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CAS No. : | 22274-75-5 | MDL No. : | |
Formula : | C13H20O5 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | - |
M.W : | 256.30 | Pubchem ID : | - |
Synonyms : |
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Signal Word: | Class: | ||
Precautionary Statements: | UN#: | ||
Hazard Statements: | Packing Group: |
* 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 |
---|---|---|
100% | With hydrotalcite at 80℃; for 6h; | |
99% | With dmap; 1-(3,5-Bis-trifluoromethyl-phenyl)-3-isopropyl-thiourea In toluene at 20℃; for 12h; | |
98% | With 1,6-bis(dodecyldimethylamino)hexane dibromide; sodium hydroxide at 25℃; for 0.0333333h; Sonication; neat (no solvent); |
92% | Stage #1: cyclohexenone; diethyl malonate With sodium hydride In diethyl ether at 20℃; Stage #2: With hydrogenchloride In diethyl ether; water | |
90% | With 1-butyl-3-methylimidazolium hydroxide at 20℃; for 4h; | |
90% | With 1-butyl-3-methylimidazolium hydroxide at 20℃; for 4h; | |
90% | In acetonitrile at 25℃; for 1.5h; | 3.d The catalyst obtained in example 1 was utilised to catalyse Michael's reactions by global budget/balance: Table 2, hereunder, groups the results observed for different kinds of acceptors and donors. The corresponding reactions (a) to (k) were achieved through reaction at a temperature of 25° C., under agitation and in 5 ml of dry acetonitril, 1 millimole of an acceptor like compound and 1 millimole of a donor like compound, in the presence of 0.1 g of ‘HDT-F’ catalyst prepared in example 1. |
90% | With lithium perchlorate; triethylamine at 20℃; for 1h; Inert atmosphere; | |
89% | With nickel(II) ferrite In ethanol; water Heating; Green chemistry; | |
87% | With lithium aluminium tetrahydride; bis N-<(1R)-1-hydroxyphenylethan-2-yl> benzylamine In tetrahydrofuran at 20℃; for 6h; | |
82% | With potassium carbonate In dichloromethane at 20℃; | |
63% | With benzoic acid In water at 20℃; for 48h; | E1. General Procedure for β-Functionalization of Enones General procedure: A 4 mL glass vial was charged with the appropriate nucleophile 3a-e or 2a (0.1 mmol, 1 equiv.), NCDs-1 (3.6% w/v, 14.4mg), the appropriate enone 1a-d (0,3 mmol, 3 equiv.), the corresponding acid (HA, 20 mol%) and solvent (finalconcentration: 0.25 M). The resulting mixture was stirred for the indicated time (generally 48 hours) at ambient temperature.The reaction crude was then extracted with ethyl acetate and the organic phase was filtered through sodium sulfate. Thesolvent was removed under reduced pressure and the residue was purified by column chromatography (eluent: hexane/ethylacetate) to give the corresponding β-functionalized carbonyl compounds 4a-h. TFA (HA) and milli-Q water/dioxane (1:1)were used for the synthesis of compounds 4a-b. Benzoic acid (HA) and pure milli-Q water were used for the synthesis ofcompounds 4c-h. |
49% | With tetrabutylammonium borohydride In methanol | |
32% | With lipozyme TLIM In water; dimethyl sulfoxide at 35℃; for 72h; Enzymatic reaction; | |
30% | With sodium carbonate for 5h; | |
15% | In acetonitrile at 79.9℃; for 60h; | |
With sodium In diethyl ether; ethanol | ||
89 % Chromat. | In 1,4-dioxane at 60℃; for 2h; | |
89 % Chromat. | In 1,4-dioxane at 60℃; for 2h; other catalysts, other solvents; | |
With triethylamine; magnesium chloride 1.) acetonitrile, 2 h, 2.) acetonitrile, RT; Yield given. Multistep reaction; | ||
With N,N,N,N,N,N-hexamethylphosphoric triamide; lithium chloride 1.) RT, 15 min, 2.) 90 deg C, 3 h; Yield given. Multistep reaction; | ||
With sodium In ethanol | 1 Example 1 A solution of 30 ml of 2-cyclohexen-1-one in 35 ml anhydrous ethanol is added dropwise at a temperature below -10° to a reagent prepared from 0.1 g sodium, 100 ml of absolute ethanol and 50 ml of diethyl malonate. The reaction mixture is allowed to warm slowly and is stirred at room temperature overnight. The mixture is evaporated to dryness, the residue is dissolved in ether, the ether solution is washed with brine, dried, filtered and evaporated to dryness. The residue is distilled under reduced pressure to yield diethyl 3-oxocyclohexylmalonate, b.p. 147°/0.5 mm. | |
With 1,8-diazabicyclo[5.4.0]undec-7-ene | ||
8 g | With 1,8-diazabicyclo[5.4.0]undec-7-ene In tetrahydrofuran at 50℃; for 16h; | Intermediate 45A: Diethyl 2-(3-oxocyclohexyl)malonate Intermediate 45A: Diethyl 2-(3-oxocyclohexyl)malonate A solution of cyclohex-2-enone (3.05 mL, 30 mmol) and diethyl malonate (4.58 mL, 30.0 mmol) in THF (30 mL) was treated with 1,8-diazabicyclo[5.4.0]undec-7-ene (4.52 mL, 30.0 mmol) and heated at 50° C. for 16 h. The cooled mixture was poured into EtOAc and washed sequentially with 1M aqueous HCl and brine. The combined aqueous layers were extracted with EtOAc, and the combined organic phases were dried and concentrated to give diethyl 2-(3-oxocyclohexyl)malonate as an oil (8.0 g), used without further purification. Mass spectrum m/z 257 (M+H)+. |
With sodium ethanolate In tetrahydrofuran at 20℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogenchloride 1.) THF, r.t., 15 h; Yield given. Multistep reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With toluene-4-sulfonic acid In benzene for 6h; Heating; removal of water; | |
With toluene-4-sulfonic acid In various solvent(s) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogenchloride In acetic acid | ||
With hydrogenchloride In water at 90℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogenchloride 1.) CH2Cl2, rt, 5 h; ether, water; Yield given. Multistep reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With ethanol; sodium ethanolate |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 53% 2: 24% | Stage #1: diethyl malonate With n-butyllithium In tetrahydrofuran at 20℃; for 0.5h; Stage #2: Trifluoro-methanesulfonate[3-(tert-butyl-dimethyl-silanyloxy)-cyclohex-2-enyl]-triphenyl-phosphonium; In tetrahydrofuran at 65℃; for 3h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With indium; chloro-trimethyl-silane In tetrahydrofuran at 20℃; for 0.5h; | |
71% | With indium; chloro-trimethyl-silane In tetrahydrofuran at 20℃; for 0.5h; Inert atmosphere; | 1.1 Synth is of 1,3-diethyl 2-(3-oxocyclohexyl)propanedioate Into a 1L round-bottom flask placed a solution of cyclohex-2-en-l-one (15.00 g, 156.04 mmol, 1.00 equiv) in anhydrous THF (300 mL) was added 1,3-diethyl 2- bromopropanedioate (56.00 g, 234.25 mmol, 1.50 equiv), In powder (18.00 g, 1.00 equiv) and TMSCI (87.00 g, 800.81 mmol, 5.00 equiv) under nitrogen. The resulting solution was stirred for 30 min at room temperature and quenched by the addition of 200 mL of saturated aqueous sodium carbonate, extracted with 3 x 300 mL of ethyl acetate. The combined organic layers were washed with brine, dried over anhydrous sodium sulfate and concentrated under vacuum. The residue was purified by silica gel column chromatography with ethyl acetate/petroleum ether (1 :5) to give 1,3-diethyl 2-(3-oxocyclohexyl)propanedioate (28.50 g, 71%) as yellow oil. |
71% | With indium; chloro-trimethyl-silane In tetrahydrofuran at 20℃; for 0.5h; Inert atmosphere; | 62 Synthesis of compound 62.2 [00472] Synthesis of compound 62.2. Into a 1 L round-bottom flask was placed a solution of cyclohex-2-en-l-one (15.00 g, 156.04 mmol, 1.00 equiv) in anhydrous THF (300 mL). 1,3- diethyl 2-bromopropanedioate (56.00 g, 234.25 mmol, 1.50 equiv), In powder (18.00 g, 1.00 equiv) and TMSC1 (87.00 g, 800.81 mmol, 5.00 equiv) were added under nitrogen. The resulting solution was stirred for 30 min at room temperature and quenched by the addition of 200 mL of saturated aqueous sodium carbonate, extracted with 3 x 300 mL of ethyl acetate. The combined organic layers were washed with brine, dried over anhydrous sodium sulfate and concentrated under vacuum. The residue was applied onto a silica gel column with ethyl acetate/petroleum ether (1 :5) to give 1,3-diethyl 2-(3-oxocyclohexyl)propanedioate (28.50 g, 71%) as a yellow oil. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | Stage #1: cyclohexanone With lithium diisopropyl amide In tetrahydrofuran at -78℃; for 0.5h; Stage #2: With N-(tert-butyl)benzenesulfinimidoyl chloride In tetrahydrofuran at -78℃; for 0.25h; Stage #3: diethyl malonate With sodium hydride In tetrahydrofuran for 6h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1.1: tetrahydrofuran / 0.67 h / 0 - 20 °C 2.1: n-BuLi / tetrahydrofuran / 0.5 h / 20 °C 2.2: 24 percent / tetrahydrofuran / 3 h / 65 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: 97 percent / p-toluenesulphonic acid / benzene / 6 h / Heating; removal of water 2: 95.7 percent / NaCl / dimethylsulfoxide; H2O / 18 h / 165 °C 3: 94 percent / LAH / diethyl ether / 2.5 h / 30 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: 97 percent / p-toluenesulphonic acid / benzene / 6 h / Heating; removal of water 2: 95.7 percent / NaCl / dimethylsulfoxide; H2O / 18 h / 165 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 4 steps 1: 97 percent / p-toluenesulphonic acid / benzene / 6 h / Heating; removal of water 2: 95.7 percent / NaCl / dimethylsulfoxide; H2O / 18 h / 165 °C 3: 94 percent / LAH / diethyl ether / 2.5 h / 30 °C 4: 81.5 percent / CrO3, pyridine / CH2Cl2 / 0.5 h / 25 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 4 steps 1: p-toluenesulfonic acid / various solvent(s) 2: LiAlH4 / diethyl ether / 3 h / Heating 3: triethylamine / CH2Cl2 / 1 h / 0 - 5 °C 4: 97 percent / tetraethylammonium p-toluenesulfonate / dimethylformamide / electrochemical reduction |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: p-toluenesulfonic acid / various solvent(s) 2: LiAlH4 / diethyl ether / 3 h / Heating |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: p-toluenesulfonic acid / various solvent(s) 2: LiAlH4 / diethyl ether / 3 h / Heating 3: triethylamine / CH2Cl2 / 1 h / 0 - 5 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: aq. HCl / acetic acid 2: aq. HCl / benzene | ||
22.7 g | With sodium chloride In water; dimethyl sulfoxide at 180℃; for 24h; | 1.2 Synthesis of ethyl 2-(3-oxocyclohexyl)acetate A solution of 1,3-diethyl 2-(3-oxocyclohexyl)propanedioate (28.50 g, 111.20 mmol, 1.00 equiv) and sodium chloride (7.02 g, 1.10 equiv) in a miture of water (4 mL) / DMSO (80 mL) was heated for 24 h at 180°C in an oil bath. After cooled down to r.t, the reaction was then diluted with water, extracted with 3 x 300 mL of ethyl acetate. The organic layers were combined, washed with water and brine, dried over anhydrous sodium sulfate and concentrated under vacuum to give ethyl 2-(3-oxocyclohexyl)acetate (22.7 g, crude) as yellow oil which was used for next step without purification. |
With water; sodium chloride In dimethyl sulfoxide at 180℃; for 24h; | 62 Synthesis of compound 62.3. [00473] Synthesis of compound 62.3. A solution of 1,3-diethyl 2-(3- oxocyclohexyl)propanedioate (28.50 g, 111.20 mmol, 1.00 equiv) and sodium chloride (7.02 g, 1.10 equiv) in a mixture of water (4 mL) and DMSO (80 mL) was heated for 24 h at 180 °C in an oil bath. After cooling to r.t, the reaction was diluted with water and extracted with 3 x 300 mL of ethyl acetate. The organic layers were combined, washed with water and brine, dried over anhydrous sodium sulfate and concentrated under vacuum to give the desired ethyl 2-(3- oxocyclohexyl)acetate (22.7 g, crude) as a yellow oil. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | Stage #1: Stage #2: Heating / reflux; | |
88% | 9.A Step A Step A 2-(3-Oxo-cyclohexyl)-malonic Acid Diethyl Ester Diester xviii is prepared in 88% yield from cyclohex-2-enone by the method described for the synthesis of diester xvi above: 1H NMR (300 MHz, CDCl3) δ 4.44-4.12 (m, 4H), 2.88-1.22 (m, 16H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
109 Diethyl (9-Benzyl-1,2,3,4-tetrahydrocarbazol-2-yl)malonate EXAMPLE 109 Diethyl (9-Benzyl-1,2,3,4-tetrahydrocarbazol-2-yl)malonate The title compound was obtained by following a procedure and using relative proportions of starting materials similar to those described in Example 48, but using N,N-benzylphenylhydrazine and diethyl 3-oxocyclohexylmalonate as starting materials. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | In tetrahydrofuran Stirring of mixt. at room temp. for 15 h.; Extg. (ether), washing of ext. (aq. HCL, H2O), drying (Na2SO4), evapn., chromy. (hexane-ethyl acetate), elem. anal.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 45% 2: 4% 3: 26% | With palladium diacetate; triethylamine; triphenylphosphine In water; acetonitrile for 2h; Reflux; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 63% 2: 28% | With formic acid; palladium diacetate; triethylamine; triphenylphosphine In acetonitrile for 1h; Reflux; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With 1-butyl-3-pyrrolidin-2-ylmethyl-3<i>H</i>-benzoimidazol-1-ium; bromide; benzene-1,2-dicarboxylic acid In 1,2-dichloro-ethane at 20℃; for 80h; Inert atmosphere; optical yield given as %ee; enantioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With 1-butyl-3-pyrrolidin-2-ylmethyl-3<i>H</i>-benzoimidazol-1-ium; bromide; benzene-1,2-dicarboxylic acid In 1,2-dichloro-ethane at 20℃; for 72h; Inert atmosphere; Resolution of racemate; optical yield given as %ee; enantioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | Stage #1: 1,3-diethyl 2-(3-oxocyclohexyl)propanedioate With sodium tetrahydroborate In ethanol at 20℃; for 3h; Stage #2: With hydrogenchloride In water |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With Saccharomyces cerevisiae AM 464 In acetone at 25℃; aq. buffer; Enzymatic reaction; optical yield given as %ee; enantioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 310 mg 2: 290 mg | With eschenmoser's salt In acetone at 28℃; for 12h; aq. buffer; Enzymatic reaction; optical yield given as %ee; enantioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With iodine; oxygen; sodium acetate In tetrahydrofuran at 35℃; for 24h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With hydroxylamine hydrochloride; triethylamine In ethanol for 1h; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: hydroxylamine hydrochloride; triethylamine / ethanol / 1 h / Reflux 2: triethylamine / dichloromethane / 2 h / 0 - 20 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: hydroxylamine hydrochloride; triethylamine / ethanol / 1 h / Reflux 2: triethylamine / dichloromethane / 2 h / 0 - 20 °C 3: sodium hydride / tetrahydrofuran / 0.5 h / Reflux |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 7 steps 1: sodium chloride / water; dimethyl sulfoxide / 24 h / 180 °C 2: sulfur; diethylamine / ethanol / 20 °C 3: 4 h / 180 °C 4: 2,3-dicyano-5,6-dichloro-p-benzoquinone / 1,4-dioxane / 2 h / 90 °C / Inert atmosphere 5: trichlorophosphate / 1 h / 90 °C 6: potassium carbonate; triethylamine / acetonitrile / 80 °C / Inert atmosphere 7: lithium aluminium tetrahydride / tetrahydrofuran / 0 - 20 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: sodium chloride / water; dimethyl sulfoxide / 24 h / 180 °C 2: sulfur; diethylamine / ethanol / 20 °C | ||
Multi-step reaction with 2 steps 1: sodium chloride; water / dimethyl sulfoxide / 24 h / 180 °C 2: diethylamine; sulfur / ethanol |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: sodium chloride / water; dimethyl sulfoxide / 24 h / 180 °C 2: sulfur; diethylamine / ethanol / 20 °C 3: 4 h / 180 °C | ||
Multi-step reaction with 3 steps 1: sodium chloride; water / dimethyl sulfoxide / 24 h / 180 °C 2: diethylamine; sulfur / ethanol 3: 4 h / 180 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 4 steps 1: sodium chloride / water; dimethyl sulfoxide / 24 h / 180 °C 2: sulfur; diethylamine / ethanol / 20 °C 3: 4 h / 180 °C 4: 2,3-dicyano-5,6-dichloro-p-benzoquinone / 1,4-dioxane / 2 h / 90 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 5 steps 1: sodium chloride / water; dimethyl sulfoxide / 24 h / 180 °C 2: sulfur; diethylamine / ethanol / 20 °C 3: 4 h / 180 °C 4: 2,3-dicyano-5,6-dichloro-p-benzoquinone / 1,4-dioxane / 2 h / 90 °C / Inert atmosphere 5: trichlorophosphate / 1 h / 90 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 6 steps 1: sodium chloride / water; dimethyl sulfoxide / 24 h / 180 °C 2: sulfur; diethylamine / ethanol / 20 °C 3: 4 h / 180 °C 4: 2,3-dicyano-5,6-dichloro-p-benzoquinone / 1,4-dioxane / 2 h / 90 °C / Inert atmosphere 5: trichlorophosphate / 1 h / 90 °C 6: potassium carbonate; triethylamine / acetonitrile / 80 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 6 steps 1: sodium chloride / water; dimethyl sulfoxide / 24 h / 180 °C 2: sulfur; diethylamine / ethanol / 20 °C 3: 4 h / 180 °C 4: 2,3-dicyano-5,6-dichloro-p-benzoquinone / 1,4-dioxane / 2 h / 90 °C / Inert atmosphere 5: trichlorophosphate / 1 h / 90 °C 6: diisobutylaluminium hydride / tetrahydrofuran / 3 h / -78 - 20 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 7 steps 1: sodium chloride / water; dimethyl sulfoxide / 24 h / 180 °C 2: sulfur; diethylamine / ethanol / 20 °C 3: 4 h / 180 °C 4: 2,3-dicyano-5,6-dichloro-p-benzoquinone / 1,4-dioxane / 2 h / 90 °C / Inert atmosphere 5: trichlorophosphate / 1 h / 90 °C 6: diisobutylaluminium hydride / tetrahydrofuran / 3 h / -78 - 20 °C / Inert atmosphere 7: 1H-imidazole / N,N-dimethyl-formamide / 20 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 8 steps 1.1: sodium chloride / water; dimethyl sulfoxide / 24 h / 180 °C 2.1: sulfur; diethylamine / ethanol / 20 °C 3.1: 4 h / 180 °C 4.1: 2,3-dicyano-5,6-dichloro-p-benzoquinone / 1,4-dioxane / 2 h / 90 °C / Inert atmosphere 5.1: trichlorophosphate / 1 h / 90 °C 6.1: diisobutylaluminium hydride / tetrahydrofuran / 3 h / -78 - 20 °C / Inert atmosphere 7.1: 1H-imidazole / N,N-dimethyl-formamide / 20 °C 8.1: sodium hydride / tetrahydrofuran; mineral oil / 0 - 20 °C / Inert atmosphere 8.2: 20 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 9 steps 1.1: sodium chloride / water; dimethyl sulfoxide / 24 h / 180 °C 2.1: sulfur; diethylamine / ethanol / 20 °C 3.1: 4 h / 180 °C 4.1: 2,3-dicyano-5,6-dichloro-p-benzoquinone / 1,4-dioxane / 2 h / 90 °C / Inert atmosphere 5.1: trichlorophosphate / 1 h / 90 °C 6.1: diisobutylaluminium hydride / tetrahydrofuran / 3 h / -78 - 20 °C / Inert atmosphere 7.1: 1H-imidazole / N,N-dimethyl-formamide / 20 °C 8.1: sodium hydride / tetrahydrofuran; mineral oil / 0 - 20 °C / Inert atmosphere 8.2: 20 °C / Inert atmosphere 9.1: tetrabutyl ammonium fluoride / tetrahydrofuran / 5 h / 20 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 7 steps 1: sodium chloride / water; dimethyl sulfoxide / 24 h / 180 °C 2: sulfur; diethylamine / ethanol / 20 °C 3: 4 h / 180 °C 4: 2,3-dicyano-5,6-dichloro-p-benzoquinone / 1,4-dioxane / 2 h / 90 °C / Inert atmosphere 5: trichlorophosphate / 1 h / 90 °C 6: potassium carbonate; triethylamine / acetonitrile / 80 °C / Inert atmosphere 7: ammonia / ethanol / 20 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
49% | In acetic acid at 20℃; Reflux; | Intermediate 45B: 5-Bromo-2-(1,3-diethoxy-1,3-dioxopropan-2-yl)-6-fluoro-2,3,4,9-tetrahydro-1H-carbazole-8-carboxylic acid Intermediate 45B: 5-Bromo-2-(1,3-diethoxy-1,3-dioxopropan-2-yl)-6-fluoro-2,3,4,9-tetrahydro-1H-carbazole-8-carboxylic acid A solution of diethyl 2-(3-oxocyclohexyl)malonate (15.26 g, 59.5 mmol) and 4-bromo-5-fluoro-2-hydrazinylbenzoic acid hydrochloride [Intermediate 24B] (17.0 g, 59.5 mmol) in acetic acid (120 mL) was heated at reflux for 2 h, then was stirred overnight at room temperature. The precipitate which formed was collected by filtration to provide a white solid. The filtrate was concentrated and purified by column chromatography on silica gel (80 g), eluting with EtOAc-hexanes (gradient from 0-100%). The resulting oily product was crystallized from a mixture of EtOAc, ether and hexanes to provide additional solid, which was combined with the first solid to provide 5-bromo-2-(1,3-diethoxy-1,3-dioxopropan-2-yl)-6-fluoro-2,3,4,9-tetrahydro-1H-carbazole-8-carboxylic acid as a white solid (10.5 g, 49% yield). Mass spectrum m/z 470, 472 (M+H)+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: hydrogenchloride / water / 90 °C 2: triethylamine; diphenyl phosphoryl azide / <i>tert</i>-butyl alcohol / 16 h / 50 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
67% | Stage #1: Methyltriphenylphosphonium bromide With potassium <i>tert</i>-butylate In toluene at 90℃; for 2h; Inert atmosphere; Stage #2: 1,3-diethyl 2-(3-oxocyclohexyl)propanedioate In toluene at 0℃; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1.1: potassium <i>tert</i>-butylate / toluene / 2 h / 90 °C / Inert atmosphere 1.2: 0 °C / Inert atmosphere 2.1: C15H27Cl2CoN2P; ammonia borane / methanol / 3 h / 20 °C / Inert atmosphere; Schlenk technique; Glovebox |