* 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.
An operation was conducted in the same manner as in Example 2 except that cyclohexanol was replaced by an alicyclic secondary alcohol compound or an alicyclic ketone compound, both shown in Table 2 as a raw material compound. The results are shown in Table 2.
Reference：
[1] Tetrahedron Letters, 2004, vol. 45, # 44, p. 8221 - 8224
[2] Patent: EP1728779, 2006, A1, . Location in patent: Page/Page column 6
[3] Patent: US1960211, 1932, ,
[4] Journal of the American Chemical Society, 1939, vol. 61, p. 2728
[5] Journal of the American Chemical Society, 1951, vol. 73, p. 2540,2542
[6] J. Appl. Chem. USSR (Engl. Transl.), 1966, vol. 39, p. 623 - 625[7] Zhurnal Prikladnoi Khimii (Sankt-Peterburg, Russian Federation), 1966, vol. 39, # 3, p. 668 - 671
[8] Patent: WO2015/189595, 2015, A1, . Location in patent: Page/Page column 29
2
[ 98-53-3 ]
[ 10347-88-3 ]
[ 98-52-2 ]
Reference：
[1] Journal of Chemical Research, Miniprint, 1993, # 12, p. 3320 - 3338
[2] Journal of Chemical Research, Miniprint, 1993, # 12, p. 3320 - 3338
3
[ 98-52-2 ]
[ 110-94-1 ]
[ 124-04-9 ]
[ 110-15-6 ]
[ 10347-88-3 ]
Reference：
[1] Journal of applied chemistry of the USSR, 1984, vol. 57, # 10 pt 2, p. 2138 - 2142
4
[ 98-54-4 ]
[ 98-52-2 ]
Yield
Reaction Conditions
Operation in experiment
99.9%
With hydrogen In tetrahydrofuran at 180℃;
Example 1 A 50 wt.-percent strength solution of p-tert-butylphenol was prepared in THF. Then 2500 g/h of this solution were passed with hydrogen at a temperature of 180° C. and an overall pressure of 2.6*107 Pa through a flow reactor, which was packed with 3.2 l of the Ru catalyst described above. Following removal of the solvent, by distillation, the hydrogenation product had the following composition: 99.9percent of cis,trans-4-tert-butylcyclohexanol <0.01percent of p-tert-butylphenol.
99.8%
With hydrogen In tetrahydrofuran at 200℃;
Example 2 The hydrogenation was carried out as described in Example 1 except that 3500 g of the 50 wt.-percent p-tert-butylphenol solution in THF were passed through the reactor at a temperature of 200° C. Following distillation of the solvent, the hydrogenation product possessed the following composition: 99.8percent of cis,trans-4-tert-butylcyclohexanol <0.01percent of p-tert-butylphenol
Reference：
[1] Patent: US6388149, 2002, B2, . Location in patent: Page column 17
[2] Patent: US6388149, 2002, B2, . Location in patent: Page column 17
[3] RSC Advances, 2014, vol. 4, # 6, p. 2729 - 2732
[4] Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, 1911, vol. 152, p. 609
[5] Journal of applied chemistry of the USSR, 1984, vol. 57, # 10 pt 2, p. 2138 - 2142
[6] Patent: US5874622, 1999, A,
[7] Chinese Journal of Catalysis, 2014, vol. 35, # 11, p. 1793 - 1799
[8] Patent: CN105198709, 2017, B, . Location in patent: Paragraph 0045; 0046
[9] Patent: CN107879932, 2018, A, . Location in patent: Paragraph 0012; 0013; 0014
[10] Patent: CN107840797, 2018, A, . Location in patent: Paragraph 0047; 0055; 0056; 0057; 0058; 0059; 0060
[11] Advanced Synthesis and Catalysis, 2018, vol. 360, # 20, p. 3924 - 3929
5
[ 92976-55-1 ]
[ 98-52-2 ]
Reference：
[1] Journal of the Indian Chemical Society, 1998, vol. 75, # 10-12, p. 565 - 567
[2] Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), 1992, # 22, p. 2997 - 2998
[3] Organic and Biomolecular Chemistry, 2014, vol. 12, # 29, p. 5442 - 5447
[4] Journal of Organic Chemistry, 2000, vol. 65, # 7, p. 2065 - 2068
[5] Journal of Organic Chemistry, 1996, vol. 61, # 9, p. 2918 - 2919
[6] Tetrahedron, 2001, vol. 57, # 11, p. 2109 - 2114
6
[ 80356-16-7 ]
[ 98-52-2 ]
Yield
Reaction Conditions
Operation in experiment
97%
With iron(III) p-toluenesulfonate hexahydrate In methanol at 20℃; for 3 h;
General procedure: Method A: A solution of the THP ether of cinnamyl alcohol (entry 5) (1.00 g, 4.58 mmol) in CH3OH (10 mL) was stirred at room temperature as Fe(OTs)3*6H2O (0.0621 g, 0.0916 mmol, 2.0 mol percent) was added. The reaction progress was monitored by TLC (EtOAc/heptane, 30/70). After 4 h 30 min, water (15 mL) was added and methanol was removed on a rotary evaporator. The resulting mixture was extracted with EtOAc (2 .x. 20 mL). The organic layer was washed with saturated aqueous NaHCO3 (15 mL), saturated aqueous NaCl (15 mL), dried (Na2SO4), and concentrated on a rotary evaporator to yield 0.59 g of the crude product. The crude product was purified by flash chromatography (35 g silica gel, EtOAc/heptane, 30/70) to yield 0.49 g (80percent) of a white solid that was identified to be cinnamyl alcohol. The purity was estimated to be >98percent by 1H and 13C NMR spectroscopy, and GC analysis. Method B: A solution of the THP ether of 1-ethynyl-1-cyclohexanol (entry 10) (0.50 g, 2.40 mmol) in CH3OH (5 mL) was stirred at room temperature as Fe(OTs)3*6H2O (0.0325 g, 0.0480 mmol, 2.0 mol percent) was added. The reaction progress was monitored by TLC (EtOAc/heptane, 30/70). After 2 h, CH3OH was removed on a rotary evaporator and the residue was purified by flash chromatography (35 g silica gel, EtOAc/pentane, 30/70) to yield 0.23 g (77percent) of a colorless liquid that was identified to be 1-ethynyl-1-cyclohexanol. The purity was estimated to be >98percent by 1H and 13C NMR spectroscopy, and GC analysis.
Reference：
[1] Bulletin of the Chemical Society of Japan, 1985, vol. 58, # 4, p. 1347 - 1348
[2] Tetrahedron Letters, 2011, vol. 52, # 51, p. 6939 - 6941
[3] Synthesis, 1981, # 11, p. 899 - 901
[4] Bulletin of the Chemical Society of Japan, 1994, vol. 67, # 1, p. 290 - 292
7
[ 98-53-3 ]
[ 98-52-2 ]
Yield
Reaction Conditions
Operation in experiment
100 %Chromat.
With potassium formate In water; N,N-dimethyl-formamide at 100℃; for 8 h; Inert atmosphere; Green chemistry
For a typical reduction, 2 mmol of the aldehyde substrate,0.504 g (6 mmol) potassium formate, 0.54 mL (30 mmol) water and5 mL (65 mmol) dimethylformamide (DMF) were added to a 25 mLround-bottom flask. After heating the reaction mixture to 100Cunder a flow of nitrogen, 100 mg of 1 wt.percent Ru/AlO(OH) (0.5 mol percentof Ru) was added. Samples were taken at regular intervals and ana-lyzed by gas chromatography (GC) and gas chromatography massspectrometry (GC–MS). For comparison, the direct hydrogenationof benzaldehyde using molecular H2at 0.5 MPa was carried out in a Parr autoclave at 100C. Due to their lower reactivity, the catalytictransfer hydrogenation of ketones was carried out using 200 mg of2 wt.percent Ru/AlO(OH). For recycling tests, the used catalyst was recov-ered by centrifugation, washed with water followed by ethanol anddried at room temperature before use
Reference：
[1] Journal of Organometallic Chemistry, 1980, vol. 195, # 1, p. 1 - 12
[2] Tetrahedron Letters, 2000, vol. 41, # 39, p. 7567 - 7570
[3] Tetrahedron Letters, 1981, vol. 22, p. 179 - 180
[4] Tetrahedron Letters, 1998, vol. 39, # 22, p. 3729 - 3732
[5] Patent: US6340775, 2002, B1, . Location in patent: Example 5
[6] Chemistry - A European Journal, 2018, vol. 24, # 62, p. 16526 - 16531
[7] Journal of the Chemical Society, Perkin Transactions 2, 2002, # 6, p. 1122 - 1125
[8] Tetrahedron Letters, 2006, vol. 47, # 1, p. 9 - 12
[9] Journal of Organic Chemistry, 1982, vol. 47, # 23, p. 4581 - 4583
[10] Liebigs Annalen, 1995, # 4, p. 677 - 684
[11] Angewandte Chemie, 1989, vol. 101, # 3, p. 329 - 330
[12] Chemistry Letters, 1991, # 2, p. 307 - 310
[13] Tetrahedron Letters, 2002, vol. 43, # 21, p. 3943 - 3945
[14] Journal of Organic Chemistry, 1997, vol. 62, # 9, p. 3019 - 3020
[15] Helvetica Chimica Acta, 1984, vol. 67, # 3, p. 669 - 683
[16] Chemistry Letters, 1982, p. 261 - 264
[17] Chemical Communications, 2007, # 7, p. 760 - 762
[18] Journal of the Chemical Society, Chemical Communications, 1981, # 20, p. 1066 - 1067
[19] Tetrahedron Letters, 2000, vol. 41, # 29, p. 5543 - 5546
[20] Journal of Organic Chemistry, 1984, vol. 49, # 1, p. 166 - 168
[21] Journal of the Chemical Society, Chemical Communications, 1995, # 4, p. 465 - 466
[22] Journal of Organic Chemistry, 1984, vol. 49, # 1, p. 163 - 166
[23] Synthesis, 2005, # 15, p. 2619 - 2622
[24] Journal of Organic Chemistry, 1982, vol. 47, # 23, p. 4581 - 4583
[25] Chemistry Letters, 1980, p. 1239 - 1242
[26] Tetrahedron Letters, 1981, vol. 22, p. 179 - 180
[27] Journal of the American Chemical Society, 1987, vol. 109, # 3, p. 908 - 910
[28] Synthetic Communications, 1984, vol. 14, # 10, p. 955 - 960
[29] Journal of the American Chemical Society, 1984, vol. 106, # 22, p. 6709 - 6716
[30] Recueil des Travaux Chimiques des Pays-Bas, 1985, vol. 104, # 9, p. 217 - 219
[31] Journal of Organometallic Chemistry, 1982, vol. 240, # 4, p. 453 - 460
[32] Tetrahedron Letters, 1996, vol. 37, # 33, p. 5987 - 5988
[33] Tetrahedron Letters, 1981, vol. 22, p. 675 - 678
[34] Tetrahedron Letters, 1980, vol. 21, p. 3963 - 3964
[35] Journal of Organic Chemistry, 1980, vol. 45, # 13, p. 2724 - 2725
[36] Journal of Organic Chemistry, 1983, vol. 48, # 20, p. 3412 - 3422
[37] Journal of the American Chemical Society, 1980, vol. 102, # 8, p. 2693 - 2698
[38] Journal of Organic Chemistry, 1993, vol. 58, # 11, p. 3046 - 3050
[39] Journal of the American Chemical Society, 1984, vol. 106, # 22, p. 6709 - 6716
[40] Journal of the Chemical Society, Chemical Communications, 1988, # 10, p. 643 - 645
[41] Journal of Organic Chemistry, 1998, vol. 63, # 6, p. 1761 - 1766
[42] Bulletin of the Chemical Society of Japan, 1997, vol. 70, # 5, p. 1101 - 1107
[43] Journal of Organic Chemistry, 1999, vol. 64, # 7, p. 2582 - 2589
[44] Journal of Organic Chemistry, 2001, vol. 66, # 5, p. 1694 - 1700
[45] Tetrahedron Letters, 2001, vol. 42, # 50, p. 8857 - 8859
[46] Journal of Organic Chemistry, 2001, vol. 66, # 22, p. 7514 - 7515
[47] Tetrahedron Letters, 2003, vol. 44, # 5, p. 1079 - 1082
[48] Journal of Catalysis, 2003, vol. 215, # 2, p. 294 - 304
[49] European Journal of Organic Chemistry, 2001, # 12, p. 2235 - 2243
[50] Patent: US5107038, 1992, A,
[51] Tetrahedron Letters, 2007, vol. 48, # 52, p. 9120 - 9123
[52] Synthetic Communications, 2010, vol. 40, # 8, p. 1187 - 1191
[53] Angewandte Chemie - International Edition, 2013, vol. 52, # 9, p. 2538 - 2542[54] Angew. Chem., 2013, vol. 125, # 9, p. 2598 - 2602,5
[55] Journal of the American Chemical Society, 2013, vol. 135, # 31, p. 11465 - 11468
[56] Applied Catalysis A: General, 2014, vol. 484, p. 51 - 58
[57] Organometallics, 2016, vol. 35, # 20, p. 3538 - 3545
8
[ 75-65-0 ]
[ 108-95-2 ]
[ 98-52-2 ]
[ 13491-79-7 ]
Reference：
[1] Patent: CN107759447, 2018, A, . Location in patent: Paragraph 0041-0051
9
[ 677-22-5 ]
[ 98-53-3 ]
[ 98-52-2 ]
[ 19437-29-7 ]
Reference：
[1] Journal of the American Chemical Society, 1989, vol. 111, # 12, p. 4392 - 4398
[2] Journal of the American Chemical Society, 1989, vol. 111, # 12, p. 4392 - 4398
Reference：
[1] Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), 1992, # 22, p. 2997 - 2998
19
[ 98-53-3 ]
[ 75-05-8 ]
[ 98-52-2 ]
[ 6555-57-3 ]
[ 6555-58-4 ]
[ 71750-16-8 ]
Reference：
[1] Journal of Organic Chemistry, 1992, vol. 57, # 28, p. 7175 - 7187
[2] Journal of Organic Chemistry, 1992, vol. 57, # 28, p. 7175 - 7187
20
[ 98-53-3 ]
[ 10347-88-3 ]
[ 98-52-2 ]
Reference：
[1] Journal of Chemical Research, Miniprint, 1993, # 12, p. 3320 - 3338
[2] Journal of Chemical Research, Miniprint, 1993, # 12, p. 3320 - 3338
21
[ 98-54-4 ]
[ 253185-03-4 ]
[ 3178-22-1 ]
[ 98-52-2 ]
Reference：
[1] Green Chemistry, 2015, vol. 17, # 5, p. 3010 - 3017
22
[ 80356-16-7 ]
[ 98-52-2 ]
Reference：
[1] Synlett, 1999, # 6, p. 777 - 779
[2] Synlett, 1999, # 6, p. 777 - 779
23
[ 98-53-3 ]
[ 98-52-2 ]
Reference：
[1] Chemical Communications, 1997, # 20, p. 1989 - 1990
Reference：
[1] Journal of the Chemical Society, Chemical Communications, 1982, # 8, p. 459 - 460
[2] Journal of the Chemical Society, Chemical Communications, 1982, # 8, p. 459 - 460
[3] Journal of the Chemical Society, Chemical Communications, 1982, # 8, p. 459 - 460
40
[ 98-53-3 ]
[ 67-63-0 ]
[ 98-52-2 ]
Reference：
[1] Chemical Communications, 1997, # 20, p. 1989 - 1990
[2] Chemical Communications, 1997, # 20, p. 1989 - 1990
41
[ 98-52-2 ]
[ 943-29-3 ]
Reference：
[1] Journal of the Chemical Society, Perkin Transactions 2: Physical Organic Chemistry (1972-1999), 1983, p. 661 - 668
With hydrogen; In tetrahydrofuran; at 180℃; under 195020.0 Torr;
Example 1 A 50 wt.-% strength solution of p-tert-butylphenol was prepared in THF. Then 2500 g/h of this solution were passed with hydrogen at a temperature of 180 C. and an overall pressure of 2.6·107 Pa through a flow reactor, which was packed with 3.2 l of the Ru catalyst described above. Following removal of the solvent, by distillation, the hydrogenation product had the following composition: 99.9% of cis,trans-4-tert-butylcyclohexanol <0.01% of p-tert-butylphenol.
99.8%
With hydrogen; In tetrahydrofuran; at 200℃;
Example 2 The hydrogenation was carried out as described in Example 1 except that 3500 g of the 50 wt.-% p-tert-butylphenol solution in THF were passed through the reactor at a temperature of 200 C. Following distillation of the solvent, the hydrogenation product possessed the following composition: 99.8% of cis,trans-4-tert-butylcyclohexanol <0.01% of p-tert-butylphenol
In butan-1-ol;
Example 4 150 ml of a solution of 50% of p-tert-butylphenol in butanol and 15 ml of the above-described catalyst were placed in a 0.3 l stirring autoclave. Hydrogenation was subsequently carried out at 200 C. for 6 hours. The conversion to 4-tert-butylcyclohexanol was quantitative, the selectivity was 99.2% at a cis/trans ratio of 48/52.
With hydrogen; In water; at 120℃; under 15001.5 Torr; for 24h;Autoclave; Green chemistry;
0.5 g of PVP (NiB) amorphous alloy was added to the autoclave, 0.16 g of p-tert-butylphenol, 8 ml of distilled water, and reacted at 120 C for 24 hours under a hydrogen pressure of 2 MPa, and the organic phase was separated by a separatory funnel Phase, the organic phase was dried, analyzed by GC, the conversion of p-tert-butylphenol was 30.1%, and the selectivity to p-tert-butylcyclohexanol was more than 99%.
With 5%-palladium/activated carbon; hydrogen; at 90 - 100℃; under 15001.5 Torr;Inert atmosphere;
c) The resulting p-tert-butylphenol reaction solution was transferred to a separatory funnel and allowed to stand for 0.5 hours.Put the oil layer into the beaker.In the water layer, 55 g of petroleum ether was added, stirred for 0.5 hours, and allowed to stand for stratification. The oil layers were put into a beaker and the water layer was concentrated in the waste liquid collection tank.In the beaker of the oil layer, 90 g of a 5% sodium hydroxide solution was metered in, the stirrer was turned on, and the collected oil layer was alkali-washed. After stirring for 0.5 hour, the mixture was allowed to stand for 0.5 hours and the lye layer was concentrated in the waste liquid collection tank.The oil layer was further washed with 300 g of clear water, and after stirring for 0.5 hours, it was allowed to stand for 0.5 hours and washed twice with water.The oil layer was transferred to the hydrogenation reactor and the water layer was concentrated in the waste collection tank.d) Into the hydrogenation reaction vessel, 5 g of a palladium carbon catalyst having a palladium content of 5% by mass is charged, and the hydrogenation reaction vessel is hermetically sealed and replaced with nitrogen gas for 4 to 6 times, and then filled with nitrogen to a pressure of 2.0 MPa.After the system pressure is stabilized, replace it with hydrogen for 4 to 6 times, then charge hydrogen, and adjust the hydrogenation reactor pressure to 2.0 MPa.After the system pressure is stabilized, close the hydrogen inlet valve and raise the temperature to 90 to 100C. After the pressure in the reaction system is balanced, the hydrogen valve is opened to maintain the reaction pressure of 2.0 Mpa and the reaction time is 5 to 10 hours.e) After 5 hours of reaction, samples were taken at intervals of 2 hours for chromatographic detection. When p-tert-butylphenol content was ? 0.5%, the reaction was terminated and the pressure was relieved.The resulting p-tert-butylcyclohexanol reaction solution was filtered, the liquid phase filtrate was transferred to a rotary evaporator, and the solid phase catalyst was cleaned with petroleum ether and transferred to a hydrogenation reaction vessel for the next batch hydrogenation reaction.
With 5%-palladium/activated carbon; hydrogen; at 120℃; under 15001.5 Torr;Large scale;
h) a 5 kg 5% palladium-carbon catalyst is dosed into a 1000 L hydrogenation reactor at a time, and the hydrogenation reactor is sealed, replaced with nitrogen for 4 to 6 times, and then filled with nitrogen to a pressure of 2.0 MPa, after the system pressure is stabilized, The hydrogenation was carried out 4 to 6 times, and then hydrogen gas was charged to adjust the pressure of the hydrogenation reactor to 2.0 MPa.i) After the system pressure is stable, close the hydrogen inlet valve and raise the temperature to 120 C. After the pressure of the reaction system is balanced, open the hydrogen valve, keep the reaction pressure 2.0Mpa, and the reaction time is 5-15 hours.j) After 5 hours of reaction, a sample was taken for sampling every 2 hours, and when the content of p-tert-butylphenol was ?0.5%, the reaction was terminated and the pressure was released.k) The produced p-tert-butylcyclohexanol reaction solution was sent to a precision filter by nitrogen pressure for filtration. The liquid phase filtrate of the filter is sent to the distillation still of the still distillation column by nitrogen gas. The solid phase catalyst of the filter is driven into the precision filter by the diaphragm pump with petroleum ether, and backwashed into the hydrogenation reactor for the next batch of hydrogenation. reaction.l) Turn on the steam valve to heat the distillation still. Under normal pressure, the kettle temperature is 60-90 C, and the petroleum ether is recovered.The recovery of petroleum ether ends when the top temperature drops or when there is no discharge. The recovered petroleum ether is pumped into the petroleum ether high tank using the material pump.The solution was applied, and the still pot liquid was sent to a 1000 L esterification reactor under nitrogen pressure.
With oxygen; trifluoroacetic acid; sodium nitrite; at 0 - 20℃; for 5.25h;Product distribution / selectivity;
An operation was conducted in the same manner as in Example 2 except that cyclohexanol was replaced by an alicyclic secondary alcohol compound or an alicyclic ketone compound, both shown in Table 2 as a raw material compound. The results are shown in Table 2.
With trifluoroacetic acid; sodium nitrite; at 0 - 20℃;
Sodium nitrite (17.0 g, 250 mmol) was added at 0 C in small portions over 90 minutes to a solution of 4-te/f-butylcyclohexanol (10.0 g, 64 mmol) in TFA (100 mL). The suspension was stirred at room temperature overnight and then concentrated. The residue was poured onto ice, treated with aqueous NaHC03 (500 mL) and then made basic by addition of solid NaOH. The aqueous solution was washed with DCM (3 x 200 mL), acidified to pH <1 with concentrated HCI and extracted with EtOAc (3 x 300 mL). The combined organic phases were dried (MgS04), filtered and concentrated, which gave the title compound (13.05 g, ~100%) which was used in the next step without further purification. 1H NMR (500 MHz, CDCI3) delta 9.63 (br.s, 2H), 2.56 (dd, J = 16.3 and 3.9 Hz, 1 H), 2.50-2.39 (m, 2H), 2.12 (dd, J = 16.3 and 8.0 Hz, 1 H), 1.98 (m, 1 H), 1.74 (m, 1 H), 1.44 (m, 1 H), 0.93 (s, 9H).
With pyridine; trichloroisocyanuric acid; In ethyl acetate; at 20℃; for 0.333333h;
General procedure: O.1 mole of 4-t-butylcyclohexanol (ACROS) was weighed and placed in a 50 mL Erlenmeyer flask with stir bar and 10 mL ethyl acetate (Fisher). 1.0 g trichloroisocyanuric acid (Leslie?s Swimming Pool Supplies) was weighed into a 30 mL beaker and dissolved in 10 mL ethyl acetate. 1.0 mL (0.12 mol) pyridine (Aldrich) was delivered to the alcohol mixture by pipet. The TCICA solution was transferred to a dropping funnel and added dropwise to the stirring alcohol solution. Following addition, stirring was continued for 20 minutes and the mixture was filtered. The filtrate was washed with 10 mL 1 M HCl, 10 mL 5% NaHCO3, and 5 mL saturated NaCl. The organic layer was dried over MgSO4, a GC sample removed, filtered and evaporated to dryness. Yield 1.50 g (100%), nmr attached.
96%
With oxygen; ascorbic acid; In toluene; at 60℃; for 45h;
EXAMPLE-7; Method for oxidation of 4-tertiary butyl cyclohexanol. Oxygen gas (25 ml min-1) was continuously bubbled through a solution of 4-tertiary butyl cyclohexanol (5 mmol), polystyrene supported [meso-(2,6-dichlorophenyl) porphinato] Iron (II) (corresponding to 0.056 mol % of metalloporphyrin) in toluene (25 ml). Ascorbic acid (15 mmol) was added to reaction mixture at intervals of 2 hours till maximum conversion of reactant to product was achieved). The reaction mixture was vigorously stirred at 60 C. and the progress of the reaction was monitored by TLC. After stirring the reaction mixture for 45 hrs, it was concentrated to half. Addition of equal volume of methanol precipitated the catalyst that was filtered and the filtrate was evaporated to dryness to give the product. The product was purified by column chromatography and characterized by physical constants and spectroscopic data (IR, 1H-NMR and mass spectra). Yield: 0.74 g (96%).
92%
General procedure: Firstly, GO (0.01 g) was added into water (3 mL) and the mixturecould generate the stable colloidal suspensions under a mild ultrasonictreatment. Afterwards, the alcohol (2 mmol) and (NH4)5H5[H2(WO4)6](0.03 mmol, M=1602) were added. The mixture was stirred for 15 min atroom temperature. Subsequently, hydrogen peroxide (30 wt%, 8 mmol)was added dropwise and the mixture was heated to 70C until thereaction was fully completed (monitored by TLC). After the reactioncompleted, GO could be readily separated from the mixtures bycentrifugation, and then ethyl acetate was added to the mixture to extract organic constituents. Finally, the organic extracts were concentratedunder reduced pressure and purified by column chromatography.
91.3%
Example 6 In a reactor equipped with a stirrer, a cooling condenser, a dropping funnel and a thermometer, <strong>[98-52-2]4-tert-butylcyclohexanol</strong> (15.6 g, 0.10 mol), dimethyl sulfoxide (117.2 g, 1.50 mol) and toluene (40 g) were added, and the resulting reaction solution was stirred at a temperature of 20 to 23 C. To this reaction solution, pyridine (7.9 g, 0.10 mol) was added dropwise, followed by dichloroacetic acid (6.4 g, 0.05 mol). The resulting mixture was maintained at a temperature of 25 C. or lower and was stirred for 10 minutes. After stirring, Carbodilite V-03 (manufactured by Nisshinbo Chemical Inc., 431.1 g/mol) (86.2 g, 0.20 mol) was added dropwise to the reaction liquid, while the reaction liquid was maintained at 25 C. or below. After the dropwise addition, the reaction liquid was stirred for 5 hours at 23 to 25 C., and the reaction was terminated with a 1.0% aqueous solution of acetic acid (16 g). After the reaction was terminated, a urea compound precipitated from the reaction liquid was separated by filtration. The filtrate was partitioned to remove the aqueous phase, and then the organic phase was washed with an aqueous sodium chloride solution.The resulting organic layer was treated such that the solvent was removed under reduced pressure, and the residue was distilled under reduced pressure. Thus, 4-tert-butylcyclohexanone (bp: 88 to 90 C./1.06 kPa, 14.1 g, 0.09 mol) was obtained (yield 91.3%). The ketone compound thus obtained was confirmed by using NMR, mass spectrometry and IR spectroscopy.
87%
With 2-azatricyclo[3.3.1.13,7]dec-2-yloxidanyl; sodium hypochlorite pentahydrate; sodium hydrogencarbonate; potassium bromide; In water; for 0.5h;Milling;
General procedure: NaOCl·5H2O (247 mg 1.5 mmol), NaHCO3 (185 mg, 2.2 mmol), and KBr (3.6mg, 0.03 mmol, 3 mol %) were placed in an Ertalyte jar (15 mL, 41.2 g) equippedwith six zirconia balls (5 mm ). The jar was ball-milled at 1800 rpm for 1 min.Following this initial grinding period, secondary alcohol 11a-19a (1.0 mmol),and 2-aza-adamantane-N-oxyl (AZADO, 1.6 mg, 0.01 mmol, 1 mol %), wereadded and the reaction mixture was milled at 30 Hz for further 30 minutes. Theprogress of the reaction was monitored by TLC (heptane/AcOEt 9:1, v/v) andGC-MS analysis of an aliquot of the crude. The milling was stopped, Na2SO3(189 mg, 1.5 mmol) added to the jar. Then, milling was continued at 30 Hz forfurther 3 minutes. AcOEt (2 × 1.5 mL) was added into the jar and the crude wastransferred to a round-bottomed flask together with silica gel (350 mg). Thecombined organic layers were concentrated in vacuo. The resulting residue waspurified through a short column on silica gel with ethyl acetate/hexane 1:9 (v/v)as the eluent to yield the target ketones 11b-19b
With rice husk ash/TiO2 nanocomposite; In neat (no solvent); at 20℃; for 0.00833333h;Green chemistry;
General procedure: 1 mmol of the substrate (alcohol, phenol or amine) wasadded to a mixture of RHA/TiO2(30%) (20 mg) and aceticanhydride (1.5 mmol per OH/NH2 group) and the resulting mixture was stirred at room temperature. After completionof the reaction (mentioned by TLC), dichloromethane(20 mL) was added and the catalyst was separated byfiltration. The organic phase was washed with 10% aqueoussolution of sodium bicarbonate (2 20 mL) and dried overNa2SO4. The solvent was removed under reduced pressureto afford the desired product in good to high yields. Thespectral (IR, 1H and 13C NMR) data of new compounds arepresented below:
With toluene-4-sulfonic acid; at 130 - 140℃;Large scale;
m) 200 kg of acetic anhydride was metered into the esterification reactor through the high-pressure tank of acetic anhydride, and 8 kg of p-toluenesulfonic acid was introduced into the reaction vessel through a hand hole, the stirrer was turned on, and the steam valve was opened to heat the esterification reactor. The reaction temperature is 130 to 140 C, the reaction time is 8 to 10 hours, and the reaction liquid is transferred to a distillation still of a still distillation column.n) Turn on the steam valve to raise the temperature of the distillation still. Under normal pressure, the acetic acid is recovered at a pot temperature of 100-120 C, and the acetic acid is recovered when the temperature at the top of the column is lowered or there is no discharge. The recovered acetic acid is pumped into the high-level tank of acetic acid by means of a material pump, and the distillation pot liquid is sent to the water washing tank by nitrogen pressure, and the water washing pot is heated and kept at 100 to 110 C.o) From the high-position tank of sodium hydroxide solution, add 80kg of 5% sodium hydroxide solution into the washing tank, turn on the stirrer, stir for 2 hours, let stand for 3 hours, the alkali layer, and drive through the material pump. The lye high tank is used for the next batch. The oil layer was further added with 300 kg of water for washing, and after stirring for 2 hours, the layer was allowed to stand for 3 hours, and the oil layer was transferred to a rectification tank of a kettle-type rectification column, and the water layer was discharged into a sewage treatment station for treatment.p) Turn on the steam valve to raise the temperature of the distillation pot. Turn on the vacuum pump at a pot temperature of 100-150 C, and carry out the fractionation conditions at the top temperature of 105-110 C, the pressure of 1000-1333 Pa, and the reflux ratio of 1:1 to 1:12. The tail acid ester product is collected, and when the temperature at the top of the tower is lowered or there is no discharge, the rectification is finished, the temperature is lowered, and the autoclave remains.The product is a colorless transparent liquid with sweet, fruity and rich woody and floral aroma. The purity of the product is 98.80% by gas chromatography, wherein the cis isomer accounts for 30.6%, and the refractive index is detected. 20 C) is 1.4522 and the relative density (25 C) is 0.9389. The total yield was 72.6%.
4-tert-butylcyclohexyl 2-cyano-3,3-diphenylacrylate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With sodium carbonate; In methanol;
EXAMPLE 3 4-tert-butylcyclohexyl 2-cyano-3,3-diphenylacrylate 139 g (0.5 mol) of <strong>[5232-99-5]ethyl 2-cyano-3,3-diphenylacrylate</strong> (Uvinul 3035), 200 ml of 4-tert-butylcyclohexanol and 10 g of Na2CO3 were reacted together at 182 C. with distillative removal of the ethanol formed, assisted by a stream of nitrogen. After about 4 h, the reaction mixture was diluted with 300 ml of methanol and filtered hot in order to remove the Na2CO3. After the filtrate had been cooled, the precipitate which had formed was filtered off, washed with petroleum ether and dried, giving 130 g (67%) of 4-tert-butyl-cyclohexyl 2-cyano-3,3-diphenylacrylate as a colorless solid. [lambdamax 302 nm; E11 (MeOH) 324]
3,5-Dichloro-4-(-cis-tert-butylcyclohexyloxy)pyridine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
2.23 g (74%)
With NaH; ammonium chloride; In dimethyl sulfoxide;
Example 16 3,5-Dichloro-4-(-cis-tert-butylcyclohexyloxy)pyridine A mixture of 1.82 g (10 mmol) of <strong>[33216-52-3]3,4,5-trichloropyridine</strong>, 2.03 g (13 mmol) of 4-cis-tert-butyl-cyclohexanol and 15 ml of DMSO is added dropwise at 25 C. to 0.36 g (12 mmol) of NaH (80% strength) in 25 ml of DMSO. The mixture is then stirred at 70 C. for 20 hours. For working up, saturated ammonium chloride solution is added at 20-25 C. and the mixture is extracted with ethyl acetate. The reaction product is purified by chromatography (SiO2; hexane/diisopropyl ether [1:3]). Yield: 2.23 g (74%); 1 H-NMR (CDCl3)=8.4 (s, 2H), 4.3 (m, 1H), 0.9-2.3 (m, 9H), 0.8 (s, 9H) ppm
2-Methyl-3-methoxy-4-(4-cis-tert-butylcyclohexyloxy)pyridine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
1.26 g (45.6%)
With NaH; ammonium chloride; In dimethyl sulfoxide;
Example 15 2-Methyl-3-methoxy-4-(4-cis-tert-butylcyclohexyloxy)pyridine A mixture of 1.57 g (10 mmol) of <strong>[107512-34-5]2-methyl-3-methoxy-4-chloropyridine</strong>, 2.03 g (13 mmol) of 4-cis-tert-butylcyclohexanol and 15 ml of DMSO is added dropwise at 25 C. to 0.36 g (12 mmol) of NaH (80% strength) in 25 ml of DMSO. The mixture is then stirred at 60 C. for 7 hours. For working up, saturated ammonium chloride solution is added at 20-25 C. and the mixture is extracted with ethyl acetate. The reaction product is purified by chromatography (SiO2; EtOAc). Yield: 1.26 g (45.6%); 1 H-NMR (CDCl3)=8.1 (d, 1H), 6.7 (d, 1H), 4.6 (m, 1H), 3.9 (s, 3H), 2.5 (s, 3H), 0.9-2.3 (m, 9H), 0.9 (s, 9H) ppm
4-tert-butylcyclohexene 4-tert-butylcyclohexanol (20 g, 128 mmol, purchased from Aldrich) and triphenylphosphate (45.9 g, 141 mmol, purchased from Aldrich) were combined in 1methylpyrrolidinone (120 mL) and heated at 190 C. for 72 hours and then at 200 C. for another 52 hours. The mixture was cooled to room temperature, diluted with H2O (250 mL) and extracted with CH2Cl2 (100 mL). The organic extract was washed with 1N aqueous HCl (100 mL), H2O (2*200 mL) and concentrated to give a dark brown oil (50.3 g). The crude product was distilled under reduced pressure to afford the title compound as a colorless oil (13.0 g, 74% yield).
74%
In 1-methyl-pyrrolidin-2-one;
EXAMPLE 51A 4-tert-butylcyclohexene 4-tert-butylcyclohexanol (20 g, 128 mmol, purchased from Aldrich) and triphenylphosphate (45.9 g, 141 mmol, purchased from Aldrich) were combined in 1-methylpyrrolidinone (120 mL) and heated at 190 C. for 72 hours and then at 200 C. for another 52 hours. The mixture was cooled to room temperature, diluted with H2O (250 mL) and extracted with CH2Cl2 (100 mL). The organic extract was washed with 1N aqueous HCl (100 mL), H2O (2*200 mL) and concentrated to give a dark brown oil (50.3 g). The crude product was distilled under reduced pressure to afford the title compound as a colorless oil (13.0 g, 74% yield).
6-(trans-4-tert-butyl-cyclohexyloxy)-quinoline[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
42%
With di-isopropyl azodicarboxylate; triphenylphosphine In tetrahydrofuran at 20℃; Inert atmosphere; Cooling with cold water;
14
Quinolin-6-ol (7.52 g, 0.0518 mol, Aldrich), 4-tert-butyl-cyclohexanol (9.71 g, 0.0621 mol) and triphenylphosphine (16.32 g, 0.06222 mol, Aldrich) were placed in a flask, and dissolved in tetrahydrofuran (150 mL, Acros). The reaction was cooled in a cold water bath. Diisopropyl azodicarboxylate (13.0 mL, 0.0620 mol, Acros) in tetrahydrofuran (50 mL, Acros) was then added dropwise. The reaction mixture was then allowed to stir at room temperature. After 26 h,the solvent was removed, and the residue was taken up in DCM. Silica gel was added and the solvent was removed. The residue was then purified via silica gel chromatography using 0-40% ethyl acetate in hexanes as eluent to give the product (Rf=0.22 in 3:1 hexanes/ethyl acetate), 6.1 1 g yield (42%).
2-(4-(tert-butyl)cyclohexyl)-1-(pyridin-3-yl)ethanone[ No CAS ]
C17H25NO[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
80 % de
With [carbonylchlorohydrido{bis[2-(diphenylphosphinomethyl)ethyl]amino}ethylamino] ruthenium(II); potassium <i>tert</i>-butylate In toluene at 125℃; for 4h; Overall yield = 90 percent;
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