* 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] Acad. romine Stud. Cerc. Chim., 1956, vol. 4, p. 57,60[2] Chem.Abstr., 1957, p. 3534
[3] Justus Liebigs Annalen der Chemie, 1973, p. 910 - 935
[4] Journal of Medicinal Chemistry, 1967, vol. 10, p. 99 - 101
[5] Journal of Organic Chemistry, 1980, vol. 45, # 4, p. 702 - 705
[6] Photochemical and Photobiological Sciences, 2011, vol. 10, # 6, p. 920 - 930
2
[ 765944-63-6 ]
[ 42523-29-5 ]
Yield
Reaction Conditions
Operation in experiment
95%
at 110 - 120℃; for 2 h;
A mixture of 5 (50 g, 0.20 mol), ZnCl2 (50 g, 0.37 mol), PPA (33 mL) was stirred at 110–120 °C for 2 h and then cooled to r.t., precipitated by addition of water (500 mL). The precipitate was filtered and dried to obtain 40 g red-brown crystallized powder (2). Yield 95percent; m.p. 336–337 °C (Lit. 338 C [24]); IR (KBr), ν (cm1): 3388.9, 3360.6 (OH), 1700.7 (C=O); ESI-MS (m/z):211.0 [M H], C13H8O3 (MW. = 212.0); 1H-NMR (300 MHz, DMSO-d6), δ (ppm): 9.89 (s, 2H), 7.37 (d,J = 4.8 Hz, 2H), 6.90 (dd, J = 4.9, 2.4 Hz, 2H), 6.86 (d, J = 2.4 Hz, 2H).
Reference：
[1] Molecules, 2015, vol. 20, # 12, p. 21458 - 21463
[2] Bioorganic and Medicinal Chemistry, 2004, vol. 12, # 17, p. 4601 - 4611
3
[ 202865-84-7 ]
[ 100-83-4 ]
[ 42523-29-5 ]
Yield
Reaction Conditions
Operation in experiment
74%
With palladium diacetate; potassium hydrogencarbonate; DL-Pro-NHMe In tert-Amyl alcohol at 120℃; for 24 h; Inert atmosphere
General procedure: A mixture of arylaldehyde (0.1 g, 1 mmol), dihaloarene (0.565 g, 2 mmol), Pd(OAc)2 (0.022 g, 10.0 molpercent), N-phenylpicolinamide (L7, 0.019 g, 15.0 molpercent) and potassium hydrogen carbonate (0.5 g, 5 mmol) in tert-amyl alcohol (5.0 ml) was taken in 100.0 ml round bottom flask under N2 atmosphere and stirred for 120°C for 24 h. Progress of the reaction was monitored continuously by TLC with ethyl acetate: hexane (2:3) eluent system. After completion of reaction, crude was poured into crushed ice and then filter the reaction mixture. Filtrate then extracted with ethyl acetate (3 times). Organic layer was separated, dried (over anhydrous Na2SO4) and evaporated under reduced pressure and purified by column chromatography to obtain desired product. Characterization data of compounds 3a, 3b, 3c, 3d, 3e, 3f, 3g, 3h, 3i, 3j, 3k, 3l, 3v and 3x were found exactly similar as reported in the literature (References of above compound are mentioned in Supplementary data).
Reference：
[1] Photochemical and Photobiological Sciences, 2011, vol. 10, # 6, p. 920 - 930
[2] Molecules, 2015, vol. 20, # 12, p. 21458 - 21463
13
[ 84185-72-8 ]
[ 42523-29-5 ]
Reference：
[1] Chemistry of Heterocyclic Compounds (New York, NY, United States), 1983, vol. 19, # 11, p. 1221 - 1224[2] Khimiya Geterotsiklicheskikh Soedinenii, 1983, # 11, p. 1537 - 1539
14
[ 84185-84-2 ]
[ 42523-29-5 ]
Reference：
[1] Chemistry of Heterocyclic Compounds (New York, NY, United States), 1983, vol. 19, # 11, p. 1221 - 1224[2] Khimiya Geterotsiklicheskikh Soedinenii, 1983, # 11, p. 1537 - 1539
15
[ 35450-36-3 ]
[ 42523-29-5 ]
Reference：
[1] Justus Liebigs Annalen der Chemie, 1973, p. 910 - 935
16
[ 42523-25-1 ]
[ 42523-29-5 ]
Reference：
[1] Justus Liebigs Annalen der Chemie, 1973, p. 910 - 935
17
[ 89450-82-8 ]
[ 42523-29-5 ]
Reference：
[1] Chemistry of Heterocyclic Compounds (New York, NY, United States), 1983, vol. 19, # 11, p. 1221 - 1224[2] Khimiya Geterotsiklicheskikh Soedinenii, 1983, # 11, p. 1537 - 1539
With sulfuryl dichloride; acetic acid; at 42 - 45℃; for 0.666667h;Inert atmosphere;
Under nitrogen to 2, 7-dihydroxy-fluorenone (10. 490g, 49. 5mmol) was dissolved in 250mL acetic acid to form a suspension, stirred, was slowly warmed to 42 ° C. Was slowly added dropwise sulfuryl chloride (20mL, 247. 4mmol), and to ensure that the temperature is below 45 ° C. From dark red suspension gradually turns orange. After the dropping reaction 40min. Cooled, suction filtered, and washed with water, washed with acetone. Orange solid (12. 541g, yield 90.2percent)
With sodium hydroxide; In dimethyl sulfoxide; at 70℃;
2,7-Dihydroxy-fluoren-9-one (20 g, 0.094 mol) was solved in 200 ml DMSO, NaOH (8 g, 0.2 mol) and ethylene chlorohydrin (13.4 ml, 0.2 mol) were added into the solution. The resulting solution was stirred overnight at 70C, and then poured into 1 M NaOH water solution. The precipitate was washed by 1 M NaOH till colorless eluate and dried in vacuum drying oven then recrystallized from 2-propanol to obtain compound 6a. Orange solid. Yield 55%. M.p. 166-168C. 1H NMR (400 MHz, DMSO) delta: 7.54 (s, 2H),7.08 (s, 4H), 4.05 (s, 4H), 3.72 (s, 4H). 13C NMR (101 MHz, DMSO) delta:192.81, 159.09, 136.72, 135.07, 121.41, 120.82, 110.06, 70.08, 59.45.Anal. Calcd. for C17H16O5: C 67.99, H 5.37; Found C 68.01, H 5.37.
8,11,14,26,29,32-hexaoxaheptacyclo[31.3.1.13,7.115,19.121,25.04,36.018,22]tetraconta-1(37),3(40),4,6,15(39),16,18,21(38),22,24,33,35-dodecaene-2,20-dione[ No CAS ]
8,11,14,17,20,32,35,38,41,44-decaoxaheptacyclo[43.3.1.13,7.121,25.127,31.04,48.024,28]dopentaconta-1(49),3(52),4,6,21(51),22,24,27(50),28,30,45,47-dodecaene-2,26-dione[ No CAS ]
8,11,14,17,29,32,35,38-octaoxaheptacyclo[37.3.1.13,7.118,22.124,28.04,42.021,25]hexatetraconta-1(43),3(46),4,6,18(45),19,21,24,25,27,39,41-dodecaene-2,23-dione[ No CAS ]
A mixture of 5 (50 g, 0.20 mol), ZnCl2 (50 g, 0.37 mol), PPA (33 mL) was stirred at 110?120 °C for 2 h and then cooled to r.t., precipitated by addition of water (500 mL). The precipitate was filtered and dried to obtain 40 g red-brown crystallized powder (2). Yield 95percent; m.p. 336?337 °C (Lit. 338 C [24]); IR (KBr), nu (cm1): 3388.9, 3360.6 (OH), 1700.7 (C=O); ESI-MS (m/z):211.0 [M H], C13H8O3 (MW. = 212.0); 1H-NMR (300 MHz, DMSO-d6), delta (ppm): 9.89 (s, 2H), 7.37 (d,J = 4.8 Hz, 2H), 6.90 (dd, J = 4.9, 2.4 Hz, 2H), 6.86 (d, J = 2.4 Hz, 2H).
2,7-bis[(3S)-1-azabicyclo[2.2.2]octan-3-yloxy]-fluoren-9-one[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
23%
With triphenylphosphine on polystyrene; diethylazodicarboxylate; In tetrahydrofuran; at 0 - 20℃;
To a 0° C. mixture of 2,7-dihydroxyfluoren-9-one (113 mg, 0.533 mmol; see Synth. Commun. 1976, 6, 371), (3F)-quinuclidin-3-ol (280 mg, 2.20 mmol; Acros), and polymer-bound triphenylphosphine (933 mg, 3 mmol/g; Aldrich) in THF (5 mL) was added diethylazodicarboxylate (340 muL, 2.16 mmol; Aldrich). After 1 h, the reaction mixture was allowed to warm to room temperature and was stirred over the weekend. The mixture was filtered through diatomaceous earth, the filter pad rinsed with ethyl acetate, and the organic extracts purified by flash chromatography (35 g silica gel, eluting with 2-10percent of 10percent NH4OH/MeOH in CH2Cl2). Acetonitrile was then added to the residue, and the resulting precipitate collected by filtration to yield the title compound (53 mg, 0.12 mmol, 23percent yield).
With triphenylphosphine on polystyrene; di-tert-butyl-diazodicarboxylate; In tetrahydrofuran; at 20℃; for 16h;
To a solution of 2,7-dihydroxyfluoren-9-one (0.21 g, 1.0 mmol; see Synth. Commun. 1976, 6, 371) and (2R)-(+)-1-Boc-2-pyrrolidinemethanol (0.81 g, 4.0 mmol; Aldrich) in dry THF (10 mL) was added polymer-bound triphenylphosphine (1.3 g, 4.0 mmol; Aldrich) followed by di-tert-butylazodicarboxylate (920 mg, 4.00 mmol; Aldrich). The mixture was stirred overnight (16 h) at room temperature, then filtered through diatomaceous earth, rinsing with ethyl acetate. After concentrating the solution, the residue was purified by flash chromatography (35 g silica gel, 10-30percent ethyl acetate-hexane) to afford the title compound (310 mg, 0.54 mmol; 54percent).
2,7-bis-[(2R)-1-Boc-azetidin-2-ylmethoxy]-fluoren-9-one[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
56%
With potassium hydroxide; In DMF (N,N-dimethyl-formamide); at 80℃; for 16h;
A mixture of the product of Example 2A (795 mg, 3 mmol), 2,7-dihydroxyfluoren-9-one (212 mg, 1.00 mmol; see Synth. Commun. 1976, 6, 371) and powdered potassium hydroxide (135 mg, 2.4 mmol; Fisher) in DMF (10 mL) was heated to 80° C. with stirring for 16 hours. After cooling to room temperature, the reaction mixture was concentrated. Dichloromethane (10 mL) was added, and the solution was washed with water and brine, concentrated and purified by flash chromatography (80 g silica gel, psi 30percent isopropanol-hexanes) to afford the title compound (310 mg, 0.56 mmol; 56percent yield).
2,7-bis-[(S)-1-methylpyrrolidin-2-ylmethoxy]-fluoren-9-one[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
47%
To a solution of <strong>[42523-29-5]2,7-dihydroxyfluorenone</strong> (150 mg, 0.708 mmol; see Synth. Commun. 1976, 6, 371) and (S)-2-hydroxymethyl-1-methylpyrrolidine (420 muL, 3.54 mmol; Aldrich) in THF (5 mL) was added polymer-bound triphenylphosphine (1.2 g, 3 mmol/g; Aldrich) followed by di-tert-butylazodicarboxylate (800 mg, 3.48 mmol; Aldrich). The mixture was stirred overnight (16 h) at room temperature, then filtered through diatomaceous earth, rinsing with CH2Cl2. After concentrating the solution, the residue was stirred with 4 M HCl in dioxane (5 mL; Aldrich) for 1 h. The reaction mixture then was adjusted to pH>10 with 1 N NaOH, extracted twice with CH2Cl2 and dried over K2CO3. Purification by flash chromatography (35 g silica gel, 2-10percent gradient of NH4OH-MeOH (1:10) in CH2Cl2) followed by reverse-phase HPLC (Waters Symmetry C8 40.x.100 mm column, gradient 5-95percent MeCN-0.1percent aq. TFA) afforded the title compound (134 mg, 0.329 mmol; 47percent yield): MS (DCl/NH3) m/z 407 (M+H)+.
2,7-bis-(8-methyl-8-aza-bicyclo[3.2.1]oct-3-yloxy)-fluoren-9-one[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
17%
With potassium hydroxide; In DMF (N,N-dimethyl-formamide); at 80℃; for 16h;
A mixture of the product of Example 25A (800 mg, 3.6 mmol), <strong>[42523-29-5]2,7-dihydroxy-fluoren-9-one</strong> (200 mg, 0.95 mmol) and powdered potassium hydroxide (120 mg, 2.1 mmol; Fisher) in DMF (10 mL) was heated to 80° C. with stirring for 16 h. After cooling to room temperature, the reaction mixture was concentrated, and the residue was dissolved in CH2Cl2 (10 mL) and washed with water and brine. The organic phase was concentrated and purified by flash chromatography (80 g silica gel, 0-30percent gradient of MeOH in CH2Cl2) to afford the title compound (75 mg, 0.16 mmol; 17percent yield): 1H NMR (300 MHz, CD3OD) delta ppm 7.41 (2H, dd, J=8, 6 Hz), 7.08 (2H, dd, J=18, 2 Hz), 6.99 (2H, ddd, J=15, 8, 2 Hz), 4.55-4.70 (2H, m), 3.15-3.30 (4H, m), 2.33 (6H, d, J=4 Hz), 1.72-2.24 (16H, m); MS (DCl/NH3): 459 (M+1)+.
2,7-bis[(2R)-1-boc-pyrrolidin-2-ylmethoxy]-fluoren-9-one[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
54%
With di-tert-butyl-diazodicarboxylate; polymer-bound triphenylphosphine; In tetrahydrofuran; at 20℃; for 16h;
To a solution of 2,7-dihydroxyfluoren-9-one (0.21 g, 1.0 mmol; see Synth. Commun. 1976, 6, 371) and (2R)-(+)-1-Boc-2-pyrrolidinemethanol (0.81 g, 4.0 mmol; Aldrich) in dry THF (10 mL) was added polymer-bound triphenylphosphine (1.3 g, 4.0 mmol; Aldrich) followed by di-tert-butylazodicarboxylate (920 mg, 4.00 mmol; Aldrich). The mixture was stirred overnight (16 h) at room temperature, then filtered through diatomaceous earth, rinsing with ethyl acetate. After concentrating the solution, the residue was purified by flash chromatography (35 g silica gel, 10-30percent ethyl acetate-hexane) to afford the title compound (310 mg, 0.54 mmol; 54percent). MS (DCl/NH3): m/z 596 (M+18)+.
(2R)-1-boc-2-(methanesulfonyloxymethoxy)azetidine[ No CAS ]
[ 42523-29-5 ]
2,7-bis-[(2R)-1-Boc-azetidin-2-ylmethoxy]-fluoren-9-one[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
56%
With potassium hydroxide; In DMF (N,N-dimethyl-formamide); at 80℃; for 16h;
A mixture of the product of Example 2A (795 mg, 3 mmol), 2,7-dihydroxyfluoren-9-one (212 mg, 1.00 mmol; see Synth. Commun. 1976, 6, 371) and powdered potassium hydroxide (135 mg, 2.4 mmol; Fisher) in DMF (10 mL) was heated to 80° C. with stirring for 16 hours. After cooling to room temperature, the reaction mixture was concentrated. Dichloromethane (10 mL) was added, and the solution was washed with water and brine, concentrated and purified by flash chromatography (80 g silica gel, 0-30percent isopropanol-hexanes) to afford the title compound (310 mg, 0.56 mmol; 56percent yield). MS (DCl/NH3): 568 (M+18)+.
2,7-bis[(3S)-1-azabicyclo[2.2.2]octan-3yloxy]fluoren-9-one[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
23%
With polymer-bound triphenylphosphine; diethylazodicarboxylate; In tetrahydrofuran; at 0 - 20℃; for 1h;
To a 0° C. mixture of 2,7-dihydroxyfluoren-9-one (113 mg, 0.533 mmol; see Synth. Commun. 1976, 6, 371), (3R)-quinuclidin-3-ol (280 mg, 2.20 mmol; Acros), and polymer-bound triphenylphosphine (933 mg, 3 mmol/g; Aldrich) in THF (5 mL) was added diethylazodicarboxylate (340 muL, 2.16 mmol; Aldrich). After 1 h, the reaction mixture was allowed to warm to room temperature and was stirred over the weekend. The mixture was filtered through diatomaceous earth, the filter pad rinsed with ethyl acetate, and the organic extracts purified by flash chromatography (35 g silica gel, eluting with 2-10percent of 10percent NH4OH/MeOH in CH2Cl2). Acetonitrile was then added to the residue, and the resulting precipitate collected by filtration to yield the title compound (53 mg, 0.12 mmol, 23percent yield). MS (DCl/NH3): m/z 431 (M+1)+.
EXAMPLE 32 According to a known method, optically active 2-octyl bromide and 2,7-dihydroxylfluorenone were reacted in ethanol in the presence of potassium hydroxide. The resultant reaction mixture was purified by a column chromatography and recrystallization to obtain optically active 2-hydroxy-7-(2-octyloxy)-fluorenone.
EXAMPLE 5 2,7-dipivaloyloxyfluorenone 2.1 g (0.01 mole) of <strong>[42523-29-5]2,7-dihydroxyfluorenone</strong> and 2.5 g (0.025 mole) of pivaloyl chloride were warmed to 50° C. in 6 mls of pyridine in a drying tube attached for 2 hrs. The solvent was removed via rotary evaporator and H2 O was added. The crystals were filtered and air dried. Recrystallized from ethanol; 3 g (79percent); M.P.~174°-175° C. Anal. Calcd. for C23 H24 O5: C, 72.61; H, 6.36. Found: C, 72.20; H, 6.27.
With sodium hydroxide; In ethanol; chloroform; water;
A. To a stirred, refluxing mixture of 21.2 g (0.10 mole) of 2,7-dihydroxyfluoren-9-one and 43.0 g (0.30 mole) of 1-bromo-2-chloroethane in 400 ml of water is added dropwise, over a period of 30 minutes, 80 ml (0.20 mole) of 10percent aqueous sodium hydroxide. After complete addition of the alkali, the mixture is refluxed with stirring for eighteen hours. Upon cooling, the supernatant water layer is decanted and the residue taken up in ethanol. The solid that separates is filtered, washed with ethanol, and dried in the air, M.P. 161°-174°C. The material is dissolved in chloroform, washed with 10percent aqueous sodium hydroxide, with water and dried over anhydrous magnesium sulfate. The mixture is filtered, the solvent evaporated, the residue recrystallized from a mixture of five parts ethanol to one part chloroform and the product air dried to give intermediated 2,7-bis(2-chloroethoxy)fluoren-9-one, M.P. 135°-139°C.
2,7-bis(3-piperidin-1-ylpropoxy)fluoren-9-one dihydrochloride[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With potassium hydroxide; sodium chloride; In water; toluene;
EXAMPLE III 2,7-Bis(3-piperidinopropoxy) fluoren-9-one dihydrochloride A mixture of 63.6 g (0.30 mole) of <strong>[42523-29-5]2,7-dihydroxy-fluoren-9-one</strong>, 188 g (0.95 mole) of 1-(3-chloropropyl) piperidine hydrochloride, 132 g (2.0 mole) of 85percent potassium hydroxide in 900 ml of toluene and 300 ml of water is refluxed with vigorous stirring for 20 hours. The layers are separated upon cooling and the organic layer is washed 3 times with water, once with a saturated solution of sodium chloride and dried over anhydrous magnesium sulfate. The mixture is filtered and the solvent removed in vacuo. The residue is taken up in isopropyl alcohol and acidified to Congo Red with ethereal hydrogen chloride. The solid which precipitates is filtered, recrystallized from a mixture of 3 parts isopropyl alcohol to 1 part methanol, and the 2,7-bis (3-piperidinopropoxy)fluoren-9-one dihydrochloride so prepared is dried at 100° C. for 24 hours under vacuum, m.p. 279.5°-80.5° C., lambdamaxH2 O 270, and E1cm1percent 1370.
Chemistry
Pharmaceutical Intermediates
Inhibitors/Agonists
Material Science
For Research Only
110K+ Compounds
Competitive Price
1-2 Day Shipping
