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CAS No. : | 20383-28-2 | MDL No. : | MFCD00026370 |
Formula : | C13H19NO | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | UYXMMJPYFKRKKM-UHFFFAOYSA-N |
M.W : | 205.30 | Pubchem ID : | 88516 |
Synonyms : |
|
Num. heavy atoms : | 15 |
Num. arom. heavy atoms : | 6 |
Fraction Csp3 : | 0.46 |
Num. rotatable bonds : | 4 |
Num. H-bond acceptors : | 1.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 63.57 |
TPSA : | 20.31 Ų |
GI absorption : | High |
BBB permeant : | Yes |
P-gp substrate : | No |
CYP1A2 inhibitor : | No |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -5.78 cm/s |
Log Po/w (iLOGP) : | 2.63 |
Log Po/w (XLOGP3) : | 2.5 |
Log Po/w (WLOGP) : | 2.95 |
Log Po/w (MLOGP) : | 2.99 |
Log Po/w (SILICOS-IT) : | 2.4 |
Consensus Log Po/w : | 2.69 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 0.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -2.72 |
Solubility : | 0.391 mg/ml ; 0.00191 mol/l |
Class : | Soluble |
Log S (Ali) : | -2.57 |
Solubility : | 0.55 mg/ml ; 0.00268 mol/l |
Class : | Soluble |
Log S (SILICOS-IT) : | -3.33 |
Solubility : | 0.0951 mg/ml ; 0.000463 mol/l |
Class : | Soluble |
PAINS : | 0.0 alert |
Brenk : | 0.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 1.0 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H302-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 |
---|---|---|
99% | With diisobutylaluminum borohydride In tetrahydrofuran at 0 - 25℃; Inert atmosphere; | General procedure: The following procedure is a representative. An oven-dried 50-mL round bottom flask was equipped with a magnetic stir bar and cooled under an argon atmosphere. N,N-Diethylbenzamide (0.886 g, 5 mmol, 1 equiv) was added to the flask. The flask was fitted with a rubber septum and purged with argon and cooled to 0 C. Anhydrous THF (5 mL) was added to the flask via a syringe. Diisobutylaluminum borohydride (6.0 mL, 5.5 mmol, 1.1 equiv) was added dropwise over 15 min with stirring. Upon the completion of the addition of diisobutylaluminum borohydride, the ice-bath was removed and the reaction mixture was allowed to stir at 25 C for one hour. The reduction was complete after one hour as evidenced by the disappearance of the signal due to diisobutylaluminum borohydride (d 36.81 p, J = 85 Hz) and appearance of asignal due to amine-borane complex (d 7.0 q, J = 96 Hz) in the 11B NMR spectral analysis of an aliquot. The reaction mixture was then concentrated under reduced pressure using a rota-vap and the reaction flask was recappedwith a septum. Methanol (15 mL) was added slowly to the residue (Caution Hydrogen evolution) and the mixture was stirred for one hour at 25 C. The reaction mixture was concentrated under reduced pressure using a rota-vap togive a white solid. Methanol (15 mL) and then conc. HCl (1 mL) were added and the mixture was refluxed for 1 h, then filtered and concentrated. Pentane(10 mL) and deionized water (5 mL) were added to the filtrate. The layers wereseparated and to the aqueous layer was added sodium hydroxide (NaOHpellets) until the pH of the aqueous layer was 10. The aqueous layer was thenextracted with diethyl ether (3 10 mL). The combined organic layers weredried with anhydrous MgSO4, filtered, and concentrated in vacuo (25 C,1 Torr). The product was essentially pure amine as evidenced by 1H, 13C and 11BNMR spectroscopic analyses. This workup procedure allowed the isolation ofessentially pure amine products without the need for further purificationtechniques, such as column chromatography, distillation, or recrystallization. |
99% | With diisobutylaluminum borohydride In tetrahydrofuran at 25℃; for 1h; Inert atmosphere; | |
98% | With n-butyllithium; borane-THF; di-i-propyl amine at 25℃; |
98% | With lithium diisopropylaminoborohydride In tetrahydrofuran at 25℃; for 2h; | |
95% | With phenylsilane; C28H16F24O8S2Si In 1,2-dichloro-benzene at 100℃; for 48h; Inert atmosphere; | |
92% | With phenylsilane; Cs2CO3 at 80℃; for 24h; Schlenk technique; | |
90% | With dihydrogen hexachloroplatinate(IV) hexahydrate In tetrahydrofuran at 60℃; for 3h; | |
87% | Stage #1: N,N-diisopropyl benzamide With trifluoromethylsulfonic anhydride In dichloromethane at 0 - 5℃; for 0.5h; Stage #2: With sodium tetrahydridoborate In tetrahydrofuran; dichloromethane at 20℃; | |
86% | Stage #1: N,N-diisopropyl benzamide With dicobalt octacarbonyl; phenylsilane In toluene at 100℃; for 16h; Schlenk technique; Inert atmosphere; Stage #2: With sodium hydroxide In methanol; water monomer; toluene at 20℃; for 1h; Schlenk technique; Inert atmosphere; chemoselective reaction; | |
78% | With phenylsilane; C36H61FeN2PSi2 In benzene at 80℃; for 24h; Inert atmosphere; Sealed tube; | |
65% | With 1,1,3,3-Tetramethyldisiloxane; [((CH3)5C5)IrCl((CH3)2NC6H3C5H4N)]; triphenylmethylium tetrakis(pentafluorophenyl)borate In 1,1,2,2-tetrachloroethane at 100℃; for 48h; Inert atmosphere; Schlenk technique; Glovebox; chemoselective reaction; | |
59% | With dodecacarbonyltri-iron In dibutyl ether at 100℃; for 24h; Inert atmosphere; | |
27% | With Pt(I<SUP>t</SUP>Bu)(divinyltetramethyldisiloxane); diphenylsilane In tetrahydrofuran; Hexadecane at 40℃; for 1h; Schlenk technique; Inert atmosphere; | |
With lithium aluminium hydride In diethyl ether | ||
With N,N,N,N,-tetramethylethylenediamine; dimethylsulfide borane complex; boron trifluoride diethyl ether complex 1.) THF, 1 h, 2.) ether, 30 min; Yield given. Multistep reaction; | ||
With lithium aluminium hydride In tetrahydrofuran Heating; | ||
With ethyldimethylsilane; [(POCOP)Ir(H)(acetone)]+[B(C6F5)4]- In chlorobenzene-d5 at 60℃; for 19h; Inert atmosphere; | ||
89 %Chromat. | With tris(pentafluorophenyl)borate In toluene at 100℃; for 18h; Sealed tube; | |
27 %Chromat. | With Pt(I<SUP>t</SUP>Bu)(divinyltetramethyldisiloxane); diphenylsilane In tetrahydrofuran at 40℃; for 1h; Schlenk technique; Inert atmosphere; | |
Multi-step reaction with 2 steps 1: dichloromethane / 20 °C / Cooling with ice 2: platinum on carbon; potassium etoxide; hydrogen / ethanol / 0.2 h / 20 °C / 30003 Torr / Autoclave | ||
> 99 %Spectr. | With phenylsilane; (bis[(2-diphenylphosphino)phenyl]ether)CoCl2; lithium triethylhydroborate In tetrahydrofuran; hexadeuterobenzene at 60℃; for 5h; Inert atmosphere; Sealed tube; | |
With phenylsilane; C33H58N3NiPSi2 In tetrahydrofuran at 75℃; for 18h; Inert atmosphere; Glovebox; | ||
With trimethylsilylmethyllithium; 4,4,5,5-tetramethyl-1,3,2-dioxaborolane In neat (no solvent) at 70℃; for 12h; Schlenk technique; Glovebox; Inert atmosphere; chemoselective reaction; | 5.3 General procedure for the synthesis of compounds 5a-5p General procedure: An oven-dried Schlenk flask was charged with 3mol% of catalyst 1, the required amount of amide precursor (0.50mmol, 1 equiv), and HBpin (1.5mmol, 3 equiv.). The flask was equipped with a magnetic stir bar inside the glove box. The reaction mixture was then heated to 70°C for 12h. The progress of the reaction was monitored by 1H NMR in C6D6 and 1H NMR yield was determined based on the internal standard, HMB (10mol%). In all cases, the product peaks were integrated for the -CH3- peak of the internal standard, which was normalized to 1.8. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70.4% | With n-butyllithium In diethyl ether; hexane at 0℃; for 2h; | |
(i) THF, nBuLi, hexane, (ii) /BRN= 1072099/; Multistep reaction; | ||
(i) nBuLi, THF, (ii) /BRN= 1072099/; Multistep reaction; |
With aluminum (III) chloride at 20℃; for 3h; Milling; | 9 Example 9 20.63 g of methyl benzoate (content 99.0%), 15.49 g of diisopropylamine (content 98.0%) and 6.81 g of aluminum chloride (content 98.0%) were added to a ball mill, and after grinding at room temperature for 3 h, 60 ml of distilled water After washing three times, the layer was allowed to stand to obtain a pale yellow oily liquid, which was the target collector product.The content of N,N-diisopropylbenzamide was 87.63%, and the yield of N,N-diisopropylbenzamide based on methyl benzoate was 89.64%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | Stage #1: N,N-diisopropyl benzamide With tert.-butyl lithium In tetrahydrofuran at -78℃; for 0.75h; Inert atmosphere; Stage #2: 4-butanolide In tetrahydrofuran at -78 - 20℃; for 1h; Inert atmosphere; | 2-(4-Hydroxybutanoyl)-N,N-diisopropylbenzamide (S41) Ν,Ν-Diisopropylbenzamide (S39) (2 g, 9.742 mmol, 1 equiv.) was dissolved in dry THF (75 niL), cooled to -78 °C, and t-BuLi (6.35 niL, 10.81 mmol, 1.11 equiv., 1.7 M in THF) was added. The reaction was stirred for 45 minutes, then γ-butyrolactone (S40) (1.023 g, 11.89 mmol, 1.22 equiv.) was added drop wise. The reaction was stirred for 1 hour while returning to room temperature, then quenched with saturated ammonium chloride (75 mL) and extracted with ethyl acetate (5 x 75 mL). The combined organic extracts were dried (Na2SO4), filtered, and concentrated by rotary evaporation. Purification by silica flash chromatography (100% EtOAc) yielded the product (S41) as a clear and colorless oil (2.570 g, 91%). IR (ATR): 3392.03, 3063.48, 2971.43, 2933.90, 2876.05, 2239.51, 1771.67, 1688.89, 1615.28, 1438.39, 1370.16, 1343.38, 1212.67, 1163.10, 1035.36, 919.87, 773.75, 749.77. 1H-NMR (500 MHz): δ 7.7457 (d, J= 7.68, IH), 7.4867 (t, J=7.46, IH), 7.4035 (t, J= 7.57, IH), 7.1973 (d, J= 7.43, IH), 3.6422 (m, 3H), 3.5089 (p, J= 6.78, IH), 3.0421 (t, J= 6.87, IH), 2.8090 (m, IH), 1.9310 (p, J= 6.39, 6.20, 2H), 1.5585 (d, J=6.78, 6H), 1.1351 (d, J= 6.58, 6H). 13C-NMR (125 MHz): δ δ 202.2687, 170.5203, 138.8097, 136.1131, 131.6439, 128.4759, 128.1557, 126.1526, 61.3600, 51.2894, 45.7528, 36.7801, 26.9920, 20.2568. HRMS (ESI) m/z calcd for C17H26NO3 ([M+H]+) 292.1913; found 292.1934. |
83% | With N,N,N,N,-tetramethylethylenediamine; tert.-butyl lithium In tetrahydrofuran -78 deg C to RT; | |
76% | Stage #1: N,N-diisopropyl benzamide With tert.-butyl lithium In tetrahydrofuran at -78℃; for 1h; Inert atmosphere; Stage #2: 4-butanolide In tetrahydrofuran for 1h; Inert atmosphere; | 4.1; 23.1 Step 1: 2-(4-Hydroxybutyryl)-N,N-diisopropylbenzamide (2) In a 250 mL dry round bottom flask,Compound 1 (23.0 g, 0.11 mol) and anhydrous THF were added under dry nitrogen.Cool the reaction solution to -78 ° C,Slow dropTert-butyllithium (1.3M, 90mL, 0.12mmol),The reaction was completely incubated for 1 h.Γ-butyrolactone (11.2 g, 0.13 mol) was slowly added dropwise.After the addition, the reaction was completed for 1 h. TLC [V (petroleum ether): V (ethyl acetate) = 2:1 as a developing solvent] showed that the reaction was substantially complete.A saturated ammonium chloride solution (200 mL) was added dropwise to the reaction solution.After warming to room temperature, transfer to a separatory funnel.The THF layer was separated and the aqueous layer was extracted with DCM (50 mL×2).Collect the oil layer for use. DecompressionThe THF solution was diluted to dryness, combined with water to a DCM layer (3×30 mL),Wash with saturated aqueous NaCl (60 mL) and collect organic phase.Dry over anhydrous sodium sulfate and concentrate under reduced pressure.The silica gel column separated 25.0 g of a yellow oily liquid.The yield was 76.0%. |
76% | With tert.-butyl lithium In tetrahydrofuran at -78℃; for 1h; | 4.1.7. 2-(4-Hydroxybutanoyl)-N, N-diisopropylbenzamide (22) To a solution of compound 21 (23.0 g, 110 mmol) in anhydrousTHF (100 mL) was slowly added t-BuLi (1.3 M, 90 mL, 0.12 mmol)andg-butyrolactone (11.2 g, 0.13 mol) dropwise and stirred for 1hat78C. The reaction mixture was quenched with saturatedammonium chloride solution (200 mL) at room temperature andextracted with DCM. The organic layer was separated, washed withbrine, dried overNa2SO4,and concentrated in vacuo. The residuewas purified by column chromatography (EA/PE1:2, V/V) to yield;1Hintermediate 22 as yellow oil; yield 76.0%NMR (400 MHz,CD3OD)8.03 (d, J8.1, 1H, ArH), 7.71e7.48 (m, 2H, ArH), 7.29:d(dd,J17.5,J21.4 Hz, 1H, ArH), 3.71e3.48 (m, 4H,eCH2CH2,2-CH2-),3.20e2.90 (m, 2H,eCOCH2, eCH2-),2.01e1.80 (m, 2H,eCH2CH2, eCH2-),1.59 (s, 6H, CH(CH3)2,2-CH3-),1.16e1.50 (s, 6H,13CCH(CH3)2,2-CH3-);NMR (100 MHz,CD3OD)d: 201.93, 172.90,139.37, 135.72, 133.33, 130.32, 129.59, 127.24, 61.78, 52.65, 46.69,36.54, 27.77, 20.26, 19.97; ESI-MS: m/z292.1 [MH] . |
With tert.-butyl lithium 1.) THF, tetramethylethylenediamine, -78 deg C, 0.3 h 2.) THF, tetramethylethylenediamine; Yield given. Multistep reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | Stage #1: N,N-diisopropyl benzamide With MeCu(TMP)(CN)Li2 In tetrahydrofuran; diethyl ether; hexane at 0℃; for 3h; Stage #2: chloro-trimethyl-silane In tetrahydrofuran; diethyl ether; hexane at 50℃; for 16h; Further stages.; | |
62% | Stage #1: N,N-diisopropyl benzamide With (2,2,6,6-tetramethylpiperidido)<SUB>2</SUB>Ag(CN)Li<SUB>2</SUB><SUB> </SUB> at 0℃; for 2h; Stage #2: chloro-trimethyl-silane at 80℃; for 16h; chemoselective reaction; | |
With N,N,N,N,-tetramethylethylenediamine; sec.-butyllithium 1.) THF, cyclohexane, -78 deg C, 1 h, 2.) THF, cyclohexane, RT, 8 h; Yield given. Multistep reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With N-Bromosuccinimide; silver hexafluoroantimonate; dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer; Trimethylacetic acid In 1,2-dichloro-ethane at 60℃; for 16h; Inert atmosphere; regioselective reaction; | |
96% | With N-Bromosuccinimide; bis[dichloro(pentamethylcyclopentadienyl)iridium(III)]; silver trifluoromethanesulfonate; acetic acid In 1,2-dichloro-ethane at 60℃; for 4h; | |
65% | Stage #1: N,N-diisopropyl benzamide With tert.-butyl lithium In glycerol; pentane at 20℃; for 0.000555556h; Stage #2: With ethylene dibromide In pentane at 20℃; chemoselective reaction; |
60% | With N-Bromosuccinimide; dodecacarbonyl-triangulo-triruthenium; silver adamantane-1-carboxylate In 1,2-dichloro-ethane at 120℃; for 16h; Inert atmosphere; | |
With N,N,N,N,-tetramethylethylenediamine; sec.-butyllithium; allyl bromide 1.) THF, -78 deg C, 15 min, 2.) -78 deg C; Yield given. Multistep reaction; | ||
100 %Chromat. | With N-Bromosuccinimide; C16H24Cl2N3Rh(2+)*2F6Sb(1-); Trimethylacetic acid In 1,2-dichloro-ethane at 60℃; for 16h; | 4.3.2. Procedure for screening of the ortho-bromination of N,N-diisopropylbenzamide 6 using PivOH to promote reaction. To a solution of N,N-diisopropylbenzamide 6 (1.375 mmol, 282 mg, 1 equiv), NBS (1.51 mmol, 269 mg,1.1 equiv), PivOH (1.51 mmol,155 mg,1.1 equiv) in DCE (8.8 mL) was added RhCp*(MeCN)3[SbF6]2 (0.028 mmol,23 mg, 2.0 mol %). The reaction mixture was distributed into 11reaction vessels (0.8 mL, 0.125 mmol of N,N-diisopropylbenzamide 6 per reaction), 10 containing one of each additive (0.125 mmol) and one control reaction containing no additive. The reactions were then heated at 60 °C for 16 h before cooling, the addition of mesitylene (0.125 mmol, 17.5 ml) and subsequent GC analysis. For GC sample preparation, the reaction mixture was filtered througha short plug of silica or Celite (vide infra). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | Stage #1: N,N-diisopropyl benzamide With Li(2,2,6,6-tetramethylpiperidide)*Al(iBu)3 In tetrahydrofuran; hexane at 20℃; for 3h; Stage #2: With water-d2 In tetrahydrofuran; hexane at 20℃; for 0.5h; | |
100% | Stage #1: N,N-diisopropyl benzamide With Li(2,2,6,6-tetramethylpiperidide)*Al(iBu)3 In tetrahydrofuran; hexane at 20℃; for 3h; Stage #2: With water-d2 In tetrahydrofuran; hexane at 20℃; for 0.5h; | |
100% | Stage #1: N,N-diisopropyl benzamide In tetrahydrofuran; diethyl ether; hexane at 0℃; for 3h; Stage #2: With water-d2 In tetrahydrofuran; diethyl ether; hexane at 20℃; for 0.5h; Further stages.; |
96% | Stage #1: N,N-diisopropyl benzamide With (2,2,6,6-tetramethylpiperidido)<SUB>2</SUB>Ag(CN)Li<SUB>2</SUB><SUB> </SUB> at 0℃; for 2h; Stage #2: With water-d2 at 20℃; for 16h; chemoselective reaction; | |
95% | With d(4)-methanol; sec.-butyllithium 1.) THF, -78 deg C; | |
90% | Stage #1: N,N-diisopropyl benzamide With n-butyllithium In tetrahydrofuran at -78℃; Stage #2: With 9-Phenylfluorene In tetrahydrofuran at -78 - 20℃; | |
66% | Stage #1: N,N-diisopropyl benzamide With tert.-butyl lithium In glycerol; pentane at 20℃; for 0.000555556h; Stage #2: With d(4)-methanol In glycerol; pentane at 20℃; chemoselective reaction; | |
With N,N,N,N,-tetramethylethylenediamine; water-d2; sec.-butyllithium 1.) THF, -78 deg C, 1 h, 2.) -78 deg C; Yield given. Multistep reaction; | ||
Multi-step reaction with 2 steps 1: 1.) n-BuLi/TMEDA, 2.) CH3OD / 1.) THF, cyclohexane, -78 deg C, 10 min, 2.) -78 deg C 2: 1.) sec-BuLi/TMEDA, 2.) CH3OH / 1.) -78 deg C, 15 min, 2.) -78 deg C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With silver hexafluoroantimonate; vinyl acetate; [Rh(η5-cyclopentadienyl)I2]; tetradeuterioacetic acid; copper(II) acetate monohydrate In tetrahydrofuran at 80℃; for 6h; | |
85% | Stage #1: N,N-diisopropyl benzamide With N,N,N,N,-tetramethylethylenediamine; sec.-butyllithium In tetrahydrofuran at -78℃; Stage #2: With deuteromethanol In tetrahydrofuran at -78 - 20℃; | |
With n-butyllithium; deuteromethanol; N,N,N,N,-tetramethylethylenediamine 1.) THF, cyclohexane, -78 deg C, 10 min, 2.) -78 deg C; Yield given. Multistep reaction; |
With water-d2 In N,N-dimethyl acetamide at 200℃; for 0.0833333h; microwave irradiation; | ||
With dodecacarbonyl-triangulo-triruthenium; d(4)-methanol; silver adamantane-1-carboxylate In 1,2-dichloro-ethane at 100℃; for 16h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With n-butyllithium; borane-THF; 2,3-dihydropyrrole at 65℃; | |
99% | With LiPyrrBH3 In tetrahydrofuran at 25℃; for 2h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | In diethyl ether at 0 - 20℃; | |
100% | With triethylamine In diethyl ether at 20℃; | |
100% | In dichloromethane at 20℃; for 18h; |
97% | With triethylamine In dichloromethane at 20℃; for 0.333333h; | |
92% | With triethylamine In dichloromethane at 20℃; Inert atmosphere; | |
92% | With triethylamine In dichloromethane at 20℃; Inert atmosphere; | |
90% | With 4-dimethylaminopyridine; triethylamine In tetrahydrofuran; dichloromethane at 0 - 20℃; for 12h; | |
90% | With triethylamine In dichloromethane at 0 - 20℃; for 12h; | |
89.8% | With triethylamine In tetrahydrofuran at 0 - 20℃; Inert atmosphere; | |
86% | In tetrahydrofuran at 0℃; for 3h; | |
85% | With sodium hydroxide; tetrabutylammonium bromide In various solvent(s) at 25℃; for 1h; | |
83% | With triethylamine In dichloromethane at 0 - 20℃; | |
80% | With triethylamine In dichloromethane at 20℃; for 2h; | |
62% | With triethylamine In dichloromethane at 20℃; Inert atmosphere; | |
40% | With potassium carbonate In dichloromethane at 20℃; for 22h; Inert atmosphere; | |
In toluene Yield given; | ||
In 1,4-dioxane | ||
In benzene for 3h; 0 deg C to RT; | ||
With triethylamine In dichloromethane at 20℃; Cooling with ice; | 1.1 (1). Synthesis of Coupound 3: Diisopropylamine (1.3 mol) was placed into a 2000 mL round bottom flask, and 1000 mL anhydrous dichloromethane was added. After dissolving, triethylamine (2.0 mol) was added, and Compound 2 (1.0 mol) was added dropwise in an ice bath. After completing the dropwise addition, the reaction mixture was warmed to room temperature, and stirred overnight. 500 mL Dichloromethane was added to dilute, and the reaction mixture was washed respectively with 5% dilute hydrochloric acid (500 mL×1), water (500 mL×1) and brine (500 mL×1), dried over anhydrous sodium sulfate, and concentrated, to obtain 202.4 g Compound 3. The crude yield was 99%, MS (m/z): 206.1. | |
With triethylamine In dichloromethane at 0 - 20℃; | General Procedure for Preparation of N,N-Diisopropylbenzamides General procedure: To a 100 mL two-necked flask with a reflux condenser, and a balloon were added diisopropylamine (1.1 eq.), triethylamine (1.1 eq.), and dichloromethane (0.5 M). Then, benzoyl chloride (1.0 eq.) was slowly added at 0 °C for a while. After that, the resulting mixture was stirred at room temperature over night. The resulting mixture was extracted with dichloromethane (50 mL), washed with brine and dried over Na2SO4. After evaporation of the solvents under vacuum, benzamide was isolated by column chromatography using hexaneethyl acetate eluent. | |
With triethylamine In dichloromethane | ||
With triethylamine In dichloromethane at 0℃; | ||
With triethylamine In dichloromethane at 0 - 20℃; for 1h; | ||
With triethylamine | ||
With triethylamine In dichloromethane at 20℃; for 2h; | ||
With triethylamine In dichloromethane at 0 - 20℃; Inert atmosphere; Schlenk technique; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
4% | In neat (no solvent) at 100℃; for 24h; | |
3 % Chromat. | at 100℃; for 50h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | With N,N,N,N,-tetramethylethylenediamine; tert.-butyl lithium In tetrahydrofuran -78 deg C to RT; | |
With tert.-butyl lithium 1.) THF, tetramethylethylenediamine, -78 deg C, 0.3 h 2.) THF, tetramethylethylenediamine; Yield given. Multistep reaction; | ||
222.4 g | Stage #1: N,N-diisopropyl benzamide With N,N,N,N,-tetramethylethylenediamine; tert.-butyl lithium In tetrahydrofuran at -78℃; for 0.5h; Stage #2: 5-methyl-dihydro-furan-2-one In tetrahydrofuran at -78 - 20℃; for 5h; | 1.2 (2). Synthesis of Compound 4: Compound 3 (0.8 mol) was dissolved in 500 mL dry tetrahydrofuran, and tert-butyllithium (1.0 mol) was gradually added dropwise at -78 °C. After the completion of the dropwise addition, tetramethylethylenediamine (1.2 mol) was added, and stirred at -78 °C for 30 min. Lactone (1.0 mol) was added dropwise into the above mixture, gradually warmed to room temperature, and continued to react for 5 hr. The reaction was quenched by adding saturated ammonium chloride solution, and the organic solvent was removed by reduced pressure distillation. The residue was extracted by ethyl acetate, concentrated under reduced pressure, and recrystallized, to obtain 222.4 g Compound 4. The yield was 91%. HNMR (400Hz, CDCl3): 8.08-8.06 (m, 1H), 8.04-8.02 (m, 1H), 7.63-7.61 (m, 1H), 7.60-7.58 (m, 1H), 3.95-3.93 (m, 2H), 3.40-3.38 (m, 1H), 2.55 (t, J=1.2 Hz, 2H), 1.64-1.62 (m, 2H), 1.25 (d, J=1.5 Hz, 12H), 1.21(d, J=1.6 Hz, 3H); MS(m/z): 306.2. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | Stage #1: N,N-diisopropyl benzamide With MeCu(TMP)(CN)Li2 In tetrahydrofuran; diethyl ether; hexane at 0℃; for 3h; Stage #2: benzoyl chloride In tetrahydrofuran; diethyl ether; hexane at 20℃; for 16h; Further stages.; | |
82% | Stage #1: N,N-diisopropyl benzamide With (2,2,6,6-tetramethylpiperidido)<SUB>2</SUB>Ag(CN)Li<SUB>2</SUB><SUB> </SUB> at 0℃; for 2h; Stage #2: benzoyl chloride at 80℃; for 16h; chemoselective reaction; | |
81% | Stage #1: N,N-diisopropyl benzamide With Li(2,2,6,6-tetramethylpiperidide)*Al(iBu)3 In tetrahydrofuran; hexane at 20℃; for 3h; Stage #2: benzoyl chloride With tris(dibenzylideneacetone)dipalladium (0); tri-tert-butyl phosphine In tetrahydrofuran; hexane at 20℃; for 24h; |
81% | Stage #1: N,N-diisopropyl benzamide With Li(2,2,6,6-tetramethylpiperidide)*Al(iBu)3 In tetrahydrofuran; hexane at 20℃; for 3h; Stage #2: benzoyl chloride With tris(dibenzylideneacetone)dipalladium (0); tri-tert-butyl phosphine In tetrahydrofuran; hexane at 20℃; for 24h; | |
With tert.-butyl lithium; zinc(II) chloride 1.) Et2O, THF, pentane, -78 deg C, 1 h; -78 deg C to r.t., 1 h, 2.) Et2O, r.t., 12 h; Yield given. Multistep reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | Stage #1: N,N-diisopropyl benzamide With sec.-butyllithium Stage #2: N,N-dimethyl-formamide Further stages.; | |
76% | With sec.-butyllithium | |
68% | Stage #1: N,N-diisopropyl benzamide With tert.-butyl lithium In glycerol; pentane at 20℃; for 0.000555556h; Stage #2: N,N-dimethyl-formamide In pentane at 20℃; chemoselective reaction; |
With sec.-butyllithium 1.) THF, -78 deg C, 1 h, 2.) THF; Yield given. Multistep reaction; | ||
With N,N,N,N,-tetramethylethylenediamine; sec.-butyllithium In tetrahydrofuran at -78℃; | ||
Stage #1: N,N-diisopropyl benzamide With N,N,N,N,-tetramethylethylenediamine; sec.-butyllithium In tetrahydrofuran; cyclohexane at -78℃; for 0.666667h; Stage #2: N,N-dimethyl-formamide In tetrahydrofuran; cyclohexane at -78 - 20℃; for 1h; | ||
Stage #1: N,N-diisopropyl benzamide With (2-methylpropyl)lithium In tetrahydrofuran; cyclohexane at -78℃; for 1h; Stage #2: N,N-dimethyl-formamide In tetrahydrofuran; cyclohexane at 20℃; for 0.5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | Stage #1: N,N-diisopropyl benzamide With MeCu(TMP)(CN)Li2 In tetrahydrofuran; diethyl ether; hexane at 0℃; for 3h; Stage #2: methyl iodide In tetrahydrofuran; diethyl ether; hexane at 20℃; for 16h; Further stages.; | |
70% | Stage #1: N,N-diisopropyl benzamide With tert.-butyl lithium In glycerol; pentane at 20℃; for 0.000555556h; Stage #2: methyl iodide In glycerol; pentane at 20℃; chemoselective reaction; | |
With sec.-butyllithium 1.) THF, -78 deg C, 1 h, 2.) THF; Yield given. Multistep reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With [bis(acetoxy)iodo]benzene; [Ru(MesCO2)2(p-cymene)]; trifluoroacetic acid; trifluoroacetic anhydride at 120℃; for 30h; | |
94% | Stage #1: N,N-diisopropyl benzamide With (TMP)2Cu(CN)Li2 In tetrahydrofuran at -78 - 0℃; for 2h; Inert atmosphere; Schlenk technique; Stage #2: With tert.-butylhydroperoxide In tetrahydrofuran; decane at -78℃; for 0.5h; Inert atmosphere; Schlenk technique; regioselective reaction; | |
66% | Stage #1: N,N-diisopropyl benzamide With dirhodium tetraacetate; triethylamine triflouroacetate; trifluoroacetic acid; trifluoroacetic anhydride at 20℃; Electrolysis; Inert atmosphere; Schlenk technique; Stage #2: With water; sodium hydrogencarbonate Inert atmosphere; Schlenk technique; |
56% | Stage #1: N,N-diisopropyl benzamide With Li(2,2,6,6-tetramethylpiperidide)*Al(iBu)3 In tetrahydrofuran; hexane at 20℃; for 3h; Stage #2: With oxygen; zinc(II) chloride In tetrahydrofuran; hexane at 40℃; for 24h; | |
56% | Stage #1: N,N-diisopropyl benzamide With Li(2,2,6,6-tetramethylpiperidide)*Al(iBu)3 In tetrahydrofuran; hexane at 20℃; for 3h; Stage #2: With oxygen; zinc(II) chloride In tetrahydrofuran; hexane at 40℃; for 24h; | |
56% | Stage #1: N,N-diisopropyl benzamide In tetrahydrofuran; diethyl ether; hexane at 0℃; for 3h; Stage #2: With oxygen In tetrahydrofuran; diethyl ether; hexane at 20℃; for 0.5h; Further stages.; | |
55% | With iodobenzene; [Ru(OAc)2(p-cymene)]; tert-butylammonium hexafluorophosphate(V); trifluoroacetic acid; trifluoroacetic anhydride at 50℃; Electrochemical reaction; | |
With n-butyllithium; lithium tert-butyl hydroperoxide 1.) -78 deg C, THF, hexane; 2.) THF, hexane, toluene, 0 deg C, 3.5 h; Yield given. Multistep reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | Stage #1: N,N-diisopropyl benzamide With sec.-butyllithium In tetrahydrofuran; cyclohexane at -78℃; for 1h; Stage #2: ethyl iodide In tetrahydrofuran; cyclohexane at -78 - 20℃; Further stages.; | |
100% | Stage #1: N,N-diisopropyl benzamide With sec.-butyllithium In tetrahydrofuran; cyclohexane at -78℃; for 1h; Stage #2: ethyl iodide In tetrahydrofuran; cyclohexane at -78 - 20℃; Further stages.; | |
85% | With sec.-butyllithium In tetrahydrofuran |
With sec.-butyllithium | ||
Stage #1: N,N-diisopropyl benzamide With sec.-butyllithium In tetrahydrofuran; cyclohexane at -78℃; for 1h; Stage #2: ethyl iodide In tetrahydrofuran; cyclohexane at -78℃; for 0.5h; Further stages.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With N-iodo-succinimide; silver hexafluoroantimonate; dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer; Trimethylacetic acid In 1,2-dichloro-ethane at 60℃; for 16h; Inert atmosphere; regioselective reaction; | |
96% | With N-iodo-succinimide; bis[dichloro(pentamethylcyclopentadienyl)iridium(III)]; silver trifluoromethanesulfonate; acetic acid In 1,2-dichloro-ethane at 60℃; for 1h; | |
94% | Stage #1: N,N-diisopropyl benzamide With Li(2,2,6,6-tetramethylpiperidide)*Al(iBu)3 In tetrahydrofuran; hexane at 20℃; for 3h; Stage #2: With iodine In tetrahydrofuran; hexane at 0℃; for 1h; |
94% | Stage #1: N,N-diisopropyl benzamide With Li(2,2,6,6-tetramethylpiperidide)*Al(iBu)3 In tetrahydrofuran; hexane at 20℃; for 3h; Stage #2: With iodine In tetrahydrofuran; hexane at -78 - 0℃; for 1h; | |
94% | Stage #1: N,N-diisopropyl benzamide With (PMDETA)<SUB>2</SUB>K<SUB>2</SUB>Mg(CH<SUB>2</SUB>SiMe<SUB>3</SUB>)<SUB>4</SUB> at 0℃; for 1.5h; Inert atmosphere; Schlenk technique; Stage #2: With iodine for 1h; Inert atmosphere; Schlenk technique; regioselective reaction; | |
92% | Stage #1: N,N-diisopropyl benzamide In tetrahydrofuran; diethyl ether; hexane at 0℃; for 3h; Stage #2: With iodine In tetrahydrofuran; diethyl ether; hexane at 20℃; for 16h; Further stages.; | |
92% | Stage #1: N,N-diisopropyl benzamide With (2,2,6,6-tetramethylpiperidido)<SUB>2</SUB>Ag(CN)Li<SUB>2</SUB><SUB> </SUB> In tetrahydrofuran at 0℃; for 2h; Stage #2: With iodine In tetrahydrofuran at 20℃; for 3h; chemoselective reaction; | |
88% | Stage #1: N,N-diisopropyl benzamide With (N,N,N’,N’-tetramethylethylenediamine)LiZn(cis-2,6-dimethylpiperidide)Et2 In hexane for 22h; Schlenk technique; Inert atmosphere; Stage #2: With iodine In tetrahydrofuran; hexane at 0 - 20℃; Schlenk technique; Inert atmosphere; | |
82% | Stage #1: N,N-diisopropyl benzamide With [{(cis-2,6-dimethylpiperidide)2CuLi(OEt2)}2LiBr] In tetrahydrofuran at -78 - 0℃; for 3h; Inert atmosphere; Schlenk technique; Stage #2: With iodine In tetrahydrofuran at -78 - 20℃; for 16h; Inert atmosphere; Schlenk technique; | |
79% | Stage #1: N,N-diisopropyl benzamide Stage #2: With 1,1,1-trifluoro-2-iodoethane | |
62% | Stage #1: N,N-diisopropyl benzamide With tert.-butyl lithium In glycerol; pentane at 20℃; for 0.000555556h; Stage #2: With iodine In 2-methyltetrahydrofuran; pentane at 20℃; chemoselective reaction; | |
53% | With N-iodo-succinimide; dodecacarbonyl-triangulo-triruthenium; silver adamantane-1-carboxylate In 1,2-dichloro-ethane at 120℃; for 22h; Inert atmosphere; | |
With 2,2,6,6-tetramethylpiperidinyl-lithium; iodine; di-tert-butylzinc 1.) THF, RT, 2.) THF, RT; Yield given; Multistep reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | Stage #1: N,N-diisopropyl benzamide With N,N,N,N,-tetramethylethylenediamine; sec.-butyllithium In tetrahydrofuran; cyclohexane at -78℃; for 1h; Stage #2: Trimethyl borate In tetrahydrofuran; cyclohexane at -78 - 20℃; Stage #3: With hydrogenchloride; ammonium chloride In tetrahydrofuran; cyclohexane | |
98% | With hydrogenchloride; ammonium chloride In tetrahydrofuran; cyclohexane (Ar or N2); dropwise addn. of soln. C6H5CON((CH3)2CH)2 in anhyd. THF tostirred soln. of BuLi/C6H12-TMEDA complex in THF at -78°C for 1 h; addn. of excess of B(OMe)3, warming to room temp. 8-12 h, addn. of satd. aq. NH4Cl and 2M HCl until pH 5-6; removal of solvent in vacuo; | |
Stage #1: N,N-diisopropyl benzamide With N,N,N,N,-tetramethylethylenediamine; sec.-butyllithium In tetrahydrofuran at -78℃; for 1h; Stage #2: Trimethyl borate In tetrahydrofuran at -78 - 20℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | With tert.-butyl lithium In pentane at -30℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With triethylamine In N,N-dimethyl acetamide at 130℃; for 1.5h; Autoclave; Green chemistry; | 2.3. The procedure for the aminocarbonylation reaction General procedure: reactionThe catalytic reactions were carried out in a 150 ml stainlesssteel autoclave equipped with a mechanical stirrer. Palladium cat-alyst (0.07 mmol), aryl iodide (10 mmol), amine (20 mmol), base(30 mmol) and solvent (15 ml) were loaded into the reactor. Theautoclave was purged three times with CO and pressurized to1.5 MPa with CO at room temperature. The reaction was carriedout at 130C for appropriate time. After the reaction, the reactorwas cooled to room temperature and depressurized. The reac-tion mixture was centrifuged at 5000 rpm for 10 min and the clearsupernatant which was added naphthalene as an internal standardwas analyzed with GC. For the study of substrate scope, after com-pletion of the reaction, the catalyst was centrifuged at 5000 rpmfor 10 min and the clear supernatant was diluted with 20% HCland extracted with diethyl ether. The organic layer was washedwith saturated NaHCO3and NaCl solutions, respectively, dried overanhydrous Na2SO4, and evaporated under vacuum after filtration.The residue obtained was purified by column chromatography (sil-ica gel, 200-300 mesh; petroleum-ethyl acetate, 20:1) to afford thepure products. |
31% | With potassium phosphate In 1,4-dioxane at 100℃; for 15h; | |
With triethylamine In N,N-dimethyl-formamide at 100℃; for 3h; | 2.2.2. Catalytic reactions at elevated pressure General procedure: In a typical experiment the catalyst (containing 3.6 molPd) was placed in a stainless steel autoclave. Iodobenzene (4)(0.2 mmol, 22.4 l), the amine (5a-g) (0.5 mmol), base (0.25 mmol)and solvent (1 ml) were transferred into it under an inert atmo-sphere. It was charged with carbon monoxide (30 bar) and heatedwith stirring in an oil bath at 100C for 3, 8 or 12 h. After cooling toroom temperature, the liquid phase was removed with a syringe.The reaction mixture was analysed by gas chromatography and thecatalyst was reused |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | Stage #1: N,N-diisopropyl benzamide With Li(2,2,6,6-tetramethylpiperidide)*Al(iBu)3 In tetrahydrofuran; hexane at 20℃; for 3h; Stage #2: iodobenzene With tris(dibenzylideneacetone)dipalladium (0); tri-tert-butyl phosphine In tetrahydrofuran; hexane at 20℃; for 24h; | |
79% | Stage #1: N,N-diisopropyl benzamide With Li(2,2,6,6-tetramethylpiperidide)*Al(iBu)3 In tetrahydrofuran; hexane at 20℃; for 3h; Stage #2: iodobenzene With tri-tert-butyl phosphine In tetrahydrofuran; hexane at 20℃; for 24h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | Stage #1: N,N-diisopropyl benzamide With Li(2,2,6,6-tetramethylpiperidide)*Al(iBu)3 In tetrahydrofuran; hexane at 20℃; for 3h; Stage #2: allyl bromide With Th(CN)CuLi In tetrahydrofuran; hexane at 20℃; for 24h; | |
100% | Stage #1: N,N-diisopropyl benzamide With Li(2,2,6,6-tetramethylpiperidide)*Al(iBu)3 In tetrahydrofuran; hexane at 20℃; for 3h; Stage #2: allyl bromide In tetrahydrofuran; hexane at 20℃; for 24h; | |
99% | Stage #1: N,N-diisopropyl benzamide With MeCu(TMP)(CN)Li2 In tetrahydrofuran; diethyl ether; hexane at 0℃; for 3h; Stage #2: allyl bromide In tetrahydrofuran; diethyl ether; hexane at 20℃; for 16h; Further stages.; |
81% | Stage #1: N,N-diisopropyl benzamide With (N,N,N’,N’-tetramethylethylenediamine)LiZn(cis-2,6-dimethylpiperidide)Et2 In tetrahydrofuran; hexane for 22h; Schlenk technique; Inert atmosphere; Stage #2: With copper(l) chloride In tetrahydrofuran; hexane at 0℃; for 0.0833333h; Schlenk technique; Inert atmosphere; Stage #3: allyl bromide In tetrahydrofuran; hexane at 0 - 20℃; for 22h; Schlenk technique; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | Stage #1: N,N-diisopropyl benzamide With N,N,N,N,-tetramethylethylenediamine; sec.-butyllithium In tetrahydrofuran; cyclohexane at -78℃; for 0.5h; Stage #2: With zinc(II) chloride In tetrahydrofuran; cyclohexane at -78 - 20℃; for 0.5h; Stage #3: 4-(benzoyloxy)morpholine With copper dichloride In tetrahydrofuran; cyclohexane at 20℃; for 12h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | Stage #1: N,N-diisopropyl benzamide With sec.-butyllithium In tetrahydrofuran; cyclohexane at -78℃; for 0.5h; Stage #2: (1R,2S,5R,SS)-(-)-menthyl p-toluenesulfinate In tetrahydrofuran; cyclohexane at -78℃; for 0.5h; Further stages.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | Stage #1: N,N-diisopropyl benzamide In tetrahydrofuran; hexane at 0℃; for 3h; Stage #2: With nitrobenzene In tetrahydrofuran; hexane at 0℃; for 16h; Further stages.; | |
70% | With dipotassium peroxodisulfate; silver trifluoromethanesulfonate; sodium triflate; palladium dichloride In 1,4-dioxane at 80℃; for 36h; Sealed tube; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | Stage #1: N,N-diisopropyl benzamide; MeCu(TMP)(CN)Li2 In tetrahydrofuran; diethyl ether; hexane at 0℃; for 3h; Stage #2: With nitrobenzene In tetrahydrofuran; diethyl ether; hexane at 0℃; for 16h; Further stages.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | Stage #1: N,N-diisopropyl benzamide; PhCu(TMP)(CN)Li2 In various solvents at 0℃; for 3h; Stage #2: With nitrobenzene In various solvents at 20℃; for 16h; Further stages.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | With silver hexafluoroantimonate; [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2; acetic acid In 1,4-dioxane at 100℃; for 5h; Inert atmosphere; regioselective reaction; | |
70% | With [RhCp*(CH3CN)3] (SbF6)2; copper(II) acetate monohydrate In 1,4-dioxane at 100℃; for 4h; Inert atmosphere; | General Procedure for the Reaction of Thioamides with Alkynes General procedure: To a 20 mL two-necked flask with a reflux condenser, a balloon, and a rubber cup were added thioamide 1 (0.25 mmol), alkyne 4 (0.25 mmol), [Cp*Rh(MeCN)3][SbF6]2 (0.01 mmol, 8.3 mg), AgSbF6 (0.04 mmol, 14 mg), Cu(OAc)2•H2O (0.5 mmol, 100 mg), dibenzyl (ca. 30 mg) as internal standard, and diglyme (3 mL). Then, the resulting mixture was stirred under nitrogen at 140 °C (bath temperature) for 4 h. After cooling, to the reaction mixture were added water (30 mL) and ethylenediamine (2 mL). The mixture was extracted with ethyl acetate (3x30 mL) and dried over Na2SO4. After evaporation of the solvents under vacuum, product 5 was isolated by column chromatography using eluent shown below. Further purification by gel permeation chromatography (GPC) was performed, if needed. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62% | With Schwartz's reagent In tetrahydrofuran at 60℃; for 12h; Inert atmosphere; Schlenk technique; | |
With Schwartz's reagent In tetrahydrofuran at 20 - 60℃; for 12h; Inert atmosphere; Schlenk technique; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer; silver tetrakis(pentafluorophenyl)borate In methanol at 65℃; for 40h; | |
55% | With silver hexafluoroantimonate; dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer In chlorobenzene at 120℃; for 12h; Inert atmosphere; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
51% | Stage #1: N,N-diisopropyl benzamide With 2,6-di-tert-butyl-4-methylpyridine; trifluoromethylsulfonic anhydride In dichloromethane at -78 - 0℃; for 2h; Inert atmosphere; Stage #2: ethylmagnesium bromide In diethyl ether; dichloromethane at -78℃; for 2h; Inert atmosphere; chemoselective reaction; | 7 4.2. General procedure for the direct transformation of tertiary amides into ketones and amines General procedure: Tf2O (1.2 equiv) was added dropwise to a cooled (-78 °C) solution of amide 5 (1.0 equiv) and DTBMP (1.2 equiv) in CH2Cl2 (5 mL). The reaction was allowed warming to 0 °C over 2 h. A solution of Grignard reagent (1.0 equiv) in Et2O was added dropwise to the resultant mixture at -78 °C, and the mixture was stirred at the same temperature for 2 h. The reaction mixture was then quenched with an aqueous solution of 15% HCl (5 mL). The organic layer was separated and the aqueous phase was extracted with diethyl ether (3×5 mL). The combined organic layers were washed with brine, dried over anhydrous Na2SO4, filtered, and concentrated under reduced pressure. The residue was purified by flash column chromatography on silica gel to afford the desired ketone 1. To isolate the corresponding amine, the aqueous solution layer was basified with an aqueous solution of 15% NaOH (6 mL), and extracted with dichloromethane (3×10 mL), the combined organic layers were dried over anhydrous Na2SO4, filtered, and concentrated under reduced pressure. The residue was purified by flash column chromatography on silica gel to afford the desired amine 6. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
61% | Stage #1: benzoic acid With 7,7-dichlorocyclohepta-1,3,5-triene; triethylamine In dichloromethane at 20℃; for 1h; Stage #2: diisopropylamine In dichloromethane at 20℃; | |
Stage #1: benzoic acid With 1,2-dibromo-1,1,2,2-tetrachloroethane; triphenylphosphine In dichloromethane at 20℃; Stage #2: diisopropylamine In dichloromethane at 20℃; for 0.5h; | 3.4. General procedure for conversion to acid derivatives General procedure: PPh3 (1.1 mmol) was dissolved in freshly distilled dichloromethane (4.0 mL) at 20 °C. A solution of DBTCE (1.1 mmol) in freshly distilled dichloromethane (4.0 mL) was added to the solution dropwise and the white colloidal mixture was stirred for 2 min. Benzoic acid (1.0 mmol) in freshly distilled dichloromethane (4.0 mL) was added to the mixture dropwise. The resulting solution was stirred for 30 min and amine (1.1 mmol) or alcohol (1.1 mmol) was added to the mixture followed by stirring for 30 min. The mixture was purified by flash column on 20 g of silica gel using a mixture of petroleum ether/EtOAc (1:1). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With Lawessons reagent In toluene at 105 - 110℃; for 3h; Inert atmosphere; | |
84% | With Lawessons reagent In toluene at 100℃; | |
With Lawessons reagent In toluene at 110℃; Inert atmosphere; | General Procedure for Preparation of Thiocarbonyl Compounds from Carbonyl Compounds General procedure: To a 100 mL flask with a reflux condenser, and a balloon were added a carbonyl compound (1.0 eq.), Lawesson’s reagent (0.6 eq.), and toluene (0.5 M). The resulting mixture was stirred under nitrogen at 110 °C over night. After evaporation of the solvents under vacuum, a thiocarbonyl compound was isolated by column chromatography using hexane-ethyl acetate eluent. Further purification by recrystallization was performed, if needed. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With bis[dichloro(pentamethylcyclopentadienyl)iridium(III)]; silver(I) acetate; silver(I) triflimide In 1,2-dichloro-ethane at 90℃; for 10h; Schlenk technique; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With bis[dichloro(pentamethylcyclopentadienyl)iridium(III)]; silver(I) acetate; silver(I) triflimide In 1,2-dichloro-ethane at 90℃; for 10h; Schlenk technique; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With potassium <i>tert</i>-butylate; benzyl alcohol In N,N-dimethyl-formamide at 90℃; for 2h; Schlenk technique; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With silver hexafluoroantimonate; dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer In 1,2-dichloro-ethane at 80℃; for 20h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With silver nitrate; N-fluorobis(benzenesulfon)imide; palladium dichloride In 1,2-dichloro-ethane at 100℃; for 24h; Sealed tube; | |
91% | With silver nitrate; N-fluorobis(benzenesulfon)imide; palladium dichloride In 1,2-dichloro-ethane at 100℃; for 24h; Sealed tube; | 24 Example 24 In a sealed reaction vessel into the N,N-diisopropylbenzamide (41.0 mg, 0.2 mmol), palladium chloride(3.6 mg, 0.02 mmol), N-fluorobenzenesulfonimide (126.1 mg, 0.4 mmol), silver nitrate (13.6 mg, 0.08 mmol), 1,2-dichloroethane (2.0 mL), reaction mixture Stir the reaction at 100 ° C,TLC tracking was detected and the reaction was complete at 24 h. The reaction was quenched and the mixture was diluted with ethyl acetate. EtOAc was evaporated. Separation and purification were carried out, and the eluent containing the product was collected, and the solvent was evaporated to give 40.6 mg of pure 2-fluoro-N,N-diisopropylbenzamide in a yield of 91%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 90% 2: 8% | With silver hexafluoroantimonate; [Rh(η5-cyclopentadienyl)I2]; tetradeuterioacetic acid; copper(II) acetate monohydrate In tetrahydrofuran at 80℃; for 6h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With silver hexafluoroantimonate; [Rh(η5-cyclopentadienyl)I2]; tetradeuterioacetic acid; copper(II) acetate monohydrate In tetrahydrofuran at 80℃; for 6h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
37% | With silver hexafluoroantimonate; C14H14I4O4Rh2; copper(II) acetate monohydrate In tetrahydrofuran at 80℃; for 12h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With silver hexafluoroantimonate; [Rh(η5-cyclopentadienyl)I2]; copper(II) acetate monohydrate In tetrahydrofuran at 80℃; for 12h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With silver hexafluoroantimonate; [Rh(η5-cyclopentadienyl)I2]; copper(II) acetate monohydrate In tetrahydrofuran at 80℃; for 12h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With silver hexafluoroantimonate; [Rh(η5-cyclopentadienyl)I2]; copper(II) acetate monohydrate In tetrahydrofuran at 80℃; for 12h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With silver hexafluoroantimonate; [Rh(η5-cyclopentadienyl)I2]; copper(II) acetate monohydrate In tetrahydrofuran at 80℃; for 12h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With silver hexafluoroantimonate; [Rh(η5-cyclopentadienyl)I2]; copper(II) acetate monohydrate In tetrahydrofuran at 80℃; for 12h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With silver hexafluoroantimonate; [Rh(η5-cyclopentadienyl)I2]; copper(II) acetate monohydrate In tetrahydrofuran at 80℃; for 12h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | With silver hexafluoroantimonate; [Rh(η5-cyclopentadienyl)I2]; copper(II) acetate monohydrate In tetrahydrofuran at 80℃; for 12h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With silver hexafluoroantimonate; [Rh(η5-cyclopentadienyl)I2]; copper(II) acetate monohydrate In tetrahydrofuran at 80℃; for 12h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With silver hexafluoroantimonate; [Rh2(η(5)-C5Me4CF3)2Cl2(μ-Cl)2]; copper(II) acetate monohydrate In tetrahydrofuran at 100℃; for 24h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | With silver hexafluoroantimonate; [Rh(η5-cyclopentadienyl)I2]; copper(II) acetate monohydrate In tetrahydrofuran at 80℃; for 12h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With silver hexafluoroantimonate; [Rh(η5-cyclopentadienyl)I2]; copper(II) acetate monohydrate In acetone at 80℃; for 12h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
45% | With silver hexafluoroantimonate; [Rh(η5-cyclopentadienyl)I2]; copper(II) acetate monohydrate In tetrahydrofuran at 80℃; for 12h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
58%Chromat. | General procedure: Various N,N-dimethyl benzamides were obtained followinga simple procedure which involves charging the reactionmixture containing benzyl alcohols (1mmol), catalyst(20wt%) and DMF (5mL) into a two necked 50mL roundbottom flask (RBF) and stirred for 10min at RT and then70% aqueous TBHP (5mmol) was introduced dropwiseto the mixture under continuous stirring at RT. The RBFwas fitted with a water condenser and heated for 24h at100C. After 24h, the reaction mixture was cooled to RTand catalyst was then separated by filtration. The reactionmixture was diluted with 100mL of DW and extractedusing ethyl acetate (2 × 60mL). The combined organiclayer was dried using Na2SO4and concentrated underrotatory evaporator. The crude products were purified bychromatography using silica gel, hexane and ethyl acetate.Similarly a range of N,N-substituted benzamides werealso obtained by taking the stoichiometric amount of variousN-substituted formamides in 5mL of toluene keepingother parameters constant. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: N,N-diisopropyl benzamide With tert.-butyl lithium In tetrahydrofuran at -78℃; for 1h; Inert atmosphere; Stage #2: zinc(II) chloride In tetrahydrofuran; diethyl ether at -78 - 20℃; | Procedure B. Preparation of Aryl Zinc reagents General procedure: To a cold (-78 °C), stirred solution of the aryl DMG compound (2 mmol) in THF (10 mL) under Ar or N2 was added a solution of t-BuLi (2.4 mmol). After 1 h, a solution of ZnCl2 (3 mmol) was added and the solution allowed to warm to rt. This solution was then subsequently used. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | Stage #1: N,N-diisopropyl benzamide With [κ2-{Ph2P(Se)NC9H6N}Al(Me)2]; 4,4,5,5-tetramethyl-1,3,2-dioxaborolane at 20℃; for 12h; Schlenk technique; Glovebox; Stage #2: With hydrogenchloride In water monomer chemoselective reaction; | |
90% | Stage #1: N,N-diisopropyl benzamide With [(η6-p-cymene){(IMes)P}RuCl]; 4,4,5,5-tetramethyl-1,3,2-dioxaborolane at 80℃; for 18h; Schlenk technique; Glovebox; Inert atmosphere; Stage #2: With hydrogenchloride In water monomer at 20℃; for 2h; Schlenk technique; Glovebox; Inert atmosphere; | |
40 %Chromat. | Stage #1: N,N-diisopropyl benzamide With phenylsilane-d3; C36H48F6N6NiO5S2 In toluene at 110℃; for 24h; Inert atmosphere; Schlenk technique; Stage #2: With hydrogenchloride In diethyl ether |
Multi-step reaction with 2 steps 1: trimethylsilylmethyllithium; 4,4,5,5-tetramethyl-1,3,2-dioxaborolane / neat (no solvent) / 12 h / 70 °C / Schlenk technique; Glovebox; Inert atmosphere 2: hydrogenchloride / water monomer / 2 h / 20 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | Stage #1: N,N-diisopropyl benzamide With n-butyllithium In tetrahydrofuran; hexane at -78℃; Inert atmosphere; Stage #2: ortho-anisaldehyde In tetrahydrofuran; hexane at -78 - 20℃; for 17h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62% | Stage #1: benzoic acid anhydride With methanesulfonyl chloride; triethylamine In dichloromethane at -78℃; for 0.5h; Inert atmosphere; Stage #2: diisopropylamine In dichloromethane at -78 - 20℃; Inert atmosphere; | Nucleophilic Acyl Substitution of Benzoic Anhydride and Different Anhydrides with Different Nucleophiles; General Procedure (Schemes 3 and 5) General procedure: To a solution of the respective anhydride (0.5 mmol, 1.0 equiv) in CH2Cl2 (5 mL) at -78 °C was added MsCl (60 mg, 0.52 mmol, 1.05 equiv) followed by Et3N (111 mg, 1.1 mmol, 2.2 equiv). The reaction mixture was stirred for 30 min at -78 °C and the corresponding nucleophile (1.1 mmol, 2.2 equiv) was added. The progress of the reaction was monitored by TLC. After 2 h, the reaction mixture was diluted with CH2Cl2 (20 mL) and washed with 1 N aq HCl (10 mL) followed by aq NaHCO3 (10 mL) and then brine (10 mL). The organic layer was dried (anhyd Na2SO4) and concentrated under reduced pressure to give the desired product. If required, a further purification was done using flash column chromatography using EtOAc/hexane as the eluent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | Stage #1: bis(pinacol)diborane With C18H20IrNS In tetrahydrofuran at 20℃; for 0.0333333h; Inert atmosphere; Glovebox; Stage #2: N,N-diisopropyl benzamide In tetrahydrofuran at 100℃; for 12h; Inert atmosphere; Sealed tube; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
46% | Stage #1: benzoic acid methyl ester; lithium diisopropyl amide In tetrahydrofuran at -78℃; for 0.916667h; Inert atmosphere; Stage #2: With water-d2 In tetrahydrofuran at -78 - 20℃; for 0.5h; Inert atmosphere; | A typical procedure for the synthesis of 2-(arylthio)benzoic acid esters General procedure: To a solution of methyl 3-bromobenzoate (1a) (21.5 mg, 0.100 mmol) in THF (2.0 mL) was added lithiumdiisopropylamide (LDA) (1.0 M in THF, 0.150 mL, 0.15 mmol, 1.5 equiv) dropwise over 10 min at -78 °C. Afterstirring for 45 min at the same temperature, S-(4-tolyl) 4-toluenethiosulfonate (4a) (39.0 mg, 0.140 mmol, 1.4equiv) was added to the mixture. After stirring for 10 min at the same temperature, the mixture was allowed towarm to room temperature. After stirring for 2 h at room temperature, to the mixture was added an aqueoussaturated NH4Cl solution (10 mL). The mixture was extracted with EtOAc (20 mL × 2). The combined organicextract was washed with brine (20 mL) and dried with Na2SO4. After filtration, the filtrate was concentrated underreduced pressure. The residue was purified by preparative TLC (CH2Cl2/n-hexane = 2/1) to give methyl 3-bromo-2-(4-tolylthio)benzoate (2a) (23.6 mg, 69.9 μmol, 70%) as a yellow oil. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With chloro-trimethyl-silane In tetrahydrofuran at -78℃; for 0.5h; Inert atmosphere; | Preparation of Amides 3; General Procedure General procedure: Reactions of lithium amide with acyl fluoride. A 30 mL Schlenk flaskwas charged with acyl fluoride (2.0 mmol) and flushed with argon.Then, THF (4 mL) was added, the mixture was placed in a cooling bathat -78 °C, and TMSCl (0.38 mL, 3.0 mmol) was added. To the resultingmixture a preformed solution of lithium amide in THF (see procedureabove) was added over ca. 1 min. After 30 min, the cooling bath wasremoved, the mixture was immediately quenched with saturatedaqueous NaHCO3 (20 mL), and then extracted with EtOAc (3 × 25 mL).The combined organic phases were washed with brine (25 mL), driedwith MgSO4, filtered off and evaporated. The product was purified bycolumn chromatography (cyclohexane/EtOAc v/v 20:1→10:1). Preliminaryexperiments (Scheme 3) were carried out according to theGeneral Procedure. Products of reaction with LiHMDS were isolated asN-unsubstituted amides. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
25% | With chloro-trimethyl-silane In tetrahydrofuran at -78℃; for 0.5h; Inert atmosphere; | Preparation of Amides 3; General Procedure General procedure: Reactions of lithium amide with acyl fluoride. A 30 mL Schlenk flaskwas charged with acyl fluoride (2.0 mmol) and flushed with argon.Then, THF (4 mL) was added, the mixture was placed in a cooling bathat -78 °C, and TMSCl (0.38 mL, 3.0 mmol) was added. To the resultingmixture a preformed solution of lithium amide in THF (see procedureabove) was added over ca. 1 min. After 30 min, the cooling bath wasremoved, the mixture was immediately quenched with saturatedaqueous NaHCO3 (20 mL), and then extracted with EtOAc (3 × 25 mL).The combined organic phases were washed with brine (25 mL), driedwith MgSO4, filtered off and evaporated. The product was purified bycolumn chromatography (cyclohexane/EtOAc v/v 20:1→10:1). Preliminaryexperiments (Scheme 3) were carried out according to theGeneral Procedure. Products of reaction with LiHMDS were isolated asN-unsubstituted amides. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | Stage #1: N,N-diisopropyl benzamide With bis(triphenylphosphine)carbonyliridium(I) chloride; H2SiEt2 In toluene at 20℃; for 0.166667h; Schlenk technique; Glovebox; Stage #2: phenylacetylene With copper(l) iodide; (R)-BTFM-Garphos; triethylamine In toluene at 20℃; for 1h; Schlenk technique; Glovebox; enantioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | Stage #1: N,N-diisopropyl benzamide With bis(triphenylphosphine)carbonyliridium(I) chloride; H2SiEt2 In toluene at 20℃; for 0.166667h; Schlenk technique; Glovebox; Stage #2: 1-ethynyl-2-methylbenzene With copper(l) iodide; (R)-BTFM-Garphos; triethylamine In toluene at 20℃; for 1h; Schlenk technique; Glovebox; enantioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | Stage #1: N,N-diisopropyl benzamide With bis(triphenylphosphine)carbonyliridium(I) chloride; H2SiEt2 In toluene at 20℃; for 0.166667h; Schlenk technique; Glovebox; Stage #2: 1-ethynyl-3-methyl-benzene With copper(l) iodide; (R)-BTFM-Garphos; triethylamine In toluene at 20℃; for 1h; Schlenk technique; Glovebox; enantioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | Stage #1: N,N-diisopropyl benzamide With bis(triphenylphosphine)carbonyliridium(I) chloride; H2SiEt2 In toluene at 20℃; for 0.166667h; Schlenk technique; Glovebox; Stage #2: 4-n-methylphenylacetylene With copper(l) iodide; (R)-BTFM-Garphos; triethylamine In toluene at 20℃; for 1h; Schlenk technique; Glovebox; enantioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | Stage #1: N,N-diisopropyl benzamide With bis(triphenylphosphine)carbonyliridium(I) chloride; H2SiEt2 In toluene at 20℃; for 0.166667h; Schlenk technique; Glovebox; Stage #2: 4-methoxyphenylacetylen With copper(l) iodide; (R)-BTFM-Garphos; triethylamine In toluene at 20℃; for 1h; Schlenk technique; Glovebox; enantioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | Stage #1: N,N-diisopropyl benzamide With bis(triphenylphosphine)carbonyliridium(I) chloride; H2SiEt2 In toluene at 20℃; for 0.166667h; Schlenk technique; Glovebox; Stage #2: 4-bromo-1-ethynylbenzene With copper(l) iodide; (R)-BTFM-Garphos; triethylamine In toluene at 20℃; for 1h; Schlenk technique; Glovebox; enantioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | Stage #1: N,N-diisopropyl benzamide With bis(triphenylphosphine)carbonyliridium(I) chloride; H2SiEt2 In toluene at 20℃; for 0.166667h; Schlenk technique; Glovebox; Stage #2: (4-Nitrophenyl)acetylene With copper(l) iodide; (R)-BTFM-Garphos; triethylamine In toluene at 20℃; for 1h; Schlenk technique; Glovebox; enantioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | Stage #1: N,N-diisopropyl benzamide With bis(triphenylphosphine)carbonyliridium(I) chloride; H2SiEt2 In toluene at 20℃; for 0.166667h; Schlenk technique; Glovebox; Stage #2: 4-Ethynylbenzaldehyde With copper(l) iodide; (R)-BTFM-Garphos; triethylamine In toluene at 20℃; for 1h; Schlenk technique; Glovebox; enantioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | Stage #1: N,N-diisopropyl benzamide With bis(triphenylphosphine)carbonyliridium(I) chloride; H2SiEt2 In toluene at 20℃; for 0.166667h; Schlenk technique; Glovebox; Stage #2: 4-ethynyl-1,2-difluorobenzene With copper(l) iodide; (R)-BTFM-Garphos; triethylamine In toluene at 20℃; for 1h; Schlenk technique; Glovebox; enantioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | Stage #1: N,N-diisopropyl benzamide With bis(triphenylphosphine)carbonyliridium(I) chloride; H2SiEt2 In toluene at 20℃; for 0.166667h; Schlenk technique; Glovebox; Stage #2: 1-Ethynyl-3,5-dimethoxy-benzene With copper(l) iodide; (R)-BTFM-Garphos; triethylamine In toluene at 20℃; for 1h; Schlenk technique; Glovebox; enantioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | Stage #1: N,N-diisopropyl benzamide With bis(triphenylphosphine)carbonyliridium(I) chloride; H2SiEt2 In toluene at 20℃; for 0.166667h; Schlenk technique; Glovebox; Stage #2: 2-ethynylnaphthalene With copper(l) iodide; (R)-BTFM-Garphos; triethylamine In toluene at 20℃; for 1h; Schlenk technique; Glovebox; enantioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | Stage #1: N,N-diisopropyl benzamide With bis(triphenylphosphine)carbonyliridium(I) chloride; H2SiEt2 In toluene at 20℃; for 0.166667h; Schlenk technique; Glovebox; Stage #2: 3-Ethynylpyridine With copper(l) iodide; (R)-BTFM-Garphos; triethylamine In toluene at 20℃; for 1h; Schlenk technique; Glovebox; enantioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | Stage #1: N,N-diisopropyl benzamide With bis(triphenylphosphine)carbonyliridium(I) chloride; H2SiEt2 In toluene at 20℃; for 0.166667h; Schlenk technique; Glovebox; Stage #2: 3-ethynylthiophene With copper(l) iodide; (R)-BTFM-Garphos; triethylamine In toluene at 20℃; for 1h; Schlenk technique; Glovebox; enantioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | Stage #1: N,N-diisopropyl benzamide With bis(triphenylphosphine)carbonyliridium(I) chloride; H2SiEt2 In toluene at 20℃; for 0.166667h; Schlenk technique; Glovebox; Stage #2: C6H3ClN2 With copper(l) iodide; (R)-BTFM-Garphos; triethylamine In toluene at 20℃; for 1h; Schlenk technique; Glovebox; enantioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | Stage #1: N,N-diisopropyl benzamide With bis(triphenylphosphine)carbonyliridium(I) chloride; H2SiEt2 In toluene at 20℃; for 0.166667h; Schlenk technique; Glovebox; Stage #2: 1-ethenylcyclohexene With copper(l) iodide; (R)-BTFM-Garphos; triethylamine In toluene at 20℃; for 1h; Schlenk technique; Glovebox; enantioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | Stage #1: N,N-diisopropyl benzamide With bis(triphenylphosphine)carbonyliridium(I) chloride; H2SiEt2 In toluene at 20℃; for 0.166667h; Schlenk technique; Glovebox; Stage #2: Propiolaldehyde diethyl acetal With copper(l) iodide; (R)-BTFM-Garphos; triethylamine In toluene at 20℃; for 1h; Schlenk technique; Glovebox; enantioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | Stage #1: N,N-diisopropyl benzamide With bis(triphenylphosphine)carbonyliridium(I) chloride; H2SiEt2 In toluene at 20℃; for 0.166667h; Schlenk technique; Glovebox; Stage #2: Cyclopropylacetylene With copper(l) iodide; (R)-BTFM-Garphos; triethylamine In toluene at 20℃; for 1h; Schlenk technique; Glovebox; enantioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
40% | Stage #1: N,N-diisopropyl benzamide With bis(triphenylphosphine)carbonyliridium(I) chloride; H2SiEt2 In toluene at 20℃; for 0.166667h; Schlenk technique; Glovebox; Stage #2: erlotinib With copper(l) iodide; (R)-BTFM-Garphos; triethylamine In toluene at 20℃; for 1h; Schlenk technique; Glovebox; enantioselective reaction; |
Tags: 20383-28-2 synthesis path| 20383-28-2 SDS| 20383-28-2 COA| 20383-28-2 purity| 20383-28-2 application| 20383-28-2 NMR| 20383-28-2 COA| 20383-28-2 structure
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P304 + P312 | IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell. |
P304 + P340 | IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing. |
P304 + P341 | IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P305 + P351 + P338 | IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. |
P306 + P360 | IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes. |
P307 + P311 | IF exposed: call a POISON CENTER or doctor/physician. |
P308 + P313 | IF exposed or concerned: Get medical advice/attention. |
P309 + P311 | IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician. |
P332 + P313 | IF SKIN irritation occurs: Get medical advice/attention. |
P333 + P313 | IF SKIN irritation or rash occurs: Get medical advice/attention. |
P335 + P334 | Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages. |
P337 + P313 | IF eye irritation persists: Get medical advice/attention. |
P342 + P311 | IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician. |
P370 + P376 | In case of fire: Stop leak if safe to Do so. |
P370 + P378 | In case of fire: |
P370 + P380 | In case of fire: Evacuate area. |
P370 + P380 + P375 | In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion. |
P371 + P380 + P375 | In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion. |
Storage | |
Code | Phrase |
P401 | |
P402 | Store in a dry place. |
P403 | Store in a well-ventilated place. |
P404 | Store in a closed container. |
P405 | Store locked up. |
P406 | Store in corrosive resistant/ container with a resistant inner liner. |
P407 | Maintain air gap between stacks/pallets. |
P410 | Protect from sunlight. |
P411 | |
P412 | Do not expose to temperatures exceeding 50 oC/ 122 oF. |
P413 | |
P420 | Store away from other materials. |
P422 | |
P402 + P404 | Store in a dry place. Store in a closed container. |
P403 + P233 | Store in a well-ventilated place. Keep container tightly closed. |
P403 + P235 | Store in a well-ventilated place. Keep cool. |
P410 + P403 | Protect from sunlight. Store in a well-ventilated place. |
P410 + P412 | Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF. |
P411 + P235 | Keep cool. |
Disposal | |
Code | Phrase |
P501 | Dispose of contents/container to ... |
P502 | Refer to manufacturer/supplier for information on recovery/recycling |
Physical hazards | |
Code | Phrase |
H200 | Unstable explosive |
H201 | Explosive; mass explosion hazard |
H202 | Explosive; severe projection hazard |
H203 | Explosive; fire, blast or projection hazard |
H204 | Fire or projection hazard |
H205 | May mass explode in fire |
H220 | Extremely flammable gas |
H221 | Flammable gas |
H222 | Extremely flammable aerosol |
H223 | Flammable aerosol |
H224 | Extremely flammable liquid and vapour |
H225 | Highly flammable liquid and vapour |
H226 | Flammable liquid and vapour |
H227 | Combustible liquid |
H228 | Flammable solid |
H229 | Pressurized container: may burst if heated |
H230 | May react explosively even in the absence of air |
H231 | May react explosively even in the absence of air at elevated pressure and/or temperature |
H240 | Heating may cause an explosion |
H241 | Heating may cause a fire or explosion |
H242 | Heating may cause a fire |
H250 | Catches fire spontaneously if exposed to air |
H251 | Self-heating; may catch fire |
H252 | Self-heating in large quantities; may catch fire |
H260 | In contact with water releases flammable gases which may ignite spontaneously |
H261 | In contact with water releases flammable gas |
H270 | May cause or intensify fire; oxidizer |
H271 | May cause fire or explosion; strong oxidizer |
H272 | May intensify fire; oxidizer |
H280 | Contains gas under pressure; may explode if heated |
H281 | Contains refrigerated gas; may cause cryogenic burns or injury |
H290 | May be corrosive to metals |
Health hazards | |
Code | Phrase |
H300 | Fatal if swallowed |
H301 | Toxic if swallowed |
H302 | Harmful if swallowed |
H303 | May be harmful if swallowed |
H304 | May be fatal if swallowed and enters airways |
H305 | May be harmful if swallowed and enters airways |
H310 | Fatal in contact with skin |
H311 | Toxic in contact with skin |
H312 | Harmful in contact with skin |
H313 | May be harmful in contact with skin |
H314 | Causes severe skin burns and eye damage |
H315 | Causes skin irritation |
H316 | Causes mild skin irritation |
H317 | May cause an allergic skin reaction |
H318 | Causes serious eye damage |
H319 | Causes serious eye irritation |
H320 | Causes eye irritation |
H330 | Fatal if inhaled |
H331 | Toxic if inhaled |
H332 | Harmful if inhaled |
H333 | May be harmful if inhaled |
H334 | May cause allergy or asthma symptoms or breathing difficulties if inhaled |
H335 | May cause respiratory irritation |
H336 | May cause drowsiness or dizziness |
H340 | May cause genetic defects |
H341 | Suspected of causing genetic defects |
H350 | May cause cancer |
H351 | Suspected of causing cancer |
H360 | May damage fertility or the unborn child |
H361 | Suspected of damaging fertility or the unborn child |
H361d | Suspected of damaging the unborn child |
H362 | May cause harm to breast-fed children |
H370 | Causes damage to organs |
H371 | May cause damage to organs |
H372 | Causes damage to organs through prolonged or repeated exposure |
H373 | May cause damage to organs through prolonged or repeated exposure |
Environmental hazards | |
Code | Phrase |
H400 | Very toxic to aquatic life |
H401 | Toxic to aquatic life |
H402 | Harmful to aquatic life |
H410 | Very toxic to aquatic life with long-lasting effects |
H411 | Toxic to aquatic life with long-lasting effects |
H412 | Harmful to aquatic life with long-lasting effects |
H413 | May cause long-lasting harmful effects to aquatic life |
H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
Sorry,this product has been discontinued.
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