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CAS No. : | 1143-38-0 | MDL No. : | MFCD00053409 |
Formula : | C14H10O3 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | - |
M.W : | 226.23 | Pubchem ID : | - |
Synonyms : |
Anthralin;1,8,9-Anthracenetriol;Batridol;NSC 629313;NSC 43970
|
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H315-H319-H335 | Packing Group: | N/A |
GHS Pictogram: |
* 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.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With triethylamine In tetrahydrofuran for 0.5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With 1,8-diazabicyclo[5.4.0]undec-7-ene In dichloromethane at 0℃; for 0.5h; Yield given; | ||
With 1,8-diazabicyclo[5.4.0]undec-7-ene In dichloromethane at 0℃; for 0.5h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With 1,8-diazabicyclo[5.4.0]undec-7-ene In dichloromethane at 0℃; for 0.5h; Yield given; | ||
With 1,8-diazabicyclo[5.4.0]undec-7-ene In dichloromethane at 0℃; for 0.5h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
40% | With pyridine In toluene for 3h; Ambient temperature; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
10% | With pyridine In toluene at 80℃; for 3h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
36% | With pyridine In toluene at 80℃; for 3h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With 1,8-diazabicyclo[5.4.0]undec-7-ene In dichloromethane at 0℃; for 0.5h; Yield given; | ||
With 1,8-diazabicyclo[5.4.0]undec-7-ene In dichloromethane at 0℃; for 0.5h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
41% | With pyridine In toluene at 80℃; for 3h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With 1,8-diazabicyclo[5.4.0]undec-7-ene In dichloromethane at 0℃; for 0.5h; Yield given; | ||
With 1,8-diazabicyclo[5.4.0]undec-7-ene In dichloromethane at 0℃; for 0.5h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With 1,8-diazabicyclo[5.4.0]undec-7-ene In dichloromethane at 0℃; for 0.5h; Yield given; | ||
With 1,8-diazabicyclo[5.4.0]undec-7-ene In dichloromethane at 0℃; for 0.5h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
41% | With lead acetate In methanol | |
In acetone | ||
With Ringer-buffer In acetone Ambient temperature; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With isopropylamine In tetrahydrofuran for 5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
44% | With pyridine In toluene at 80℃; for 3h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
36% | With pyridine In toluene at 80℃; for 3h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
40% | With pyridine In toluene at 80℃; for 3h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
45% | With pyridine In toluene at 80℃; for 3h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With triethylamine In tetrahydrofuran for 7h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
43% | With pyridine In toluene at 80℃; for 3h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With pyridine In benzene Heating; | ||
With pyridine In dichloromethane; toluene | 1.a (a) (a) 1,8-Dihydroxy-10-acetylanthrone To a solution of 56.5 g (0.25 mol) of purified anthralin in 1750 cm3 of anhydrous toluene being stirred at room temperature, 27.3 cm3 (0.34 mol) of anhydrous pyridine was added first and then 21.4 cm3 (0.3 mol) of acetyl chloride was added dropwise by means of a dropping funnel. Slight heating occurred during addition then, after the end of addition, the mixture was heated to a temperature of around 90° C. for 1 hour. The mixture was cooled and 27.3 cm3 of pyridine and then, dropwise, 21.4 cm3 of acetyl chloride were again added at 30°-35° C. The mixture was then stirred for 1 hour at 85°-90° C. After a check to insure that the anthralin had been transformed to the 10-acetyl derivative, the reaction mixture was cooled to room temperature then washed 3 times with water (250 cm3). The toluene phase was decanted, dried over sodium sulfate and then concentrated to around 300 cm3. The solution was then deposited on a column of silica gel and eluted with toluene and a 1:1 mixture of toluene and methylene chloride. The first fractions were combined and then concentrated under vacuum. The solid obtained was then recrystallized from toluene to yield 21 g of bright-yellow crystals of 1,8-dihydroxy-10-acetylanthrone having a melting point of 146° C. Analysis: C16 H12 O4 Calc.: C 71.63, H 4.51, O 23.85; Found: C 71.44, H 4.34, O 23.97. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
30% | With pyridine In tetrahydrofuran at 20℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
22% | With pyridine; dicyclohexyl-carbodiimide In tetrahydrofuran at 20℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
26% | With pyridine; dicyclohexyl-carbodiimide In tetrahydrofuran at 20℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
20% | With pyridine; dicyclohexyl-carbodiimide In tetrahydrofuran at 20℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
28% | With pyridine; dicyclohexyl-carbodiimide In tetrahydrofuran at 20℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
25% | With pyridine In tetrahydrofuran at 20℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
34% | With pyridine In tetrahydrofuran at 20℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
26% | With pyridine; dicyclohexyl-carbodiimide In tetrahydrofuran at 20℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
16% | With pyridine; N-(3-dimethylaminopropyl)-N-ethylcarbodiimide In tetrahydrofuran at 50℃; for 2h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
21% | With pyridine; dicyclohexyl-carbodiimide In tetrahydrofuran at 20℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
18% | With pyridine; dicyclohexyl-carbodiimide In tetrahydrofuran at 20℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
29% | With pyridine; dicyclohexyl-carbodiimide In tetrahydrofuran at 20℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
31% | With pyridine; dicyclohexyl-carbodiimide In tetrahydrofuran at 20℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
24% | With pyridine In tetrahydrofuran at 20℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
20% | With pyridine In tetrahydrofuran at 20℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
18% | With pyridine In tetrahydrofuran at 20℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
28% | With pyridine In tetrahydrofuran at 20℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
23% | With pyridine In tetrahydrofuran at 20℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
34% | With pyridine In tetrahydrofuran at 20℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
21% | With pyridine In tetrahydrofuran at 20℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
31% | With pyridine In tetrahydrofuran at 20℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
21% | With pyridine In tetrahydrofuran at 20℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
25% | With pyridine In tetrahydrofuran at 20℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
24% | With pyridine In tetrahydrofuran at 20℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
34% | With pyridine In tetrahydrofuran at 20℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
39% | With pyridine In tetrahydrofuran at 20℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
20% | With pyridine; dicyclohexyl-carbodiimide In tetrahydrofuran at 20℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With triethylamine In tetrahydrofuran at 20℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | In dichloromethane at -20℃; for 7h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In dichloromethane at -20℃; for 8h; Title compound not separated from byproducts; | ||
With 1-{3,5-bis(trifluoromethyl)phenyl}-3-{(1R,2R)-2-(dimethylamino)cyclohexyl}thiourea In toluene at 20℃; for 14h; optical yield given as %ee; enantioselective reaction; | ||
With 1-{3,5-bis(trifluoromethyl)phenyl}-3-{(1R,2R)-2-(dimethylamino)cyclohexyl}thiourea In toluene at 20℃; for 14h; optical yield given as %ee; enantioselective reaction; | 4.5. General experimental procedure for the addition of anthrones to maleimides General procedure: To a stirred solution of catalyst (R,R)-V (10 mg, 0.025 mmol) in toluene (1 mL) were added the maleimide (0.30 mmol) and the anthrone (1a or 1b, 0.25 mmol). The reaction mixture was vigorously stirred at room temperature during 14 h, and the crude product was directly purified by column chromatography on silica gel (hexane/ethyl acetate mixtures) to afford the Diels-Alder or the Michael adduct. Racemic products were obtained from the corresponding substrates by catalysis with DABCO in toluene at room temperature. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | In dichloromethane at -20℃; for 8h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | In dichloromethane at -20℃; for 8h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In dichloromethane at -20℃; for 7h; Title compound not separated from byproducts; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | In dichloromethane at -20℃; for 6h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In dichloromethane at -20℃; for 7h; Title compound not separated from byproducts; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: 26 percent / pyridine / tetrahydrofuran / 4 h / Ambient temperature 2: 80 percent / K2CO3 / methanol / Ambient temperature | ||
Multi-step reaction with 2 steps 1: 36 percent / pyridine / toluene / 3 h / 80 °C 2: 45 percent / H2 / 10percent Pd/C / tetrahydrofuran / 24 h / 760 Torr / Ambient temperature |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
28% | With camphor-10-sulfonic acid In toluene | 6 Preparation of 10-(3,4-Dihydroxy-benzylidene)-1,8-dihydroxy-10H-anthracen-9-one Example 6 Preparation of 10-(3,4-Dihydroxy-benzylidene)-1,8-dihydroxy-10H-anthracen-9-one A solution of dithranol (452 mg, 2.0 mmol), 3,4-dihydroxybenzadehyde (276 mg, 2.0 mmol), and camphorsulfonic acid (464 mg, 2.0 mmol) in 10 mL toluene was refluxed overnight The solvents were removed under reduced pressure and the residues were chromatographed (silica gel, methylene chloride-methanol 1:0 to 100:1 to 100:2), yielded 190 mg of product (28%). 1H-NMR (300 Hz, D3CCl) δ ppm) 7.47 (t, J=8.0 Hz, 1H), 7.40-7.30 (m, 2H), 7.27-7.10 (m, 2H), 6.95-6.75 (m, 2H), 6.75-6.60 (m, 3H). 13C-NMR (75 Hz, Cl3CD) δ (ppm) 192.8, 162.0, 161.5, 145.1, 144.5, 142.7, 137.8, 136.8,136.8, 136.0, 134.4,129.2,128.7, 121.9, 121.0,116.3,115.8,115.7,115.3, 114.6,114.0. MS (APCI) m/z 347 (M+1, 100). |
Multi-step reaction with 3 steps 1: 1,8-diazabicyclo<5.4.0>undec-7-ene / CH2Cl2 / 0.5 h / 0 °C 2: 87 percent / pyridine / 0.5 h / 116 °C 3: 78 percent / BBr3 / CH2Cl2 / 24 h / Ambient temperature |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogen In 1-methyl-pyrrolidin-2-one | 1 EXAMPLE 1 EXAMPLE 1 A mixture containing 18 wt% t-butyl anthrahydroquinone (H2BAQ) and 7 wt% t-butyl anthraquinone (TBAQ) in n-methyl-2-pyrrolidinone (NMP) is dehydrogenated at 275° C and 72 psia using three catalysts in three separate runs. One catalyst composition is 2.75 wt% platinum (Pt) metal dispersed on a silica support (Grace Grade 57), the second catalyst composition is 2.75 wt% palladium (Pd) metal on a silica support (Grace Grade 57), and the third catalyst composition is 2.75 wt% tungsten (W) metal on the same support. The electronegativities of the Pd, Pt and W metals are 2.20, 2.28, and 2.36, respectively. The electronegativity of the support is estimated to be significantly below 2.30. The selectivity of converting the H2BAQ to hydrogen and TBAQ is 68 mole% using the Pt catalyst, 25 mole% using the Pd catalyst, and 100% using the W catalyst. In each instance, the balance of the H2BAQ is converted to the corresponding anthrone or anthranol and water. These results, as correlated to the electronegativity of the metal catalysts, are illustrated in FIG. 1, and demonstrate that a metal electronegativity greater than 2.30 is sufficient to yield a selectivity to TBAQ and hydrogen of 100 mole % without production of unwanted anthrone or anthranol and water. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With pyridine In water; toluene | 13.a (a) (a) 1,8-Dihydroxy-10-butyrylanthrone To a stirred suspension of 51 g (0.22 mol) of 1,8-dihydroxyanthrone in 1.5 liters of toluene, kept under an inert atmosphere and shielded from light, 23.8 cm3 of pyridine was first added all at once and then 27.4 cm3 of butyryl chloride was added dropwise over 15 minutes. The mixture was then heated to a temperature of 80°-90° C. for 1 hour. Subsequently, the same quantities as before of pyridine and butyryl chloride (i.e., a total of 2.7 molar equivalents for pyridine and of 2.4 molar equivalents for the acid chloride) were added at room temperature. The reaction mixture was then reheated to 80°-90° C. for 1 hour. After being cooled to room temperature, the mixture was poured into 500 cm3 of acidulated water. The organic phase was decanted, washed with water until the washings became neutral and dried over magnesium sulfate. This phase was then fractionated by chromatography on a silica gel column, using toluene as the mobile phase. The eluted phases were concentrated and poured into hexane, thus causing crystallization of 1,8-dihydroxy-10-butyrylanthrone. The solvent was sucked from this product, which was then dried to yield 20 g of yellow crystals having a melting point of 138° C. Analysis: C18 H16 O4 Calc.: C 72.96, H 5.44, O 21.60; Found: C 72.75, H 5.48, O 21.38. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With pyridine In ethyl acetate; toluene | 4.a (a) (a) 1,8-Dihydroxy-10-isobutyrylanthrone To a solution of 56.6 g (0.25 mol) of anthralin in 1750 cm3 of absolute toluene and 27.3 cm3 of pyridine, 31.5 cm3 (0.3 mol) of isobutyryl chloride was added with stirring over 30 minutes at room temperature. The reaction mixture was then heated to 85° C. for 1 hour. After this mixture had recooled to room temperature, 27.3 cm3 of pyridine and 31.5 cm3 of isobutyryl chloride were again added. The suspension obtained was then heated to 85°-90° C. for 1 hour. The precipitated pyridinium hydrochloride was eliminated by filtration then washed with toluene. The toluene filtrates were concentrated to around 500 cm3 under reduced pressure, washed several times with water then dried over magnesium sulfate. The product was then fractionated by chromatography on silica gel, using toluene and then a mixture of toluene and ethyl acetate as the mobile phase. The different fractions containing the 1,8-dihydroxy-10-isobutyrylanthrone were then concentrated and recrystallized from a toluene-hexane mixture. In this way 25 g of yellow crystals of 1,8-dihydroxy-10-isobutyrylanthrone having a melting point of 160° C. was obtained. Analysis: C18 H16 O4 Calc.: C 72.97, H 5.44, O 21.59; Found: C 73.00, H 5.42, O 21.77. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sulfuric acid In chloroform | 3 2-tert. Butyl-1,8-dihydroxy-9-(10H)anthracenone by method A EXAMPLE 3 2-tert. Butyl-1,8-dihydroxy-9-(10H)anthracenone by method A About 7 gm of isobutylene were introduced into a refluxing solution of 11.3 gm of 1,8-dihydroxy-9-(10H)anthracenone in 100 ml of chloroform and 6 ml of sulfuric acid. The resulting mixture was poured into water, and the organic phase was separated and worked up as described in Example 2. 3.9 gm of 2-tert. butyl-1,8-dihydroxy-9-(10H)anthracenone, m.p. 126°-127° C., corresponding to 27% of theory, were obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With (2S)-2-{diphenyl[(trimethylsilyl)oxy]methyl}pyrrolidine In toluene at -40℃; for 240h; optical yield given as %ee; enantioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With (2S)-2-{diphenyl[(trimethylsilyl)oxy]methyl}pyrrolidine In toluene at -40℃; for 240h; optical yield given as %ee; enantioselective reaction; | |
95% | With (2S)-2-{diphenyl[(trimethylsilyl)oxy]methyl}pyrrolidine In toluene at -40℃; for 240h; optical yield given as %ee; enantioselective reaction; | 4.2. General experimental procedure for the addition of anthrones to α,β-unsaturated aldehydes General procedure: To a stirred solution of catalyst (S)-III (20 mg, 0.06 mmol) in toluene (2 mL) were added the α,β-unsaturated aldehyde (0.25 mmol) and the anthrone (1a or 1b, 0.30 mmol). The reaction crude was vigorously stirred at -40 °C until the starting anthrone was not detected by 1H NMR. After warming up the reaction flask to room temperature, the reaction crude was directly purified by column chromatography on silica gel (hexane/ethyl acetate mixtures) to afford the Michael adduct. Racemic products were obtained from the corresponding substrates by catalysis with an artificially constructed racemic mixture of III in toluene at room temperature during 5 days. Enantiomeric purities were directly determined from the crude reaction mixture immediately after complete conversion, because racemization took place at room temperature. This fact precluded in most instances the reliable determination of specific rotations for adducts 3 and 4. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With (2S)-2-{diphenyl[(trimethylsilyl)oxy]methyl}pyrrolidine In toluene at -40℃; for 240h; optical yield given as %ee; enantioselective reaction; | |
92% | With (2S)-2-{diphenyl[(trimethylsilyl)oxy]methyl}pyrrolidine In toluene at -40℃; for 240h; optical yield given as %ee; enantioselective reaction; | 4.2. General experimental procedure for the addition of anthrones to α,β-unsaturated aldehydes General procedure: To a stirred solution of catalyst (S)-III (20 mg, 0.06 mmol) in toluene (2 mL) were added the α,β-unsaturated aldehyde (0.25 mmol) and the anthrone (1a or 1b, 0.30 mmol). The reaction crude was vigorously stirred at -40 °C until the starting anthrone was not detected by 1H NMR. After warming up the reaction flask to room temperature, the reaction crude was directly purified by column chromatography on silica gel (hexane/ethyl acetate mixtures) to afford the Michael adduct. Racemic products were obtained from the corresponding substrates by catalysis with an artificially constructed racemic mixture of III in toluene at room temperature during 5 days. Enantiomeric purities were directly determined from the crude reaction mixture immediately after complete conversion, because racemization took place at room temperature. This fact precluded in most instances the reliable determination of specific rotations for adducts 3 and 4. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With (2S)-2-{diphenyl[(trimethylsilyl)oxy]methyl}pyrrolidine In toluene at -40℃; for 240h; optical yield given as %ee; enantioselective reaction; | |
88% | With (2S)-2-{diphenyl[(trimethylsilyl)oxy]methyl}pyrrolidine In toluene at -40℃; for 240h; optical yield given as %ee; enantioselective reaction; | 4.2. General experimental procedure for the addition of anthrones to α,β-unsaturated aldehydes General procedure: To a stirred solution of catalyst (S)-III (20 mg, 0.06 mmol) in toluene (2 mL) were added the α,β-unsaturated aldehyde (0.25 mmol) and the anthrone (1a or 1b, 0.30 mmol). The reaction crude was vigorously stirred at -40 °C until the starting anthrone was not detected by 1H NMR. After warming up the reaction flask to room temperature, the reaction crude was directly purified by column chromatography on silica gel (hexane/ethyl acetate mixtures) to afford the Michael adduct. Racemic products were obtained from the corresponding substrates by catalysis with an artificially constructed racemic mixture of III in toluene at room temperature during 5 days. Enantiomeric purities were directly determined from the crude reaction mixture immediately after complete conversion, because racemization took place at room temperature. This fact precluded in most instances the reliable determination of specific rotations for adducts 3 and 4. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
46% | With triethylamine In toluene at 20℃; for 3.5h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
31% | With triethylamine In dichloromethane at 26℃; for 24h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With 1-{3,5-bis(trifluoromethyl)phenyl}-3-{(1R,2R)-2-(dimethylamino)cyclohexyl}thiourea In toluene at 20℃; for 14h; optical yield given as %ee; enantioselective reaction; | |
93% | With 1-{3,5-bis(trifluoromethyl)phenyl}-3-{(1R,2R)-2-(dimethylamino)cyclohexyl}thiourea In toluene at 20℃; for 14h; optical yield given as %ee; enantioselective reaction; | 4.5. General experimental procedure for the addition of anthrones to maleimides General procedure: To a stirred solution of catalyst (R,R)-V (10 mg, 0.025 mmol) in toluene (1 mL) were added the maleimide (0.30 mmol) and the anthrone (1a or 1b, 0.25 mmol). The reaction mixture was vigorously stirred at room temperature during 14 h, and the crude product was directly purified by column chromatography on silica gel (hexane/ethyl acetate mixtures) to afford the Diels-Alder or the Michael adduct. Racemic products were obtained from the corresponding substrates by catalysis with DABCO in toluene at room temperature. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With 1-{3,5-bis(trifluoromethyl)phenyl}-3-{(1R,2R)-2-(dimethylamino)cyclohexyl}thiourea; In toluene; at 20℃; for 14h; | General procedure: To a stirred solution of catalyst (R,R)-V (10 mg, 0.025 mmol) in toluene (1 mL) were added the maleimide (0.30 mmol) and the anthrone (1a or 1b, 0.25 mmol). The reaction mixture was vigorously stirred at room temperature during 14 h, and the crude product was directly purified by column chromatography on silica gel (hexane/ethyl acetate mixtures) to afford the Diels-Alder or the Michael adduct. Racemic products were obtained from the corresponding substrates by catalysis with DABCO in toluene at room temperature. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With 1-{3,5-bis(trifluoromethyl)phenyl}-3-{(1R,2R)-2-(dimethylamino)cyclohexyl}thiourea; In toluene; at 20℃; for 14h; | General procedure: To a stirred solution of catalyst (R,R)-V (10 mg, 0.025 mmol) in toluene (1 mL) were added the maleimide (0.30 mmol) and the anthrone (1a or 1b, 0.25 mmol). The reaction mixture was vigorously stirred at room temperature during 14 h, and the crude product was directly purified by column chromatography on silica gel (hexane/ethyl acetate mixtures) to afford the Diels-Alder or the Michael adduct. Racemic products were obtained from the corresponding substrates by catalysis with DABCO in toluene at room temperature. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With 1-{3,5-bis(trifluoromethyl)phenyl}-3-{(1R,2R)-2-(dimethylamino)cyclohexyl}thiourea In toluene at -40℃; for 14h; optical yield given as %ee; enantioselective reaction; | 4.4. General experimental procedure for the addition of anthrones to trans-β-nitrostyrenes General procedure: To a stirred solution of catalyst (R,R)-V (10 mg, 0.025 mmol) in toluene (1 mL) were added the nitrostyrene (0.30 mmol) and the anthrone (1a or 1b, 0.25 mmol). The reaction crude was vigorously stirred at room temperature (anthrone 1a) or at -40 °C (dithranol 1b) during 14 h. After warming up the reaction flask to room temperature, the crude product was directly purified by column chromatography on silica gel (hexane/ethyl acetate mixtures) to afford the Michael adduct. Racemic products were obtained from the corresponding substrates by catalysis with DABCO in toluene at room temperature. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With 1-{3,5-bis(trifluoromethyl)phenyl}-3-{(1R,2R)-2-(dimethylamino)cyclohexyl}thiourea In toluene at 20℃; for 14h; | 4.4. General experimental procedure for the addition of anthrones to trans-β-nitrostyrenes General procedure: To a stirred solution of catalyst (R,R)-V (10 mg, 0.025 mmol) in toluene (1 mL) were added the nitrostyrene (0.30 mmol) and the anthrone (1a or 1b, 0.25 mmol). The reaction crude was vigorously stirred at room temperature (anthrone 1a) or at -40 °C (dithranol 1b) during 14 h. After warming up the reaction flask to room temperature, the crude product was directly purified by column chromatography on silica gel (hexane/ethyl acetate mixtures) to afford the Michael adduct. Racemic products were obtained from the corresponding substrates by catalysis with DABCO in toluene at room temperature. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With 1-{3,5-bis(trifluoromethyl)phenyl}-3-{(1R,2R)-2-(dimethylamino)cyclohexyl}thiourea In toluene at 20℃; for 14h; optical yield given as %ee; enantioselective reaction; | 4.5. General experimental procedure for the addition of anthrones to maleimides General procedure: To a stirred solution of catalyst (R,R)-V (10 mg, 0.025 mmol) in toluene (1 mL) were added the maleimide (0.30 mmol) and the anthrone (1a or 1b, 0.25 mmol). The reaction mixture was vigorously stirred at room temperature during 14 h, and the crude product was directly purified by column chromatography on silica gel (hexane/ethyl acetate mixtures) to afford the Diels-Alder or the Michael adduct. Racemic products were obtained from the corresponding substrates by catalysis with DABCO in toluene at room temperature. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With 1-{3,5-bis(trifluoromethyl)phenyl}-3-{(1R,2R)-2-(dimethylamino)cyclohexyl}thiourea In toluene at 20℃; for 14h; | 4.5. General experimental procedure for the addition of anthrones to maleimides General procedure: To a stirred solution of catalyst (R,R)-V (10 mg, 0.025 mmol) in toluene (1 mL) were added the maleimide (0.30 mmol) and the anthrone (1a or 1b, 0.25 mmol). The reaction mixture was vigorously stirred at room temperature during 14 h, and the crude product was directly purified by column chromatography on silica gel (hexane/ethyl acetate mixtures) to afford the Diels-Alder or the Michael adduct. Racemic products were obtained from the corresponding substrates by catalysis with DABCO in toluene at room temperature. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With (2S)-2-{diphenyl[(trimethylsilyl)oxy]methyl}pyrrolidine In toluene at -40℃; for 240h; optical yield given as %ee; enantioselective reaction; | 4.2. General experimental procedure for the addition of anthrones to α,β-unsaturated aldehydes General procedure: To a stirred solution of catalyst (S)-III (20 mg, 0.06 mmol) in toluene (2 mL) were added the α,β-unsaturated aldehyde (0.25 mmol) and the anthrone (1a or 1b, 0.30 mmol). The reaction crude was vigorously stirred at -40 °C until the starting anthrone was not detected by 1H NMR. After warming up the reaction flask to room temperature, the reaction crude was directly purified by column chromatography on silica gel (hexane/ethyl acetate mixtures) to afford the Michael adduct. Racemic products were obtained from the corresponding substrates by catalysis with an artificially constructed racemic mixture of III in toluene at room temperature during 5 days. Enantiomeric purities were directly determined from the crude reaction mixture immediately after complete conversion, because racemization took place at room temperature. This fact precluded in most instances the reliable determination of specific rotations for adducts 3 and 4. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With 1-{3,5-bis(trifluoromethyl)phenyl}-3-{(1R,2R)-2-(dimethylamino)cyclohexyl}thiourea In toluene at -40℃; for 14h; optical yield given as %ee; enantioselective reaction; | 4.4. General experimental procedure for the addition of anthrones to trans-β-nitrostyrenes General procedure: To a stirred solution of catalyst (R,R)-V (10 mg, 0.025 mmol) in toluene (1 mL) were added the nitrostyrene (0.30 mmol) and the anthrone (1a or 1b, 0.25 mmol). The reaction crude was vigorously stirred at room temperature (anthrone 1a) or at -40 °C (dithranol 1b) during 14 h. After warming up the reaction flask to room temperature, the crude product was directly purified by column chromatography on silica gel (hexane/ethyl acetate mixtures) to afford the Michael adduct. Racemic products were obtained from the corresponding substrates by catalysis with DABCO in toluene at room temperature. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With 1-{3,5-bis(trifluoromethyl)phenyl}-3-{(1R,2R)-2-(dimethylamino)cyclohexyl}thiourea In toluene at -40℃; for 14h; optical yield given as %ee; enantioselective reaction; | 4.4. General experimental procedure for the addition of anthrones to trans-β-nitrostyrenes General procedure: To a stirred solution of catalyst (R,R)-V (10 mg, 0.025 mmol) in toluene (1 mL) were added the nitrostyrene (0.30 mmol) and the anthrone (1a or 1b, 0.25 mmol). The reaction crude was vigorously stirred at room temperature (anthrone 1a) or at -40 °C (dithranol 1b) during 14 h. After warming up the reaction flask to room temperature, the crude product was directly purified by column chromatography on silica gel (hexane/ethyl acetate mixtures) to afford the Michael adduct. Racemic products were obtained from the corresponding substrates by catalysis with DABCO in toluene at room temperature. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With 1-{3,5-bis(trifluoromethyl)phenyl}-3-{(1R,2R)-2-(dimethylamino)cyclohexyl}thiourea In toluene at -40℃; for 14h; optical yield given as %ee; enantioselective reaction; | 4.4. General experimental procedure for the addition of anthrones to trans-β-nitrostyrenes General procedure: To a stirred solution of catalyst (R,R)-V (10 mg, 0.025 mmol) in toluene (1 mL) were added the nitrostyrene (0.30 mmol) and the anthrone (1a or 1b, 0.25 mmol). The reaction crude was vigorously stirred at room temperature (anthrone 1a) or at -40 °C (dithranol 1b) during 14 h. After warming up the reaction flask to room temperature, the crude product was directly purified by column chromatography on silica gel (hexane/ethyl acetate mixtures) to afford the Michael adduct. Racemic products were obtained from the corresponding substrates by catalysis with DABCO in toluene at room temperature. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With 1,4-diaza-bicyclo[2.2.2]octane In toluene at 20℃; for 14h; optical yield given as %de; diastereoselective reaction; | 4.5. General experimental procedure for the addition of anthrones to maleimides General procedure: To a stirred solution of catalyst (R,R)-V (10 mg, 0.025 mmol) in toluene (1 mL) were added the maleimide (0.30 mmol) and the anthrone (1a or 1b, 0.25 mmol). The reaction mixture was vigorously stirred at room temperature during 14 h, and the crude product was directly purified by column chromatography on silica gel (hexane/ethyl acetate mixtures) to afford the Diels-Alder or the Michael adduct. Racemic products were obtained from the corresponding substrates by catalysis with DABCO in toluene at room temperature. | |
With 1-{3,5-bis(trifluoromethyl)phenyl}-3-{(1R,2R)-2-(dimethylamino)cyclohexyl}thiourea In toluene at 20℃; for 14h; optical yield given as %de; diastereoselective reaction; | 4.5. General experimental procedure for the addition of anthrones to maleimides General procedure: To a stirred solution of catalyst (R,R)-V (10 mg, 0.025 mmol) in toluene (1 mL) were added the maleimide (0.30 mmol) and the anthrone (1a or 1b, 0.25 mmol). The reaction mixture was vigorously stirred at room temperature during 14 h, and the crude product was directly purified by column chromatography on silica gel (hexane/ethyl acetate mixtures) to afford the Diels-Alder or the Michael adduct. Racemic products were obtained from the corresponding substrates by catalysis with DABCO in toluene at room temperature. |