxide at 140℃; for 2h;
2.1. General procedure
General procedure: To a 4-mL screw-cap vial was added 2-nitrobenzyl alcohol (15.3 mg, 0.1 mmol), phenylacetic acid (34.0 mg, 0.25 mmol), base, elemental sulfur, urea, and DMSO (0.3 mL).The reaction tube was tightly capped and the resulting mixture was then stirred at a given temperature. After completion of the reaction, the mixture was cooled to room temperature and diphenyl ether (17.2 mg, 0.1 mmol) as an internal standard was added. The organic components were then extracted into ethyl acetate (3×2 mL), washed with NaHCO3 solution (10% in water, 3×1 mL), dried over anhydrous Na2SO4, filtered, and analyzed by GC with reference to diphenyl ether.
With 1,4-diaza-bicyclo[2.2.2]octane; sulfur; urea; In dimethyl sulfoxide; at 140℃; for 8h;
General procedure: To a 4-mL screw-cap vial was added 2-nitrobenzyl alcohol (15.3 mg, 0.1 mmol), phenylacetic acid (34.0 mg, 0.25 mmol), base, elemental sulfur, urea, and DMSO (0.3 mL).The reaction tube was tightly capped and the resulting mixture was then stirred at a given temperature. After completion of the reaction, the mixture was cooled to room temperature and diphenyl ether (17.2 mg, 0.1 mmol) as an internal standard was added. The organic components were then extracted into ethyl acetate (3×2 mL), washed with NaHCO3 solution (10% in water, 3×1 mL), dried over anhydrous Na2SO4, filtered, and analyzed by GC with reference to diphenyl ether.
With copper(II)-manganese(II) bimetallic complex immobilized on magnetite nanoparticles; air In neat (no solvent) at 70℃; for 3h; Green chemistry;
General procedure: For the Biginelli reaction, benzyl alcohol (1.2mmol),ethyl acetoacetate (1.2mmol), and urea (1.0mmol) were reacted in the presence of Fe3O4Cu-Mn catalyst (0.008g,0.280mol% Cu, 0.078mol% Mn) under solvent-free and aerobic conditions at 70°C. Repeatedly, the reaction performance and product purification was as same as the benzimidazole reaction. After the reaction completion, the magnetic catalyst was separated easily by an external magnet and the product was extracted to dichloromethane (3 × 5mL).The organic layers were combined, dried over Na2SO4 and purified by silica-gel column chromatography (n-hexane:EtOAc = 12: 3). The products were characterized and identified by comparing their melting point and NMR analyses with those authentic samples.
2-((2,5-dimethyl-1H-indol-1-yl)amino)benzaldehyde[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
77%
With tetraethylammonium iodide; acetic acid In dichloromethane at 20℃; for 24h; Schlenk technique; Sealed tube; UV-irradiation;
77%
With tetraethylammonium iodide; acetic acid In dichloromethane at 20℃; for 24h; UV-irradiation;
2 Preparation Example 2
Add 0.2mmol of indoline compound V into a 10mL reaction tube, 0.4mmol of o-nitrobenzyl alcohol compound VI, 0.2mmol of acetic acid, and 0.2mmol of tetraethylammonium iodide,Dichloromethane 4mL, irradiated with 385-405nm ultraviolet light at room temperature, and reacted for 24h.After the reaction, the N-(2-arylcarbaldehyde)-1-aminoindole derivative is obtained by column chromatography.(R1=2,5-dimethyl, R2=hydrogen), a brown solid was obtained with a yield of 77%.
2-((3-methyl-1H-indol-1-yl)amino)benzaldehyde[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
73%
With tetraethylammonium iodide; acetic acid In dichloromethane at 20℃; for 24h; Schlenk technique; Sealed tube; UV-irradiation;
73%
With tetraethylammonium iodide; acetic acid In dichloromethane at 20℃; for 24h; UV-irradiation;
3 Preparation Example 3
Add 0.2mmol of indoline compound V into the 10mL reaction tube,Add 0.4 mmol of o-nitrobenzyl alcohol compound VI and 0.2 mmol of acetic acid,Tetraethylammonium iodide 0.2mmol, dichloromethane 4mL, irradiated with 385-405nm ultraviolet light at room temperature, and reacted for 24h. After the reaction,The N-(2-arylcarbaldehyde)-1-aminoindole derivative (R1=3-methyl, R2=hydrogen) was obtained through column chromatography to obtain a gray solid with a yield of 73%.
2-((4-fluoro-1H-indol-1-yl)amino)benzaldehyde[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
66%
With tetraethylammonium iodide; acetic acid In dichloromethane at 20℃; for 24h; Schlenk technique; Sealed tube; UV-irradiation;
66%
With tetraethylammonium iodide; acetic acid In dichloromethane at 20℃; for 24h; UV-irradiation;
4 Preparation Example 4
Add 0.2mmol of indoline compound V into a 10mL reaction tube, 0.4mmol of o-nitrobenzyl alcohol compound VI, 0.2mmol of acetic acid, and 0.2mmol of tetraethylammonium iodide,Dichloromethane 4mL, irradiated with 385-405nm ultraviolet light at room temperature, and reacted for 24h.After the reaction, the N-(2-arylcarbaldehyde)-1-aminoindole derivative is obtained by column chromatography.(R1=4-fluoro, R2=hydrogen), a brown solid was obtained with a yield of 66%.
2-((5-fluoro-1H-indol-1-yl)amino)benzaldehyde[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
79%
With tetraethylammonium iodide; acetic acid; In dichloromethane; at 20℃; for 24h;UV-irradiation;
Add 0.2mmol of indoline compound V into the 10mL reaction tube,Add 0.4mmol of o-nitrobenzyl alcohol compound VI, 0.2mmol of acetic acid, 0.2mmol of tetraethylammonium iodide, 4mL of dichloromethane, and irradiate with 385-405nm ultraviolet light at room temperature.Reaction for 24h. After the reaction, it is separated by column chromatography to obtainN-(2-arylcarboxaldehyde)-1-aminoindole derivative (R1=5-fluoro, R2=hydrogen) to obtain a brown jelly with a yield of 79%.
2-((5-bromo-1H-indol-1-yl)amino)benzaldehyde[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
85%
With tetraethylammonium iodide; acetic acid In dichloromethane at 20℃; for 24h; Schlenk technique; Sealed tube; UV-irradiation;
85%
With tetraethylammonium iodide; acetic acid In dichloromethane at 20℃; for 24h; UV-irradiation;
7 Preparation Example 7
Add 0.2mmol of indoline compound V into a 10mL reaction tube, 0.4mmol of o-nitrobenzyl alcohol compound VI, 0.2mmol of acetic acid, and 0.2mmol of tetraethylammonium iodide,Dichloromethane 4mL, irradiated with 385-405nm ultraviolet light at room temperature, and reacted for 24h.After the reaction, the N-(2-arylcarboxaldehyde)-1-aminoindole derivative (R1=5-bromo, R2=hydrogen) was separated by column chromatography to obtain a yellow-brown solid with a yield of 85%.
2-((5-methyl-1H-indol-1-yl)amino)benzaldehyde[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
71%
With tetraethylammonium iodide; acetic acid In dichloromethane at 20℃; for 24h; Schlenk technique; Sealed tube; UV-irradiation;
71%
With tetraethylammonium iodide; acetic acid In dichloromethane at 20℃; for 24h; UV-irradiation;
9 Preparation Example 9
Add 0.2mmol of indoline compound V into a 10mL reaction tube, 0.4mmol of o-nitrobenzyl alcohol compound VI, 0.2mmol of acetic acid, and 0.2mmol of tetraethylammonium iodide,Dichloromethane 4mL, irradiated with 385-405nm ultraviolet light at room temperature, and reacted for 24h.After the reaction, the N-(2-arylcarbaldehyde)-1-aminoindole derivative is obtained by column chromatography.(R1=5-methyl, R2=hydrogen), a yellow oil was obtained with a yield of 71%.
2-((5-methoxy-1H-indol-1-yl)amino)benzaldehyde[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
78%
With tetraethylammonium iodide; acetic acid; In dichloromethane; at 20℃; for 24h;UV-irradiation;
Add 0.2mmol of indoline compound V into a 10mL reaction tube, 0.4mmol of o-nitrobenzyl alcohol compound VI, 0.2mmol of acetic acid, and 0.2mmol of tetraethylammonium iodide,Dichloromethane 4mL, irradiated with 385-405nm ultraviolet light at room temperature, and reacted for 24h.After the reaction, the N-(2-arylcarbaldehyde)-1-aminoindole derivative is obtained by column chromatography.(R1=5-methoxy, R2=hydrogen), a brown solid was obtained with a yield of 78%.
methyl 1-((2-formylphenyl)amino)-1H-indole-5-carboxylate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
78%
With tetraethylammonium iodide; acetic acid; In dichloromethane; at 20℃; for 24h;UV-irradiation;
Add 0.2mmol of indoline compound V into a 10mL reaction tube, 0.4mmol of o-nitrobenzyl alcohol compound VI, 0.2mmol of acetic acid, and 0.2mmol of tetraethylammonium iodide,Dichloromethane 4mL, irradiated with 385-405nm ultraviolet light at room temperature, and reacted for 24h.After the reaction, the N-(2-arylcarbaldehyde)-1-aminoindole derivative is obtained by column chromatography.(R1 = 5-formate methyl group, R2 = hydrogen), a brown solid was obtained with a yield of 78%.
With tetraethylammonium iodide; glacial acetic acid In dichloromethane at 20℃; for 4h; UV-irradiation;
22 Example 22
In a 10 mL reaction tube, add 0.2 mmol of o-nitrobenzyl alcohol compound A, 0.4 mmol of N-methylamine compound B, 0.8 mmol of acetic acid, and 0.2 mmol of tetraethylammonium iodide, and under air atmosphere, add 4 mL of dichloromethane as a solvent , and irradiated with UV light for 4 hours at room temperature.After the reaction, the indazole compound 22 was obtained by column chromatography as a yellow solid with a yield of 66%.
With tetraethylammonium iodide; glacial acetic acid In dichloromethane at 20℃; for 4h; UV-irradiation;
25 Example 25
In a 10 mL reaction tube, add 0.2 mmol of o-nitrobenzyl alcohol compound A, 0.4 mmol of N-methylamine compound B, 0.8 mmol of acetic acid, and 0.2 mmol of tetraethylammonium iodide, and under air atmosphere, add 4 mL of dichloromethane as a solvent , and irradiated with UV light for 4 hours at room temperature.After the reaction, the indazole compound 25 was obtained by column chromatography as a yellow solid with a yield of 74%.
With tetraethylammonium iodide; glacial acetic acid In dichloromethane at 20℃; for 4h; UV-irradiation;
27 Example 27
General procedure: In a 10 mL reaction tube, add 0.2 mmol of o-nitrobenzyl alcohol compound A, 0.4 mmol of N-methylamine compound B, 0.8 mmol of acetic acid, and 0.2 mmol of tetraethylammonium iodide, and under air atmosphere, add 4 mL of dichloromethane as a solvent , and irradiated with UV light for 4 hours at room temperature.After the reaction, the indazole compound 27 was obtained by column chromatography as a yellow solid with a yield of 68%.
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