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CAS No. : | 1195-14-8 | MDL No. : | MFCD00216250 |
Formula : | C9H8S | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | BLZKSRBAQDZAIX-UHFFFAOYSA-N |
M.W : | 148.23 | Pubchem ID : | 70952 |
Synonyms : |
|
Num. heavy atoms : | 10 |
Num. arom. heavy atoms : | 9 |
Fraction Csp3 : | 0.11 |
Num. rotatable bonds : | 0 |
Num. H-bond acceptors : | 0.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 46.79 |
TPSA : | 28.24 Ų |
GI absorption : | High |
BBB permeant : | Yes |
P-gp substrate : | No |
CYP1A2 inhibitor : | Yes |
CYP2C19 inhibitor : | Yes |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -4.57 cm/s |
Log Po/w (iLOGP) : | 2.27 |
Log Po/w (XLOGP3) : | 3.71 |
Log Po/w (WLOGP) : | 3.21 |
Log Po/w (MLOGP) : | 2.96 |
Log Po/w (SILICOS-IT) : | 4.17 |
Consensus Log Po/w : | 3.26 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 2.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -3.76 |
Solubility : | 0.0256 mg/ml ; 0.000173 mol/l |
Class : | Soluble |
Log S (Ali) : | -3.99 |
Solubility : | 0.015 mg/ml ; 0.000101 mol/l |
Class : | Soluble |
Log S (SILICOS-IT) : | -3.71 |
Solubility : | 0.029 mg/ml ; 0.000195 mol/l |
Class : | Soluble |
PAINS : | 0.0 alert |
Brenk : | 0.0 alert |
Leadlikeness : | 2.0 |
Synthetic accessibility : | 1.61 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P264-P270-P301+P312-P330-P403-P501 | UN#: | N/A |
Hazard Statements: | H302 | 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 |
---|---|---|
96% | With bromine; sodium acetate In chloroform at 20℃; for 20 h; | A solution of Br2 (2.10 mL, 6.55 g, 41.5 mmol, 1.02 equiv) inCHCl3 (60 mL) was slowly added to a solution of 5 (6.00 g, 40.8mmol, 1.00 equiv) in CHCl3 (300 mL) over 5 h at r.t. The mixturewas stirred for 15 h at r. t., quenched with sat. aq Na2SO3 (50mL), and extracted with CH2Cl2 (4 × 100 mL). The combinedorganic layers were washed with sat. aq NaCl (2 × 100 mL),dried over Na2SO4, and the solvents were removed in vacuo.Purification by flash chromatography (silica, hexane) gave 6 asa colourless solid in 96percent yield (8.68 g, 38.2 mmol). TLC (SiO2,hexane): Rf = 0.25. 1H NMR (400 MHz, DMSO-d6): δ = 8.00–7.94(m, 1 H), 7.68–7.63 (m, 1 H), 7.51–7.38 (m, 2 H), 2.54 (s, 3 H) ppm. 13C NMR (101 MHz, DMSO-d6): δ = 137.62, 136.57, 135.65,125.38, 125.14, 122.75, 121.92, 105.78, 15.17 ppm. MS (EI): m/z[M] + calcd for C9H7BrS: 225.9448; found: 225.9446. |
86% | for 24 h; Cooling with ice | Under ice-water bath conditions, the compound of formula 3 (2.67 g, 18 mmol)As raw materials dissolved in acetic acid, stirring slowly and evenly addedBromosuccinimide (3.20 g, 18 mmol) was added and the reaction was continued for an additional 24 h with an ice bath. The reaction was quenched with water and the organic phase and the aqueous phase were separated. The aqueous phase was neutralized with sodium hydroxide and extracted with methylene chloride , Before and after the merger of the organic phase, then saturatedSodium carbonate solution three times, dried over anhydrous sodium sulfate,Silica gel column chromatography with petroleum ether to give 3.52 g of a white solid,Yield: 86percent. |
55% | With N-Bromosuccinimide In tetrahydrofuran at -0.16℃; | Compound 5b was prepared by an analogous methodsimilar to that used for 5a and obtained as a light yellow liquid in 55percent yield.1H NMR (400 MHz, CDCl3, TMS): δ2.56 (s, 3H, –CH3), 7.33 (t, 1H, phenyl–H, J = 8.0 Hz), 7.41 (t, 1H, phenyl–H, J = 8.0 Hz), 7.72 (t, 2H, phenyl–H, J = 8.0 Hz) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
64% | With 1,1,1,3',3',3'-hexafluoro-propanol at 20℃; for 5h; Inert atmosphere; | |
61% | With tin(IV) chloride In benzene for 2h; Heating; | |
With tin(IV) chloride |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With bromine In chloroform at 0 - 20℃; for 2h; Inert atmosphere; | Step 1: heteroaryl halogenation General procedure: Under argon, at 0°C, to a solution of heteroaryl (1.0 eq.) in chloroform (C = 0.2 M), bromine (1.1 eq.) was added dropwise. The mixture was stirred from 0°C to rt for 2 h. The reaction mixture was diluted with a saturated aqueous Na2S203 solution and the aqueous layer was extracted with DCM. Combined organic layers were washed with brine, dried over MgS04, filtered and concentrated. |
99% | With bromine In chloroform at 0℃; for 2h; | |
96% | With bromine; sodium acetate In chloroform at 20℃; for 20h; | A solution of Br2 (2.10 mL, 6.55 g, 41.5 mmol, 1.02 equiv) inCHCl3 (60 mL) was slowly added to a solution of 5 (6.00 g, 40.8mmol, 1.00 equiv) in CHCl3 (300 mL) over 5 h at r.t. The mixturewas stirred for 15 h at r. t., quenched with sat. aq Na2SO3 (50mL), and extracted with CH2Cl2 (4 × 100 mL). The combinedorganic layers were washed with sat. aq NaCl (2 × 100 mL),dried over Na2SO4, and the solvents were removed in vacuo.Purification by flash chromatography (silica, hexane) gave 6 asa colourless solid in 96% yield (8.68 g, 38.2 mmol). TLC (SiO2,hexane): Rf = 0.25. 1H NMR (400 MHz, DMSO-d6): δ = 8.00-7.94(m, 1 H), 7.68-7.63 (m, 1 H), 7.51-7.38 (m, 2 H), 2.54 (s, 3 H) ppm. 13C NMR (101 MHz, DMSO-d6): δ = 137.62, 136.57, 135.65,125.38, 125.14, 122.75, 121.92, 105.78, 15.17 ppm. MS (EI): m/z[M] + calcd for C9H7BrS: 225.9448; found: 225.9446. |
95% | With N-Bromosuccinimide; acetic acid In chloroform at 0℃; for 17h; | |
92% | With oxygen; lithium bromide; copper(ll) bromide In acetic acid at 60℃; for 18h; Inert atmosphere; | |
92.69% | With bromine In chloroform at 0℃; for 2h; | |
92% | With N-Bromosuccinimide; acetic acid In chloroform at 0℃; for 4h; | |
91% | With bromine; acetic acid In water at 20℃; for 5h; | |
87% | With hydrogen bromide; dimethyl sulfoxide In water; ethyl acetate at 60℃; for 5h; | |
86% | With N-Bromosuccinimide; acetic acid for 24h; Cooling with ice; | 1.1 Under ice-water bath conditions, the compound of formula 3 (2.67 g, 18 mmol)As raw materials dissolved in acetic acid, stirring slowly and evenly addedBromosuccinimide (3.20 g, 18 mmol) was added and the reaction was continued for an additional 24 h with an ice bath. The reaction was quenched with water and the organic phase and the aqueous phase were separated. The aqueous phase was neutralized with sodium hydroxide and extracted with methylene chloride , Before and after the merger of the organic phase, then saturatedSodium carbonate solution three times, dried over anhydrous sodium sulfate,Silica gel column chromatography with petroleum ether to give 3.52 g of a white solid,Yield: 86%. |
63% | With oxygen; lithium bromide; copper(ll) bromide In acetic acid at 60℃; regioselective reaction; | |
55% | With N-Bromosuccinimide In tetrahydrofuran at -0.16℃; | Synthesisof 3-bromo-2-methylbenzothiophene Compound 5b was prepared by an analogous methodsimilar to that used for 5a and obtained as a light yellow liquid in 55% yield.1H NMR (400 MHz, CDCl3, TMS): δ2.56 (s, 3H, -CH3), 7.33 (t, 1H, phenyl-H, J = 8.0 Hz), 7.41 (t, 1H, phenyl-H, J = 8.0 Hz), 7.72 (t, 2H, phenyl-H, J = 8.0 Hz) |
With chloroform; bromine Eindampfen des Reaktionsgemisches; | ||
With bromine; sodium acetate In acetic acid at 20℃; for 1h; | 17.A Example 17 A. 3-Bromo-2-methyl-benzo[b]thiophene. To a mixture of Compound 17a (10.0 g; 67.4 mmol) and anhydrous NaOAc (6.74 g; 82.2 mmol), in AcOH (100 mL), at ambient temperature, was added Br2, drop-wise, and the reaction mixture was stirred at ambient temperature for 1 h. The reaction mixture was poured into H2O, extracted with CHCl3 several times, and the combined extracts were washed sequentially with H2O, 1N NaOH, H2O, and dried over Na2SO4. The mixture was filtered and the solvent evaporated under reduced pressure to afford Compound 17b. 1H NMR (400 MHz, DMSO-d6): δ 7.95-7.97 (m, 1H), 7.64-7.67 (m, 1H), 7.46-7.50 (m, 1H), 7.39-7.43 (m, 1H), 2.52 (s, 3H). LC/MS C9H7BrS: m/z 227.0 (M+). | |
With bromine; sodium acetate In acetic acid at 20℃; for 1h; | 17.A A. 3-Bromo-2-methyl-benzo[b]thiophene. To a mixture of Compound 17a (10.0 g; 67.4 mmol) and anhydrous NaOAc (6.74 g; 82.2 mmol), in AcOH (100 mL), at ambient temperature, was added Br2, drop-wise, and the reaction mixture was stirred at ambient temperature for 1 h. The reaction mixture was poured into H2O, extracted with CHCl3 several times, and the combined extracts were washed sequentially with H2O, 1N NaOH, H2O, and dried over Na2SO4. The mixture was filtered and the solvent evaporated under reduced pressure to afford Compound 17b. 1H NMR (400 MHz, DMSO-d6): δ 7.95-7.97 (m, 1H), 7.64-7.67 (m, 1H), 7.46-7.50 (m, 1H), 7.39-7.43 (m, 1H), 2.52 (s, 3H). LC/MS C9H7BrS: m/z 227.0 (M+). | |
With bromine In chloroform at 0 - 20℃; | ||
With N-Bromosuccinimide In tetrahydrofuran at 0 - 20℃; | ||
With bromine; sodium acetate; acetic acid at 20℃; for 1h; | 17.A To a mixture of Compound 17a (10.0 g; 67.4 mmol) and anhydrous NaOAc (6.74 g; 82.2 mmol), in AcOH (100 ml_), at ambient temperature, was added Br2, drop-wise, and the reaction mixture was stirred at ambient temperature for 1 h. The reaction mixture was poured into H2O, extracted with CHCI3 several times, and the combined extracts were washed sequentially with H2O, 1 N NaOH, H2O, and dried over Na2SO4. The mixture was filtered and the solvent evaporated under reduced pressure to afford Compound 17b. 1H NMR (400 MHz, DMSO-d6): δ 7.95-7.97 (m, 1 H), 7.64-7.67 (m, 1 H), 7.46- 7.50 (m, 1 H), 7.39-7.43 (m, 1 H), 2.52 (s, 3H). LC/MS C9H7BrS: m/z 227.0 (M+). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With dihydrogen peroxide; C22H44N6Nb2O14 In methanol; water at 45℃; for 3h; Inert atmosphere; Sealed tube; | 2.2 Catalytic reactions General procedure: General procedure. 0.5mmol of sulfide and 1.0mL of solvent (methanol or acetonitrile, concentration 0.5M) were introduced into a 3mL vial, then dinitrogen was fluxed for ca. 3 minutes. Then, while keeping the vial under a cone under N2 flux, the catalyst (1.0mol %) and the appropriate amount (2.0 or 3.0 equiv.) of 30% aqueous solution of hydrogen peroxide were added to the mixture. The sealed vial was either thermostated at 45°C through an oil bath or left at room temperature, under stirring. After 1.5 or 2.0h (in relation to the substrate), additional equivalent of oxidant was added dropwise when necessary. At the end of the reaction, the mixture was treated with 5.0mg of MnO2 to quench the excess of oxidant and, after 10 minutes, filtered. The progress of the reaction was monitored through GC-FID analysis, by withdrawing an aliquot of 20 μL and adding 5 μL of n-hexadecane (internal standard). The oxidation products were identified by comparison of their GC retention times with those of authentic samples. |
83% | With dihydrogen peroxide; acetic acid In water at 100℃; for 1h; | |
With dihydrogen peroxide; acetic acid |
With chloro(meso-tetrakis(2,6-dichlorophenyl)porphyrinato)manganese(III); ammonium acetate; dihydrogen peroxide In hexane; water; acetonitrile at 22 - 25℃; for 2h; Darkness; | ||
Multi-step reaction with 2 steps 1: dihydrogen peroxide; TBA4H2[BW11Mn(H2O)O39]*H2O / acetonitrile; water / 22 - 24 °C / Darkness; Green chemistry 2: dihydrogen peroxide; TBA4H2[BW11Mn(H2O)O39]*H2O / acetonitrile; water / 22 - 24 °C / Darkness; Green chemistry | ||
With dihydrogen peroxide; acetic acid In water at 100℃; for 1h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With chromium corundum at 450℃; Erhitzen des Reaktionsprodukts mit Schwefel; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | In 1,2-dichloro-ethane for 120h; Ambient temperature; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | With aluminium trichloride In nitromethane at 0 - 20℃; for 3h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | With aluminium trichloride In nitromethane at 0 - 20℃; for 3h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With zinc(II) chloride In 1,2-dichloro-ethane for 1h; | |
In dichloromethane; water | S.1.2 (2) (2) Synthesis of a 2-methyl-3-chloromethylbenzothiophene To 10 ml of a dichloromethane containing 1.5 g (10.0 mmol) of a 2-methylbenzothiophene was dropwisely added 5 ml (68 mmol) of a chloromethyl methyl ether at room temperature, and to which was then added 0.1 g (0.70 mmol) of zinc chloride. The mixture was stirred at room temperature for one hour. The water was added thereto, and the product was extracted with chloroform and was dried using the anhydrous magnesium sulfate. The solvent was distilled off to obtain an object compound. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With aluminium trichloride In nitromethane at 0 - 20℃; for 3h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
43% | With N-Bromosuccinimide; dibenzoyl peroxide Irradiation; | |
With N-Bromosuccinimide; dibenzoyl peroxide In tetrachloromethane Heating; | ||
With N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile) In tetrachloromethane for 24h; Heating; |
With N-Bromosuccinimide In tetrachloromethane Reflux; | ||
Stage #1: 2-Methylbenzothiophene With N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile) In α,α,α-trifluorotoluene for 1.5h; Reflux; Stage #2: In ethanol |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | Stage #1: Benzo[b]thiophene With n-butyllithium In diethyl ether; hexane at -78℃; for 0.5h; Inert atmosphere; Stage #2: dimethyl sulfate In diethyl ether; hexane at -78℃; for 0.5h; Inert atmosphere; | |
With n-butyllithium 1.) diethyl ether, THF, a) -78 deg C, 45 min, b) RT, 45 min, 2.) diethyl ether, THF, -78 deg C, 30 min; Yield given. Multistep reaction; | ||
Stage #1: Benzo[b]thiophene With lithiating agent Stage #2: dimethyl sulfate |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | With aluminium trichloride In dichloromethane at 20℃; for 2h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | With pyridine In dichloromethane Irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | at 140℃; for 0.5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With n-butyllithium In tetrahydrofuran; hexane at -78 - 20℃; for 2.5h; Inert atmosphere; | General procedure: To a stirred solution of 9he, 9hh or 9hi (200 mmol) in dried THF (200 mL) held at -78 °C in N2atmosphere was added dropwise 1.6 M n-BuLi in n-hexane (125 mL, 200 mmol) via syringe, and theresulting solution was stirred at -78 °C for 1 h ( for 9he and 9hh) or returned to room temperaturefor 5 h (for 9hi) before dropwise addition of dried DMF (21.93 g, 300 mmol) via syringe. Thereafterthe reaction mixture was stirred at -78 °C for 0.5 h and at room temperature for another 1 h. Thereaction mixture was poured into ice-water (600 mL) while stirring and the resulting mixture wasextracted with CH2Cl2 (300 mL × 3). The combined extracts were washed with 5% brine (500 mL),dried (Na2SO4) and evaporated on a rotary evaporator to give a residue, which was purified bycolumn chromatography to afford the pure product 10he, 10hh or 10hi. |
42% | With oxygen; 2,6-dimethylpyridine perchlorate In acetonitrile at 20℃; for 12h; Electrolysis; | |
With cerium (IV) sulfate In acetic acid |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With aluminium trichloride | ||
Stage #1: oxalyl dichloride With aluminum (III) chloride In 1,2-dichloro-ethane at 0℃; for 0.333333h; Stage #2: 2-Methylbenzothiophene In 1,2-dichloro-ethane Stage #3: With hydrogenchloride; water In 1,2-dichloro-ethane | P33 Preparation 33 (P33): 2-Methyl-benzo[b]thiophene-3-carboxylic acid methyl ester To a stirred suspension of AICI3 (0.93 g) in dry 1, 2-dichloroethane (2 ml) at 0 °C was added oxalyl chloride (0.61 ml). After 20 min 2-methyl-benzo [b] thiophene (0.62 g) in dry 1, 2-DICHLOROETHANE (1 ML) was added dropwise via syringe. After an additional 15 min the mixture was poured onto ice and conc. aqueous HCI (2 ML). This was extracted twice with CH2CI2. Evaporation of the volatiles in vacuo gave A residue which was vigorously stirred with NAOH (ca. 1.5 G) in water until a clear solution was obtained. This was washed with Et2O, acidified using excess HCI and EXTRACTED WITH ET2O. This extract was washed (brine) and concentrated to give A cream solid (0. 6 g). This was dissolved in dry CH2Cl2 (15 mi) containing catalytic DMF (2 drops) and at 0 °C was added with stirring oxalyl chloride (0.41 ml). The ice bath was removed. After gas evolution had ceased (2 h) volatiles were removed in vacuo. To the residue was added dry methanol (5 ML) and the mixture was kept FOR 16 h. The material obtained after evaporation of the volatiles was submitted to column chromatography to give the title compound (0.12 g) as a yellow oil. NMR (1H, CDCI3) : 8. 41 (d, 1H), 7.75 (T, 1H), 7. 42 (t, 1H), 7.35 (d, 1H), 3. 98 (s, 3H), 2.85 (s, 3H) [n. b. in a major by-product these protons are shifted to 2.75 (s, 3H)]. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium acetate; acetic anhydride at 140℃; Erhitzen des Reaktionsprodukts mit Zink und Essigsaeure; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | In benzene at 80℃; for 19h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | In benzene at 80℃; for 24h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
67% | With tin(IV) chloride In benzene at 20℃; for 3h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With ammonium iodide; sulfuric acid; dimethyl sulfoxide In ethyl acetate at 80℃; for 10h; | |
93% | With iodine; iodic acid; acetic acid In water at 70℃; for 3h; | |
93% | With iodine In nitromethane at 120℃; for 1h; Sealed tube; regioselective reaction; |
91% | With periodic acid dihydrate; sulfuric acid; iodine In water; acetic acid at 65℃; | |
73% | With periodic acid dihydrate; sulfuric acid; iodine; acetic acid In water at 65℃; for 5h; | |
47% | With iodine; periodic acid In sulfuric acid; water; acetic acid for 3h; Darkness; | |
47% | With sulfuric acid; iodine; periodic acid In water; acetic acid for 3h; | |
With iodine; iodic acid; acetic acid In tetrachloromethane; water | ||
With ammonium iodide; sulfuric acid In dimethyl sulfoxide; ethyl acetate at 60℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | Under inert conditions benzo[b]thiophene (7.00 g, 51.1 mmol,1.00 equiv) was dissolved in dry THF and stirred for 30 min at-78 C. n-BuLi (26.6 mL, 2.5 M in hexane, 66.5 mmol, 1.30equiv) was added slowly, and the mixture was stirred for 30min. MeI (4.90 mL, 11.2 g, 78.9 mmol, 1.54 equiv) was addedover 15 min. The reaction was stirred for 20 min at -78 C, for 3h at r.t., quenched with water (100 mL), and extracted withEtOAc (4 × 50 mL). The organic layer was dried over Na2SO4, andthe solvents were removed in vacuo. After purification by flashchromatography (silica, hexane), 5 could be obtained as acolourless solid in 97% yield (7.26 g, 49.0 mmol). TLC (SiO2, hexane):Rf = 0.54. 1H NMR (400 MHz, DMSO-d6): delta = 7.85 (dp, J =7.8, 0.7 Hz, 1 H), 7.74-7.64 (m, 1 H), 7.35-7.21 (m, 2 H), 7.12 (p,J = 1.2 Hz, 1 H), 2.56 (d, J = 1.2 Hz, 3 H) ppm. 13C NMR (101 MHz,DMSO-d6): delta = 140.57, 140.09, 138.88, 124.19, 123.46, 122.57,122.05, 121.78, 15.74 ppm. MS (EI): m/z [M]+ calcd for C9H8S:148.0342; found: 148.0341. | |
90% | 1) The compound of formula 2 benzothiophene (2.68 g, 20 mmol)Dissolved in refined tetrahydrofuran, stirred under argon and 195K conditions,2.4 mol / L of n-butyllithium (9.75 mL, 23 mmol) was slowly injected,Continue low temperature reaction for half an hour. Iodomethane (3 mL, 23 mmol)Injected into the reaction flask, the reaction mixture was stirred at low temperature for an hour,Naturally rose to room temperature, adding an appropriate amount of water to terminate the reaction.Liquid separation and extraction with methylene chloride. Combine the organic phases, whirl, remove the solvent and dry. The residue was chromatographed on petroleum ether, silica gel to give 2.67 g of a colorless solid,Yield: 90%. | |
77% | General procedure: In 0.5 M hexane solvent, 1.25 molar equivalents of Na-TMP was reacted with 0.4 mmol of benzo[b]thiophene (arene) at 25 C. for 30 minutes, 1.5 molar equivalents of heavy water (D2O: electrophilic reagent) was then added thereto and reacted therewith at 0 C. for 1 hour. The product was evaluated through analysis by 1H-NMR, and the yield of isolated deuterated benzo[b]thiophene in which a hydrogen atom located at 2-position of benzo[b]thiophene was substituted by heavy hydrogen was calculated in the same manner as in Experiment Number 1. The isolated yield was 99%.A reaction was performed using benzo[b]thiophene as an arene and iodomethane (MeI) as an electrophilic reagent in the same manner as in Experiment Number 2, the product was then evaluated, and the yield of isolated 2-methyl-benzo[b]thiophene in which a methyl group (-Me) was added at 2-position of benzo[b]thiophene was calculated. The isolated yield was 77% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With boron trifluoride diethyl etherate; 3-chloro-benzenecarboperoxoic acid In dichloromethane at -20℃; Inert atmosphere; | General Procedure B. Oxidation of Benzothiophenes to Benzothiophene-S-oxides Using mCPBA General procedure: The benzothiophene was dissolved in CH2Cl2 (0.25 M) in an oven-dried tube flushed with N2 at -20 Cand BF3·OEt2 (8 equiv) was added. mCPBA (1.2 equiv) was then added in portions (3 times) over 1.5 h atthe same temperature. The reaction was monitored by TLC, and after the disappearance of the starting material, saturated Na2CO3 was added to the mixture, followed by K2CO3 at -20 C. The mixture was then filtered through a plug loaded with MgSO4 and K2CO3, washing with CH2Cl2. The combined organic layers were dried with MgSO4 and concentrated in vacuo. The crude mixture was purified by column chromatography (EtOAc in CH2Cl2). |
90% | With boron trifluoride diethyl etherate; 3-chloro-benzenecarboperoxoic acid In dichloromethane at -30℃; Inert atmosphere; | |
73% | With dihydrogen peroxide; trifluoroacetic acid In water at 20℃; for 0.5h; |
72% | With boron trifluoride diethyl etherate; 3-chloro-benzenecarboperoxoic acid In dichloromethane at -18℃; | |
With TBA4H2[BW11Mn(H2O)O39]*H2O; dihydrogen peroxide In water; acetonitrile at 22 - 24℃; Darkness; Green chemistry; | ||
With boron trifluoride diethyl etherate; 3-chloro-benzenecarboperoxoic acid In dichloromethane at -20℃; for 1.5h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
59% | With aluminium trichloride In hexane; 1,2-dichloro-ethane at 15 - 17℃; for 5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With lithium aluminium tetrahydride; titanium tetrachloride; zinc In dichloromethane for 1h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: 94 percent / ethanol / 3 h / Heating 2: 1.) sodium hydride, 2.) acetophenone / 1.) THF, DMSO, 0 deg C, 20 min, 2.) 0 deg C, 14 h. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
64% | With sulfuryl dichloride In N,N-dimethyl-formamide at 0 - 85℃; for 2.83333h; | |
0.89 g (64%) | With sulfuryl dichloride In <i>N</i>-methyl-acetamide; N,N-dimethyl-formamide | 40.B B. B. 2-Methylbenzo[b]thiophene-3-sulfonyl chloride Sulfuryl chloride (9.5 mmoles, 0.76 ml) was added to a stirred solution of dimethylformamide (DMF; 11.2 mmoles, 0.87 ml) at 0° C., and the resulting faint yellow solution was stirred for 20 min at 0° C. 2-Methylbenzo[b]thiophene (5.6 mmoles, 0.83 g) was then added, the reaction mixture was diluted with 2 ml of DMF, and then heated to 85° C. After 2.5 hrs at 85° C., the brown reaction mixture was cooled to ambient temperature and added to ice ('100 ml). The aqueous phase was extracted with ethyl acetate (100 ml), and the organic phase was dried (MgSO4), filtered and concentrated to collect an orange-brown solid. Flash chromatography (4% ethyl acetate/hexanes) provided 0.89 g (64%) of 2-methylbenzo[b]thiophene-3-sulfonyl chloride as a yellow solid. |
0.89 g (64%) | With sulfuryl dichloride In <i>N</i>-methyl-acetamide; N,N-dimethyl-formamide | 40.B B. B. 2-Methylbenzo[b]thiophene-3-sulfonyl chloride Sulfuryl chloride (9.5 mmoles, 0.76 ml) was added to a stirred solution of dimethylformamide (DMF; 11.2 mmoles, 0.87 ml) at 0° C., and the resulting faint yellow solution was stirred for 20 min at 0° C. 2-Methylbenzo[b]thiophene (5.6 mmoles, 0.83 g) was then added, the reaction mixture was diluted with 2 ml of DMF, and then heated to 85° C. After 2.5 hrs at 85° C., the brown reaction mixture was cooled to ambient temperature and added to ice (~100 ml). The aqueous phase was extracted with ethyl acetate (100 ml), and the organic phase was dried (MgSO4), filtered and concentrated to collect an orange-brown solid. Flash chromatography (4% ethyl acetate/hexanes) provided 0.89 g (64%) of 2-methylbenzo[b]thiophene-3-sulfonyl chloride as a yellow solid. |
0.89 g (64%) | With sulfuryl dichloride In <i>N</i>-methyl-acetamide; N,N-dimethyl-formamide | 40.B B. B. 2-Methylbenzo[b]thiophene-3-sulfonyl chloride Sulfuryl chloride (9.5 mmoles, 0.76 ml) was added to a stirred solution of dimethylformamide (DMF; 11.2 mmoles, 0.87 ml) at 0° C., and the resulting feint yellow solution was stirred for 20 min at 0° C. 2-Methylbenzo[b]thiophene (5.6 mmoles, 0.83 g) was then added, the reaction mixture was diluted with 2 ml of DMF, and then heated to 85° C. After 2.5 hrs at 85° C., the brown reaction mixture was cooled to ambient temperature and added to ice (~100 ml). The aqueous phase was extracted with ethyl acetate (100 ml), and the organic phase was dried (MgSO4), filtered and concentrated to collect an orange-brown solid. Flash chromatography (4% ethyl acetate/hexanes) provided 0.89 g (64%) of 2-methylbenzo[b]thiophene-3-sulfonyl chloride as a yellow solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | In 1,1-dichloroethane | 11 EXAMPLE 11 EXAMPLE 11 Compounds of the general formula I-3c may be made, for example by the following general scheme. 3-chloromethyl-2-methylbenzo[b]thiophene 1 To a solution of chloromethyl methyl ether(30.0 g) in dichloroethane (250 mL) was added 2-methylbenzothiophene (2.0 g, 0.014 mol) and ZnCI2 (200 mg). The resulting mixture was stirred for 1 h. The reaction mixture was poured into water and extracted with chloroform. The organic layer was dried (MgSO4) and concentrated to afford the compound 1 (2.4 g, 90% yield) which was used directly in next step. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With pyridine; dmap; sodium hydroxide In methanol | 40.C C. C. N-(3,4-Dimethyl-5-isoxazolyl)-2-methylbenzo[b]thiophene-3-sulfonamide 2-Methylbenzo[b]thiophene-3-sulfonyl chloride (1.7 mmoles, 0.41 g) was added to a solution of 3,4-dimethyl-5-aminoisoxazole (0.75 mmoles, 84 mg), 4-dimethylaminopyridine (DMAP; 50 mg) and pyridine (5 ml) at ambient temperature. After 24 h, the reaction mixture was diluted with ethyl acetate (50 ml) and washed with 2% HCl (3*50 ml). The organic phase was dried (MgSO4), filtered and concentrated to collect a brown-orange solid, which was dissolved in a solution of methanol (10 ml) and NaOH (60 mg). The solution was stirred 1 h at ambient temperature, then the methanol was evaporated and the resulting residue was diluted with 2% HCl (50 ml), and extracted with ethyl acetate (75 ml). The organic phase was dried (MgSO4), filtered and concentrated to collect a tan solid. Recrystallization from chloroform and hexanes resulted in 93 mg (38%) of N-(3,4-dimethyl-5-isoxazolyl)-2-methylbenzo[b]thiophene-3-sulfonamide as light yellow crystals, m.p. 174-176° C. | |
With pyridine; dmap; sodium hydroxide In methanol | 40.C C. C. N-(3,4-Dimethyl-5-isoxazolyl)-2-methylbenzo[b]thiophene-3-sulfonamide 2-Methylbenzo[b]thiophene-3-sulfonyl chloride (1.7 mmoles, 0.41 g) was added to a solution of 3,4-dimethyl-5-aminoisoxazole (0.75 mmoles, 84 mg), 4-dimethylaminopyridine (DMAP; 50 mg) and pyridine (5 ml) at ambient temperature. After 24 h, the reaction mixture was diluted with ethyl acetate (50 ml) and washed with 2% HCl (3*50 ml). The organic phase was dried (MgSO4), filtered and concentrated to collect a brown-orange solid, which was dissolved in a solution of methanol (10 ml) and NaOH (60 mg). The solution was stirred 1 h at ambient temperature, then the methanol was evaporated and the resulting residue was diluted with 2% HCl (50 ml), and extracted with ethyl acetate (75 ml). The organic phase was dried (MgSO4), filtered and concentrated to collect a tan solid. Recrystallization from chloroform and hexanes resulted in 93 mg (38%) of N-(3,4-dimethyl-5-isoxazolyl)-2-methylbenzo[b]thiophene-3-sulfonamide as light yellow crystals, m.p. 174°-176° C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In 1,1-dichloroethane | 20 3-(4-Chloro-3-sulfamoylbenzoyl)-2-methylbenzo[b]thiophene EXAMPLE 20 3-(4-Chloro-3-sulfamoylbenzoyl)-2-methylbenzo[b]thiophene is obtained as described in Example 10 (a) from 4-chloro-3-sulfamoylbenzoyl chloride and 2-methylbenzo[b]thiophene in dichloro-ethane in the presence of aluminum chloride. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | With aluminum (III) chloride In 1,2-dichloro-ethane at 0 - 20℃; for 4h; | 12.12 Example 12; Synthesis of 2-(2-methyl-benzo[b]thiophen-3-ylsulfanyl)-benzoic acid methyl ester (Method 12.) 2-(Methoxycarbonyl)phenyl sulfenyl chloride (10 mL 0.29 M solution in 1,2-dichloro-ethane, 2.9 mmol) is added to a solution of 2-methyl-benzo[b]thiophene (445 mg, 3mmol) in 5 mL 1,2-dichloro-ethane. The reaction mixture is cooled to 0° C. Aluminium chloride (400 mg, 3 mmol) is added and the reaction mixture is stirred for 4 hours at room temperature. The reaction is quenched with water. The organic phase is washed with brine, dried with MgSO4 and concentrated in vacuo. The residue is purified by flash chromatography on silica gel using ethyl acetate-heptane as eluent. This furnishes 651 mg (69%) of the title compound as an oil. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With tin(IV) chloride; In dichloromethane; | a) 2-Methylbenzo[b]thiophene-3-carboxaldehyde SnCl4 (20 mL, 67 mmole) was added over 5 min to a stirred solution of 2-methylbenzo[b]thiophene (5.0 g, 33.7 mmole) in CH2Cl2 (75 mL) at 0 C under argon. After 15 minutes, dichloromethyl methyl ether (3.7 mL, 41 mmole) was added. The reaction became a yellowish colored suspension. The reaction was allowed to warm to RT and stirred for 16 h, then was poured onto ice water (200 mL). The aqueous mixture was acidified with 1.0 N HCl (100 mL) and stirred until the suspension dissolved. The organic phase was separated, dried (MgSO4), and concentrated under vacuum. Purification by flash chromatography on silica gel (10% ethyl acetate/hexane) gave the title compound (5.83 g, 98%) as a white crystalline solid: 1H NMR (400 MHz, CDCl3) δ 10.38 (s, 1 H), 8.61 (d, J = 8.1 Hz, 1 H), 7.77 (d, J = 8.0 Hz, 1 H), 7.48 (t, 1 H), 7.39 (t, 1 H), 2.93 (s, 3 H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
57% | In dichloromethane under N2; HBF4 is added to a soln. of the starting complex in CH2Cl2 at -78°C with stirring, stirred for 2 min, then the thiophene is added, stirred, slowly warmed to room temp. over 8 h; the solvent is removed under vac., the oily residue is taken up in CH2Cl2, cooled to 0°C, Et2O is added, elem. anal.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With aluminum (III) chloride In dichloromethane at 0 - 20℃; for 2h; | |
92% | With aluminium trichloride In dichloromethane at 20℃; for 2h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With tin(IV) chloride In benzene at 5 - 20℃; for 3.5h; | |
83% | With aluminum (III) chloride In dichloromethane Inert atmosphere; | 1-(2-Methylbenzo[b]thiophen-3-yl)ethanone A mixture of 2-methylbenzothiophene 11 (1.5g, 10.12mmol), acetyl chloride (0.9 mL, 12.14 mmol) and anhydrous aluminum chloride (1.62 g, 12.14 mol) in dry DCM (60 mL) was stirred overnight. After the reaction was completed (monitored by TLC), it was poured over crushed ice containing HCl (2 mL), extracted with DCM (2 x 10 mL) and dried (Na2SO4). After removing the solvent in vacuo, the residue was purified by column chromatography on silica gel (ethyl acetate/hexane: 1:3)to give 2-methyl-3-acetyl benzo[b]thiophene 12 as a colorless solid (1.59 g, 83%); mp: 68-70 oC; 1H NMR(300 MHz, CDCl3): δ 8.21 (d, J = 8.1 Hz, 1 H), 7.75 (d, J = 7.8 Hz, 1 H), 7.43 (t, J = 7.5 Hz, 1 H), 7.34 (t, J =7.8 Hz, 1 H) ppm; 13C NMR (75 MHz, CDCl3): δ 195.9, 149.0, 138.4, 137.3, 133.0, 125.2, 124.4, 123.9, 121.7,31.9, 17.0 ppm. |
80% | With aluminum (III) chloride In dichloromethane |
67% | In dichloromethane at 20℃; | |
47% | With 1,1,1,3',3',3'-hexafluoro-propanol at 20℃; for 5h; Inert atmosphere; | |
With aluminum (III) chloride In 1,2-dichloro-ethane |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
61% | With aluminium trichloride In dichloromethane at -10℃; for 2.75h; | |
61% | With aluminum (III) chloride at -5 - 10℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
63% | With oxygen; lithium chloride; copper dichloride In acetic acid at 110℃; for 24h; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | With aluminum (III) chloride In 1,2-dichloro-ethane at -5 - 20℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
53% | With aluminum (III) chloride In dichloromethane at -15 - 20℃; for 8h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With ethylaluminum dichloride In hexane; toluene at 100℃; for 3h; Autoclave; Inert atmosphere; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | Stage #1: 2-Methylbenzothiophene With 2,2,6,6-tetramethylpiperidinyl-lithium In tetrahydrofuran at -78℃; for 0.25h; Inert atmosphere; Stage #2: With zinc(II) chloride In tetrahydrofuran at 25℃; Inert atmosphere; Stage #3: 3-Bromopyridine With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; palladium diacetate In tetrahydrofuran at 50℃; for 2h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | Stage #1: 2-Methylbenzothiophene With 2,2,6,6-tetramethylpiperidinyl-lithium In tetrahydrofuran at -78℃; for 0.25h; Inert atmosphere; Stage #2: With zinc(II) chloride In tetrahydrofuran at 25℃; Inert atmosphere; Stage #3: 1-bromo-4-methoxy-benzene With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; palladium diacetate In tetrahydrofuran at 50℃; for 2h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | Stage #1: 2-Methylbenzothiophene With 2,2,6,6-tetramethylpiperidinyl-lithium In tetrahydrofuran at -78℃; for 0.25h; Inert atmosphere; Stage #2: With zinc(II) chloride In tetrahydrofuran at 25℃; Inert atmosphere; Stage #3: 1,2-(methylenedioxy)-4-bromobenzene With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; palladium diacetate In tetrahydrofuran at 50℃; for 2h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | Stage #1: 2-Methylbenzothiophene With 2,2,6,6-tetramethylpiperidinyl-lithium In tetrahydrofuran at -78℃; for 0.25h; Inert atmosphere; Stage #2: With zinc(II) chloride In tetrahydrofuran at 25℃; Inert atmosphere; Stage #3: Ethyl 4-bromobenzoate With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; palladium diacetate In tetrahydrofuran at 50℃; for 2h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | Stage #1: 2-Methylbenzothiophene With 2,2,6,6-tetramethylpiperidinyl-lithium In tetrahydrofuran at -78℃; for 0.25h; Inert atmosphere; Stage #2: With zinc(II) chloride In tetrahydrofuran at 25℃; Inert atmosphere; Stage #3: p-trifluoromethylphenyl bromide With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; palladium diacetate In tetrahydrofuran at 50℃; for 2h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | Stage #1: 2-Methylbenzothiophene With 2,2,6,6-tetramethylpiperidinyl-lithium In tetrahydrofuran at -78℃; for 0.25h; Inert atmosphere; Stage #2: With zinc(II) chloride In tetrahydrofuran at 25℃; Inert atmosphere; Stage #3: 4-bromo-N,N-dimethylaniline With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; palladium diacetate In tetrahydrofuran at 50℃; for 2h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | Stage #1: 2-Methylbenzothiophene With 2,2,6,6-tetramethylpiperidinyl-lithium In tetrahydrofuran at -78℃; for 0.25h; Inert atmosphere; Stage #2: With zinc(II) chloride In tetrahydrofuran at 25℃; Inert atmosphere; Stage #3: 4-bromophenyl 2,2-dimethylpropanoate With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; palladium diacetate In tetrahydrofuran at 50℃; for 2h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With C54H50N4Ru; hydrogen In hexane at 25℃; for 24h; Inert atmosphere; Autoclave; enantioselective reaction; | |
90% | With [bis(2-methylallyl)cycloocta-1,5-diene]ruthenium(II); 1,3-bis((R)-1-(naphthalen-1-yl)ethyl)-4,5-dihydro-1H-imidazol-3-ium tetrafluoroborate; potassium <i>tert</i>-butylate; hydrogen In hexane at 25℃; for 24h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
63% | With aluminum (III) chloride In dichloromethane at 0 - 25℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | With palladium(II) trifluoroacetate; silver(I) acetate In 1,2-dimethoxyethane; dimethyl sulfoxide at 100℃; for 24h; Glovebox; Schlenk technique; Inert atmosphere; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With trifluorormethanesulfonic acid In dichloromethane at 0 - 20℃; for 2h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With Cu(2,9-bis(panisyl)-1,10-phenanthroline)<SUB>2</SUB>Cl; 1-azido-1λ3-benzo[d][1,2]iodaoxol-3(1H)-one In acetonitrile at 20℃; for 16h; Sealed tube; Inert atmosphere; Irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | Stage #1: [bis(acetoxy)iodo]benzene; di(4-tosyl)amine In acetonitrile at 20℃; for 0.5h; Inert atmosphere; Stage #2: 2-Methylbenzothiophene In acetonitrile at 20℃; for 7h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With tin(IV) chloride In toluene at 5 - 20℃; for 2h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
58% | With nickel(II) acetylacetonate dihydrate; 1,3-bis-(diphenylphosphino)propane In 1,4-dioxane; hexane at 170℃; for 16h; Inert atmosphere; Sealed tube; chemoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
9 %Spectr. | In 1,2-dichloro-ethane at 50℃; for 0.416667h; Microwave irradiation; | 1,2,5-Trimethylthiophenium Hexafluoroantimonate; Typical Procedure for Microwave-Assisted Synthesis General procedure: In a 10-mL closed system microwave vessel, 2,5-dimethylthiophene (11.2mg, 0.1mmol), MeI (21.5mg, 0.15mmol), and AgSbF6 (34.4mg, 0.1mmol) were added to dry DCE under infrared light. The vessel was closed and the microwave-assisted reaction was carried out with the following fixed conditions: mode, sps; Δ temperature, 1 °C; stirring, high; max power, off. The reaction temperature was maintained at 50°C and 200W of power for 25min. The workup was the same as in thermal conditions; yield: 26.0mg (0.074mmol, 74%). The aqueous phase was brought to volume for UV-visible quantification. Some replicates were also evaporated with centrifugal evaporation to isolate the product and assess its stability. Alternatively, extraction was carried out with an aliquot of D2O for direct NMR characterization. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
24% | In 1,2-dichloro-ethane at 50℃; for 0.416667h; Microwave irradiation; | 1,2,5-Trimethylthiophenium Hexafluoroantimonate; Typical Procedure for Microwave-Assisted Synthesis General procedure: In a 10-mL closed system microwave vessel, 2,5-dimethylthiophene (11.2mg, 0.1mmol), MeI (21.5mg, 0.15mmol), and AgSbF6 (34.4mg, 0.1mmol) were added to dry DCE under infrared light. The vessel was closed and the microwave-assisted reaction was carried out with the following fixed conditions: mode, sps; Δ temperature, 1 °C; stirring, high; max power, off. The reaction temperature was maintained at 50°C and 200W of power for 25min. The workup was the same as in thermal conditions; yield: 26.0mg (0.074mmol, 74%). The aqueous phase was brought to volume for UV-visible quantification. Some replicates were also evaporated with centrifugal evaporation to isolate the product and assess its stability. Alternatively, extraction was carried out with an aliquot of D2O for direct NMR characterization. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
30 %Spectr. | In 1,2-dichloro-ethane at 50℃; for 0.416667h; Microwave irradiation; | 1,2,5-Trimethylthiophenium Hexafluoroantimonate; Typical Procedure for Microwave-Assisted Synthesis General procedure: In a 10-mL closed system microwave vessel, 2,5-dimethylthiophene (11.2mg, 0.1mmol), MeI (21.5mg, 0.15mmol), and AgSbF6 (34.4mg, 0.1mmol) were added to dry DCE under infrared light. The vessel was closed and the microwave-assisted reaction was carried out with the following fixed conditions: mode, sps; Δ temperature, 1 °C; stirring, high; max power, off. The reaction temperature was maintained at 50°C and 200W of power for 25min. The workup was the same as in thermal conditions; yield: 26.0mg (0.074mmol, 74%). The aqueous phase was brought to volume for UV-visible quantification. Some replicates were also evaporated with centrifugal evaporation to isolate the product and assess its stability. Alternatively, extraction was carried out with an aliquot of D2O for direct NMR characterization. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
24% | With silver(I) hexafluorophosphate In 1,2-dichloro-ethane at 50℃; for 0.416667h; Microwave irradiation; | 1,2,5-Trimethylthiophenium Hexafluoroantimonate; Typical Procedure for Microwave-Assisted Synthesis General procedure: In a 10-mL closed system microwave vessel, 2,5-dimethylthiophene (11.2mg, 0.1mmol), MeI (21.5mg, 0.15mmol), and AgSbF6 (34.4mg, 0.1mmol) were added to dry DCE under infrared light. The vessel was closed and the microwave-assisted reaction was carried out with the following fixed conditions: mode, sps; Δ temperature, 1 °C; stirring, high; max power, off. The reaction temperature was maintained at 50°C and 200W of power for 25min. The workup was the same as in thermal conditions; yield: 26.0mg (0.074mmol, 74%). The aqueous phase was brought to volume for UV-visible quantification. Some replicates were also evaporated with centrifugal evaporation to isolate the product and assess its stability. Alternatively, extraction was carried out with an aliquot of D2O for direct NMR characterization. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | In 1,2-dichloro-ethane at 50℃; for 0.416667h; Microwave irradiation; | 1,2,5-Trimethylthiophenium Hexafluoroantimonate; Typical Procedure for Microwave-Assisted Synthesis General procedure: In a 10-mL closed system microwave vessel, 2,5-dimethylthiophene (11.2mg, 0.1mmol), MeI (21.5mg, 0.15mmol), and AgSbF6 (34.4mg, 0.1mmol) were added to dry DCE under infrared light. The vessel was closed and the microwave-assisted reaction was carried out with the following fixed conditions: mode, sps; Δ temperature, 1 °C; stirring, high; max power, off. The reaction temperature was maintained at 50°C and 200W of power for 25min. The workup was the same as in thermal conditions; yield: 26.0mg (0.074mmol, 74%). The aqueous phase was brought to volume for UV-visible quantification. Some replicates were also evaporated with centrifugal evaporation to isolate the product and assess its stability. Alternatively, extraction was carried out with an aliquot of D2O for direct NMR characterization. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With C21H30ClNPPd; potassium <i>tert</i>-butylate In tert-Amyl alcohol at 65℃; for 18h; Sealed tube; Inert atmosphere; Glovebox; | |
76 %Spectr. | With copper(l) iodide; lithium iodide; lithium tert-butoxide at 50℃; for 16h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With tris(trimethylsilyl)amine; tetramethylammonium fluoride In N,N-dimethyl-formamide at 60℃; for 24h; Inert atmosphere; Glovebox; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With tris(trimethylsilyl)amine; tetramethylammonium fluoride In N,N-dimethyl-formamide at 80℃; for 24h; Inert atmosphere; Glovebox; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With tris(trimethylsilyl)amine; tetramethylammonium fluoride In N,N-dimethyl-formamide at 80℃; for 24h; Inert atmosphere; Glovebox; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
63% | With tris(trimethylsilyl)amine; tetramethylammonium fluoride In N,N-dimethyl-formamide at 80℃; for 24h; Inert atmosphere; Glovebox; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With tris(trimethylsilyl)amine; tetramethylammonium fluoride In N,N-dimethyl-formamide at 80℃; for 24h; Inert atmosphere; Glovebox; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With tris(trimethylsilyl)amine; cesium fluoride at 60℃; for 24h; Glovebox; Inert atmosphere; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
38% | With tris(trimethylsilyl)amine; tetramethylammonium fluoride In N,N-dimethyl-formamide at 60℃; for 6h; Inert atmosphere; Glovebox; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With [bis(acetoxy)iodo]benzene; ammonium carbonate In methanol at 20℃; for 21h; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: cesium fluoride; potassium <i>tert</i>-butylate / 13 h / 130 °C / 760.05 Torr / Sealed tube 2: methanol; hexane / 0.25 h / 0 - 20 °C / Inert atmosphere | ||
Multi-step reaction with 2 steps 1: lithium tert-butoxide; cesium fluoride; 18-crown-6 ether / 13 h / 130 °C / 760.05 Torr / Sealed tube 2: methanol; hexane / 0.25 h / 0 - 20 °C / Inert atmosphere | ||
Multi-step reaction with 3 steps 1: lithium tert-butoxide; cesium fluoride; 18-crown-6 ether / 13 h / 130 °C / 760.05 Torr / Sealed tube 2: lithium tert-butoxide; cesium fluoride / 13 h / 150 °C / 760.05 Torr / Sealed tube 3: methanol; hexane / 0.25 h / 0 - 20 °C / Inert atmosphere |
Multi-step reaction with 3 steps 1: lithium tert-butoxide; cesium fluoride; 18-crown-6 ether / 13 h / 130 °C / 760.05 Torr / Sealed tube 2: lithium tert-butoxide; cesium fluoride / 13 h / 150 °C / 760.05 Torr / Sealed tube 3: methanol; hexane / 0.25 h / 0 - 20 °C / Inert atmosphere | ||
Multi-step reaction with 3 steps 1: cesium fluoride; potassium <i>tert</i>-butylate / 13 h / 130 °C / 760.05 Torr / Sealed tube 2: lithium tert-butoxide; cesium fluoride / 13 h / 150 °C / 760.05 Torr / Sealed tube 3: methanol; hexane / 0.25 h / 0 - 20 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94 %Spectr. | With cesium fluoride; lithium tert-butoxide at 150℃; for 13h; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With bis(η3-allyl-μ-chloropalladium(II)); cesium fluoride; 1,4-di(diphenylphosphino)-butane In 1,4-dioxane at 160℃; for 24h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With palladium diacetate; cesium fluoride; 1,2-bis-(dicyclohexylphosphino)ethane In 1,4-dioxane at 160℃; for 24h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 43% 2: 26% 3: 9% | Stage #1: 3-bromo-2-methylbenzo[b]thiophene With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.666667h; Inert atmosphere; Stage #2: hexafluorocyclobut-1-ene In tetrahydrofuran; hexane at -78 - 20℃; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | With cerium(III) chloride; 1,1,1-trichloroethanol; oxygen In acetonitrile at 60℃; Irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 10% 2: 87% | With dihydrogen peroxide; C22H44N6Nb2O14 In water; acetonitrile at 45℃; for 3.5h; Inert atmosphere; Sealed tube; | 2.2 Catalytic reactions General procedure: General procedure. 0.5mmol of sulfide and 1.0mL of solvent (methanol or acetonitrile, concentration 0.5M) were introduced into a 3mL vial, then dinitrogen was fluxed for ca. 3 minutes. Then, while keeping the vial under a cone under N2 flux, the catalyst (1.0mol %) and the appropriate amount (2.0 or 3.0 equiv.) of 30% aqueous solution of hydrogen peroxide were added to the mixture. The sealed vial was either thermostated at 45°C through an oil bath or left at room temperature, under stirring. After 1.5 or 2.0h (in relation to the substrate), additional equivalent of oxidant was added dropwise when necessary. At the end of the reaction, the mixture was treated with 5.0mg of MnO2 to quench the excess of oxidant and, after 10 minutes, filtered. The progress of the reaction was monitored through GC-FID analysis, by withdrawing an aliquot of 20 μL and adding 5 μL of n-hexadecane (internal standard). The oxidation products were identified by comparison of their GC retention times with those of authentic samples. |
Tags: 1195-14-8 synthesis path| 1195-14-8 SDS| 1195-14-8 COA| 1195-14-8 purity| 1195-14-8 application| 1195-14-8 NMR| 1195-14-8 COA| 1195-14-8 structure
[ 3541-37-5 ]
Benzo[b]thiophene-2-carbaldehyde
Similarity: 0.83
[ 55219-11-9 ]
Benzo[b]thiophene-2-carbonitrile
Similarity: 0.83
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