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CAS No. : | 2396-68-1 | MDL No. : | MFCD00022067 |
Formula : | C10H14S | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | GNXBFFHXJDZGEK-UHFFFAOYSA-N |
M.W : | 166.28 | Pubchem ID : | 75454 |
Synonyms : |
|
Num. heavy atoms : | 11 |
Num. arom. heavy atoms : | 6 |
Fraction Csp3 : | 0.4 |
Num. rotatable bonds : | 1 |
Num. H-bond acceptors : | 0.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 52.96 |
TPSA : | 38.8 Ų |
GI absorption : | High |
BBB permeant : | Yes |
P-gp substrate : | No |
CYP1A2 inhibitor : | Yes |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -4.81 cm/s |
Log Po/w (iLOGP) : | 2.55 |
Log Po/w (XLOGP3) : | 3.53 |
Log Po/w (WLOGP) : | 3.27 |
Log Po/w (MLOGP) : | 3.83 |
Log Po/w (SILICOS-IT) : | 3.26 |
Consensus Log Po/w : | 3.29 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 2.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -3.43 |
Solubility : | 0.0614 mg/ml ; 0.000369 mol/l |
Class : | Soluble |
Log S (Ali) : | -4.03 |
Solubility : | 0.0156 mg/ml ; 0.0000935 mol/l |
Class : | Moderately soluble |
Log S (SILICOS-IT) : | -3.71 |
Solubility : | 0.0324 mg/ml ; 0.000195 mol/l |
Class : | Soluble |
PAINS : | 0.0 alert |
Brenk : | 1.0 alert |
Leadlikeness : | 2.0 |
Synthetic accessibility : | 1.0 |
Signal Word: | Danger | Class: | 6.1 |
Precautionary Statements: | P501-P261-P270-P271-P264-P280-P337+P313-P305+P351+P338-P361+P364-P332+P313-P301+P310+P330-P302+P352+P312-P304+P340+P311-P403+P233-P405 | UN#: | 2810 |
Hazard Statements: | H301+H311+H331-H315-H319 | Packing Group: | Ⅲ |
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 |
---|---|---|
93.7% | With hydrogenchloride; chlorosulfonic acid; sodium sulfide; iron; triphenylphosphine; In water; at 200℃; for 4h; | 60.0 g of p-tert-butylbenzenesulfonyl chloride, 250 ml of water and 150 ml of chlorosulfonic acid were added to the reaction vessel, mechanically stirred, and 1.3 g of triphenylphosphine, 5.7 g of iron and 34 g of sodium sulfide were added, and reacted at 200 C for 4 hours.TLC tracking monitoring.Allow to stand, separate the water layer, adjust the pH to 1.0, and concentrate the organic phase after extraction.Distillation under reduced pressure gave 40.3 g of p-tert-butylthiophenol in a yield of 93.7%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; oxygen; In ethanol; under 750.075 Torr; for 0.5h;Sealed tube; Irradiation; | General procedure: 0.6 mmol of thiol 1 and 90 muL (1/3 mol/L) TEMPO/EtOH (and 1.8 mmol of thiol 3) were combined in a 10 mL Pyrex vessel with 1 mL of EtOH dissolved. Subsequently, O2 was injected into the sealed vessel to reach 0.1 MPa of pressure. Then the reaction mixture was magnetically stirred at 1500 rpm and simultaneously illuminated with 3 W blue LEDs until it came to an end monitored by thin layer chromatography (TLC). The reaction pressure was released and the crude products were purified with column chromatograph (petroleum ether: ethyl acetate = 80:1). Then the target product was obtained. |
80% | With iodine; dimethyl sulfoxide; In neat (no solvent); at 20℃; for 0.7h; | General procedure: To a test tube, provided with magnetic stirring bar, was added iodine (51.0 mg, 20.0 mol%), DMSO (37.0 muL, 1.0 mmol) and thiol (1.0 mmol), the mixture were stirred for 5 to 50 minutes, depending on substrate. Reactions were monitored by TLC and when the reaction was complete, the product was extracted with ethyl acetate (20.0 mL) and Na2S2O3 (3 x 20.0 mL). The organic phase was dried with MgSO4, filtered and the solvent removed under reduced pressure. The product was purified by flash column chromatography eluting with an appropriate mixture of hexane/ethyl acetate. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydroxide | ||
With hydroxide In water | ||
With sodium hydroxide at 120 - 130℃; for 5h; | Materials General procedure: Phenylsulfinylacetic acid and several para- and meta substituted phenylsulfinyl acetic acids were prepared from the corresponding phenylmercaptoacetic acids by controlled oxidation using equimolar quantity of H2O2 and recrystallised from suitable solvents. The recrystallised phenylsulfinylacetic acids were dried, melting points were determined and checked with the literature values. Thepurity was also ascertained by LC-MS for all the phenylsulfinylacetic acids. Then they were stored in the vacuum desiccator and used for the kinetic studies. Phenylmercaptoacetic acids required for the synthesis of PSAAs were synthesized by condensing chloroacetic acid (4.7 g in 20 ml of 20% sodium hydroxide) with appropriate thiophenol (0.05 mole) dissolved in 10 ml of 20% sodium hydroxide at 120-130°C for five hours. The phenylmercaptoacetic acids formed were recrystallised from water and their melting points were verified with the literature values.32 Potassium dichromate (Merck), sodium perchlorate (Merck), perchloric acid (Merck) and all other reagents used were of AnalaR grade. Solvents, acetonitrile and water were purified by established procedures. |
Alkaline conditions; | ||
Alkaline conditions; | 2.2. Preparation of the phenylmercaptoacetic acids General procedure: Twelve phenylmercaptoacetic acids (Scheme 1) with differentsubstituents, viz. H, p-Cl, p-Br, p-F, m-F, p-OMe, m-OMe, p-OEt,p-Me, p-Et, p-i-Pr and p-t-Bu, were used in this work. They wereprepared using a standard procedure by the condensation ofthe corresponding thiophenols with chloroacetic acid in alkalinemedium [35,51]. The purity of the PMAAs was checked using theirmelting points and LCMS spectra, which were found to agree withthe literature values. The LCMS analysis of each PMAA on a HPLCcoupled Agilent ion trap mass spectrometer using an inestsil-ODS-3 V column of the size 4.6 250 mm confirmed the presenceof a single species. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62% | In xylene at 145 - 170℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogenchloride; potassium hydroxide Yield given; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With chlorine; In tetrachloromethane; | EXAMPLE V Preparation of 4-(tert-Butyl)phenylsulfenyl Chloride To a mixture of 332 grams (2.0 moles) of 4-(tert-butyl)thiophenol and 800 ml of carbon tetrachloride was slowly added with stirring and cooling a solution of 150 grams (2.0+ moles) of chlorine in 600 ml of carbon tetrachloride at 0 C. After chlorine addition was complete the mixture was stirred at 0-10 C. for two hours, hydrogen chloride and carbon tetrachloride removed in vacuo and the residue was distilled in a one-foot packed column to give 378 grams of 4-(tert-butyl)phenylsulfenyl chloride, b.p. 95-97/1.0 mm (yield 94%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With potassium fluoride impregnated on clinoptilolite; air; In dimethyl sulfoxide; at 110 - 115℃; for 0.666667h; | General procedure: Coupling of Aryl Fluorides withThiophenols in DMSO: A mixture of the thiophenol (2.6mmol), the appropriate aryl halide (2.4 mmol), and 35%(w/w) potassium fluoride/Clinoptilolite (0.62 g) in DMSO(4-6 mL) was heated at 110-115 C (bath temperature). Themixture was stirred under air until the reaction was complete(monitored by TLC or GC). The reaction mixture was cooledto room temperature, diluted with ethyl acetate, and filtered.The resulting solution was placed in a separating funnel andwashed twice with water. The organic layer was dried withanhydrous sodium sulfate, filtered, and concentrated invacuo to afford the crude product which was then purifiedeither by recrystallization in methanol (for high yields,>95%) or by column chromatography on silica gel (ethylacetate/hexane). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | With zinc(II) chloride In dichloromethane at 20℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: 83 percent / ZnI2 / 1,2-dichloro-ethane / 1 h / Ambient temperature 2: 1.) LDMAN / 1.) THF, -78 deg C, 10 min, 2.) THF, 0 deg C, 1.5 h |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
57% | With potassium carbonate; In acetone; | EXAMPLE 2 Ethyl 2-(4-t-Butylphenylthio)octanoate A mixture of 5.0 g (0.02 mole) <strong>[138286-76-7]ethyl 2-bromooctanoate</strong>, 3.37 g (0.02 mole) p-t-butylthiophenol and 3.31 g (0.24 mole) potassium carbonate in 70 ml acetone was refluxed under nitrogen overnight. The reaction mixture was cooled to room temperature and filtered and the filtrate was concentrated in vacuo. The residue was chromatographed on 500 g silica gel, eluding with 6:4 methylene chloride/hexane to yield 3.8 g (57% yield) of the desired product as an oil. 1 H NMR(CDCl3): delta 0.88 (c,3H); 1.1-1.52 (c,total 20H) including 1.14 (t, 3H) and 1.3 (s); 1.66-2.11 (c, 2H); 358 (q, 1H); 4.1 (q, 2H); 7.36 (m, 4H). |
57% | With potassium carbonate; In acetone; | EXAMPLE 2 Ethyl 2-(4-t-Butylphenylthio)octanoate A mixture of 5.0 g (0.02 mole) <strong>[138286-76-7]ethyl 2-bromooctanoate</strong>, 3.37 g (0.02 mole) p- t -butylthiophenol and 3.31 g (0.24 mole) potassium carbonate in 70 ml acetone was refluxed under nitrogen overnight. The reaction mixture was cooled to room temperature and filtered and the filtrate was concentrated in vacuo . The residue was chromatographed on 500 g silica gel, eluding with 6:4 methylene chloride/hexane to yield 3.8 g (57% yield) of the desired product as an oil. 1H NMR(CDCl3): delta 0.88 (c,3H); 1.1-1.52 (c,total 20H) including 1.14 (t,3H) and 1.3 (s); 1.66-2.11 (c,2H); 358 (q,1H); 4.1 (q,2H); 7.36 (m,4H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogenchloride; sodium hydroxide; potassium carbonate In water | 13.i EXAMPLE 13 (i) Sodium chloroacetate (6.29 g, 54 mmol) was added in portions to a solution of 4-t-butylbenzenethiol (9.0 g, 54 mmol) in a 30% (w/v) aqueous solution of sodium hydroxide (10.8 ml, 81 mmol) with stirring at 80° C. When the addition was complete, stirring was continued for an additional 2 hours at 80° C., during which time a thick white precipitate had formed. The reaction mixture was added to water (200 ml) and was acidified to pH 2 by the addition of 2M hydrochloric acid. The mixture was extracted with ethyl acetate. The combined extracts were then extracted with a 10% (w/v) aqueous solution of potassium carbonate. The aqueous extracts were acidified to pH 2 by the addition of 2M hydrochloric acid and again extracted with ethyl acetate. These combined extracts were dried (MgSO4) and the solvent was removed by evaporation to give 2-(4-t-butylphenylthio)acetic acid (B) as a straw coloured oil (9.07 g); which had a satisfactory NMR spectrum. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With caesium carbonate;copper(l) iodide; In N,N-dimethyl-formamide; for 48h;Reflux; | 1,4-Bis(4'-t-butylphenylthio)-2,3,5,6-tetramethylbenzene; To a solution of 1,4-dibromo-2,3,5,6-tetramethylbenzene (2.0 g, 6.85 mmol) and 4-t-butylthiophenol (2.6 g, 15.66 mmol) in dimethylformamide (60.0 mL) was added cesium carbonate (8.92 g, 27.38 mmol) and copper iodide (0.13 g, 0.068 mmol). The resulting suspension was heated to boiling for 2 days. Upon completion, the reaction mixture was cooled, filtered and extracted with ethyl acetate. The organic layer was separated and washed with water followed by brine and then dried to give the crude product which was further purified by column chromatography using hexanes:ethyl acetate (10:1) to furnish off-white solid product (2.78 g, 88% yield). 1H NMR (500 MHz, CDCl3): delta 7.23 (d, 4H, J=8.53 Hz), 6.87 (d, 4H, J=8.53 Hz), 2.50 (s, 12H), 1.28 (s, 18H). 13C NMR (125.68 MHz, CDCl3): delta 147.9, 140.5, 134.9, 133.4, 126.1, 125.8, 34.5, 31.5, 20.1. The 1H NMR spectrum of 1,4-bis(4'-t-butylphenylthio)-2,3,5,6-tetramethylbenzene and the compound structure is shown in FIG. 7. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With caesium carbonate;copper(l) iodide; In N,N-dimethyl-formamide; for 48h;Reflux; | 1,2,3,4-Tetra(4'-t-butylphenylthio)-5,6-dimethylbenzene; To a solution of 1,2,3,4-tetrabromo-5,6-dimethylbenzene (2.0 g, 4.74 mmol) and 4-t-butylthiophenol (4.73 g, 28.44 mmol) in dimethylformamide (40.0 mL) was added cesium carbonate (13.00 g, 39.89 mmol) and copper iodide (0.36 g, 0.19 mmol). The resulting suspension was heated to boiling for 2 days. Upon completion, the reaction mixture was cooled, filtered and extracted with ethyl acetate. The organic layer was separated and washed with water and brine and then dried to give a crude product that was further purified by column chromatography using hexanes:ethyl acetate (9:1) as eluant to furnish the off-white solid product (3.14 g, 87% yield). 1H NMR (500 MHz, CDCl3): delta 7.19 (d, 4H, J=8.54 Hz), 7.15 (d, 4H, J=8.54 Hz), 6.93 (d, 4H, J=8.78 Hz), 6.86 (d, 4H, J=8.78 Hz), 2.43 (s, 6H), 1.27 (s, 18H), 1.24 (s, 18H). 13C NMR (125.68 MHz, CDCl3): delta 148.7, 148.6, 145.3, 145.2, 142.1, 135.8, 134.6, 127.8, 127.0, 126.1, 125.9, 34.53, 34.49, 31.5, 21.4. The 1H and 13C NMR spectra for 1,2,3,4-tetra(4'-t-butylphenylthio)-5,6-dimethylbenzene and the compound structure are shown in FIGS. 10A & B. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium carbonate; In dimethyl sulfoxide; at 20℃; for 24h; | Intermediate 2 was synthesized by reaction of 2,3-dicyanohydroquinone and trifluoromethanesulfonic anhydride for 24 h, in accordance with a description from the literature [8]. Intermediates 3 were synthesized, respectively, from 2 and thiophenols such as p-toluenethiol, 4-methoxybenzenethiol and tert-butylthiophenol at room temperature for 24 h to obtain 3,6-bis(metylthiophenyl)phthalonitrile (3a), 3,6-bis(methoxythiophenyl)phthalonitrile (3b) and 3,6-bis(tert-butyl thiophenyl)phthalonitrile (3c) | |
With potassium carbonate; In dimethyl sulfoxide; at 20℃; for 24h;Inert atmosphere; | 3,6-Bis(thiophenyl-tert-butyl)phthalonitrile (2): Tert-butylthiophenol (0.784 g, 4.72 mmol), was added to a stirred mixture of 1 (1.0 g, 2.36 mmol), potassium carbonate (0.96 g) in dimethylsulfoxide (15 mL) solvent under the nitrogen atmosphere. The stirring was continued at room temperature for 24 h. After the reaction mixture was poured into water and the organic layer was extracted with dichloromethane, dried on sodium sulfate, then filtered. The filtrate was evaporated on rotary evaporator. The crude product was then washed with methanol and recrystallized from toluene to obtain the desired compound as yellow solid. Elemental Anal. Calc. for C28H28N2S2: C, 73.64; H, 6.18; N, 6.13. Found: C, 73.60; H, 6.20; N, 6.10%. 1H NMR (300 MHz, DMSO-d6): delta 7.46-7.39 (m, 8H), 7.00 (s, 2H), 1.31 (s, 12H); FT IR(KBr): cm-1 3058 (nuC-H), 2958 (nuC-H), 2215 (nuC-N), 1667 (nuC-C), 1530 (nuC-C), 1482 (nuC-C), 1262, 830 (nuC-H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With potassium fluoride impregnated on clinoptilolite; air; In dimethyl sulfoxide; at 110 - 115℃; for 0.833333h; | General procedure: Coupling of Aryl Fluorides withThiophenols in DMSO: A mixture of the thiophenol (2.6mmol), the appropriate aryl halide (2.4 mmol), and 35%(w/w) potassium fluoride/Clinoptilolite (0.62 g) in DMSO(4-6 mL) was heated at 110-115 C (bath temperature). Themixture was stirred under air until the reaction was complete(monitored by TLC or GC). The reaction mixture was cooledto room temperature, diluted with ethyl acetate, and filtered.The resulting solution was placed in a separating funnel andwashed twice with water. The organic layer was dried withanhydrous sodium sulfate, filtered, and concentrated invacuo to afford the crude product which was then purifiedeither by recrystallization in methanol (for high yields,>95%) or by column chromatography on silica gel (ethylacetate/hexane). |
With sodium carbonate; In N,N-dimethyl-formamide; at 170℃; for 1h;Microwave irradiation; | In a 5 mL microwave tube, 200 mg of the substituted thiol (9) and 1 equiv. of l-fluoro-4-nitrobenzene (10) were dissolved in 4 mL of DMF, then 2.9 equiv. of Na2CO3 was added. The reaction mixture was heated in the microwave at 170 0C for 1 h. The mixture was partitioned between EtOAc and water; the organic phase was washed with brine and then dried over MgSO4. EtOAc was evaporated on the rotary evaporator to give the crude product (11). (60-70 % yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With 1-(2,6-diisopropylphenyl)-3-[2-(mesitylamino)-2-oxoethyl]-1H-imidazol-3-ium bromide; palladium diacetate; sodium hexamethyldisilazane; In dimethyl sulfoxide; at 80℃; for 12h; | General procedure: Pd(OAc)2 (6.7mg, 0.03mmol), ligand 1 or 2 (0.036mmol), aryl halides (3.0mmol), thiol (3.0mmol) and NaHMDS (825mg, 4.5mmol) or KOtBu (505mg, 4.5mmol) were combined with DMSO (10mL) in a small round-bottomed flask. The resulting mixture was stirred at 80C for 12h. The reaction mixture was poured into water and extracted with EtOAc. The solvent was removed under vacuum, and the resulting crude product was purified by flash chromatography on silica gel to give the desired product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
55% | With potassium fluoride; chlorine; In acetonitrile; at 0 - 20℃; for 20h;Cooling with ice; | General procedure: Note: The synthesis, distillation or crystallization of compounds 2 was performed in ordinary borosilicate glassware; however, purified compounds 2 were stored in fluoropolymer containers. To a solution of 1a-f (21-89mmol) in dry acetonitrile (7.5-32mL) spray-dried KF (16 equiv.) was added. The mixture was cooled with an ice bath and chlorine was introduced into the solution. After several hours the temperature of the reaction mixture was allowed to reach room temperature and the color of the mixture changed from yellow to white. After 8h of passing chlorine the mixture was yellow again. At this point the chloride bubbling was stopped and the mixture was stirred for another 12h. The solid was removed by filtration, washed with hexane, solvent was removed under reduced pressure, and the product was distilled under reduced pressure (2a-c and 2e), recrystallized form hexane (2d), or used without further purification (2f), and stored in a fluoropolymer container at 2-8C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With chloro(1,5-cyclooctadiene)rhodium(I) dimer; triphenylphosphine; sodium t-butanolate; In toluene; at 100℃; for 24h;Inert atmosphere; | General procedure: A 4-mL sealable vial equipped with a magnetic stir bar was charged with base (0.4 mmol), [RhCl(cod)]2 (4.93 mg, 0.01 mmol), ligand (0.02 mmol) and aryl iodide (0.24 mmol) under a nitrogen atmosphere. The aliphatic thiol or aromatic thiol (0.2 mmol) and solvent (0.2 mL) were added by syringe, and the vial was sealed with a cap containing a PTFE septum and the reaction vessel was heated at 100 C in an oil bath. After stirring at this temperature for 24 h, the heterogeneous mixture was cooled to room temperature and diluted with ethyl acetate (20 mL). The resulting solution was filtered through a pad of silica gel then washed with ethyl acetate (20 mL) and concentrated to give the crude material which was then purified by column chromatography on silica gel to yield product 3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | In toluene for 6h; Reflux; | 3.9 4.2 General experimental procedure for the synthesis of 4-thio-substituted-4H-chromenes (6) General procedure: A mixture of 4 (0.5 mmol) and thiols (5) (0.55 mmol) was heated at reflux in anhydrous toluene (3.0 mL). After the reactant disappeared (6-10 h, monitored by thin layer chromatography), the mixture was cooled to room temperature. The reaction mixture was directly added to the column chromatography using petroleum ether as the eluent to remove toluene, then eluting with petroleum ether or petroleum ether/ethyl acetate to give the expected compounds 6. 4-(4-tert-Butylphenylthio)-2-phenyl-4H-chromene (6j) Yellow oil; IR (KBr, cm-1) 2959, 1638, 1231, 1013, 825, 691; 1H NMR (300 MHz, CDCl3) δ (ppm) 7.81-7.74 (m, 4H), 7.50-7.35 (m, 7H), 7.26-7.24 (m, 1H), 7.13 (t, J=7.5 Hz, 1H), 6.95 (d, J=4.7 Hz, 1H), 5.71 (d, J=4.7 Hz, 1H), 1.29 (s, 9H); 13C NMR (75 MHz, CDCl3) δ (ppm) 175.6, 159.7, 156.0, 153.1, 151.7, 133.3, 130.0, 129.6, 128.8, 128.5, 126.5, 125.9, 125.3, 124.3, 119.6, 117.2, 116.8, 93.0, 53.0, 35.1, 31.0; HRMS-EI: m/z calcd for C25H24OS: 372.1548, found: 372.1555. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With lithium perchlorate; In acetonitrile; at 20℃; for 0.533333h;Electrolysis; Sonication; | General procedure: The electrolytic cell was filled with 10 mL of an acetonitrile solution of LiClO4 (0.1 M), 1 mmol of enone 4-6 and 2 mmol of the corresponding nuclephile 7a-h. The cell was placed in the ultrasound bath (at a frequency of 37 kHz, with an effective ultrasonic power of 30W and a peak of 240 W) and the constant current electrolysis (20 mA) was run 32 min (0.4 F mol1) at room temperature. After the electrolysis was finished, the reaction mixture was left 30 min in the same bath and the solvent evaporated. The residue was diluted with 20 mL of water, the obtained mixture extracted with three 20 mL portions of ethyl acetate and collected organic layers dried overnight (anhydrous sodium sulfate). After evaporation of the solvent the crude reaction product was purified by column chromatography to give the products of the reaction.The spectral data of known compounds were in complete agreement with those published elsewhere (1a [28], 1c [29], 1d [29],1g [29], 1h [29], 2a [30], 2h [30], and 3a [30]), whereas the data confirming structures of newly synthesized ones follow. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With lithium perchlorate; In acetonitrile; at 20℃; for 0.533333h;Electrolysis; Sonication; | General procedure: The electrolytic cell was filled with 10 mL of an acetonitrile solution of LiClO4 (0.1 M), 1 mmol of enone 4-6 and 2 mmol of the corresponding nuclephile 7a-h. The cell was placed in the ultrasound bath (at a frequency of 37 kHz, with an effective ultrasonic power of 30W and a peak of 240 W) and the constant current electrolysis (20 mA) was run 32 min (0.4 F mol1) at room temperature. After the electrolysis was finished, the reaction mixture was left 30 min in the same bath and the solvent evaporated. The residue was diluted with 20 mL of water, the obtained mixture extracted with three 20 mL portions of ethyl acetate and collected organic layers dried overnight (anhydrous sodium sulfate). After evaporation of the solvent the crude reaction product was purified by column chromatography to give the products of the reaction.The spectral data of known compounds were in complete agreement with those published elsewhere (1a [28], 1c [29], 1d [29],1g [29], 1h [29], 2a [30], 2h [30], and 3a [30]), whereas the data confirming structures of newly synthesized ones follow. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With lithium perchlorate; In acetonitrile; at 20℃; for 0.533333h;Electrolysis; Sonication; | General procedure: The electrolytic cell was filled with 10 mL of an acetonitrile solution of LiClO4 (0.1 M), 1 mmol of enone 4-6 and 2 mmol of the corresponding nuclephile 7a-h. The cell was placed in the ultrasound bath (at a frequency of 37 kHz, with an effective ultrasonic power of 30W and a peak of 240 W) and the constant current electrolysis (20 mA) was run 32 min (0.4 F mol1) at room temperature. After the electrolysis was finished, the reaction mixture was left 30 min in the same bath and the solvent evaporated. The residue was diluted with 20 mL of water, the obtained mixture extracted with three 20 mL portions of ethyl acetate and collected organic layers dried overnight (anhydrous sodium sulfate). After evaporation of the solvent the crude reaction product was purified by column chromatography to give the products of the reaction.The spectral data of known compounds were in complete agreement with those published elsewhere (1a [28], 1c [29], 1d [29],1g [29], 1h [29], 2a [30], 2h [30], and 3a [30]), whereas the data confirming structures of newly synthesized ones follow. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
6.7 g | Stage #1: 4-t-butylbenzenethiol; Bromoacetaldehyde diethyl acetal With sodium hydride In tetrahydrofuran at 20℃; for 15h; Stage #2: With phosphorus pentoxide at 175℃; for 0.75h; | 5 12125] A mixture of 7.80 g of bromoacetaldehyde diethylacetal and 20 ml oftetrahydrofuran was added to a mixture of 8.00 g of 4-tert-butylbenzenthiol, 2.10 g of sodium hydride, and 70 ml of tetrahydroffiran. The reaction mixture was stirred for 15 hours at room temperature. Twenty (20) ml of an aqueous saturated ammonium chloride solution was added to the reaction mixture, and extraction was performed three times by using tert-butyl methyl ethet The collected organic layer was washed with water and saturated saline, dried over magnesium sulfate, and then concentrated under reduced pressure. The residues were added to a mixture of 10 g of diphosphorus pentoxide which had been stirred for 45 minutes at 175° C. and 20 g of phosphoric acid, and the residue was stirred for 5 minutes. The reaction mixture was poured into ice water, and extraction was performed three times by using tert-butyl methyl ethet The collected organic layer was washed with water and saturated saline, dried over magnesium sulfate, and then concentrated under reduced pressure. The residues were subjected to silica gel colunm chromatography, thereby obtaining 6.7 g of 5-tert-butylbenzo[b] thiophene. |
6.7 g | Stage #1: 4-t-butylbenzenethiol; Bromoacetaldehyde diethyl acetal With sodium hydride In tetrahydrofuran at 20℃; for 15h; Stage #2: With phosphorus pentoxide; phosphoric acid at 175℃; for 0.75h; | 15.1 A mixture of 7.80 g of bromoacetaldehyde diethylacetal and 20 ml of tetrahydrofuran was added to a mixtureof 8.00 g of 4-tert-butylbenzenthiol, 2.10 g of 60% sodium hydride, and 70 ml of tetrahydrofuran. The reaction mixturewas stirred for 15 hours at room temperature. Twenty (20) ml of an aqueous saturated ammonium chloride solution wasadded to the reaction mixture, and extraction was performed three times by using tert-butyl methyl ether. The collectedorganic layer was washed with water and saturated saline, dried over magnesium sulfate, and then concentrated underreduced pressure. The residues were added to a mixture of 10 g of diphosphorus pentoxide which had been stirred for 45 minutes at 175°C and 20 g of phosphoric acid, and the residue was stirred for 5 minutes. The reaction mixture waspoured into ice water, and extraction was performed three times by using tert-butyl methyl ether. The collected organiclayer was washed with water and saturated saline, dried over magnesium sulfate, and then concentrated under reducedpressure. The residues were subjected to silica gel column chromatography, thereby obtaining 6.7 g of 5-tert-butylbenzo[b]thiophene |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | With triethylamine In tetrahydrofuran at 20℃; for 24h; | 5 4.1. Synthesis of compounds 2a-e General procedure: A solution of pentafluorobenzaldehyde (2 mmol) in THF (2.5 ml) was added to a solution of the relevant nucleophile (2-4 mmol) in THF (2.5 ml), with Et3N (4-10 mmol) used in the reactions of compounds 2c-e. The resulting solution was stirred at room temperature for up to 24 h. The reaction mixture was poured into deionized water and was extracted with ethyl acetate (15 ml x 3). Organic extracts for compounds 2c-e were further washed with 0.2 M HCl (aq) and deionized water, combined and dried over NaSO4. The solution was concentrated and the crude residue purified by column chromatography (elution with light petroleum/ethyl acetate). 4.1.5 4-[(4-(tert-Butyl)phenyl)thio]-2,3,5,6-tetrafluorobenzaldehyde (2e) Yield 73%, yellow solid, m.p. 42-44 °C NMR δH (CDCl3), 10.30 (1H, s, CHO), 7.44-7.36 (4H, m), 1.33 (9H, s); NMR δF (CDCl3), 29.1-29.2 (2F, m), 147.0-16.9 (2F, m); NMR δc (CDCl3), 182.3 (s, CHO), 152.6, 146.6 (dd, J = 260, 16 Hz), 146.1 (dd, J = 260, 10 Hz), 132.3, 127.2, 126.7, 123.4 (t, J = 18 Hz), 114.4 (t, J = 10 Hz), 34.7, 31.2; IR, νmax/cm-1 1705 (CHO); MS, m/z found 343.0778, C17H15F4OS, (M+H+) requires 343.0774; elemental analysis, C17H14F4OS requires: C, 59.64; H, 4.12; found: C, 59.61; H, 4.06. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | With dipotassium peroxodisulfate; silver nitrate; In water; acetonitrile; at 80℃; for 24h;Inert atmosphere; | General procedure: A reaction tube was charged with 4-methylbenzenethiol (1b) (24.8 mg, 0.2 mmol) at room temperature, then trifluoromethanesulfinate (62.4 mg, 0.4 mmol), silver nitrate (3.4 mg, 0.02 mmol), potassium persulfate (108 mg, 0.4 mmol) and MeCN/H2O (1:1, 0.8 mL) were added. The resulting mixture was stirred at 80 under argon atmosphere for 24 h. After cooling to room temperature, the reaction mixture was quenched and purified by flash silica gel column chromatography (eluent: petroleum ether/EtOAc) to afford the desired product 3b (23.0 mg, 60%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | With pyridine In neat (no solvent) at 0℃; for 72h; Inert atmosphere; diastereoselective reaction; | 3 4.2 General procedure for the Michael addition reactions General procedure: To a solution of (1R)-(-)-myrtenal 1 (0.90g, 6.0mmol) and dry pyridine (1mL, 2.0equiv), the appropriate thiophenol (2.5equiv) was added under an argon atmosphere. The reaction mixture was stirred at 0°C for 3 days, then diluted with CH2Cl2 (15mL) and quenched with 1N HCl (10mL). The organic phase was washed with 10% NaOH, water, brine, dried over Na2SO4, and the solvent was evaporated. The crude product was chromatographed on a silica gel using CH2Cl2/n-hexane (2:1 v/v), yielding a light yellow oil (-)-2. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | Stage #1: 4-t-butylbenzenethiol With N-chloro-succinimide In dichloromethane at 20℃; for 0.5h; Inert atmosphere; Green chemistry; Stage #2: 1,2,4-trimethoxy-benzene In dichloromethane at 20℃; for 0.5h; Green chemistry; | General Procedure for the NCS promoted thiolation of the Methoxybenzenes with Thiophenols General procedure: An oved dried two neck flask was charged with NCS (1.7 mmol), thiophenol 1a ( 2.3 mmol) and dichloromethane (2-3 mL). The above mixture was stirred for 30 min, then 1,3,5- trimethoxy benzene 3a (1.1 mmol) was added. Stirring was continued for another 30 min at room temperature and then the mixture was poured into 20 mL of saturated sodium bicarbonate solution. The product was extracted with dichloromethane (10 mL × 3) and dried over anhydrous Na2SO4. Removal of the solvent under reduced pressure, the left out residue was purified through column chromatography using silica gel (10 % EtOAc/hexane) to get 4a in 89% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
It was added 18.0 parts of ethanol 90 parts of the compound represented by formula (I-7-a), and stirred for 1 hour at 23 C. To the resulting mixed solution, after addition of 4.33 parts of sodium hydroxide, 23 After stirring for 1 hour at C, over 30 minutes compound 13.05 parts of the formula (I-7-b) It dropped, and 25 hours reflux and stirred at 75 C. The resulting reaction mass was concentrated, added to 90 parts of chloroform and 30 parts of ion exchange water and stirred for 30 min at 23 C, the organic layer was removed by liquid separation. This operation was repeated five times. The recovered organic layer was filtered and concentrated the filtrate to give the compound 18.97 parts of the formula (I-7-c). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
61% | With dipotassium peroxodisulfate; silver nitrate; In water; acetonitrile; at 80℃; for 24h;Inert atmosphere; | General procedure: A reaction tube was charged with 4-methylbenzenethiol (1b) (24.8 mg, 0.2 mmol) at room temperature, then trifluoromethanesulfinate (62.4 mg, 0.4 mmol), silver nitrate (3.4 mg, 0.02 mmol), potassium persulfate (108 mg, 0.4 mmol) and MeCN/H2O (1:1, 0.8 mL) were added. The resulting mixture was stirred at 80 under argon atmosphere for 24 h. After cooling to room temperature, the reaction mixture was quenched and purified by flash silica gel column chromatography (eluent: petroleum ether/EtOAc) to afford the desired product 3b (23.0 mg, 60%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With benzoic acid; 9-(2-mesityl)-10-methylacridinium perchlorate; In chloroform; at 20℃; for 10h;Inert atmosphere; Irradiation; | General procedure: An oven-dried Schlenk tube (10 mL) was equipped with a magnetic stir bar, 4-methylbenzenethiol (1a, 0.3 mmol), dimethyl but-2-ynedioate (2, 0.9 mmol), 5% Mes-Acr-Me+ (0.015 mmol), PhCOOH (2 equiv., 0.6 mmol). The flask was evacuated and backfilled with Ar for 3 times. Then CHCl3 (3.0 mL) was added with syringe. The reaction mixture was then stirred for 10 h at room temperature. After the reaction, 6 mL water was added to quench the reaction, and the resulting mixture was extracted twice with EtOAc. The combined organic extracts were washed with brine, dried over Na2SO4 and concentrated. Purification of the crude product by flash column chromatography afforded the product (petroleum ether/ethyl acetate as eluent (8:1)). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | In a 15 mL reaction tube equipped with a magnetic stir bar, p-tert-butylthiophenol (1 mmol), trichloroisocyanuric acid (0.35 mmol) and 2 mL of acetonitrile were added,Stir the reaction at room temperature for 10 min, then add triethyl phosphite (1.2 mmol),Continue stirring at room temperature for 10 min. Filtration, the filtrate was evaporated under reduced pressure,Separate with column chromatography, and use the mixture of petroleum ether/ethyl acetate volume ratio of 20:1 as the eluent to collect the eluent containing the target compound.Distilling off the solvent yields the product O,O-diethyl-S-p-tert-butylphenyl phosphorothioate,The isolated yield was 84%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | With potassium carbonate In tetrahydrofuran at 20℃; for 3h; Schlenk technique; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72.8% | With sodium hydrogencarbonate In ethanol; water at 20℃; Inert atmosphere; | 15 General method for the synthesis of 2a-2u General procedure: To a 100-mL, one-necked, round-bottomed flask, sequentiallycharged with NaHCO3 0.26 g (3.2 mmol, 1.05 equiv.), dissolved in10 mL of water, compound RSH (3 mmol, 1 equiv.), SFA (3 mmol, 1equiv.) and 20 mL of ethanol. The mixture was stirred for0.5e10 h at RT. TLC analysis was used to indicate the completion ofthe reaction. The thus-obtained product was purified by silica gelpacked column chromatography. After concentration and freezedrying,we obtained the final products. 1H and 13C NMR andHRMS were performed to determine their structures. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | In a 25 mL reactor, add sodium borohydride (56.7mg, 1.5mmol, fill with CO2 gas under vacuum, and then p-tert-butylphenylthiophenol (83.1mg, 0.5mmol), 1,4-dioxygen in order. Hexacyclic (1mL), slowly heated to 80 C, kept for 30 minutes and cooled to room temperature. After adding iodine particles (126.9mg, 0.5mmol), the reactor was sealed and reacted at 100 C for 24 hours. After the reaction system was cooled, dropwise 10 mL of water and 10 mL of ethyl acetate were stirred for 20 min, and then extracted twice with 20 mL of ethyl acetate, and the organic phases were combined. The organic phases were dried over anhydrous magnesium sulfate for 0.5 h, filtered, and the organic phase was rotary evaporated to obtain a crude product. The crude product was petroleum ether. As an eluent, 200-300 mesh neutral alumina column adsorption phase column chromatography separation was performed to obtain 71 mg of bis (p-tert-butylphenylsulfide) methane as a colorless oily product with a purity of more than 99%, with an isolation yield of 90%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With tris-(dibenzylideneacetone)dipalladium(0); caesium carbonate; XPhos; In N,N-dimethyl-formamide; at 110℃;Inert atmosphere; | 4-tert-Butylthiophenol (88 ul, 0.5 mmol), 1a (127 mg, 0.25 mmol), 60748-47-2 (2.3 mg,0.0025 mmol), 657408-07-6 (2.1 mg, 0.005 mmol) and cesium carbonate (245 mg, 0.75 mmol) added to 50 mlIn a three-necked flask, the solvent was DMF, vacuumed, and replaced with nitrogen three times, placed at 110 C and stirred overnight. deal withIn the reaction, the catalyst, the ligand and the inorganic salt of the reaction solution are first filtered off with diatomaceous earth to obtain a black filtrate, which is then distilled off under reduced pressure.Solvent N,N-dimethylformamide to give a tan solid, add dichloromethane and extract twice with water, organic phaseDrying with anhydrous magnesium sulfate, filtration, the filtrate was dried, and the residue was purified by column chromatography.Get a yellow-brown solid 9,The yield was 76%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With 1,8-diazabicyclo[5.4.0]undec-7-ene; In acetonitrile; at 50℃; for 6h; | 0.2 mmol of 5-ethylcarbonyl-1-phenyl-1 yn-3-ene-5-one was added to the reaction tube.0.2 mmol of 1,8-diazabicycloundec-7-ene, 0.2 mmol of p-tert-butylthiophenol and 2 ml of acetonitrile as a solvent, and the reaction was stirred at a rotation speed of 700 rpm at 50 C for 6 hours; Stir, add 5mL water,Extracted 3 times with ethyl acetate,The organic phases were combined and dried using 0.5 g anhydrous magnesium sulfate.Filtered, concentrated under reduced pressure,Separated and purified by column chromatography.The column chromatography eluent used was 20:1 by volume.Petroleum ether: ethyl acetate mixed solvent to obtain the target product,The yield was 90%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | p-tert-Butylthiophenol (100 mg, 0.60 mmol), DMF (4 mL),Potassium tert-butoxide (202 mg, 1.8 mmol, 3 eq.) was added to the reaction flask in turn.After stirring at room temperature for 5 minutes, after the potassium tert-butoxide is uniformly dispersed,Slowly inject methyl trifluoroacetate (0.24 mL, 2.4 mmol, 4 eq.) into the reaction flask.After reacting for 10 hours, the TLC plate, the starting point disappeared, that is, the reaction was completed, and the stirring was stopped.It is extracted twice with ethyl acetate and distilled water, and then washed with a saturated NaCI solution. The organic phase is combined, and the organic phase is dried over anhydrous magnesium sulfate. Butyl benzyl sulfide (88 mg, yield 81%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With air; In ethanol; at 20℃; for 24h;Schlenk technique; | The structure of 9-((4-tert-butylphenyl)thio)-9H-xanthene is as follows:The specific preparation process is as follows: 66.4 mg of p-tert-butylthiophenol (0.4 mmol) and 36.4 mg of xanthene (0.2 mmol) are put into 15 mL of Schlenk, 2 mL of absolute ethanol is added, and the solution is completely dissolved by magnetic stirring at room temperature, and passed through TLC. Monitor the progress of the reaction. After reacting at room temperature for 24 hours, the solvent ethanol was distilled off to obtain a crude product, which was then obtained by column chromatography using a petroleum ether/ethyl acetate volume ratio of 100/1 to obtain 9-((4-tert-butylphenyl). ) thio)-9H-xanthene, a colorless oily liquid. The yield in this step was 96% (66.4 mg). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphinane-2,4,6-trioxide; N-ethyl-N,N-diisopropylamine In ethyl acetate at 20℃; for 12h; Green chemistry; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With dihydrogen peroxide; sodium iodide; In dimethyl sulfoxide; at 100℃; for 27h;Schlenk technique; | Add 0.2 mmol of uracil, 0.1 mmol of NaI and a stirrer to a clean Schlenk reaction tube, then add 3 mL of DMSO solvent with a syringe.Finally, 0.3 mmol of <strong>[2396-68-1]4-tert-butylthiophenol</strong> and 1.8 mmol were added using a micro syringe.H2O2 (3 hours apart, added in three portions), reacted at 100 C for 24 hours,TLC dot plate detection; after the reaction is over,The reaction solution was added with water and extracted with ethyl acetate three times.The organic layer is concentrated and separated by column chromatography to obtain pure5-(4-tert-Butylphenyl)thiouracil, white solid, yield 93%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With potassium phosphate; 18-crown-6 ether; In tetrahydrofuran; at 20℃; for 3h; | General procedure: In a glovebox, K3PO4 (10 mol %, 5.3 mg), 18-Crown-6 (20 mol %, 13.2 mg) , and 2.5 mL tetrahydrofuran were added into a Schlenk tube equipped with a stir bar, then thiol (0.25 mmol) and nitrobenzene derivative (0.25 mmol) were added on the outside under an air atmosphere. The reaction mixture was stirred at room temperature 3 h (450 rpm). The resultant solution was concentrated and purified by silica gel column chromatography with EtOAc and petroleum ether as the eluent to give the corresponding thioether. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With cercosporin; In dimethyl sulfoxide; at 25℃; for 20h;Irradiation; | In a 10 mL reaction tube, add cerosporin (0.005 mmol), 4-chlorobenzenetetrafluoroborate diazonium salt (0.6 mmol), p-tert-butylthiophenol (0.5 mmol), 2 mL DMSO, then in air, 15W white light was irradiated, and the reaction was performed at room temperature of 25 C for 20h. The reaction solution was washed three times with water, and the organic phase was collected and then dried over anhydrous magnesium sulfate. After filtration, the solvent was evaporated by rotary evaporation and quickly separated by a 300-500 mesh thin silica gel plate. The eluent used was ethyl acetate/petroleum ether (v: v = 3: 100), 4-tert-butyl-4'-chloro-diphenylsulfide was obtained in a yield of 96%, |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | Stage #1: 4-t-butylbenzenethiol With sodium hydride In N,N-dimethyl-formamide at 20℃; Inert atmosphere; Stage #2: 1,3,5-trisbromobenzene In N,N-dimethyl-formamide at 150℃; Inert atmosphere; Heating; | 1,3,5-Tris((4-tert-butyl)phenyl)thio)benzene 4-tert-Butylbenzenethiol (2.6 g, 16 mmol) was added dropwise to a suspension of NaH(800 mg, 20 mmol) in DMF (20 mL) placed in a 100 mL three-necked round-bottomflask at room temperature under N2 flow. Then, 1,3,5-tribromobenzene (1.5 g, 5 mmol)was added, and the mixture was stirred at 150 °C for 5 h under N2. After cooling toroom temperature, the reaction was quenched with water, and extracted with EtOAc.The organic layer was washed with water, dried over Na2SO4, and evaporated. Theresidue was chromatographed on silica gel (hexane/toluene = 9/1) to give the titlecompound as white solid (2.7 g, 96% yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | With oxygen; acetic acid; In 1,2-dichloro-ethane; at 65℃; under 760.051 Torr; for 5h;Sealed tube; | General procedure: A 10 mL sealed tube equipped with a magnetic stir were charged with 2-aminobenzenethiols (0.4 mmol), thiophenols (0.4 mmol), AcOH (0.5 mL) and DCE (0.5mL) at room temperature. alpha,beta-Unsaturated aldehyde (0.3 mmol) were added and stirred the mixture rapidly. Then, the reaction tube was flushed with O2 and equipped with an O2 balloon. And the reaction mixture was stirred at 65 C in an oil bath for 5 h under O2 atmosphere. TLC was used to monitor the progress of reactions. After completion ofthe reaction, the mixture was cooled to room temperature and the volatiles were evaporated under reduced pressure. The resulting residue was purified by flash column chromatography on silica gel using petroleum ether/dichloromethane = 5:1~2:3 (v/v) as eluent to provide the desired products. Characterization data of products was obtained from 1H-NMR, 13C-NMR, 19C-NMR , mass spectroscopy, etc. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: natrium tetrabromoaurate(III) With tetraoctyl ammonium bromide In dichloromethane; water for 0.5h; Stage #2: 4-t-butylbenzenethiol In dichloromethane; water for 1h; Stage #3: sodium hexafluoroantimonate; copper(II) nitrate; bis(2-cyanoethyl)phenylphosphine Further stages; | 1-2 Synthesis of AuCu14 nanoclusters The whole preparation process was carried out at room temperature and stirring at a uniform speed of 1200 rpm. First, 400 microliters of sodium tetrabromoaurate aqueous solution (0.1 g per ml), 130 mg of tetraoctyl ammonium bromide and 15 ml of dichloromethane were added to a 100 ml pear-shaped flask. After 30 minutes, 150 microliters of 4-tert-butylthiophenol was added to the reaction system; after 60 minutes of reaction, 80 mg of Cu(NO3)2 was dissolved in 5 ml of methanol and then added to the above solution; after 30 minutes of reaction, Add 150 mg of bis (2-cyanoethyl) phenyl phosphine; after 60 minutes, weigh 150 mg of sodium borohydride solid and add 5 ml of deionized water to make a solution and then quickly add it to the pear-shaped flask. It turned black immediately; after the reaction continued stirring for 18 hours, Remove the stirring magnet and the aqueous solution from the reaction system, and add 5 ml of methanol solution containing 100 mg of sodium hexafluoroantimonate; Then, the organic solvent is removed by a rotary evaporator, and washed with methanol and toluene several times to remove excess ligands and by-products. Finally, the product was dissolved in dichloromethane, and the n-hexane was diffused into the dichloromethane solution using a gas phase diffusion method. After a week, red crystals were obtained, which was the target product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With [Pd2(dba)3]*CHCl3; N-ethyl-N,N-diisopropylamine; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene; In 1,4-dioxane; at 90.0℃;Schlenk technique; Inert atmosphere; | General procedure: To a flame-dried Schlenk flask was added the following insequence under an inert atmosphere of argon: 4-iodothalidomide4a (200 mg, 0.52 mmol), Pd2(dba)3CHCl3 (16 mg, 0.016 mmol)and XantPhos (16 mg, 0.032 mmol), 1,4-dioxane (2 mL), diisopropylethylamine(0.50 mL, 1.04 mmol) and the required thiol(0.57 mmol). The reaction mixturewas heated to 90 C with stirringfor 16 h, cooled to room temperature and diluted with ethyl acetate(10 mL). The mixture was filtered through a pad of Celite, washingwith ethyl acetate and DCM (ca. 20 mL each). The filtrate wasadsorbed to silica and purified via flash column chromatography onsilica to furnish the desired sulfide-functionalised thalidomidederivative. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With tris(pentafluorophenyl)borate In 1,2-dichloro-ethane at 20℃; Irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With tris(pentafluorophenyl)borate In 1,2-dichloro-ethane at 20℃; Irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With tris(pentafluorophenyl)borate In 1,2-dichloro-ethane at 20℃; Irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With potassium <i>tert</i>-butylate In acetonitrile at 70℃; for 8h; | 2. General procedure for polyfluorinated aromatic ethers General procedure: Reaction conditions: To a 25 mL Shrek tube were sequentially added (thio)alcohol or (thio)phenol (0.2 mmol), B(C6F5)3 (35mol%, 35.8 mg), t-BuOK (0.2 mmol, 1.0 equiv, 22.4 mg) and CH3CN (2.0 mL). The formed mixture was stirred at 70 °C for 8h as monitored by TLC and GC-MS. After completion of the reaction, the crude product was concentrated and purified by flash column chromatography on silica gel (petroleum ether/ethyl acetate) to afford the corresponding products. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
47% | With triethylamine tris(hydrogen fluoride) In acetonitrile at 40℃; for 6h; Inert atmosphere; Electrochemical reaction; | Method A: General procedure for the electrochemical vicinal fluorosulfenylation of alkenes(constant cell-potential electrolysis) General procedure: In an oven-dried undivided three-necked glassware (25 mL) equipped with a stirring bar, thiophenolsubstrate (0.3 mmol) were added. The glassware was equipped with carbon cloth (15 mm × 15 mm ×0.1 mm) as the anode and platinum plate (15 mm × 15 mm × 0.3 mm) as the cathode. Under theprotection of N2, olefin substrate (1.5 equiv.), Et3N3HF (0.5 mL), and CH3CN (10 mL) were injectedrespectively into the glassware via syringes. The reaction mixture was stirred and electrolyzed at aconstant cell potential of 1.8 V at 40 oC for 6 h. The reaction mixture was subsequently poured into asaturated sodium bicarbonate solution (ca. 15 mL). The aqueous layer was separated and extracted withdichloromethane (3×5 mL), and the combined organic layers were washed with brine and dried oversodium sulfate. Following concentration in vacuo, the crude residue was subjected to flash columnchromatography on silica gel to yield the desired product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With copper(II) bis(trifluoromethanesulfonate) In 1,2-dichloro-ethane at 70℃; for 12h; Schlenk technique; | General procedure for the reaction of tertiary alkyl alcohols with thiols General procedure: To a flame-dried Schlenk tube was charged with a tertiary alcohol (0.30 mmol, 100 mol %), Cu(OTf)2 (1.1 mg, 0.003 mmol, 1 mol %). The tube was capped with a rubber septum. Mercaptan (0.30 mmol, 100 mol %) was added followed by addition of DCE (1 mL) via syringes. The reaction mixture was allowed to stir in an oil bath for 12 h under an air atmosphere at 70oC. Then, the reaction mixture was directly loaded onto a silica column without work-up. The residue was rinsed with PE or the eluent for column chromatography, with which the product was isolated. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With air; In dimethyl sulfoxide; at 30℃; for 14h;Sealed tube; Schlenk technique; | General procedure: A mixture of amide 1 (0.2 mmol), thiophenol derivative 2 (0.3 mmol), and DMSO (2 mL) was added to a 25 mL flame-dried Young-type tube under air atmosphere, and then the tube was sealed and the contents were stirred at 30 C for the indicated reaction time (Schemes 2 and 3). After evaporation of the solvent under reduced pressure, the residue was purified by flash column chromatography on silica gel to give the desired product 3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With calcium hydroxide In water monomer at 20℃; for 21h; Sealed tube; Inert atmosphere; | Aqueous S-Methylation of 4-tert-Butylbenzenethiol (65) A 10-mL glass reaction tube fitted with a resealable Teflon valve wasequipped with a magnetic stir bar and charged with 4-tert-butylbenzenethiol(65; 166 mg, 1.0 mmol, 1.0 equiv), Ca(OH)2 (110 mg, 1.5mmol, 1.5 equiv), TMP (0.20 mL, 1.7 mmol, 1.7 equiv), and H2O (1.0mL). The flask was filled with argon, sealed, and stirred at RT for 21 h.1 N HCl (5 mL) was added, the mixture was extracted with CH2Cl2 (2 ×10 mL), and the organic phase was separated, dried over Na2SO4, filtered,and concentrated in vacuo. The resulting residue was purifiedby silica gel flash column chromatography (petroleum ether/CH2Cl2,4:1) to afford 1-tert-butyl-4-(methylsulfanyl)benzene (67)68 (177 mg,98% yield) as a colorless oil.1H NMR (500 MHz, CDCl3): = 7.38 (d, J = 8.5 Hz, 2 H), 7.28 (d, J = 8.5Hz, 2 H), 2.52 (s, 3 H), 1.37 (s, 9 H).13C NMR (126 MHz, CDCl3): = 148.33, 134.93, 126.90, 125.94, 34.43,31.39, 16.29. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | With potassium carbonate In 1-methyl-pyrrolidin-2-one at 150℃; for 5h; Inert atmosphere; | 7 Under argon atmosphere, weigh m-1 (13.6g, 0.05mol), 4-tert-butylphenol (7.5g, 0.05mol), 4-tert-butylthiophenol (8.3g, 4-tert-butylthiophenol) in a 500mL three-necked flask. 0.05mol), K2CO3(13.8 g, 0.10 mol) was added to a bottle with 80 mL of N-methylpyrrolidone (NMP), the temperature was raised to 150 ° C, and the reaction was stirred for 5 hours under argon protection, and then cooled to room temperature. The reaction solution was diluted with toluene and poured into water. The organic phase was separated and dried by adding anhydrous sodium sulfate. The organic phase obtained by filtration was removed from the solvent, and the crude product was column-separated to obtain product m-21 (16.5 g, yield: 60%). |
Tags: 2396-68-1 synthesis path| 2396-68-1 SDS| 2396-68-1 COA| 2396-68-1 purity| 2396-68-1 application| 2396-68-1 NMR| 2396-68-1 COA| 2396-68-1 structure
[ 41889-65-0 ]
4'-(tert-Butyl)-[1,1'-biphenyl]-4-thiol
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Precautionary Statements-General | |
Code | Phrase |
P101 | If medical advice is needed,have product container or label at hand. |
P102 | Keep out of reach of children. |
P103 | Read label before use |
Prevention | |
Code | Phrase |
P201 | Obtain special instructions before use. |
P202 | Do not handle until all safety precautions have been read and understood. |
P210 | Keep away from heat/sparks/open flames/hot surfaces. - No smoking. |
P211 | Do not spray on an open flame or other ignition source. |
P220 | Keep/Store away from clothing/combustible materials. |
P221 | Take any precaution to avoid mixing with combustibles |
P222 | Do not allow contact with air. |
P223 | Keep away from any possible contact with water, because of violent reaction and possible flash fire. |
P230 | Keep wetted |
P231 | Handle under inert gas. |
P232 | Protect from moisture. |
P233 | Keep container tightly closed. |
P234 | Keep only in original container. |
P235 | Keep cool |
P240 | Ground/bond container and receiving equipment. |
P241 | Use explosion-proof electrical/ventilating/lighting/equipment. |
P242 | Use only non-sparking tools. |
P243 | Take precautionary measures against static discharge. |
P244 | Keep reduction valves free from grease and oil. |
P250 | Do not subject to grinding/shock/friction. |
P251 | Pressurized container: Do not pierce or burn, even after use. |
P260 | Do not breathe dust/fume/gas/mist/vapours/spray. |
P261 | Avoid breathing dust/fume/gas/mist/vapours/spray. |
P262 | Do not get in eyes, on skin, or on clothing. |
P263 | Avoid contact during pregnancy/while nursing. |
P264 | Wash hands thoroughly after handling. |
P265 | Wash skin thouroughly after handling. |
P270 | Do not eat, drink or smoke when using this product. |
P271 | Use only outdoors or in a well-ventilated area. |
P272 | Contaminated work clothing should not be allowed out of the workplace. |
P273 | Avoid release to the environment. |
P280 | Wear protective gloves/protective clothing/eye protection/face protection. |
P281 | Use personal protective equipment as required. |
P282 | Wear cold insulating gloves/face shield/eye protection. |
P283 | Wear fire/flame resistant/retardant clothing. |
P284 | Wear respiratory protection. |
P285 | In case of inadequate ventilation wear respiratory protection. |
P231 + P232 | Handle under inert gas. Protect from moisture. |
P235 + P410 | Keep cool. Protect from sunlight. |
Response | |
Code | Phrase |
P301 | IF SWALLOWED: |
P304 | IF INHALED: |
P305 | IF IN EYES: |
P306 | IF ON CLOTHING: |
P307 | IF exposed: |
P308 | IF exposed or concerned: |
P309 | IF exposed or if you feel unwell: |
P310 | Immediately call a POISON CENTER or doctor/physician. |
P311 | Call a POISON CENTER or doctor/physician. |
P312 | Call a POISON CENTER or doctor/physician if you feel unwell. |
P313 | Get medical advice/attention. |
P314 | Get medical advice/attention if you feel unwell. |
P315 | Get immediate medical advice/attention. |
P320 | |
P302 + P352 | IF ON SKIN: wash with plenty of soap and water. |
P321 | |
P322 | |
P330 | Rinse mouth. |
P331 | Do NOT induce vomiting. |
P332 | IF SKIN irritation occurs: |
P333 | If skin irritation or rash occurs: |
P334 | Immerse in cool water/wrap n wet bandages. |
P335 | Brush off loose particles from skin. |
P336 | Thaw frosted parts with lukewarm water. Do not rub affected area. |
P337 | If eye irritation persists: |
P338 | Remove contact lenses, if present and easy to do. Continue rinsing. |
P340 | Remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P341 | If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P342 | If experiencing respiratory symptoms: |
P350 | Gently wash with plenty of soap and water. |
P351 | Rinse cautiously with water for several minutes. |
P352 | Wash with plenty of soap and water. |
P353 | Rinse skin with water/shower. |
P360 | Rinse immediately contaminated clothing and skin with plenty of water before removing clothes. |
P361 | Remove/Take off immediately all contaminated clothing. |
P362 | Take off contaminated clothing and wash before reuse. |
P363 | Wash contaminated clothing before reuse. |
P370 | In case of fire: |
P371 | In case of major fire and large quantities: |
P372 | Explosion risk in case of fire. |
P373 | DO NOT fight fire when fire reaches explosives. |
P374 | Fight fire with normal precautions from a reasonable distance. |
P376 | Stop leak if safe to do so. Oxidising gases (section 2.4) 1 |
P377 | Leaking gas fire: Do not extinguish, unless leak can be stopped safely. |
P378 | |
P380 | Evacuate area. |
P381 | Eliminate all ignition sources if safe to do so. |
P390 | Absorb spillage to prevent material damage. |
P391 | Collect spillage. Hazardous to the aquatic environment |
P301 + P310 | IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician. |
P301 + P312 | IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell. |
P301 + P330 + P331 | IF SWALLOWED: Rinse mouth. Do NOT induce vomiting. |
P302 + P334 | IF ON SKIN: Immerse in cool water/wrap in wet bandages. |
P302 + P350 | IF ON SKIN: Gently wash with plenty of soap and water. |
P303 + P361 + P353 | IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower. |
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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