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Structure of 90-15-3 * Storage: {[proInfo.prStorage]}
* 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] J. Gen. Chem. USSR (Engl. Transl.), 1988, vol. 58, # 6, p. 1233 - 1237[2] Zhurnal Obshchei Khimii, 1988, vol. 58, # 6, p. 1384 - 1389
2
[ 123-39-7 ]
[ 90-15-3 ]
[ 63-25-2 ]
Yield
Reaction Conditions
Operation in experiment
45%
With tert.-butylhydroperoxide; 1,10-Phenanthroline; copper diacetate In decane at 20℃; for 2 h; Molecular sieve; Inert atmosphere
General procedure: In a reaction vessel Cu(OAc)2 (20 molpercent), 1,10-phenanthroline (20 molpercent) was dissolved with 2 mL of formamide source. The reaction mixture stirred for 5 minutes and added the phenol (1) substrates. To the above reaction mixture, TBHP (5-6 M in decane solution) was added dropwise, with stirring over a period of 5 min. Then the reaction temperature was increased to 80 °C and stirred for eight hours. After cooling to room temperature, the reaction mixture was directly subjected to purification with column chromatography on silica gel using 5-10percent ethyl acetate and hexane mixture to afford the required product (3). Care should be taken while doing the product separation by column chromatography. We have observed that in some cases both the starting materials and products are very close, in which TLC’s have to be monitored by both UV and iodine. A slightly modified procedure was adopted for N-methylformamide reactions, in which the reactions were performed at room temperature for two hours. The crude products were directly subjected to column chromatography on silica gel to afford the required product (5).
Reference：
[1] Journal of Organic Chemistry, 1991, vol. 56, # 21, p. 6148 - 6151
13
[ 67-56-1 ]
[ 90-15-3 ]
[ 14093-86-8 ]
Reference：
[1] Journal of Organic Chemistry, 1968, vol. 33, p. 1480 - 1488
14
[ 90-15-3 ]
[ 77-78-1 ]
[ 7469-77-4 ]
[ 14093-86-8 ]
[ 2216-69-5 ]
Reference：
[1] Indian Journal of Chemistry, Section B: Organic Chemistry Including Medicinal Chemistry, 1982, vol. 21, # 5, p. 474
15
[ 90-15-3 ]
[ 79-07-2 ]
[ 86-86-2 ]
Reference：
[1] Journal of Medicinal Chemistry, 2013, vol. 56, # 20, p. 7851 - 7861
16
[ 90-15-3 ]
[ 607-58-9 ]
Yield
Reaction Conditions
Operation in experiment
91%
With potassium carbonate In acetonitrile at 125℃; for 0.333333 h; Microwave irradiation
General procedure: A mixture of 0.14 g (1.0 mmol) of 1- and 2-naphthol (1)and (6), in most cases 1.0 mmol of alkali carbonate (0.14 g of K2CO3 or 0.33 g of Cs2CO3), in certain cases 11.4 mg(0.05 mmol) of TEBAC and 1.2 mmol of alkyl halide (0.14ml of benzyl bromide, 0.10 ml of ethyl iodide, 0.12 mol ofbutyl bromide or 0.11 ml of i-propyl bromide) in a closedvial was irradiated (20–30 W) in a CEM Discover [300 W]MW reactor at 125 °C for the appropriate time. The reactionmixture was taken up in 25 ml of ethyl acetate and the suspensionwas filtered. Evaporation of the volatile componentsprovided the crude product that was passed through a thin(ca. 2–3 cm) layer of silica gel using ethyl acetate as theeluant to give an oil that was analysed by GC–MS or GC.Similar reactions were carried out in 3 ml of MeCN asthe solvent. The work-up was similar to that described forthe solventless alkylations above, but in this case, ethyl acetatedid not have to be added.The major components of the above reactions, such ascompounds 2, 7, 8, 10a-c and 13a,b were obtained in a pureform by repeated chromatography.Control experiments were performed with benzyl bromidein a similar way under conventional heating.
86%
With potassium phosphate; tetrabutylammomium bromide In water at 20℃; for 2 h; Sealed tube; Green chemistry
General procedure: General procedure for benzylation of phenols: Phenol (0.5mmol), benzyl bromide (1.2equiv), TBAB (0.5equiv), K3PO4 (1.5equiv), and water (2mL) were added to a reaction vessel. The mixture was stirred at room temperature for 2h under air. After the reaction was completed, the mixture was diluted with water and extracted with CH2Cl2 (15mL×3). The combined organic layer was dried with anhydrous sodium sulfate and concentrated under reduced pressure. The residue was purified by thin layer chromatography (TLC) on silica gel GF254 (ethyl acetate/petroleum ether) to give the pure product.
Reference：
[1] Letters in Organic Chemistry, 2013, vol. 10, # 5, p. 330 - 336
[2] Chemistry - A European Journal, 2016, vol. 22, # 42, p. 15058 - 15068
[3] Tetrahedron, 2014, vol. 70, # 16, p. 2669 - 2673
[4] Bulletin de la Societe Chimique de France, 1987, # 6, p. 1027 - 1035
[5] Journal of Organic Chemistry, 2009, vol. 74, # 3, p. 1367 - 1370
[6] Journal of Heterocyclic Chemistry, 1996, vol. 33, # 4, p. 1371 - 1385
[7] Tetrahedron, 2000, vol. 56, # 36, p. 6913 - 6925
[8] Organic Letters, 2011, vol. 13, # 16, p. 4340 - 4343
[9] Green Chemistry, 2015, vol. 17, # 7, p. 3910 - 3915
17
[ 90-15-3 ]
[ 53772-44-4 ]
[ 607-58-9 ]
Reference：
[1] Chemistry Letters, 2003, vol. 32, # 1, p. 22 - 23
[2] Bulletin of the Chemical Society of Japan, 2003, vol. 76, # 8, p. 1645 - 1667
[3] Journal of the American Chemical Society, 2004, vol. 126, # 23, p. 7359 - 7367
18
[ 90-15-3 ]
[ 100-39-0 ]
[ 28178-96-3 ]
[ 607-58-9 ]
Yield
Reaction Conditions
Operation in experiment
62 %Chromat.
With caesium carbonate In neat (no solvent) at 125℃; for 1 h; Microwave irradiation
General procedure: A mixture of 0.14 g (1.0 mmol) of 1- and 2-naphthol (1)and (6), in most cases 1.0 mmol of alkali carbonate (0.14 g of K2CO3 or 0.33 g of Cs2CO3), in certain cases 11.4 mg(0.05 mmol) of TEBAC and 1.2 mmol of alkyl halide (0.14ml of benzyl bromide, 0.10 ml of ethyl iodide, 0.12 mol ofbutyl bromide or 0.11 ml of i-propyl bromide) in a closedvial was irradiated (20–30 W) in a CEM Discover [300 W]MW reactor at 125 °C for the appropriate time. The reactionmixture was taken up in 25 ml of ethyl acetate and the suspensionwas filtered. Evaporation of the volatile componentsprovided the crude product that was passed through a thin(ca. 2–3 cm) layer of silica gel using ethyl acetate as theeluant to give an oil that was analysed by GC–MS or GC.Similar reactions were carried out in 3 ml of MeCN asthe solvent. The work-up was similar to that described forthe solventless alkylations above, but in this case, ethyl acetatedid not have to be added.The major components of the above reactions, such ascompounds 2, 7, 8, 10a-c and 13a,b were obtained in a pureform by repeated chromatography.Control experiments were performed with benzyl bromidein a similar way under conventional heating.
Reference：
[1] Letters in Organic Chemistry, 2013, vol. 10, # 5, p. 330 - 336
19
[ 90-15-3 ]
[ 100-44-7 ]
[ 607-58-9 ]
Reference：
[1] Synthetic Communications, 1998, vol. 28, # 24, p. 4495 - 4499
[2] Indian Journal of Chemistry, Section B: Organic Chemistry Including Medicinal Chemistry, 1982, vol. 21, # 8, p. 800 - 802
[3] Justus Liebigs Annalen der Chemie, 1883, vol. 217, p. 44
[4] Journal of the American Chemical Society, 1920, vol. 42, p. 2067
[5] Justus Liebigs Annalen der Chemie, 1925, vol. 442, p. 243[6] Angewandte Chemie, 1923, vol. 36, p. 478
[7] Journal of Organic Chemistry, 1958, vol. 23, p. 1622
[8] Journal of Organic Chemistry, 1991, vol. 56, # 20, p. 5875 - 5882
20
[ 90-15-3 ]
[ 607-58-9 ]
Reference：
[1] Journal of the Indian Chemical Society, 2013, vol. 90, # 10, p. 1871 - 1884
21
[ 90-15-3 ]
[ 3204-68-0 ]
[ 607-58-9 ]
Reference：
[1] Journal of the Indian Chemical Society, 1926, vol. 3, p. 102[2] Chem. Zentralbl., 1926, vol. 97, # II, p. 1643
Reference：
[1] Journal of the American Chemical Society, 1951, vol. 73, p. 4970
33
[ 90-15-3 ]
[ 56874-95-4 ]
[ 315-53-7 ]
Yield
Reaction Conditions
Operation in experiment
32 %Spectr.
With Selectfluor; 1-(n-butyl)-3-methylimidazolium triflate In isopropyl alcohol at 80℃; for 5 h; Inert atmosphere
General procedure: A mixture of phenol (20 mg), F‐TEDA‐BF4 (1.1 equivalents), IL(0‐15 equivalents) and the organic solvent (5 mL) was stirred for 5 h at various temperatures under an argo atmosphere (Tables 1‐5). The mixture was evaporated at a reduced pressure and analysed by 1H, 19F NMR assolution in CDCl3 or CDCl3‐DMSO‐d6. Cl2CHCHCl2 and PhCF3 were used as internal standards for peakintegration.
Reference：
[1] Journal of Organic Chemistry, 1985, vol. 50, # 19, p. 3609 - 3612
[2] Journal of the Chemical Society - Perkin Transactions 1, 1996, # 16, p. 2069 - 2076
[3] Russian Journal of Organic Chemistry, 2009, vol. 45, # 10, p. 1468 - 1473
[4] Advanced Synthesis and Catalysis, 2017, vol. 359, # 4, p. 584 - 589
[5] Arkivoc, 2017, vol. 2018, # 2, p. 60 - 71
34
[ 90-15-3 ]
[ 56874-95-4 ]
[ 97295-09-5 ]
[ 315-53-7 ]
Yield
Reaction Conditions
Operation in experiment
34 %Spectr.
With Selectfluor; 1-(n-butyl)-3-methylimidazolium triflate In ethanol at 80℃; for 5 h; Inert atmosphere
General procedure: A mixture of phenol (20 mg), F‐TEDA‐BF4 (1.1 equivalents), IL(0‐15 equivalents) and the organic solvent (5 mL) was stirred for 5 h at various temperatures under an argo atmosphere (Tables 1‐5). The mixture was evaporated at a reduced pressure and analysed by 1H, 19F NMR assolution in CDCl3 or CDCl3‐DMSO‐d6. Cl2CHCHCl2 and PhCF3 were used as internal standards for peakintegration.
Reference：
[1] Bulletin of the Chemical Society of Japan, 1995, vol. 68, # 6, p. 1655 - 1660
[2] Journal of the American Chemical Society, 1990, vol. 112, # 23, p. 8563 - 8575
[3] Chemistry Letters, 1996, # 12, p. 1077 - 1078
[4] Arkivoc, 2017, vol. 2018, # 2, p. 60 - 71
35
[ 90-15-3 ]
[ 56874-95-4 ]
[ 97295-09-5 ]
[ 56874-96-5 ]
[ 315-53-7 ]
Yield
Reaction Conditions
Operation in experiment
35 %Spectr.
With Selectfluor; 1-(n-butyl)-3-methylimidazolium triflate In methanol at 80℃; for 5 h; Inert atmosphere
General procedure: A mixture of phenol (20 mg), F‐TEDA‐BF4 (1.1 equivalents), IL(0‐15 equivalents) and the organic solvent (5 mL) was stirred for 5 h at various temperatures under an argo atmosphere (Tables 1‐5). The mixture was evaporated at a reduced pressure and analysed by 1H, 19F NMR assolution in CDCl3 or CDCl3‐DMSO‐d6. Cl2CHCHCl2 and PhCF3 were used as internal standards for peakintegration.
Reference：
[1] Journal of Organic Chemistry, 1985, vol. 50, # 19, p. 3609 - 3612
[2] Arkivoc, 2017, vol. 2018, # 2, p. 60 - 71
36
[ 90-15-3 ]
[ 24063-28-3 ]
Reference：
[1] Chemische Berichte, 1884, vol. 17, p. 2494
37
[ 90-15-3 ]
[ 121-57-3 ]
[ 523-44-4 ]
Reference：
[1] Journal of the Chinese Chemical Society, 2009, vol. 56, # 5, p. 1018 - 1027
38
[ 90-15-3 ]
[ 56070-03-2 ]
[ 7189-71-1 ]
[ 5319-67-5 ]
Reference：
[1] Liebigs Annalen der Chemie, 1990, # 6, p. 611 - 612
39
[ 90-15-3 ]
[ 318-98-9 ]
Reference：
[1] Patent: CN108586273, 2018, A,
40
[ 462-06-6 ]
[ 90-15-3 ]
[ 79836-47-8 ]
[ 82101-34-6 ]
Reference：
[1] Journal of Organic Chemistry USSR (English Translation), 1982, vol. 18, # 4, p. 754 - 760[2] Zhurnal Organicheskoi Khimii, 1982, vol. 18, # 4, p. 870 - 878
41
[ 462-06-6 ]
[ 90-15-3 ]
[ 79836-47-8 ]
[ 82101-34-6 ]
[ 82101-35-7 ]
Reference：
[1] Journal of Organic Chemistry USSR (English Translation), 1982, vol. 18, # 4, p. 754 - 760[2] Zhurnal Organicheskoi Khimii, 1982, vol. 18, # 4, p. 870 - 878
42
[ 90-15-3 ]
[ 206193-17-1 ]
[ 90357-51-0 ]
Reference：
[1] Journal of Medicinal Chemistry, 2011, vol. 54, # 11, p. 3973 - 3976
General procedure: Equimolar quantities of 2-chloro acetic acid/3-chloro propionicacid (0.05 mol) and appropriate phenol (1a-q) (0.05 mol) were taken in a conical flask, to which aqueous solution of NaOH(0.12 mol in 25 mL water) was slowly added with constant stirring.The solution was stirred for 2 h until the solution turned clear,brown or yellow and then the reaction mixture was evaporatedin a evaporating dish until the solid sodium salt was precipitated. The salt was isolated, dried, dissolved in water and acidified byadding con. HCl. The precipitated aryloxy acetic/propionic acidwas filtered and recrystallized from water or ethanol
EXAMPLE 24 A solution of 72 gm 1-naphthol, 20 gm hydroxide and 38 gm sodium nitrite in 250 ml water was added slowly to a well stirred solution of 70 ml nitric acid (70 percent w/v) in 200 ml water. The mixture was maintained at 0°-5°C by an external cooling bath. The mixture (8.1 percent w/v slurry) was held at 10°C for 30 minutes, then pumped into a solution of 200 ml nitric acid (70 percent w/v) in 200 ml water at 45°C. The mixture was held at 50°C for 1.5 hours then cooled to precipitate a mixture of 2-nitro-1-naphthol and 2,4-dinitro-1-naphthol, which was separated by chromatography.
With 1,2-ethanediylbis(triphenylphosphonium) ditribromide; In methanol; dichloromethane; at 20℃; for 0.0833333h;
General procedure: To a mixture of anilines or phenols (0.7 mmol) the brominatingagent (1) (0.72 g, 0.7 mmol) in dichloromethane(30 ml)-methanol (15 ml) was added. The reactionmixture was stirred at room temperature until decolorizationof the orange solution took place. The progress of thereaction was monitored by TLC (eluent: n-hexane/ethylacetate, 7:3). After completion of the reaction, the solventwas evaporated and diethyl ether (10 ml) was added to theresidue. The supernatant was decanted and the insolubleresidue was washed by ether (3 × 10 ml). The combinedether extracts were dried on magnesium sulfate and also evaporated under vacuum to afford monobromo anilines ormonobromo phenols which was purified by flash columnchromatography over silica gel (n-hexane/ethyl acetate,7:3).
84%
With polyethylene glycol entrapped potassium tribromide; In neat (no solvent); for 0.2h;Green chemistry;
The bromination reactions were carried out in solvent free manner. In a typical reaction, PEG·KBr3 (1mmol, 4.3g) was added to the aromatic substrate (1mmol) in a mortar and was ground for the desired reaction time. The progress of the reaction was monitored by TLC (10% ethyl acetate/hexane). After completion of the reaction, the product was extracted with ethyl acetate and evaporated under vacuum to obtain the pure brominated product. The products were characterized by IR and NMR spectra (see Supporting information).
72.4%
With N-Bromosuccinimide; In dichloromethane; at 40℃;Alkaline conditions;
1-Naphthol (10 g, 69.36 mmol)and diisopropylamine (0.972 mL, 6.94 mmol) was dissolved indichloromethane (100 mL). N-Bromosuccinimide (13.58 g, 76.3 mmol)was carefully added and the reaction mixture was stirred at 40 Covernight. The resulting mixture was allowed to cool to roomtemperature, quenched with 2M H2SO4, and extracted withdichloromethane. The combined organic layer was dried overanhydrous sodium sulfate and concentrated in vacuo. The crudeproduct was purified by silica gel column eluting with petroleumether: ethyl acetate (20/1) to give the desired product (11.2 g, yield72.4%) as a white solid. 1H NMR (400 MHz, CDCl3) delta 8.23 - 8.21 (m,1H), 7.76 - 7.73 (m, 1H), 7.50 - 7.48 (m, 2H), 7.44 (d, J=8.8 Hz, 1H),7.28 (d, J=8.8 Hz, 1H), 5.97 (s, 1H). ESI-MS: [M-H]- m/z :221.0.
70%
With tetrabutylammomium bromide; isoquinolinium chlorochromate; In water; at 25 - 30℃; for 5h;
General procedure: Phenol (1 mmol, 10 mL) dissolved in 1M PEG-600, isoquinolinium dichromate (IQDC) or isoquinolinium chlorochromate (IQCC) reagent, and tetrabutylammonium halide (TBAX) (1.1 mmol each) were taken in a reaction flask and refluxed with constant stirring at about 25 to 30 C, till the completion of reaction, as as certainedby thin layer chromatography. Then the contents of reaction were diluted with ethyl acetate (10 mL) and separated from aqueous layer. Organic layer was then washed two to three time swith 5 mL water and separated. Finally, the resultant mass is dried over sodium sulphate. The anhydrous ethyl acetate layerwas separated under reduced pressure to give crude product, which was further purified by column chromatography (silicagel, 100-200 mesh) using EtOAc-hexane (3:7). For the separation and recyclization of PEG, aqueous mother liquor (reaction mixture of PEG-600 and water) was treated with ether because PEG is insoluble in ether. The aqueous layer obtained after the removal of ether, was then distilled directly at 100 C to remove water and recover PEG-600. The recovered PEG-600 could be reused for consecutive runs.
69%
With potassium hydrogensulfate; potassium bromide; isoquinolinium chlorochromate; In water; at 20℃;
General procedure: A centimolar (0.01mol) organic substrate (phenols, anilines,or acetanilides), about 0.01 mol of potassium halide (KBr orKI), 0.001 mol hypervalent Cr (VI) reagent (IQCC orIQDC), and solvent (DCE or ACN) were taken in a previouslycleaned round-bottom flask. About 50 mg of KHSO4 isalso added to the reaction flask. The reaction mixture isrefluxed for about 4-5 h at 50-60C. Progress of the reactionwas monitored by TLC technique. After completion, thereaction mixture is treated with 5% sodium thiosulfate solutionfollowed by the addition of ether. The aqueous layer wasseparated, dried, and evaporated under vacuum, and purifiedwith column chromatography using chloroform:n-hexane(9:1) as eluent to get pure product.General.
With 2-chloro-1-methyl-pyridinium iodide; water; silica gel; sodium nitrite; In hexane; at 20℃; for 4h;
General procedure: A suspension of aromatic compound (1 mmol), Mukaiyama reagent (0.510 g, 2 mmol), NaNO2 (0.207 g, 3mmol) and wet SiO2 (50percent w/w, 0.4 g) in n-hexane (7 mL)was magnetically stirred at room temperature. After completion of the reaction (0.5-7 h), the reaction mixture was filtered;the residue was washed with n-hexane (20 mL). Filtrate was dried (Anhydrous Na2SO4). Evaporation of the solvent and chromatography on a short silica gel column usingn-hexane/ethyl acetate (4/1) as eluent gave corresponding aromatic nitro compound in 65percent - 92percent yields (Table 1, entries1-12).The products were identified by comparison of their physical and spectral data with literature [10, 14, 16,33-37].
With tert.-butylnitrite; water; In tetrahydrofuran; at 25℃; for 4h;Schlenk technique; Inert atmosphere;
In a dry 10 ml schlenk bottle by adding 1 - naphthol 43.2 mg (0.3mmol), tert-butyl nitrite 61.8 mg (0.6mmol), water 10.8 mg (0.6mmol), tetrahydrofuran (2 ml), stirring at room temperature the inner side 4h. After the reaction, the reaction solution through the filter glass dropper containing silica gel, ethyl acetate after washing, filtrate turns on lathe does, column chromatography, to obtain the target product, a yellow solid, yield 82percent.
82%
With tert.-butylnitrite; water; In tetrahydrofuran; at 20 - 25℃; for 4h;Schlenk technique;
43.2 mg (0.3 mmol) of 1-naphthol was added to a dry 10 mL schlenk flask,61.8 mg (0.6 mmol) of t-butyl nitrite, 10.8 mg (0.6 mmol) of water,Tetrahydrofuran (2 mL), the reaction flask was stirred at room temperature for 4 h. After the reaction is completed,The reaction solution was filtered through a glass dropper containing silica gel and rinsed with ethyl acetateThe filtrate was spin-dried and subjected to column chromatography to obtain the desired product as a yellow solid in a yield of 82percent.
78%
With nitric acid; vanadia; silica gel; at 150℃; for 0.025h;Microwave irradiation;Catalytic behavior;
General procedure: The microwave (MW) reactor used was of CEM make, which was equipped with temperature, pressure, and MW power control units. An oven-dried MW vial was charged with a mixture containing aromatic compound, V2O5 (9 mg, 0.005 mmol) and 69percent HNO3 (0.063 mL, 1 mmol) and silica gel slurry, and irradiated in a MW (power input 140 W) at 150 °C for few minutes. After completion of the reaction, as as certained by TLC, the reaction mixture was treated with sodium bicarbonate; the organic layer was diluted with dichloromethane (DCM) and separated from aqueous layer. The crude product mixture was purified with ethyl acetate DCM mixture. The purity was checked with TLC. The products were identified by characteristic spectroscopic data.
75%
With nitric acid; for 0.5h;
General procedure: In a typical experiment, bromobenzene (1.5 g, 1 mL, 10 mmol) and PAM-10 (75 mg, 5 wt.percent to the bromobenzene) were taken in a round-bottomed flask. Then nitric acid (70percent) (1.35 mL, 15 mmol) was added and stirred at room temperature for the specified time period (Table 1). The reaction was monitored by TLC. On completion of reaction, the product was extracted with ethyl acetate, washed sequentially with 5percent aqueous solution of sodium bicarbonate (2.5 mL), and water (5 mL), and then dried with anhydrous Na2SO4. Evaporation of the solvent, followed by column chromatography of the crude mixture on silica gel using n-hexane and ethyl acetate (95:5) as eluent, afforded 2-nitro toluene and 4-nitro toluene in the ratio of 44:56 in pure form. The overall yield was 97percent. In cases of solid substrates, acetonitrile (3?5 mL) was used as the solvent.
62%
With uronium nitrate; In water; acetonitrile; at 80℃; for 0.833333h;Microwave irradiation;
General procedure: Phenol (10 mmol) and urea nitrate (10 mmol)were mixed together in acetonitrile?water (95:5, 5 ml) in a 25 ml round bottomed flask and placed in a Milestone?s Start SYNTH microwave reactor. The reaction mixture was heated at 80°C for 40?50 min. At the end of the reaction, the reaction mixture was allowed to cool at room temperature,treated with water, and extracted with dichloromethane. After removing the solvent under reduced pressure, the residue was purified by column chromatography on silica gel to give the corresponding nitrophenol. In allcases ortho-nitrophenols were obtained selectively without any evidence forthe formation of the para-substituted nitrophenols. All the compoundsobtained were characterized by 1H NMR, 13C NMR, mp (for solids), GC?MSand in comparison with authentic samples.
With ammonium cerium (IV) nitrate; sodium hydrogencarbonate; In acetonitrile; at 26℃; for 0.5h;
General procedure: Example 1 General procedure for preparation of nitro compound Experimental procedure A To a supension of phenol (3.5 mmol) and NaHCC-3 (14 mmol) in anhydrous MeCN (10 ml) CAN (7.0mmol) was added and the resulting mixture was stirred for 30 min at 26°C (rt). During this time, the yellow color of CAN has been disappeared. The reaction mixture was diluted with dichloromethane (25 mL) and filtered. The organic layer was washed with water (2 x 10 mL), dried (NaS04) and concentrated under reduced pressure. The resulting crude was purified by column chromatography (silica 100-200) to procure pure nitrophenol product. 1.1 -iodo-2-nitroaniline (NitOl) : The general experimental procedure A was followed. Yellow solid. M. P.: 172.2°C; IR (CHC13): v 3490, 3377, 1610, 1555, 1460, 1376, 1336, 1231 cm-1 ; NMR (CDC13, 200 MHz): delta 6.11 (br s, 2H), 6.61 (d, J = 8.7, Hz, 1H), 7.57 (dd, J = 2.0, 8.7 Hz, 1H), 8.43 (d, J = 2.0, Hz, 1H) ppm; NMR (CDC13, 50 MHz): delta 75.8 (s), 120.6 (d), 132.9 (d), 134.2 (s), 143.7 (s), 144.0 (d) ppm; ESI-MS (m/z): 287.0 [M+Na]+; Anal. Calcd for C6H5IN202: C, 27.29; H, 1.91; N, 10.61; Found: C, 27.31 ; H, 1.93; N, 10.57.
With potassium carbonate; In acetonitrile; at 125℃; for 0.333333h;Microwave irradiation;
General procedure: A mixture of 0.14 g (1.0 mmol) of 1- and 2-naphthol (1)and (6), in most cases 1.0 mmol of alkali carbonate (0.14 g of K2CO3 or 0.33 g of Cs2CO3), in certain cases 11.4 mg(0.05 mmol) of TEBAC and 1.2 mmol of alkyl halide (0.14ml of benzyl bromide, 0.10 ml of ethyl iodide, 0.12 mol ofbutyl bromide or 0.11 ml of i-propyl bromide) in a closedvial was irradiated (20-30 W) in a CEM Discover [300 W]MW reactor at 125 C for the appropriate time. The reactionmixture was taken up in 25 ml of ethyl acetate and the suspensionwas filtered. Evaporation of the volatile componentsprovided the crude product that was passed through a thin(ca. 2-3 cm) layer of silica gel using ethyl acetate as theeluant to give an oil that was analysed by GC-MS or GC.Similar reactions were carried out in 3 ml of MeCN asthe solvent. The work-up was similar to that described forthe solventless alkylations above, but in this case, ethyl acetatedid not have to be added.The major components of the above reactions, such ascompounds 2, 7, 8, 10a-c and 13a,b were obtained in a pureform by repeated chromatography.Control experiments were performed with benzyl bromidein a similar way under conventional heating.
86%
With potassium phosphate; tetrabutylammomium bromide; In water; at 20℃; for 2h;Sealed tube; Green chemistry;
General procedure: General procedure for benzylation of phenols: Phenol (0.5mmol), benzyl bromide (1.2equiv), TBAB (0.5equiv), K3PO4 (1.5equiv), and water (2mL) were added to a reaction vessel. The mixture was stirred at room temperature for 2h under air. After the reaction was completed, the mixture was diluted with water and extracted with CH2Cl2 (15mL×3). The combined organic layer was dried with anhydrous sodium sulfate and concentrated under reduced pressure. The residue was purified by thin layer chromatography (TLC) on silica gel GF254 (ethyl acetate/petroleum ether) to give the pure product.
The catalyst is prepared as described in Example 9, but instead of being subjected to a heat treatment at 450 °C in air, it undergoes a treatrnent at 600 °C in air for 3 hours. After this treatment, the catalyst shows the following improvements with respect to the sample described in Example 9: shorter time required to reach stable performance and distinctly higher catalytic performance than the catalyst described in Example 9, especially in terms of selectivity: 1-naphthol conversion 100percent, selectivity to 2-methyL-l-naphthol equal to 96percent.
94%
Conversion of starting material;
The catalyst described in Example 9, once the stable catalytic performance cited in the example has been reached, is subjected to treatment in a current of N2 at 450 °C for 3 hours. After this treatment, the performance is as follows : 1-naphthol conversion 98percent, selectivity to 2-methyl-1-naphthol 96percent. The treatment therefore produces, with respect to the stationary situation described in Example 9, a slight decrease of conversion but a considerable increase in selectivity. The yield of the chosen product (given by the product of conversion and selectivity) is therefore distinctly higher than the yield obtained before said treatment. The same result is achieved if the pretreatment is performed on the fresh catalyst, i. e., after calcinations in air.
93%
Conversion of starting material;
The catalyst described in Example 10, after reaching the stable catalytic performance cited in the example, is subjected to a treatment in N2 current at 450 °C for 3 hours. After this treatment, the performance is as follows: 1- naphthol conversion 98percent, selectivity to 2-methyl-1-naphthol 95percent. The treatment therefore leads, with respect to the stationary situation described in Example 10, to a negligible decrease in conversion but to a substantial increase in selectivity. The yield in the chosen product (determined by the product of conversion and selectivity) is therefore distinctly higher, in this case also, than before this treatment.
90%
Conversion of starting material;
A catalyst is prepared according to the method described above and is finally subjected to thermal treatment im air at 450 °C. The sample is characterized by a Mg/Fe ratio, expressed as atomic ratio between the two elements, equal to 0.25.The conversion of 1-naphthol is found to increase and is now equal to 98percent. Despite the high conversion, there is also high selectivity to 2-methyl-1-naphthol , which is equal to 92percent..
83%
Conversion of starting material;
A catalyst is prepared according to the method described above, and is finally subjected to heat treatment in air at 450 °C. However, differently from the catalysts described in Exarnples 7-13, the catalyst is also subjected to a preliminary treatment at the same temperature in a nitrogen current before starting the reactivity tests. The sample is characterized by a Mg/Fe ratio, expressed as atomic ratio between the two elements, equal to 2.0. Conversion of 1-naphthol equal to 92percent is observed. Selectivity to 2-methyl- 1-naphthol is equal to 90percent.
81%
Conversion of starting material;
A catalyst is prepared according to the method described above and is finally subjected to thermal treatment im air at 450 °C. The sample is characterized by a Mg/Fe ratio, expressed as atomic ratio between the two elements, equal to 0.75. . A further increase of 1-naphthol conversion is observed conversion is now equal to 100percent. However, there is a slight decrease in selectivity to 2-methyl-1-naphthol, which is now equal to 81percent.
77%
Conversion of starting material;
A catalyst is prepared according to the method described above and is finally subjected to thermal treatment im air at 450 °C. The sample is characterized by a Mg/Fe ratio, expressed as atomic ratio between the two elements, equal to 1.50. .Conversion of 1-naphthol equal to 99percent is observed.
63%
Conversion of starting material;
A catalyst is prepared according to the method described above and is finally subjected to thermal treatment im air at 450 °C. The sample is characterized by a Mg/Fe ratio, expressed as atomic ratio between the two elements, equal to 0.05. Conversion of the 1-naphthol is equal-to 74percent, while selectivity to 2-methyl-1-naphthol is equal to 85percent.
30%
ferric oxide; magnesium oxide;Conversion of starting material;
A catalyst is prepared by using the following method: first Mg and Fe hydroxates are precipitated separately; then, they are filtered separately and dried at 90 °C. The two precipitates are then simply mixed so as to have a Mg/Fe atomic ratio equal to 0.25, and the mixture is treated as usual at 450 °C]for 8 hours in air. The catalyst yields the following performance : conversion 36percent, selectivity 84percent. Accordingly, the catalyst is less active than the corresponding sample prepared with the coprecipitation method.
With palladium diacetate; sodium hydride; In N,N-dimethyl acetamide; at 50℃; for 5h;Inert atmosphere;
Palladium acetate (3.4 mg, 0.015 mmol, 5 mol%) and sodium hydride (60% in oil, 18 mg, 0.45 mmol, 1.5 equiv) were suspended in DMA (1.0 mL) under nitrogen.After stirring at 25 C for 5 minutes, a solution of Compound 1 (0.3 mmol) in DMA (0.5 mL) was added, followed by a reaction at 50 C for 5 hours.The reaction was stopped by adding ice water, the pH was adjusted to 3.5 with dilute hydrochloric acid, and extracted with ethyl acetate.Drying with sodium sulfate, rotary evaporation and purification by column chromatography gave product 2, yield 98%.
93%
With bis(2-hydroxyethyl)ammonium formate; palladium dichloride; at 20℃; for 12h;Inert atmosphere;
To a solution of nitrobenzene (9) (123 mg, 1.00 mmol) in [BHEA][HCO2] (5.00 mL, 39.7 mmol)was added PdCl2 (1.80 mg, 1.00 mol %) at rt and the reaction mixture was stirred at the same temperature for 12 h under argon atmosphere. The mixture was poured into brine (10 mL) and extracted with EtOAc (10 10 mL). The organic layer was washed with brine (150 mL) and dried with MgSO4. To a solution was added acetic anhydride (2.84 mL, 30 mmol) at rt and the reaction mixturewas stirred at the same temperature for 30 min under argon atmosphere. The mixture was washed with a saturated solution of sodium carbonate (80 mL), brine (150 mL), and dried with MgSO4. After removal of the solvent, the residue was subjected to column chromatography (Merck Kieselgel 60, Phi=2.0 cm, l=11.5 cm; EtOAc-hexane, 1:3) to give acetanilide (22); yield: 130 mg (96%).
EXAMPLE 1 Preparation of 4-(3',4'-dichlorophenyl)-3,4-dihydro-1-(2H)-naphthalenone In a 1 liter reactor, equipped with a rotary anchor agitation device, are placed 144.2 g (1 mole) of alpha-naphthol and 500 ml of orthodichlorobenzene. In 20 minutes and by portions, 280 g (2.1 moles) of anhydrous aluminium chloride are added. The temperature rises from 20 to 50 C. and the thick yellow suspension is progressively dissolved to give a green solution. The reaction medium is heated for 3 hours at 65 C., then it is poured on 1500 ml of water. The lower organic phase is separated by decantation and the aqueous phase re-extracted with 300 ml of orthodichlorobenzene. The organic phase is concentrated in a vacuum at a temperature between 60 and 80 C. under a pressure of 2 to 5 torrs and the orthodichlorobenzene thus recovered, namely 650 ml, may be recycled. The concentrate (about 300 g) is taken up with 400 ml of methyl ethyl ketone and 2 g of discoloring charcoal at 60 C., then filtered and diluted with 250 ml of methanol. The solution is cooled for 4 hours at 0 C. The light beige solid formed is separated by filtration and dried, which gives 177.8 g of the expected compound. Yield 61% with respect to the starting alpha-naphthol.
aluminum (III) chloride; at 45 - 60℃; for 6h;
Example 1 Preparation of racemic [4- (3, 4-DICHLOROPHENYL)-3, 4-DIHYDRO-1- (2H)-] naphthalenone 1450 ml of 1, [2-DICHLOROBENZENE] and 192 [G] of 1-naphthol (cca 1.33 mole) are introduced into a three-necked flask equipped with thermometer, stirrer, air condenser, and calcium chloride tube. [420 G] of anhydrous aluminum chloride is slowly added (in 10 minutes) to the solution under constant stirring. Temperature is increased to 45-48 [C] within short time, suspension is being solidified and stirring becomes difficult. After additional 15 minutes the catalytic complex suspension is liquefied and stirring becomes easy. Temperature has been kept at 60 C under constant stirring for 6 hours. The reaction mixture is cooled to 25 [C] and poured on ice. 35 ml of hydrochloric acid and 900 ml of chloroform are added. The layers are separated in a separating funnel and the aqueous layer is washed with a small portion of chloroform repeatedly. The organic extracts are combined and washed twice with water and the organic layer is dried over anhydrous sodium sulfate. Chloroform is distilled out under atmospheric pressure. The excess of 1, 2-dichlorobenzene is distilled out at 100 [C] in vacuo. 1, 2-dichlorobenzene is recuperated and can be used in another batch. After 1, [2-DICHLOROBENZENE] has been removed to the constant weight, the oily residue (approximately 405 g) is cooled and 96-% ethanol (a portion that represents threefold of volume compared to the weight of product) is added and stirred (or better expose to ultrasonics) until it has crystallized completely. A crude crystalline product is filtered after 8 hours of standing, washed twice with a small portion of cool ethanol and dried on the air (or at 60 [C).] 330 [G] of crude beige crystalline product is obtained yielding 85 % (referred to 1-naphthol), m. p. 99-101 [C.] Example 2 The ratio of 3, [4-DICHLOROPHENYL- AND] 2, [3-DICHLOROPHENYLNAPHTHALENONE] isomers is determined by HPLC with UV detection. The analysis is carried out on column Zorbax SB C-18,250 x 4.6 mm under following conditions: mobile phase: methanol-water 67: 33, flow rate: 1 ml/min, column temperature : 40 [C,] wavelength : 230 nm. The naphthalenone isomer ratio is calculated from the ratio of peak areas. (Response factors are approximately the same for the both isomers at the applied wavelength). Adrien et [AL.] (US 5,019, 655) declared 98-99 % purity (GC) of naphthalenone [(I)] obtained under similar conditions. This result cannot be considered as the correct one. We have found that the ratio of isomers originated from the synthesis changes only slightly in a broad range of temperature (40-95 [C)] and a broad ratio of reactants, and the resulting purity can hardly exceed 95 % after their complete resolution. Example 3 Purification of Crude Crystalline Product of [4- (3, 4-DICHLOROPHENYL)] 3,4- [DIHYDRO-1-(2H)-NAPHTHALENONE (I)] Purification of crude crystalline product [(I)] for the reductive amination is carried out as follows : the dried crude crystalline product is dissolved in a [SIXFOLD VOLUME] of acetone at the temperature close to b. p. of acetone and 8 % of activated charcoal is added (e. g. Norit). The mixture is left staying with occasional stirring for ten minutes and still hot is filtered. A filtrate is yellowish after refining. Acetone is evaporated to dryness. The colorless crystals are obtained, b. p. [100-102 C,] the yield is 94.5 %. The product is free from non-polar impurities, however, the content of the 2, [3-DICHLOROPHENYL] isomer is almost the same. The colorless product is undergone the fractional crystallization from ethanol. A half of crystalline product is dissolved in a sixfold portion (w/w) of 96-% boiling ethanol and then cooled slowly to crystallize. The mixture is inoculated with a small portion of nuclei at temperature of 60 [C] and is left stayed for 6 hours, filtered and washed with a small portion of ethanol. The second part of crude material is introduced to the mother liquor and recrystallized identically, filtered and washed. The both parts of product are combined and dried. The same procedure is carried out twice so that the content of the 2, [3-DICHLOROPHENYL] isomer has dropped under a critical limit. After three recrystallization runs, the yield is 86 %, m. p. 102-104 [C.] All the mother liquors are combined and evaporated to a quarter of the initial volume. The crystalline material is isolated the next day, filtered and added to another crude charge (the purity of that is similar).
A catalyst is prepared according to the method described above, and is finally subjected to heat treatment in air at 450 °C. The sample does not contain magnesium and is therefore constituted solely by Fe203. One obtains a conversion of 48percent, with selectivity to 2-methyl-1-naphthol equal to 84percent. The byproducts are essentially constituted by 4-methyl-1-naphthol and by products of methylation of the aromatic ring.
31%
magnesium oxide;Conversion of starting material;
A catalyst is prepared according to the method described above, and is finally subjected to heat treatment in air at 450degree;C. The sample does not contain iron, and therefore is constituted only by MgO. One obtains 42percent conversion, with selectivity to 2-methyl-l-naphthol equal to 74 percent. The byproducts are essentially constituted by 4-methyl-l-naphthol and by products of methylation of the aromatic ring.
With Isopropylbenzene; methanesulfonic acid; In water; toluene;
EXAMPLE 10 1-Naphthalenyl methylcarbamate To a 500 ml, 3-necked flask, equipped with an agitator and a condenser were added 36.0 g (0.25 mol) of 1-naphthol, 35.2 g (0.40 mol) of 1,3-dimethylurea, 150 ml of cumene, and 38.4 g (0.40 mol of acid) of a 98% by weight methanesulfonic acid solution (Aldrich, reagent grade). The resulting solution was heated to reflux (about 154 C.) and stirred at that temperature for about 6 hours. After 6 hours the solution was cooled to 90 C. and diluted with 100 ml of deionized water. The resulting two-phase mixture was stirred for 15 minutes at about 80 C., and then the organic layer separated from the aqueous layer. The organic layer was mixed with 50 ml of deionized water and cooled to 0 C. After stirring the mixture for 30 minutes at a temperature of about 0 C. the resulting slurry was filtered and the recovered crystals washed with 25 ml of deionized water, followed by 20 ml of cold (5 C.) cumene. The crystals were dried in a vacuum oven at 60 C. to provide 11.3 g of title product. The above product was purified by dissolving it in 50 ml of hot (90 C.) toluene. Once all product had dissolved, the solution was cooled to 0 C. and stirred for 30 minutes at that temperature. The resulting slurry was filtered and the recovered crystals washed with 30 ml of toluene. This material, dried in a vacuum oven at 60 C., provided 10.1 g of 1-naphthalenyl methylcarbamate. m.p.=139-140 C. The product was identified as 1-naphthalenyl methylcarbamate by comparing n.m.r. spectra with a 1-naphthalenyl methylcarbamate reference standard. The n.m.r. analyses were conducted on a 60 mHz instrument in CDCl3: delta=2.75 (doublet, 3H); 5.45 (singlet, 1H); 7.25-8.20 (broad multiplet, 7H).
With Isopropylbenzene; methanesulfonic acid; In water; toluene;
Example 10 1-Naphthalenyl methylcarbamate To a 500 ml, 3-necked flask, equipped with an agitator and a condenser were added 36.0 g (0.25 mol) of 1-naphthol, 35.2 g (0.40 mol) of 1,3-dimethylurea, 150 ml of cumene, and 38.4 g (0.40 mol of acid) of a 98% by weight methanesulfonic acid solution (Aldrich, reagent grade). The resulting solution was heated to reflux (about 154C) and stirred at that temperature for about 6 hours. After 6 hours the solution was cooled to 90C and diluted with 100 ml of deionized water. The resulting two-phase mixture was stirred for 15 minutes at about 80C, and then the organic layer separated from the aqueous layer. The organic layer was mixed with 50 ml of deionized water and cooled to 0C. After stirring the mixture for 30 minutes at a temperature of about 0C the resulting slurry was filtered and the recovered crystals washed with 25 ml of deionized water, followed by 20 ml of cold (5C) cumene. The crystals were dried in a vacuum oven at 60C to provide 11.3 g of title product. The above product was purified by dissolving it in 50 ml of hot (90C) toluene. Once all product had dissolved, the solution was cooled to 0C and stirred for 30 minutes at that temperature. The resulting slurry was filtered and the recovered crystals washed with 30 ml of toluene. This material, dried in a vacuum oven at 60C, provided 10.1 g of 1-naphthalenyl methylcarbamate. m.p. = 139-140C. The product was identified as 1-naphthalenyl methylcarbamate by comparing n.m.r. spectra with a 1-naphthalenyl methylcarbamate reference standard. The n.m.r. analyses were conducted on a 60 mHz instrument in CDCl3: delta = 2.75 (doublet, 3H); 5.45 (singlet, 1H); 7.25-8.20 (broad multiplet, 7H).
EXAMPLE 1 1-NAPHTHYL-N-METHYLCARBAMATE To a solution of 1-naphthyl (1.44 g, 0.01 mole) and ethyl N-methylcarbamate (1.03 g, 0.01 mole) in toluene (15 ml) was added phosphoryl chloride (1.54 g, 0.01 mol) and the mixture was heated at reflux temperature for eight hours. It was poured on to ice cold water and the organic layer separated and washed with cold 5% NaOH solution to remove the unreacted 1-naphthol, followed by water, dried and distilled to give a liquid residue, which solidified on cooling. It was further purified by crystallization, to furnish 1-naphthyl N-methylcarbamate of the formula (IV), m.p. 140-41 C.; IR: 3305 (NH), 1715 (--COO--), 1600, 1540, 770 (aromatic); PMR (CDCl3, 90 MHz): 2.86 (3H, d, J-7 Hz, NH--CH3), 5.14 (1H, brs, N--H) and 7.17 to 8 (7H, m, aromatic).
With trichlorophosphate; In water; toluene;
EXAMPLE 1 1-NAPHTHYL-N-METHYLCARBAMATE To a solution of 1-naphthol (1.44 g, 0.01 mole) and ethyl N-methylcarbamate (1.03 g, 0.01 mole) in toluene (15 ml) was added phosphoryl chloride (1.54 g, 0.01 mol) and the mixture was heated at reflux temperature for eight hours. It was poured on to ice cold water and the organic layer was separated and washed with cold 5% NaOH solution to remove the unreacted 1-naphthol, followed by water, dried and distilled to give a liquid residue, which solidified on cooling. It was further purified by crystallization, to furnish 1-naphthyl N-methylcarbamate m.p. 140-41C; IR: 3305 (NH), 1715 (-COO-), 1600, 1540, 770 (aromatic); PMR (CDCl3, 90 MHz): 2.86 (3H, d , J-7 Hz, 5.14 (1H, brs , N- H) and 7.17 to 8 (7H, m , aromatic).
With phosphorus tribromide; In 1,1-dichloroethane;
EXAMPLE 2 1-NAPHTHYL-N-METHYLCARBAMATE To a solution of 1-naphthol (1.44 g, 0.01 mole) and ethyl N-methylcarbamate (1.03 g, 0.01 mole) in dichloroethane (10 ml) was added phosphorus tribromide (2.7 g, 0.01 mol) and the reaction mixture was refluxed for ten hours. It was worked up as described earlier and the crude solid obtained, was crystallized further to get 1-naphthyl N-methylcarbamate.
EXAMPLE 1 6-Methoxy-1-naphthalenol A mixture of 50.0 g (0.28 mole) of 6-methoxy-1-tetralone and 9.2 g (0.29 mole) of elemental sulfur was stirred and heated at 250°-260° for three hours (until the evolution of hydrogen sulfide gas had ceased). The mixture was cooled and then subjected to bulb-to-bulb distillation. The distillate was dissolved in 300 ml of dichloromethane, and the solution was extracted with 1.0N potassium hydroxide solution (3*150 ml). The base extracts were combined, cooled in ice, and acidified with 10percent hydrochloric acid to precipitate the crude naphthol product as a gum. Trituration of the gum with tert-butyl methyl ether yielded 16.8 g (34percent yield) of the analytically pure naphthol, mp 84°-86° (a mp of 83°-84° is given by M. P. Sibi, J. W. Dankwardt, and V. Snieckus, J. Org. Chem., 51, 271 (1986)). Calcd. for C11 H10 O2: C, 75.84; H, 5.79. Found C, 75.66; H, 5.69.
EXAMPLE 2 PREPARATION OF CARBARYL A stirred solution of 1-naphthol (86.5 g, 0.6 mole) in 500 g of toluene was heated under nitrogen to 98 C. Phosgene (79.9 g, 0.8 mole) and methylamine (22.0 g, 0.7 mole) were then metered into this solution concurrently and gradually over a period of approximately 6.5 hours. The reaction mixture was filtered hot. The filtrate was then allowed to cool to room temperature, and the crystallized carbaryl was recovered by filtration. The yield of 1-naphthyl methylcarbamate was 78%.
PART A 2-(4-Chlorobutyryl)-1-naphthol A mixture of 1-naphthol (15.14 g, 0.105 mole), 4-chlorobutyric acid (9.90 mL, 0.100 mole), and boron trifluoride etherate (75 mL) was heated on a steam bath for 4 hours. The mixture was then treated slowly with 100 mL of water, and heating continued for 30 minutes. The mixture was poured into water, stirred, and the solution decanted. The residue was triturated with water, then crystallized from ethanol to provide the title compound (9.50 g, 38%) as a pale green solid, mp 73-79.
EXAMPLE 2 At 150 C. and 100 mm Hg, 14 g of beta-naphthol and 9 g of dimethyl urethane were reacted in the presence of 0.7 g ZnCl2. A conversion of 2% of naphthol to methyl naphthyl urethane was obtained.
With caesium carbonate; In neat (no solvent); at 125℃; for 1h;Microwave irradiation;
General procedure: A mixture of 0.14 g (1.0 mmol) of 1- and 2-naphthol (1)and (6), in most cases 1.0 mmol of alkali carbonate (0.14 g of K2CO3 or 0.33 g of Cs2CO3), in certain cases 11.4 mg(0.05 mmol) of TEBAC and 1.2 mmol of alkyl halide (0.14ml of benzyl bromide, 0.10 ml of ethyl iodide, 0.12 mol ofbutyl bromide or 0.11 ml of i-propyl bromide) in a closedvial was irradiated (20-30 W) in a CEM Discover [300 W]MW reactor at 125 C for the appropriate time. The reactionmixture was taken up in 25 ml of ethyl acetate and the suspensionwas filtered. Evaporation of the volatile componentsprovided the crude product that was passed through a thin(ca. 2-3 cm) layer of silica gel using ethyl acetate as theeluant to give an oil that was analysed by GC-MS or GC.Similar reactions were carried out in 3 ml of MeCN asthe solvent. The work-up was similar to that described forthe solventless alkylations above, but in this case, ethyl acetatedid not have to be added.The major components of the above reactions, such ascompounds 2, 7, 8, 10a-c and 13a,b were obtained in a pureform by repeated chromatography.Control experiments were performed with benzyl bromidein a similar way under conventional heating.
With tert.-butylhydroperoxide; 1,10-Phenanthroline; copper diacetate; In decane; at 20.0℃; for 2.0h;Molecular sieve; Inert atmosphere;
General procedure: In a reaction vessel Cu(OAc)2 (20 mol%), 1,10-phenanthroline (20 mol%) was dissolved with 2 mL of formamide source. The reaction mixture stirred for 5 minutes and added the phenol (1) substrates. To the above reaction mixture, TBHP (5-6 M in decane solution) was added dropwise, with stirring over a period of 5 min. Then the reaction temperature was increased to 80 C and stirred for eight hours. After cooling to room temperature, the reaction mixture was directly subjected to purification with column chromatography on silica gel using 5-10% ethyl acetate and hexane mixture to afford the required product (3). Care should be taken while doing the product separation by column chromatography. We have observed that in some cases both the starting materials and products are very close, in which TLC?s have to be monitored by both UV and iodine. A slightly modified procedure was adopted for N-methylformamide reactions, in which the reactions were performed at room temperature for two hours. The crude products were directly subjected to column chromatography on silica gel to afford the required product (5).
With potassium fluoride; In acetonitrile; at 20 - 25℃; for 2h;
Thetetrafluoro Phthalo nitrile 6.0 g (30mmol), and the potassium fluoride 15 g(1.2eq.) and acetonitrile 20ml were put in the reactor in which the entrance of100ml placing the thermometer was 4 and it was stirred and it cooled to 0. Here, alpha - naphthol 4.3 g(1.0eq.) waslittle by little injected. In 5 orless the mixture after the input end, after it reacted at 1 hour thetemperature was increased to 20 and itreacted 2 hours at 20 through 25. Thereaction mixture was emitted to water after the completion of reaction and the segregatedsolid was filtered and it took out. The obtained crude product was well wipedoff with the methanol and the compound (4-3) 7.2g of the white solid wasobtained (the yield 74percent).
N-(tert-butoxycarbonyl)-L-aspartic acid di-1-naphthyl ester[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
42%
With dmap; dicyclohexyl-carbodiimide; In hexane; ethyl acetate; at 5℃; for 5h;
General procedure: Dinaphthyl esters of N-Boc protected aminoacids were prepared by a general procedure starting from N-(tert-butoxycarbonyl)-L-amino acids. N,N'-Dicyclohexylcarbodiimide (0.42 g, 2 mmol) dissolved in dry hexane/EtOAc (1:1) mixture was added dropwise over 15 min to a stirred suspension of N-Boc-L-amino acid (1 mmol) in dry hexane/EtOAc (1:1) mixture at 5 C. To the reaction mixture 1- or 2-naphthol (0.29 g, 2 mmol) and a catalytic amount of 4-(dimethylamino)pyridine dissolved in dry hexane/EtOAc (1:1) mixture was added dropwise over 1 h. The mixture was stirred at 5 C over 4 h and then concentrated. The residue was stirred in Et2O (10 mL) and oxalic acid (0.3 g, 3.3 mmol) was introduced in portions to decompose excess DCC and precipitate DMAP. The mixture was filtered and evaporated under reduced pressure leaving oil, which was purified using radial chromatography on silica gel plates (2 mm thickness), using hexanes/EtOAc as moving phase. N-(tert-Butoxycarbonyl)-L-aspartic acid di-1-naphthyl ester (3a) Yield 176 mg (42%), small white microcrystals, mp 143-145 C (Et2O/hexane); [alpha]D20 -6.6 (c 0.5, Me2CO); IR (solid, KBr, nmax, cm-1): 3370, 3064,2983, 2940, 1769, 1746, 1686, 1599, 1508, 1441, 1385, 1368, 1256, 1224, 1205, 1136, 1048, 776, 761; 1H NMR(300 MHz, CDCl3) delta 7.93-7.84 (m, 4H), 7.75 (t, J 8.5 Hz, 2H), 7.52-7.38 (m, 6H), 7.28-7.23 (m, 2H), 5.81 (d, J 8.5Hz, 1H), 5.18 (m, 1H), 3.73 (dd, J 4.4, 17.3 Hz, 1H), 3.51 (dd, J 4.8, 17.3 Hz, 1H), 1.51 (s, 9H); 13C NMR (75 MHz,CDCl3) delta 170.20, 169.82, 155.64, 146.50, 146.36, 134.71, 134.65, 128.08, 127.96, 126.74, 126.70, 126.60,126.57, 126.49, 126.41, 125.36, 121.21, 121.13, 118.06, 117.93, 80.68, 50.54, 37.05, 28.36; HRMS (m/z)508.1731 [M + Na]+ (C29H27NO6Na, calcd 508.1736).
With water; In tetrahydrofuran; at 25℃; for 2.5h;Schlenk technique;
General procedure: To a Schlenk tube were added Phenol 1 (0.3 mmol), tert-Butyl nitrite 2a (0.6mmol), H2O (0.6 mmol), and THF (2 mL). Then the tube was stirred at 25 oC under airatmosphere for the indicated time until complete consumption of starting materialmonitored by TLC analysis. After the reaction was finished, the organic extracts weredried over anhydrous Na2SO4, concentrated in vacuum, and the resulting residue waspurified by silica gel column chromatography (hexane/ethyl acetate) to afford thedesired product 3.
General procedure: To a mixture of compound 3(1.5 mmol) and 3M HCl (1.53 mL) at 0 °C, a solution of sodium nitrite (NaNO2, 1.58mmol) in water (3 mL) was added dropwise while maintaining the temperaturebelow 5 °C. After stirring for 30 min, asolution of diazonium chloride was prepared. Subsequently, a solution ofdiazonium chloride was added gradually to a mixture of phenols/anilines (4a,b; 6a?f;8a?k or 9a?e, 1.5 mmol), and ethanol (3 mL) at 0-5 °C. The reaction mixture was adjusted to pH 8-9 with 1 Maq. NaOH. After addition, the mixture was continued to stir for 3-6 h. Thesolid was collected, washed with water (3×15 mL), dried and purified by PTLC orsilica gel column chromatography to give the target products IIa?x.
2-(naphthalen-1-yloxy)-5-nitropyrimidine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
90%
a vacuum 50ml reaction bottle is vacuumed three times, then added to the reaction bottleNaphthalen-1-ol (144 mg, 1.0 mmol, 1.0 equiv),Add 3.0 ml of dried THF and stir until all the naphthalene-1-ol is dissolved.Then add NaH (28.8mg, 1.2mmol, 1.2equiv, 60percent sodium hydride in the reaction jar) in the ice bath.Store in oil), react in ice bath for 30 min; then add <strong>[10320-42-0]2-chloro-5-nitropyrimidine</strong> (0.1593 g, into the reaction jar).1.0 mmol, 1.0 equiv). The entire mixture was slowly raised to a temperature of 50 ° C for 12 hours. Reaction detected by TLCThe progress of the reaction can be stopped if it is detected that all of the phenol is completely reacted. The experimental treatment is to drain the solution in the reaction;The solute in the reaction flask was dissolved with ethyl acetate and transferred to a 100 ml round bottom flask and added to a round bottom flask.3 ml (200-300 mesh) of silica gel was spin-dried (petroleum ether and ethyl acetate) over silica gel on a column. The intermediate product was white crystal 2-(naphthalen-1-yloxy)-5-nitropyrimidine (207 mg, 90percent yield).
With potassium carbonate; caesium carbonate; In acetone; for 24h;Reflux;
General procedure: To a stirred mixture of 1-naphthol (1.54g, 10.7mmol) and potassium carbonate (2.95g, 21.4mmol) in acetone (20mL) was added methyl 4-bromobutyrate (3.87g, 21.4mmol). The reaction mixture was refluxed for 24h then allowed to cool to room temperature, filtered and washed with acetone. The filtrate was evaporated under vacuum. The residue was purified by silica gel column chromatography (EtOAc/n-hexane=1:10) to afford compound 11a. Yield (2.96g, quantitative). 1H NMR (400MHz, CDCl3) delta 8.26-8.24 (1H, m, H-8), 7.82-7.78 (1H, m, H-5), 7.50-7.34 (4H, m, H-6, H-7, H-3, H-4), 6.79 (1H, d, J=7.5Hz, H-2), 4.19 (2H, t, J=6.6Hz, -OCH2-), 3.70 (3H, s, -COOCH3), 2.65 (2H, t, J=6.6Hz, -OCH2CH2CH2-), 2.27 (2H, q, J=6.6Hz, -OCH2CH2-).
With potassium carbonate; In acetonitrile; at 80℃; for 12h;Inert atmosphere;
In a 250 mL three-necked flask, 1-naphthol 6.00 g, F 9.75 g, and potassium carbonate 20.70 g were added.The nitrogen gas is circulated for 3 to 5 times by continuous vacuuming, and oxygen and water in the system are discharged to reach a nitrogen atmosphere.Then, 70 mL of anhydrous CH3CN was added as a solvent, and the mixture was stirred at 80 ° C for 12 hours.After the reaction is completed, the reaction is stopped.The temperature of the reaction system was cooled to room temperature.250 mL of water was added to the reaction solution, and the solid was dissolved. Extract with ethyl acetate, with water,Washed with saturated NaHCO3 solution, saturated NaCl solution, dried over anhydrous magnesium sulfate, filtered and evaporated.A pale red wine viscous liquid of 8.25 g was obtained with a yield of 94.8percent.
With copper(l) iodide; 2,2,6,6-tetramethylheptane-3,5-dione; caesium carbonate; In N,N-dimethyl-formamide; for 24h;Inert atmosphere; Sealed tube; Heating;
General procedure: To a 100 mL round bottom flask equipped with a stir bar wereadded 1?bromo?3?(tert?butyl)benzene (10.0 g, 46.9 mmol, 1 equiv), 3?(tert?butyl)phenol (10.6 g,70.4 mmol, 1.5 equiv), Cs2CO3 (30.6 g, 93.8 mmol, 2 equiv), copper(I)iodide (894 mg, 4.69 mmol,10 molpercent), 2,2,6,6?tetramethylheptane?3,5,?dione (979 L, 4.69 mmol, 10 molpercent) and DMF (9 mL).No measures were taken to exclude air or moisture. The flask was sealed and heated to 110 Cfor 24 h. The reaction was cooled to room temperature and DMF was removed by rotaryevaporation. The residue was suspended in Et2O (200 mL) and filtered through celite. The filtercake was washed with Et2O until the washings became colorless. The filtrate was extracted withwater (2 x 100 mL) followed by brine (1 x 100 mL). The organic layer was dried over MgSO4,filtered, and concentrated to dryness. The residue was purified by column chromatography (SiO2,100percent hexanes to 2percent EtOAc in hexanes) to give ether 4 (11.6 g, 41.2 mmol, 88percent yield) as acolorless oil.
2.2 eq, 2.2 mmol of di-isopropylethylamine is added to a solution of methylamine (4 eq, 4 mmol) in dichloromethane (20 mL) and carbon dioxide is purged through the solution for 45 minutes at -40 C followed by addition of 1.1 eq, 1.1 mmol POC13 and 1 eq, 1 mmol of xnaphthol. The reaction mixture is stirred for 2 minutes to 5 minutes, followed by addition of 1.1 eq. of 1,8-Diazabicyclo[5.4.Ojundec-7-ene. On completion, the reaction mixture is diluted with dichloromethane and washed first with water, then by brine. The combined organic phase is dried over Na2SO4 and concentrated to give carbaryl, which was further purified by column chromatography to obtain 160 mg (80% yield) of carbaryl.
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