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Structure of 2969-81-5 * Storage: {[proInfo.prStorage]}
Reference：
[1] Journal of Medicinal Chemistry, 2017, vol. 60, # 2, p. 608 - 626
[2] U.S.Atomic Energy Comm.WADC-TR-56-540 <1957>25,
[3] Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, 1886, vol. 102, p. 369[4] Bulletin de la Societe Chimique de France, 1886, vol. <2>46, p. 65
[5] Journal of the Chemical Society, 1937, p. 1977
[6] Journal of the American Chemical Society, 1933, vol. 55, p. 1233 - 1241
[7] ACS Chemical Neuroscience, 2017, vol. 8, # 9, p. 1949 - 1959
5
[ 64-17-5 ]
[ 927-58-2 ]
[ 2969-81-5 ]
Reference：
[1] Journal of the Chemical Society, 1950, p. 1474,1476
[2] Patent: EP1953148, 2008, A1, . Location in patent: Page/Page column 122
6
[ 2623-87-2 ]
[ 2969-81-5 ]
Yield
Reaction Conditions
Operation in experiment
85.5%
With hydrogenchloride In 1,4-dioxane; ethanol; dichloromethane
Part A Preparation of ethyl 4-bromobutyrate To a solution of 4-bromobutyric acid (3 g, 18 mmol) in ethanol (30 mL) was added 5 mL of 4N HCl in dioxane. The reaction mixture was stirred for 16 hours at room temperature, and then the volatile components were removed under vacuum. The concentrated residue was brought up in 150 mL of methylene chloride. The organic solution was washed with saturated aqueous NaHCO3 (1 x 150 mL), brine (1*150 mL), dried over MgSO4, filtered, and the filtrate was concentrated at reduced pressure. The concentrated residue was dried in vacuo to give 3 g (85.5percent) of the known product as a yellow oil. 1 H NMR (300 MHz/CDCl3): δ 1.22 (t, 3H, J=7.15 Hz), 2.13 (overlapping t, 2H, J=6.80 Hz), 2.45 (t, 2H, J=7.15 Hz), 3.43 (t, 2H, J=6.44 Hz), 4.10 (q, 2H, J=7.25 Hz).
Reference：
[1] Patent: US5753660, 1998, A,
7
[ 96-48-0 ]
[ 64-17-5 ]
[ 2969-81-5 ]
Reference：
[1] Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), 1981, p. 336 - 343
[2] Journal of the American Chemical Society, 1952, vol. 74, p. 4960
[3] Journal of the Chemical Society, 1958, p. 3377,3382
[4] Journal of the Chemical Society, 1957, p. 2312
[5] Journal of the Chemical Society, 1953, p. 3502
[6] Org.Synth.Coll.Vol. V <1973>545,
[7] U.S.Atomic Energy Comm.WADC-TR-56-540 <1957>25,
[8] Journal of Organic Chemistry, 1951, vol. 16, p. 1417,1418
[9] Tetrahedron, 1960, vol. 11, p. 154 - 157
[10] Journal of pharmaceutical sciences, 1972, vol. 61, # 12, p. 1936 - 1940
[11] The Journal of organic chemistry, 1972, vol. 37, # 26, p. 4396 - 4399
8
[ 1191-95-3 ]
[ 1801-77-0 ]
[ 2969-81-5 ]
Reference：
[1] Journal of Organic Chemistry, 1991, vol. 56, # 6, p. 2264 - 2266
9
[ 64-17-5 ]
[ 5332-06-9 ]
[ 2969-81-5 ]
Reference：
[1] Journal of the American Chemical Society, 1956, vol. 78, p. 4030
[2] U.S.Atomic Energy Comm.WADC-TR-56-540 <1957>25,
10
[ 58258-01-8 ]
[ 2969-81-5 ]
[ 125602-76-8 ]
Reference：
[1] Patent: US4929618, 1990, A,
11
[ 125603-02-3 ]
[ 2969-81-5 ]
Reference：
[1] Patent: US4929618, 1990, A,
12
[ 88535-96-0 ]
[ 2969-81-5 ]
Reference：
[1] Patent: US4929618, 1990, A,
13
[ 125603-01-2 ]
[ 125602-78-0 ]
[ 2969-81-5 ]
Reference：
[1] Patent: US4929618, 1990, A,
14
[ 125603-04-5 ]
[ 2969-81-5 ]
Reference：
[1] Patent: US4929618, 1990, A,
15
[ 999-10-0 ]
[ 2969-81-5 ]
Reference：
[1] Journal of Medicinal Chemistry, 2014, vol. 57, # 9, p. 3874 - 3883
16
[ 1617-18-1 ]
[ 2969-81-5 ]
Reference：
17
[ 64-17-5 ]
[ 56489-06-6 ]
[ 2969-81-5 ]
Reference：
[1] Collection of Czechoslovak Chemical Communications, 1956, vol. 21, p. 1602,1605
18
[ 36847-51-5 ]
[ 2969-81-5 ]
[ 4606-07-9 ]
[ 105-54-4 ]
Reference：
[1] Journal of Chemical Research, Miniprint, 1983, # 11, p. 2401 - 2416
19
[ 1617-18-1 ]
[ 10035-10-6 ]
[ 2969-81-5 ]
Reference：
20
[ 2969-81-5 ]
[ 7425-53-8 ]
Yield
Reaction Conditions
Operation in experiment
87%
With potassium iodide In acetone for 12 h; Reflux
In a 100 ml round bottom flask, ethyl4-bromobutyrate (6.0 ml, 40.2 mmol: 1H NMR (300 MHz, CDCl3) δ 4.14(q, J = 7.2 Hz, 2H), 3.47 (t, J = 6.5 Hz, 2H), 2.49 (t, J = 7.2 Hz, 2H), 2.17(m, 2H), 1.26 (t, J = 7.1 Hz, 3H).) was dissolved in 40 ml acetone. Potassium iodide (13.35 g, 80.4 mmol,2.0 equiv.) was added, a reflux condenser was attached, and the reaction was heated at reflux for 12h. Thesolution was cooled, filtered through a course fritted funnel, and concentrated in vacuo. The resultingyellow oil with fine particulates was taken up in ca 50 ml of 1:1 Hex:Et2O and filtered through neutralaluminum to remove color. After flushing with an additional 100 ml 1:1 Hex:Et2O, the solution wasconcentrated to yield 8.44 g (87percent) of ethyl 4-iodobutyrate 12. 1H NMR (300 MHz, CDCl3) δ 4.14 (q, J =7.2 Hz, 2H), 3.24 (t, J = 6.8 Hz, 2H), 2.44 (t, J = 7.1 Hz, 2H), 2.13 (m, 2H), 1.26 (t, J = 7.2 Hz, 3H). A 50ml Schlenk flask was flame dried under vacuum, cooled to 23 °C, and charged with ethyl 4-iodobutyrate(8.4 g, 34.7 mmol) and copper(I) iodide (10 mg, 0.05 mmol). After sealing with a greased ground glassstopper, the flask was evacuated and refilled with Ar. The stopper was replaced with a rubber septum andneat diethyl zinc (14 ml, 137 mmol, 4 equiv) was added via syringe. The reaction was heated at 40 °C for12 h. The excess diethyl zinc and ethyl iodide were removed under vacuum for 2 h into a trap withmethanol cooled to -78 °C with dry ice and acetone. (CAUTION: A trap cooled with liquid nitrogeneasily clogs so dry ice/acetone cooling is preferred. Methanol quenches the excess diethyl zinc, but careshould be taken when cleaning the trap as some diethyl zinc may remain.) After backfilling with Ar, THF(5 ml) was added to the reaction vessel and heated at 40 °C for 1 h under Ar. The reaction vessel wasevacuated for 1 h. This step was repeated another two times. After cooling to 23 °C, the generated bis(4-ethoxy-4-oxobutyl)zinc was diluted with 15 ml of THF and this solution was used directly in thedesymmetrization reaction.
Reference：
[1] Synthetic Communications, 2009, vol. 39, # 1, p. 61 - 69
[2] Journal of Organic Chemistry, 2004, vol. 69, # 9, p. 3025 - 3035
[3] Advanced Synthesis and Catalysis, 2007, vol. 349, # 8-9, p. 1533 - 1536
[4] Journal of Organic Chemistry, 2007, vol. 72, # 18, p. 6816 - 6823
[5] Synthesis (Germany), 2018, vol. 50, # 22, p. 4343 - 4350
[6] Tetrahedron, 1996, vol. 52, # 45, p. 14081 - 14102
[7] Journal of the American Chemical Society, 2016, vol. 138, # 24, p. 7528 - 7531
[8] Tetrahedron, 1960, vol. 11, p. 154 - 157
[9] Journal of Organic Chemistry, 1989, vol. 54, # 4, p. 890 - 896
[10] Tetrahedron Letters, 1987, vol. 28, # 37, p. 4243 - 4246
[11] Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), 1985, p. 2677 - 2688
[12] Tetrahedron, 1999, vol. 55, # 18, p. 5741 - 5758
[13] Journal of the American Chemical Society, 2000, vol. 122, # 40, p. 9600 - 9609
[14] Synthetic Communications, 2009, vol. 39, # 9, p. 1690 - 1690
[15] Patent: EP1612201, 2006, A1, . Location in patent: Page/Page column 26-28
[16] Advanced Synthesis and Catalysis, 2012, vol. 354, # 13, p. 2521 - 2530,10
[17] Advanced Synthesis and Catalysis, 2012, vol. 354, # 13, p. 2521 - 2530
21
[ 2969-81-5 ]
[ 14402-93-8 ]
[ 123-29-5 ]
Reference：
[1] Journal of Organic Chemistry, 2002, vol. 67, # 1, p. 79 - 85
Reference：
[1] Advanced Synthesis and Catalysis, 2008, vol. 350, # 10, p. 1484 - 1488
24
[ 2969-81-5 ]
[ 541-41-3 ]
[ 818-38-2 ]
Reference：
[1] Journal of Organic Chemistry, 1990, vol. 55, # 3, p. 788 - 790
25
[ 2969-81-5 ]
[ 26496-94-6 ]
Reference：
[1] Patent: US4804658, 1989, A,
26
[ 2969-81-5 ]
[ 106-48-9 ]
[ 59227-79-1 ]
Yield
Reaction Conditions
Operation in experiment
92%
With potassium carbonate In acetonitrile for 8 h; Reflux
To a solution of 4-chlorophenol (2.0 g, 15.556 mmol, 1 equiv) in acetonitrile (60 mL) was added anhydrous potassium carbonate (4.3 g, 31 .1 13 mmol, 2 equiv) and ethyl 4-bromobutanoate (3.56 mL, 24.891 mmol, 1 .6 equiv). The reaction mixture was heated to reflux and stirred for 8 h. The progress of the reaction was monitored by TLC. After completion of reaction, the reaction mixture was allowed to cool to 27 °C, filtered the solid and washed with ethyl acetate (100 mL). The filtrate was concentrated under reduced pressure to give the crude product. The crude product was purified by silica gel column chromatography using 10percent ethyl acetate in hexane as eluent to obtain the title compound ethyl 4-(4-chlorophenoxy)butanoate (3.5 g, 92 percent yield) as colourless liquid. LCMS (ES) m/z = 242.9 [M+H]+. NMR (400 MHz, CDCI3): δ ppm 1 .25 (t, J = 6.8 Hz, 3 H), 2.06 - 2.06 (m, 2 H), 2.49 (t, J = 6.8 Hz, 2 H), 3.97 (t, J = 6.0 Hz, 2 H), 4.1 1 - 4.17 (m, 2 H), 6.80 (d, J = 8.4 Hz, 2 H), 7.21 (d, J = 8.8 Hz, 2 H).
89%
With potassium carbonate In N,N-dimethyl-formamide at 140℃; for 4 h;
To a solution of 4-chlorophenol (10 g, 77.784 mmol, 1 equiv) in N,N- dimethylformamide (100 mL) was added anhydrous potassium carbonate (21 .5 g, 1 16.6 mmol, 2 equiv) and ethyl 4-bromobutanoate (16.7 mL, 1 16.677 mmol, 1 .5 equiv). The reaction mixture was heated to 140 °C and stirred for 4 h. The progress of the reaction was monitored by TLC. After completion of reaction, the reaction mixture was allowed to cool to 27 °C, filtered the solid and washed with ethyl acetate (700 mL). The filtrate was washed with water (2 x 200 mL), brine solution (100 mL), dried over anhydrous sodium sulphate, filtered and concentrated under reduced pressure to give the crude product. The crude product was purified by silica gel column chromatography using 10 percent ethyl acetate in hexane as eluent to obtain ethyl 4-(4-chlorophenoxy)butanoate (17.0 g, 89 percent yield) as white solid. LCMS (ES) m/z = 243.1 [M+H]+. NMR (400 MHz, CDCI3): δ ppm 1 .25 (t, J = 7.2 Hz, 3 H), 2.06 - 2.12 (m, 2 H), 2.49 (t, J = 7.6 Hz, 2 H), 3.97 (t, J = 6.0 Hz, 2 H), 4.1 1 - 4.17 (m, 2 H), 6.80 (d, J = 8.8 Hz, 2 H), 7.21 (d, J = 8.8 Hz, 2 H).
83%
With potassium carbonate In acetoneReflux
General procedure: General synthetic procedure for phenoxy acetic/butyric acid ethyl ester derivatives (3a-l) A mixture of substituted phenols 1a-f (0.05 mol) and 2a-b (0.075 mol) in dry acetone (40 ml) with anhydrous potassium carbonate (0.075 mol) were refluxed for 8-10 h. The reaction mixture was cooled and solvent removed by distillation. The residual mass was triturated with cold water to remove potassium carbonate, and extracted with ether (3 * 30 ml). The ether layer was washed with 10percent sodium hydroxide solution (3 * 30 ml) followed by water (3 * 30 ml) and then dried over anhydrous sodium sulfate and evaporated to afford compounds 3a-l. 4-(4-Chloro-phenoxy)-butyric acid ethyl ester (3b) Yield 83percent; FT-IR (cm-1): 1738 (C=O), 1281 (C-O-C); 1H NMR (CDCl3): δ 1.35 (t, 3H, CH3 of ester), 2.26 (m, 2H, CH2), 2.75 (t, 2H, COCH2), 4.07 (t, 2H, OCH2), 4.31 (q, 2H, CH2 of ester), 6.88 (d, J = 8.80 Hz, 2H, Ar-H), 7.27 (d, J = 8.85 Hz, 2H, Ar-H); LC-MS m/z 243 (M + 1). Anal. Calcd. for C12H15ClO3: C, 59.39; H, 6.23. Found: C, 59.50; H, 6.16percent.
Reference：
[1] Patent: WO2017/212425, 2017, A1, . Location in patent: Page/Page column 112
[2] Patent: WO2017/212423, 2017, A1, . Location in patent: Page/Page column 126
[3] Bioorganic Chemistry, 2015, vol. 60, p. 136 - 146
[4] Journal of Agricultural and Food Chemistry, 2016, vol. 64, # 37, p. 6911 - 6915
[5] Indian Journal of Heterocyclic Chemistry, 2018, vol. 28, # 3, p. 379 - 384
27
[ 117704-88-8 ]
[ 2969-81-5 ]
[ 19999-64-5 ]
Reference：
[1] Patent: US5102890, 1992, A,
28
[ 2969-81-5 ]
[ 52763-21-0 ]
Reference：
[1] Organic Process Research and Development, 2003, vol. 7, # 3, p. 418 - 425
29
[ 106-41-2 ]
[ 2969-81-5 ]
[ 55580-08-0 ]
Reference：
[1] Patent: US6166006, 2000, A,
30
[ 106-41-2 ]
[ 2969-81-5 ]
[ 157245-87-9 ]
Yield
Reaction Conditions
Operation in experiment
81%
With potassium carbonate In acetoneReflux
General procedure: General synthetic procedure for phenoxy acetic/butyric acid ethyl ester derivatives (3a-l) A mixture of substituted phenols 1a-f (0.05 mol) and 2a-b (0.075 mol) in dry acetone (40 ml) with anhydrous potassium carbonate (0.075 mol) were refluxed for 8-10 h. The reaction mixture was cooled and solvent removed by distillation. The residual mass was triturated with cold water to remove potassium carbonate, and extracted with ether (3 * 30 ml). The ether layer was washed with 10percent sodium hydroxide solution (3 * 30 ml) followed by water (3 * 30 ml) and then dried over anhydrous sodium sulfate and evaporated to afford compounds 3a-l. 4-(4-Bromo-phenoxy)-butyric acid ethyl ester (3d) Yield 81percent; FT-IR (cm-1): 1733 (C=O), 1287 (C-O-C); 1H NMR (CDCl3): δ 1.34 (t, 3H, CH3 of ester), 2.26 (m, 2H, CH2), 2.72 (t, 2H, COCH2), 4.05 (t, 2H, OCH2), 4.31 (q, 2H, CH2 of ester), 6.83 (d, J = 8.80 Hz, 2H, Ar-H), 7.35 (d, J = 8.85 Hz, 2H, Ar-H); LC-MS m/z 288 (M + 1). Anal. Calcd. for C12H15BrO3: C, 50.19; H, 5.27. Found: C, 50.29; H, 5.18percent.
Reference：
[1] Bioorganic Chemistry, 2015, vol. 60, p. 136 - 146
[2] Journal of Medicinal Chemistry, 2000, vol. 43, # 10, p. 2049 - 2063
[3] Patent: WO2016/25932, 2016, A1, . Location in patent: Page/Page column 150
[4] Chemistry - A European Journal, 2016, vol. 22, # 29, p. 9971 - 9974
[5] Indian Journal of Heterocyclic Chemistry, 2018, vol. 28, # 3, p. 379 - 384
31
[ 2969-81-5 ]
[ 95-01-2 ]
[ 152942-06-8 ]
Reference：
[1] Journal of the American Chemical Society, 2018, vol. 140, # 44, p. 15114 - 15123
[2] Organic letters, 2000, vol. 2, # 13, p. 1787 - 1790
[3] Patent: US5994378, 1999, A,
With potassium carbonate; In N,N-dimethyl-formamide;
2a 4-(4-Chloro-2-methyl-pyrrolo[2,3-d]pyrimidin-7-yl)-butyric Acid Ethyl Ester 0.5 g (3 mmol) of <strong>[71149-52-5]4-chloro-2-methyl-7H-pyrrolo[2,3-d]pyrimidine</strong> (prepared according to West and Beauchamp, J. Org. Chem. 26 (1961) 3809) was dissolved in 3 ml DMF and 2.06 g (15 mmol) of potassium carbonate was added to this solution. 0.431 ml (3 mmol) of 4-bromobutyric acid ethyl ester was added and the mixture was stirred at 50 C. for 45 minutes. The reaction mixture was diluted with 50 ml EE and washed three times with water, dried over MgSO4, filtered and the solvent was removed in vacuo. Yield: 0.8 g. MS (ES+): m/e=282.1 (M+H+, 100%); 284.1 (30%).
4-[4-[(4-chlorophenyl)(2-pyridyl)methoxy]piperidine-1-yl]butyric acid ethyl ester[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
6.26 g (91%)
With potassium carbonate; In methanol; chloroform; acetone;
EXAMPLE 26 After 4.98 g (16.45 mmol) of 4-[(4-chlorophenyl)-2-pyridylmethoxy]piperidine and 3.85 g (19.74 mmol) of ethyl 4-bromobutanoate were dissolved in 35 ml of acetone, 2.73 g (19.75 mmol) of potassium carbonate was added to the mixed solution, and the mixture was stirred under reflux by heating for 4 hours. The insolubles were filtered off, and the filtrate was concentrated under reduced pressure. The residue was separated by silica gel column chromatography using a solvent mixture of chloroform and methanol in the volume ratio of 30:1 as an eluent. The desired fraction was concentrated under reduced pressure to give 6.26 g (91%) of ethyl 4-[4-[(4-chlorophenyl)-2-pyridylmethoxy]-1-piperidyl]-butanoate as an oil. Mass analysis value: EI-MS M+ no peak, CI-MS m/e=417(M+ +1). 1 H-NMR(CDCl3): delta(ppm)=1.13(3H,t), 1.10-1.98(6H,b,m), 2.12(2H,b), 2.33(4H,t), 2.70(2H,b), 3.45(1H,m), 4.11(2H,q), 5.59(1H,s), 7.12-7.72(7H,m), 8.50(1H,m).
With hydrogenchloride; potassium hydroxide; In water;
EXAMPLE 42 In a similar manner to that described above in Example 17 ethyl 4-(3-piperidinomethylphenoxy)butyrate (b.p. 190°-200° C./0.005 mm Hg) was prepared from N-3-hydroxybenzylpiperidine and ethyl 4-bromobutyrate. The resulting ester (21.4 g) was then hydrolyzed by heating under reflux with potassium hydroxide (3.6 g), water (210 ml) and industrial methylated spirit (210 ml) for 30 minutes. 5N Hydrochloric acid (13.7 ml) was then added and the solvent removed by evaporation in vacuo. The residue was dried by azeotropic distillation with toluene and then with ethanol. The residue was digested with ethanol (420 ml). The ethanolic liquor was filtered and the solvent removed from the filtrate to give a yellow oil which was crystallized from a mixture of methanol and ether to give 4-(3-piperidinomethylphenoxy)butyric acid (m.p. 73°-77° C.).
With potassium carbonate; In N,N-dimethyl-formamide; at 20℃;
Reference Example 142-Chloropyrimidin-5-ol (3.89g) is dissolved in N,N- dimethylformamide (50ml) and thereto are added potassium carbonate (4.98g) and tert-butyl 4-bromo-butyrate (7.36g) and the mixture is stirred at room temperature overnight. To the reaction solution are added ethyl <n="169"/>acetate and water, and the mixture is separated, and the organic layer is washed with a saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure. The resulting residue is purified by silica gel column chromatography (hexane : ethyl acetate - 24: 1-->4: 1) to give tert-butyl 4-(2-chloropyrimidin-5-yloxy)bromobutyrate (6.22g). MS (m/z): 273 [M+H]+
General procedure: Constant current electrolyses (I = 25 mA cm-2) were performed under a nitrogen atmosphere, at 20C, using an Amel Model 552 potentiostat equipped with an AmelModel 731 integrator. All the experiments were carried out in a divided glass cell separated through a porous glass plug filled up with a layer of gel (i.e., methylcellulose 0.5% vol dissolved in DMF-Et4NPF6 1.0 mol dm-3); Pt spirals (apparent areas 0.8 cm2) were used both as cathode and anode. MeCN-Et4NPF6 0.1 mol dm-3 was used as solvent-supporting electrolyte system (catholite: 20 cm3; anolite: 5 cm3).1 mmol of substrate was present in the catholyte (except for D-<strong>[68-41-7]cycloserine</strong>, which was added to the catholyte after the end of the electrolysis). After 145 C (if not otherwise stated) were passed, the current was switched off and 1 mmol of alkylating agent was added to the catholyte. The solution was kept under stirring at room temperature for 2 hours, than the solvent was evaporated under reduced pressure and the residue was extracted three times with diethyl ether. The products were purified by flash column chromatography, using a mixture of ethyl acetate/light petroleum ether 2/8 in volume. The reactions on D-<strong>[68-41-7]cycloserine</strong> were carried out following the general method, but the substrate was added to the catholyte after the end of the electrolysis. After 15 minutes at room temperature, the alkylating agent was added and the solution was kept under stirring at rt for 2 hours. The solvent was evaporated under reduced pressure and the residue was treated with 1 cm3 of saturated acqueous NaHCO3 and 1 mmol of ethyl chloroformate, at 0C, for 2 h. The solution was then acidified with diluted HCl (pH 4) and extracted with diethyl ether. The products were purified by flash column chromatography.
ethyl 4-(4-(tert-butyl)pyridin-2-yl)butanoate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
50%
General procedure: In a well-ventilated fume hood, a 15 mL round-bottomed flaskequipped with a Teflon-coated magnetic stirrer bar was chargedwith NiBr2·3H2O (40.9 mg, 0.150 mmol, 0.05 equiv), bathophenanthroline(4; 49.9 mg, 0.150 mmol, 0.05 equiv), DMF (2.0 mL), andalkyl bromide 2 (3.3 mmol, 1.1 equiv). The vessel was stopperedwith a rubber septum and heated to 40 C in a fume hood until agreen homogeneous solution formed (~20 min). The vessel wasthen removed from the heat and 2-halopyridine 1 (3.00 mmol, 1.00equiv) and manganese(0) (-325 mesh; 330 mg, 6.00 mmol, 2.00equiv) were added. The vessel was resealed with the septum, purgedwith argon, and heated again to 40 C while the progress of the reactionwas monitored by GC analysis of aliquots of the crude reactionmixture. In general, the mixtures turned dark brown or blackwhen the reaction was complete. Upon completion of the reaction,the mixture was cooled to r.t., diluted with Et2O (10 mL), and filteredthrough a short pad of Celite 545 (approx. 1 × 1 × 1 inch) wettedwith Et2O (~10 mL) to remove metal salts. The Celite pad waswashed with additional Et2O (2 × 10 mL), and the filtrate was transferredto a separatory funnel and washed with 1 M aq NH4Cl (10mL). The layers were separated and the aqueous layer was washedwith additional Et2O (3 × 10 mL). The organic extracts were combined,washed with brine (10 mL), dried (MgSO4), filtered, and concentratedunder reduced pressure. The crude products were purifiedby flash column chromatography on silica gel.
ethyl 3-(3-(trifluoromethoxy)phenoxy)propanoate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
92.1%
With potassium carbonate; In acetone; at 20℃;
Step 1 ethyl 3-(3-(trifluoromethoxy)phenoxy)propanoate To a solution of ethyl 4-bromobutanoate (2 g, 10.26 mmol) in acetone (20 mL) was added 3- (trifluoromethoxy)phenol (1.52 g, 8.54 mmol), followed by potassium carbonate (3.5 g, 25.36 mmol). The reaction was stirred at room temperature overnight. The mixture was partitioned between DCM and water. The organic phase was washed with brine, dried over sodium sulfate, and concentrated to give a crude product which was purified by silica gel chromatography eluting with petroleum/ ethyl acetate (10: 1 to 5: 1) to give ethyl 3-(3- (trifluoromethoxy)phenoxy)propanoate (2.3 g, 92.1 percent yield) as a colorless oil.
4-[(5,7-dihydroxy-2-(4-methoxyphenyl)-8-(3-methylbut-2-en-1-yl)-4-oxo-4H-chromen-3-yl)oxy]butyric acid ethyl ester[ No CAS ]
4-[(3,5-dihydroxy-2-(4-methoxyphenyl)-8-(3-methylbut-2-en-1-yl)-4-oxo-4H-chromen-7-yl)oxy]butyric acid ethyl ester[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
10%; 26%
In acetone; for 6h;Reflux;
General procedure: Different bromo-carboxylic acid ethyl ester (1.0e1.5 equiv.) wasadded into a mixture of <strong>[118525-40-9]icaritin</strong> (1.0 equiv.) and anhydrous K2CO3 (1.0e1.5 equiv.) in dry acetone and stirred under reflux for 6 h. After removing the solvent under reduced pressure, the residue was dissolved in EtOAc and sequentially washed with 1% aqueous HCl solution, distilled water and dried over anhydrous Na2SO4. The crude product was purified by HPLC using CH3CN/H2O (v/v, 80:20or 85:15, based on the polarity of the final product) to afford compounds 2g-2o.
4,4'-[(5-hydroxy-2-(4-methoxyphenyl)-8-(3-methylbut-2-en-1-yl)-4-oxo-4H-chromen-3,7-diyl)bis(oxy)]dibutyric acid ethyl ester[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
80%
With potassium carbonate; In acetone; for 6h;Reflux;
General procedure: Specific bromo-carboxylic acid ethyl ester (2.5-4.0 equiv.) was added into a mixture of <strong>[118525-40-9]icaritin</strong> (1.0 equiv.) and anhydrous K2CO3 (2.5-4.0 equiv.) in dry acetone and stirred under reflux for 6 h. After removing the solvent under reduced pressure, the residue was dissolved in EtOAc and sequentially washed with 1% aqueous HCl solution, distilled water and dried over anhydrous Na2SO4. The crude product was purified by silica gel CC, eluted with petroleum/acetone (v/v from 20:1 to 4:1, based on the polarity of the final product) or HPLC using CH3CN/H2O (v/v, 80:20 or 85:15, based on the polarity of the final product) to afford compounds 2a-2f.
ethyl 1-(4-ethoxy-4-oxobutyl)-4-methyl-1H-pyrrole-3-carboxylate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
Compound (Ia) (4 g, 26.1 mmol) was dissolved in N,N-dimethylformamide (60 mL). Cesium carbonate (21.3 g, 65.3 mmol) was added thereto, and the mixture was stirred for 30 minutes. Ethyl 4-bromobutyrate (5.91 mL, 39.2 mmol) was added thereto at room temperature, followed by reaction for 3 days. When the reaction was completed, the solid was removed by filtration, and the filtrate was concentrated under reduced pressure and extracted with methylene chloride. The water was dried with anhydrous magnesium sulfate and filtered.The filtrate was concentrated under reduced pressure to obtain (IIa).The resulting compound was used as such in the next reaction without further purification.
9,10-bis-(4-ethoxy-4-oxobutoxy)anthracene[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
5.4 g
With tetrabutylammomium bromide; potassium carbonate; In water; N,N-dimethyl-formamide; at 20 - 30℃; for 1h;Inert atmosphere;
Stirrer,In a 100 ml four-necked flask with a thermometer,Under nitrogen atmosphere,catalyst0.77 g (1.19 mmol) of a 50percent aqueous solution of tetrabutylammonium bromide inEthyl 4-bromobutyrate12.1 g (61.8 mmol),5.0 g (23.8 mmol) of <strong>[4981-66-2]9,10-anthracenediol</strong>,9.9 g (71.4 mmol) of potassium carbonate,40 g of solvent N, N-dimethylformamide was added.The mixture was stirred for 1 hour while maintaining the temperature of the reaction system at 20 to 30 ° C.after that,The anthraquinone is removed by suction filtration.The resulting filtrate is dissolved in toluene,Washed twice with water.The solution was concentrated with an evaporator.When left overnight,As the whole solution solidified,Add methanol,Heat to 50 ° C,It was dissolved.The undissolved anthraquinone is removed by suction filtration.The filtrate was cooled in a freezer to precipitate crystals. By further suction-filtering the precipitated crystals,A yield of 5.4 g (crude yield 51 molpercent) of yellow crystals was obtained.
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