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CAS No. : | 4180-23-8 | MDL No. : | MFCD00009284 |
Formula : | C10H12O | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | RUVINXPYWBROJD-ONEGZZNKSA-N |
M.W : | 148.20 | Pubchem ID : | 637563 |
Synonyms : |
(E)-Anethole;(E)-Anethol;NSC 209529;4-Propenylanisole
|
Num. heavy atoms : | 11 |
Num. arom. heavy atoms : | 6 |
Fraction Csp3 : | 0.2 |
Num. rotatable bonds : | 2 |
Num. H-bond acceptors : | 1.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 47.83 |
TPSA : | 9.23 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) : | -4.86 cm/s |
Log Po/w (iLOGP) : | 2.55 |
Log Po/w (XLOGP3) : | 3.3 |
Log Po/w (WLOGP) : | 2.62 |
Log Po/w (MLOGP) : | 2.67 |
Log Po/w (SILICOS-IT) : | 2.79 |
Consensus Log Po/w : | 2.79 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 2.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -3.11 |
Solubility : | 0.115 mg/ml ; 0.000777 mol/l |
Class : | Soluble |
Log S (Ali) : | -3.17 |
Solubility : | 0.1 mg/ml ; 0.000677 mol/l |
Class : | Soluble |
Log S (SILICOS-IT) : | -2.98 |
Solubility : | 0.155 mg/ml ; 0.00104 mol/l |
Class : | Soluble |
PAINS : | 0.0 alert |
Brenk : | 0.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 1.47 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P280 | UN#: | N/A |
Hazard Statements: | H317 | 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 |
---|---|---|
50% | With sulfur In N,N-dimethyl-formamide for 8 h; Heating | Anethole (1) (32.5 g; 0.21 mol) and sulphur (45 g; 1.40 mol) were heated in dimethylformamide (250 ml) for 8 hr; the residue after removal of solvent was almost completely soluble in toluene. An attempt to extract the toluene liquors with 2N-aqueous sodium hydroxide, gave a precipitate of an orange solid (8.5 g). m.p. over 300° C. This product was dissolved in boiling water and gave an orange precipitate (2) after addition of hydrochloric acid (Yield 50percent), m.p. 188-189° C. 1H NMR (DMSO) δ 6.86 (d, 2H), 7.68 (s, 1H), 7.75 (d, 2H), 10.51 (s, -OH); MS (ESI), m/z 225(M-). |
50% | Stage #1: With sulfur In N,N-dimethyl-formamide for 8 h; Heating / reflux Stage #2: With sodium hydroxide; water In toluene Stage #3: at 100℃; |
EXAMPLE 3General synthetic procedure of:4- or 5-Amino-2-hydroxy-benzoic acid 4-(5-thioxo-5H-[1,2]dithiol-3-yl)-phenyl ester(4)4- or 5-nmlno salicylic acidSynthesis of5-p-hydroxyphenyl-1,2-dithione-3-thione (ADT-OH)Anethole 1 (32.5 g; 0.21 mol) and sulphur (45 g; 1.40 mol) were heated in dimethylformamide (250 ml) for 8 hr; the residue after removal of solvent was almost completely soluble in toluene. An attempt to extract the toluene liquors with 2N- aqueous sodium hydroxide, gave a precipitate of an orange solid (8.5 g). m.p. over 3000C. This product was dissolved in boiling water and gave an orange precipitate 2 after addition of hydrochloric acid (Yield 50percent), m.p. 188-189 0C. 1H NMR (DMSO) δ6.86 (d, 2H), 7.68 (s, 1 H), 7.75 (d, 2H), 10.51 (s, -OH); MS (ESI), m/z 225{W).; EXAMPLE 6General synthetic procedure of:4-or 5-Amino-2-[4-(5-thioxo-5H-[1,2]dithiol-3-yl)-phenoxycarbonyloxy]-benzoic acid (15)2-Hydroxy-4-or 5-[4-(5-thioxo-5H-[1,2]dithiol-3-yl)-phenoxycarbonylamino]- benzoic acid (16) EPO <DP n="48"/> EPO <DP n="49"/>Synthesis of 5-p-hydroxyphenyl-t ,2-dithione-3-thione (ADT-OH)Anetholβ 1 (32.5 g; 0.21 mol) and sulphur (45 g; 1.40 mol) were heated in dimethylformamide (250 ml) for 8 hr; the residue after removal of solvent was almost completely soluble in toluene. An attempt to extract the toluene liquors with 2 N- aqueous sodium hydroxide, gave a precipitate of an orange solid (8.5 g). m.p. over 3000C. This product was dissolved in boiling water and gave an orange precipitate 2 after addition of hydrochloric acid (Yield 50percent), m.p. 188-189 0C. 1H NMR (DMSO) δ 6.86 (d, 2H), 7.68 (s, 1 H), 7.75 (d, 2H), 10.51 (s, -OH); MS (ESI), m/z225(M"). |
50% | Stage #1: With sulfur In N,N-dimethyl-formamide for 8 h; Heating / reflux Stage #3: at 100℃; |
EXAMPLE 3General synthetic procedure of:4- or 5-Amino-2-hydroxy-benzoic acid 4-(5-thioxo-5H-[1,2]dithiol-3-yl)-phenyl ester(4)4- or 5-nmlno salicylic acidSynthesis of5-p-hydroxyphenyl-1,2-dithione-3-thione (ADT-OH)Anethole 1 (32.5 g; 0.21 mol) and sulphur (45 g; 1.40 mol) were heated in dimethylformamide (250 ml) for 8 hr; the residue after removal of solvent was almost completely soluble in toluene. An attempt to extract the toluene liquors with 2N- aqueous sodium hydroxide, gave a precipitate of an orange solid (8.5 g). m.p. over 3000C. This product was dissolved in boiling water and gave an orange precipitate 2 after addition of hydrochloric acid (Yield 50percent), m.p. 188-189 0C. 1H NMR (DMSO) δ6.86 (d, 2H), 7.68 (s, 1 H), 7.75 (d, 2H), 10.51 (s, -OH); MS (ESI), m/z 225{W).; EXAMPLE 6General synthetic procedure of:4-or 5-Amino-2-[4-(5-thioxo-5H-[1,2]dithiol-3-yl)-phenoxycarbonyloxy]-benzoic acid (15)2-Hydroxy-4-or 5-[4-(5-thioxo-5H-[1,2]dithiol-3-yl)-phenoxycarbonylamino]- benzoic acid (16) EPO <DP n="48"/> EPO <DP n="49"/>Synthesis of 5-p-hydroxyphenyl-t ,2-dithione-3-thione (ADT-OH)Anetholβ 1 (32.5 g; 0.21 mol) and sulphur (45 g; 1.40 mol) were heated in dimethylformamide (250 ml) for 8 hr; the residue after removal of solvent was almost completely soluble in toluene. An attempt to extract the toluene liquors with 2 N- aqueous sodium hydroxide, gave a precipitate of an orange solid (8.5 g). m.p. over 3000C. This product was dissolved in boiling water and gave an orange precipitate 2 after addition of hydrochloric acid (Yield 50percent), m.p. 188-189 0C. 1H NMR (DMSO) δ 6.86 (d, 2H), 7.68 (s, 1 H), 7.75 (d, 2H), 10.51 (s, -OH); MS (ESI), m/z225(M"). |
13% | Stage #1: With sulfur In N,N-dimethyl-formamide for 8 h; Heating / reflux Stage #2: With sodium hydroxide In water; toluene Stage #3: With hydrogenchloride In waterHeating / reflux |
Synthesis of 5-p-hydroxyphenyl-1,2-dithiole-3-thione (2; ADT-OH) Anethole (31 g, 0.21 mol) and sulfur (44.8 g, 1.40 mol) were heated in N,N-dimethylformamide (250 ml) for 8 hrs; after removal of solvent, the residue was almost completely soluble in toluene. An attempt to extract the toluene liquors with 2N-aqueous sodium hydroxide, gave an orange solid precipitate (8.5 g; m.p. over 300° C.). This product was dissolved in boiling water and, after addition of hydrochloric acid, gave 2 as an orange precipitate (6.2 g, yield 13percent) m.p. 188-189° C. 1H NMR (DMSO-d6) δ 6.86 (d, 2H), 7.68 (s, 1H), 7.75 (d, 2H), 10.51 (s, -OH); MS (ESI), m/z 225 (M-). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
32% | With sulfur In neat (no solvent) at 200℃; for 0.166667 h; Microwave irradiation | Entry 10: Anethole (500 mg, 1.0 eq.) and elemental sulfur (433 mg, 4.0 eq.) were added with a magnetic stir bar to a 10 mL microwave reaction vessel and a condenser was attached. The reaction conditions were regulated through the CEM-software as follows: temperature: 200°C, power: 200 Watt, ramp time: 1 min, hold time: 9 min. After reaction completion, the vessel was removed from the reactor and cooled immediately in an ice bath and the 1H ΝΜR spectrum of the crude soluble reaction mixture was recorded. The crude material was purified by flash column chromatography (Hex/EtOAc 95:5) to afford 1 (256 mg, 32percent) as a dark red solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With Polystyrene-supported 4-tert-butyl-2-(diisopropylphosphino)-1H-imidazole and ruthenium complex In [(2)H6]acetone at 25℃; for 0.166667h; Inert atmosphere; Glovebox; stereoselective reaction; | |
99% | With PdClMe(2,9-dimethyl-1,10-phenanthroline); sodium tetrakis[(3,5-di-trifluoromethyl)phenyl]borate In chloroform-d1 at 0℃; for 16h; Sealed tube; | |
97% | With nickel(II) iodide; 6,6'-dimethyl-2,2'-bipyridine; phosphonic acid diethyl ester; zinc In N,N-dimethyl acetamide at 35℃; for 24h; | 4 Synthesis of Example 4 According to the general operating procedure, piperonol methyl ether (1d) (148.1 mg, 1.0 mmol) is used as a raw material, 0.50 mol% of nickel iodide hydrate (2.1 mg, 0.005 mmol) is used as a catalyst, and 0.60 mol% of 6,6'-di Methyl-2,2'-bipyridine (1.0mg, 0.006mmol) as the ligand, zinc powder (19.5mg, 0.30mmol, 0.30equiv) as the reducing agent, diethyl phosphite (30.0mg, 0.20mmol, 0.20 equiv) was a hydrogen source, and anhydrous N, N-dimethylformamide (1.0 mL) was used as a solvent for the reaction.The reaction system was stirred at 35 ° C. for 24 hours, and was subjected to silica gel column chromatography (petroleum ether: ethyl acetate = 10: 1) to obtain a pale yellow oil (144.5 mg) with an isolated yield of 97% and an E / Z ratio of 97: 3 (obtained by detecting the reaction system by GC) |
96% | With Grotjahn's catalyst In acetone at 20℃; for 0.6h; Inert atmosphere; Glovebox; | |
95% | With tri-tert-butyl phosphine; isobutyryl chloride; bis(dibenzylideneacetone)-palladium(0) In toluene at 80℃; for 18h; Inert atmosphere; optical yield given as %de; stereoselective reaction; | |
95% | With diethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate; potassium carbonate; cobalt(II) aceylacetonate; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene In N,N-dimethyl-formamide at 25℃; for 16h; Irradiation; stereoselective reaction; | |
93% | With C44H58Cl2N4Pd In isopropyl alcohol at 20℃; for 26h; optical yield given as %de; diastereoselective reaction; | |
93% | With acetonitrile(cyclopentadienyl)[2-(di-i-propylphosphino)-4-(t-butyl)-1-methyl-1H-imidazole]ruthenium(II) hexafluorophosphate at 20℃; for 0.75h; Glovebox; Inert atmosphere; Green chemistry; diastereoselective reaction; | Estragole to (E)-Anethole In a glove box, a 25 mL round bottomed flask equipped with a magnetic stir bar was added estragole (5.0 g, 0.034 mol), capped with a rubber septum, and brought out of the glove box. In an inert atmosphere glove box, catalyst 1(21.5 mg, 0.0356 mmol, 0.1 mol%) was measured into a vial, which was capped and brought out of the glove box. The septum was removed from the reaction flask and the catalyst was quickly added, followed by bubbling nitrogen through the liquid to remove any air that had entered. Aliquots (ca. 5 μL) were removed from the reaction at 5, 10,20, 30, and 45 minutes using a gastight syringe and analyzed by 1H NMR for completion. Full conversion of estragole to (E)-anethole occurred after 45 minutes, and the product was isolated by vacuum distillation (750 torr 55 oC) to afford 4.65 g (93.0%)of (E)-anethole as a clear, colorless oil. To accurately determine amounts of starting material remaining, 104.2 mg of the distillate was added to an NMR tube containing 0.5-0.7 mL CDCl3 and analyzed by 1H NMR spectroscopy at 600 MHz; percentages were calculated assuming a two-component mixture (estragole/(E)-anethole). Peaks used: estragole 5.12 ppm (2H), 3.34 ppm (2H); (E)-anethole: 6.42 ppm (1H), 6.15 ppm (1H),1.90 ppm (3H). No peaks corresponding to those reported3 for (Z)-anethole were detected; in particular, lack of any signal near 5.69 ppm is taken as evidence of less than 0.1%. |
91% | With 4C3H9P*Ni*H(1+)*C2F6NO4S2(1-) In dichloromethane Schlenk technique; Inert atmosphere; | |
90% | With (μ-Cl)2Ni2(1,3-bis(2,6-diisopropylphenyl)-1,3-dihydro-2H-imidazol-2-ylidene)2 In chlorobenzene at 20℃; for 3h; | |
85% | With iron(II) acetate; dimethylphenyl(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)silane; lithium tert-butoxide In toluene at 100℃; for 24h; Inert atmosphere; regioselective reaction; | |
85% | With iron(II) acetate; dimethylphenyl(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)silane; lithium tert-butoxide In toluene at 100℃; for 24h; | |
With potassium hydroxide at 130℃; | ||
With sodium hydroxide at 200℃; | ||
With lithium tert-butoxide In N,N-dimethyl acetamide at 25℃; | ||
With potassium <i>tert</i>-butylate In <i>tert</i>-butyl alcohol at 75℃; | ||
In tetrahydrofuran at 20℃; | ||
In acetone for 1 - 100h; | One scintillation vial was charged with catalyst (10.7 mg; assuming that the concentration of catalyst is 0.93 meq per g, 10.7 mg = 0.010 mmol, 2 mol%) and a stir bar. A second vial was charged with 4-allylanisole (74.5 mg, 0.503 mmol) and internal standard (Me3Si)4C (0.3 mg) and the solids dissolved in acetone (0.43 mL). An aliquot (ca. 10 μL) of the solution was analyzed by 1H NMR by diluting it with acetone-^ (ca. 0.6 mL), using 10° pulses and 30 sec delays between acquisition cycles. The solution of 4-allylanisole and standard was transferred quantitatively to the catalyst vial using a pipet and additional acetone (0.50 mL, in two portions). The mixture was stirred gently. After 1 h and 100 h aliquots (ca. 20 μL) were removed for analysis by 1H NMR spectroscopy. | |
In acetone for 1 - 100h; | One scintillation vial was charged with catalyst (11.6 mg; assuming that the concentration of catalyst is 0.87 meq per g, 11.6 mg = 0.010 mmol, 2 mol%) and a stir bar. A second vial was charged with 4-allylanisole (74.8 mg, 0.505 mmol) and internal- 22 - sd-435382 475443003140 standard (MeSSi)4C (0.5 mg) and the solids dissolved in acetone (0.43 mL). An aliquot (ca. 10 μL) of the solution was analyzed by 1H NMR by diluting it with acetone-^ (ca. 0.6 mL), using 10° pulses and 30 sec delays between acquisition cycles. The solution of 4-allylanisole and standard was transferred quantitatively to the catalyst vial using a pipet and additional acetone (0.50 mL, in two portions). The mixture was stirred gently. After 1 h, 2 h, and 100 h aliquots (ca. 20 μL) were removed for analysis by 1H NMR spectroscopy. | |
> 99 %Chromat. | With [RuCl2(η6-C6H5OCH2CH2OH){trimethyl phosphite}] In methanol at 80℃; for 0.25h; Inert atmosphere; Sealed tube; stereoselective reaction; | |
99 %Chromat. | With [(dppb)Pt(C6F5)(H2O)]OTf In chloroform at 50℃; for 12h; optical yield given as %de; diastereoselective reaction; | |
> 99 %Chromat. | With Ru(η3:η3-C10H16)Cl2(P(OMe)3) In water at 35℃; for 6h; Inert atmosphere; sealed tube; | |
99 %Spectr. | With C21H35N3PRu*F6P(1-) In [(2)H6]acetone at 20℃; for 0.6h; Inert atmosphere; stereoselective reaction; | |
100 %Chromat. | With [CpRu(PN)(MeCN)]PF6 In toluene at 40℃; for 0.5h; Inert atmosphere; Glovebox; diastereoselective reaction; | |
97 %Chromat. | With bis(acetylacetonate)nickel(II); N,N,N,N,-tetramethylethylenediamine; phenylmagnesium bromide In tetrahydrofuran at 20℃; Inert atmosphere; stereoselective reaction; | |
99 %Spectr. | With C24H35IrNP; sodium t-butanolate In benzene-d6 at 25℃; for 8h; Inert atmosphere; Glovebox; Schlenk technique; stereoselective reaction; | |
92 % de | With palladium (II) acetate; bis(pinacol)diborane; tricyclohexylphosphine In toluene at 80℃; for 12h; Sealed tube; Inert atmosphere; | |
With C32H12BF24(1-)*3C4H10O*Li(1+); [κ5-(15c5NCOPiPr)Ir(H)][BArF4] In diethyl ether; dichloromethane-d2 at 25℃; Inert atmosphere; Sealed tube; | ||
With potassium hydroxide at 180℃; for 4h; Green chemistry; | 1 The purity of 50% of the raw material of natural grass Artemisia brain into the distillation tower, the purification, distillation tower tower kettle temperature 160 ° C, the temperature of the top of the tower is 120 ° C, the purified grass carp of the brain, its purity is about 98% The purified grasses of Artemisia annua were placed in a heterogeneous pot, and the catalyst potassium hydroxide was added to the isomerized pan to control the isomer Pot temperature of 180 ° C, reaction 4h, after the end of the reaction, to stop the heating of the heterogeneous pot, was anise. Wherein the mass of the added potassium hydroxide is 5% of the mass of the purified Artemisia annua. The fennel was frozen at minus 20 ° C, and the anethole was centrifuged at the same time under the freezing conditions. The centrifugation time was 20 min, and the high purity fennel was obtained. 1000kg of high purity anethole into the reactor, and to the reactor by adding 200kg dilute sulfuric acid, 300kgMn02, control the temperature inside the reactor l0 ° C, reaction 4h, anise anirone crude. The concentration of dilute sulfuric acid is 20%. The aniseed aldehyde crude into the centrifuge for centrifugal separation, centrifugal separation and then washed with salt water. Among them, the brine is a mass percentage of 5% sodium chloride solution. The washed anodic aldehyde crude product with the solute mass percentage of 5% of the baking soda water for the second washing, so that the anisedehyde crude product pH value of 8.0, that is, the product. And then the product into the distillation tower purification, distillation tower tower temperature of 160 ° C, the top temperature of 120 ° C, the purity of 98-99% purity of the product. | |
> 99 %Chromat. | With [RuCl{κ2-(1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine)}(η6-p-cymene)] In methanol at 80℃; for 3h; Inert atmosphere; Sealed tube; | |
With palladium nanoparticles-decorated TiO2 In isopropyl alcohol at 85℃; for 24h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
32% | With sulfur; In neat (no solvent); at 200℃; for 0.166667h;Microwave irradiation; | Entry 10: Anethole (500 mg, 1.0 eq.) and elemental sulfur (433 mg, 4.0 eq.) were added with a magnetic stir bar to a 10 mL microwave reaction vessel and a condenser was attached. The reaction conditions were regulated through the CEM-software as follows: temperature: 200C, power: 200 Watt, ramp time: 1 min, hold time: 9 min. After reaction completion, the vessel was removed from the reactor and cooled immediately in an ice bath and the 1H NuMuR spectrum of the crude soluble reaction mixture was recorded. The crude material was purified by flash column chromatography (Hex/EtOAc 95:5) to afford 1 (256 mg, 32%) as a dark red solid. |
With sulfur; at 200℃; for 6h;Product distribution / selectivity; | Synthesis of 2-acetoxy-benzoic acid 4-(thioxo-5H-[1,2]dithiol-3-yl)-phenyl ester; To 280 mmol of sulfur, 40 mmol of anethole were added. After heating at 200 0C for 6 hours, 2.5 g of anethole dithiolethione were obtained. The product, washed with ether, was crystallized by ethyl acetate: melting point 110-1110C. Then 1.5 g of anetholedithiolethione were mixed with 7.5 g of pyridine HCl and the mixture was heated for 25 minutes at 2150C. Aftercooling, IN HCl in excess was added and the precipitate was filtered, washed and crystallized from ethanol. The obtained compound melted at 191-1920C.The ester of acetyl salicylic acid with 5-(4- hydroxyphenyl) -3H-1,2-dithiol-3-thione was prepared via the acyl chloride of acetyl salicylic acid. 5-(4-hydroxyphenyl) -3H-1, 2-dithiol-3-thione and N-(Et) (iPr)2(0,62 ml) were added to a solution of acylchloride of EPO <DP n="18"/>acethyl salicylic acid (3.5 mmoles)in dry THF and themixture was refluxed for 6 hours under nitrogen.After removal of THF, the mixture was dissolved indichloromethane, washed with 0.25 M HCl followed by water and finally by 0.1 N NaOH. After evaporation of thesolvent, the residue was chromatographed on silica gel eluting with dichloromethane/ciclohexane (8/2) . The compound was crystallized from ethanol and showed amelting point of 128-129C. | |
With sulfur; In N,N-dimethyl acetamide; at 145℃; for 6h; | EXAMPLE 1; Synthesis of (Z) -5-Pluoro-2-methyl-l- [ [4- (methylsulfiny1) phenyl] methylene] -IH-indene-3-acetic acid 4- (thioxo-5H- [1,2] dithiol-3-yl) -phenyl ester; To 280 mmol of sulphur, 40 mmol of anethole in 20 ml of dimethylacetamide were added. After heating at 145 0C for 6 hours, 2.5 g of anethole dithiolethione (ADT) were obtained. The product, washed with ether, was crystallized by ethyl acetate: melting point HO-IIl0C. Then 1.5 g of ADT were EPO <DP n="15"/>mixed with 7.5 g of pyridine HCl and the mixture was heated for 25 minutes at 215C. After cooling, IN HCl in excess was added and the precipitate was filtered, washed and crystallized from ethanol . The obtained compound, 5- (p-hydroxyphenyl) -3H-1, 2-ditiol-3-thione, melted at 191-192C.A IN solution of dicyclohexylcarbodiimide (DCC, 612 mg) in dichloromethane (2.7 ml) is added to 100 ml of a dichloromethane solution containing 5- (p- hydroxyphenyl) -3H-1 , 2-dithiol-3-thione (610.2 mg, 2.7 mmol) prepared as above described, sulindac (601 mg, 2.7 mmol), and a catalytic amount (15 mg) of 4- dimethylaminopyridine (DMAP) . The mixture is stirred at room temperature under nitrogen for 1 hour. At the end of the reaction dicyclohexylurea (DCU) is removed by filtration. The solution is washed with 0. IN NaOH and cold water. The organic solution is then dried on anhydrous sodium sulphate and evaporated. After removal of the solvent, the mixture was chromatographed on silica gel eluting with a mixture of dichloromethane/ methanol (99.5/0.5) .The compound, after washing first with ether and then with ethanol, has a melting point of 103-106 0C. |
With sulfur; at 200℃; for 6h; | To 280 mmol of sulfur, 40 mmol of anethole were added. After heating at 2000C for 6 hours, 2.5 g of anethole trithione (ADT) were obtained. The product, washed with ether, was crystallized by ethyl acetate: melting point 110-1110C. Then 1.5 g of ADT were mixed with 7.5 g of pyridine HCl and the mixture was heated for 25 minutes at 215C. After cooling, IN HCl in excess was added and the precipitate was filtered, washed and crystallized from ethanol . The obtained 5- (p- hydroxyphenyl ) -3H-1 , 2-dithiole-3-thione melted at 191- 1920C.Diclofenac free acid (766 mg, 2.59 mmol) was dissolved in dichloromethane (90 ml) and 5- (p- hydroxyphenyl ) -3H-1 , 2-dithiol-3-thione (585 mg, 2.59 mmol), dicyclohexylcarbodiimide (DCC) (587 mg, 2.85 mmol) and a catalytic amount (13 mg) of 4-dimethylaminopyridine(DMAP) were added. The mixture was stirred at room temperature for 40 minutes.At the end of the reaction the mixture was filtered to remove the dicyclohexylurea (DCU) , and the solution was washed with 0.1 N NaOH and cold water. The organic solution was dried on sodium sulphate and evaporated. The residue was chromatographed on silica gel column eluting EPO <DP n="11"/>with a mixture of dichloromethane/cyclohexane 8/2. The obtained compound had a melting point of 85-88 0C. | |
With sulfur; In ISOPROPYLAMIDE; at 145℃; for 6h; | EXAMPLE 3. Synthesis of 4-(5-thioxo-5H-1,2-dithiol-3-yl)phenyl 2-(5-fluoro-2,4-dioxo-1,2,3,4-tetrahydro pyrimidine-1-carboxamido)acetate. Step 1: Preparation of 5-(p-hydroxyphenyl)-3H-1,2-ditiol-3-thione.; To 280 mmol of sulphur, 40 mmol of anethole in 20 ml of dimethylacetamide were added. After heating at 145 C for 6 hours, 2.5 g of anethole dithiolethione (ADT) were obtained. The product, washed with ether, was crystallized by ethyl acetate: melting point 110-111 C. Then 1.5g of ADT were mixed with 7.5g of pyridine HCl and the mixture was heated for 25 minutes at 215 C. After cooling, 1N HCl in excess was added and the precipitate was filtered, washed and crystallized from ethanol. The obtained compound, 5-(p-hydroxyphenyl)-3H-1,2-ditiol-3-thione, melted at 191-192 C. | |
With sulfur; In ISOPROPYLAMIDE; at 145℃; for 6h; | Step 1: Preparation of 5- (p-hydroxyphenyl) -3H-1, 2- dithiol-3-thione .; <n="19"/>To 280 mmol of sulphur, 40 mmol of anethole in 20 ml of dimethylacetamide are added. After heating at145C for 6 hours, 2.5 g of anethole dithiolethione(ADT) are obtained. The product, washed with ether, was crystallized by ethyl acetate: melting point 110-1110C. Then 1.5 g of ADT are mixed with 7.5 g of pyridine HCl and the mixture is heated for 25 minutes at 215C. After cooling, IN HCl in excess is added and the precipitate is filtered, washed and crystallized from ethanol . The obtained compound, 5- (p-hydroxyphenyl) -3H-1, 2-ditiol-3-thione, melts at 191-192C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With magnesium; nickel dichloride In water at 20℃; for 12h; Sealed tube; Photolysis; Inert atmosphere; | |
91% | With oxygen; hydrazine hydrate In propan-1-ol at 120℃; for 0.5h; | |
91% | With oxygen; hydrazine hydrate In propan-1-ol at 120℃; for 0.166667h; Flow reactor; |
85% | With formic acid; palladium 10% on activated carbon; ammonium formate In methanol at 60℃; for 36h; | |
79% | With hydrazine hydrate In ethanol at 70℃; for 8h; | |
75% | With sodium tetrahydroborate; cobalt(II) sulphate heptahydrate In methanol; water at 0 - 21℃; for 0.05h; Sealed tube; | |
70% | With formic acid; (4,4'-di-tert-butyl-2,2'-dipyridyl)-bis-(2-phenylpyridine(-1H))-iridium(III) hexafluorophosphate; N-ethyl-N,N-diisopropylamine In methanol; water at 20℃; for 24h; Irradiation; | |
62% | With [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2; Butane-1,4-diol; caesium carbonate; bis[2-(diphenylphosphino)phenyl] ether In toluene for 24h; Inert atmosphere; Reflux; | |
55% | With triphenylstannane; tris-(4-bromophenyl)aminium hexachloroantimonate In dichloromethane for 0.0333333h; | |
55% | With (BrC6H5)3N(+)*SbCl6(-); triphenylstannane In dichloromethane at 0℃; for 0.0166667h; | |
With ethanol; nickel Hydrogenation; | ||
With Pd-BaSO4; ethanol Hydrogenation; | ||
70 % Spectr. | With sodium hydrogen telluride In ethanol for 2.5h; Heating; | |
With hydrogen In ethyl acetate for 24h; | ||
> 99 %Chromat. | With 10% Pd/C; cyclohexa-1,4-diene In ethyl acetate at 100℃; for 0.25h; Microwave irradiation; | |
78 %Chromat. | With aluminum 1,4-benzenedicarboxylate; ammonia; hydrazine hydrate In acetonitrile at 25℃; for 24h; chemoselective reaction; | |
With formic acid; ammonium formate; silica gel; palladium dichloride In water at 120℃; Microwave irradiation; | ||
With O,N-bis-(trifluoroacetyl)-hydroxylamine; hydroxylamine In 1,4-dioxane; water at 140℃; for 0.333333h; | ||
94 %Chromat. | With sodium tetrahydroborate; nickel(II) chloride hexahydrate; ethanol at 30℃; for 2h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With iodine; silver(l) oxide In 1,4-dioxane; water at 20℃; for 1h; | |
With diethyl ether; iodine; mercury(II) oxide optically inactive substance; | ||
Multi-step reaction with 2 steps 1: bromine; petroleum ether 2: aqueous ethanol.H2SO4 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With potassium permanganate; Rexyn 101 In dichloromethane at 20℃; for 1.33333h; | |
93.8% | Stage #1: E-1-(4'-methoxyphenyl)prop-1-ene With acetic acid In cyclohexane at 20℃; for 0.333333h; Stage #2: With sodium hydrogensulfite for 0.666667h; | 1-7 Example 4: extract 3.08g of anisole (anethole content 90%), dissolved in 8g cyclohexane and 2g mixed solvent of acetic acid, and the remaining conditions and procedures are the same as in Example 1. The anisaldehyde 2.39g was obtained with a yield of 93.8% (calculated as anethole). |
85% | With sodium periodate; osmium(VIII) oxide; N-benzyl-N,N,N-triethylammonium chloride In tetrahydrofuran; water Microwave irradiation; |
71% | With sodium periodate In THF-H2O; ethyl acetate | III Preparation of 4-methoxybenzaldehyde from anethole (by microwave method): Example III Preparation of 4-methoxybenzaldehyde from anethole (by microwave method): A solution of OsO4 (0.004-0.007 g), anethole (2.22 g, 0.015 mole), finely powdered NaIO4 (9.0 g, 0.044 mole) in THF-H2O(20-25 mL) was irradiated in a microwave oven for 2-8 minutes in parts. The precipitated sodium iodate was filtered and the filtrate was washed with CH2Cl2. The combined organic layers were washed with sodium thiosulphate, brine and dried over Na2SO4. Evaporation of the solvent furnished a crude mixture, which was loaded on silica gel column, and the column was eluted with increasing amount of hexane/ethyl acetate (98:2 to 80:20). The fractions were monitored on TLC plate and the desired fractions were combined and solvent was removed under vacuum to afford 4-methoxybenzaldehyde in 71% yield as a sweet smell liquid; 1H NMR δ 9.95 (1H, s, CHO), 7.82 (1H, s, 6H), 7.79 (1H, s, 2H), 6.99 (1H, s, 5H), 6.96 (1H, s, 5H), 3.84 (3H, s, 4-OCH3). The remaining physical and spectral data was found similar as reported and yield was found less may be due to evaporation of anethole during microwave irradiation. |
With oxygen; benzaldehyde at 140 - 150℃; | ||
With osmium(VIII) oxide; dihydrogen peroxide; sodium sulfate Reagens 4:Aether; | ||
With vanadia; <i>tert</i>-butyl alcohol | ||
With tert-Amyl alcohol; vanadia | ||
With methanol; dichloromethane bei der Ozonolyse; | ||
20 % Chromat. | With 9-cyanoanthracene; oxygen In acetonitrile for 7h; Irradiation; other reagent; | |
83 % Chromat. | With Trametes Hirsuta cell-free extract; dihydrogen peroxide In ethanol; water at 25℃; for 24h; | |
With oxygen at 25℃; for 24h; aq. buffer; Enzymatic reaction; chemoselective reaction; | ||
With tert.-butylhydroperoxide In ethanol; water; ethyl acetate at 30℃; for 20h; Enzymatic reaction; chemoselective reaction; | ||
With manganese(IV) oxide; sulfuric acid at 100℃; for 4h; Large scale; Green chemistry; | 1 The purity of 50% of the raw material of natural grass Artemisia brain into the distillation tower, the purification, distillation tower tower kettle temperature 160 ° C, the temperature of the top of the tower is 120 ° C, the purified grass carp of the brain, its purity is about 98% The purified grasses of Artemisia annua were placed in a heterogeneous pot, and the catalyst potassium hydroxide was added to the isomerized pan to control the isomer Pot temperature of 180 ° C, reaction 4h, after the end of the reaction, to stop the heating of the heterogeneous pot, was anise. Wherein the mass of the added potassium hydroxide is 5% of the mass of the purified Artemisia annua. The fennel was frozen at minus 20 ° C, and the anethole was centrifuged at the same time under the freezing conditions. The centrifugation time was 20 min, and the high purity fennel was obtained. 1000kg of high purity anethole into the reactor, and to the reactor by adding 200kg dilute sulfuric acid, 300kgMn02, control the temperature inside the reactor l0 ° C, reaction 4h, anise anirone crude. The concentration of dilute sulfuric acid is 20%. The aniseed aldehyde crude into the centrifuge for centrifugal separation, centrifugal separation and then washed with salt water. Among them, the brine is a mass percentage of 5% sodium chloride solution. The washed anodic aldehyde crude product with the solute mass percentage of 5% of the baking soda water for the second washing, so that the anisedehyde crude product pH value of 8.0, that is, the product. And then the product into the distillation tower purification, distillation tower tower temperature of 160 ° C, the top temperature of 120 ° C, the purity of 98-99% purity of the product. | |
0.597 g | With water; ozone In ethyl acetate at 0℃; for 0.00277778h; Flow reactor; | Standard ozonolysis procedure. General procedure: The syringe pumps and the lm-shear reactorwere primed by running 50 mL EtOAc at 10 mL/min and 50 mL deionized H2O at 10 ml/min with the rotor running at 2000 RPM. This procedure was repeated with pure oxygen also owing at 0.8 L/min The lm-shear reaction chamberwas cooled to 0 C with a recirculator. Both a 0.10 M solution of alkene in EtOAc at 0 °C and deionized water at 0 °C were pumped into a ‘T’ valve (10 mL/min each) generating the plug-ow mixture that entered the film-shear reactor. Ozone was sparged through the reaction chamber at 0.8 L/min. Aproduct ask was primed with 2 mol equiv of a sodium sulte solution toquench any hydrogen peroxide produced. The resulting product mixture was collected in a fume hood (CAUTION residual ozone, formaldehyde, andhydrogen peroxide may be present as an aerosol; perform only in a well ventilated hood). The pH was adjusted to 3 using 3 M HCl (aq) . The two resulting layers were separated. The aqueous layer was washed three times with 15 mLof EtOAc, then the organic layers were combined, dried over Na2SO4, filtered,and the solvent was removed under vacuum. The products were puried asnoted in Supplemental information. |
With tert-Amyl alcohol; vanadia | ||
With vanadia; <i>tert</i>-butyl alcohol | ||
With pleurotus sapidus at 20℃; for 16h; Darkness; | ||
With linoleic acid; oxygen at 37℃; Enzymatic reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With ammonium peroxydisulfate In nitromethane for 22h; Irradiation; Inert atmosphere; | |
88% | With ammonium peroxydisulfate; tris(2,2′-bipyrazine-N1,N1′)ruthenium(II) hexafluorophosphate In acetonitrile for 27h; Irradiation; Schlenk technique; | |
80% | With lithium perchlorate; acetic acid In acetonitrile for 2h; Ambient temperature; electrolysis, platinum electrodes; |
77% | With ammonium peroxydisulfate; 6-(dimethylamino)-9-mesityl-1-methoxy-10-phenylacridinium bromide In acetonitrile for 40h; Inert atmosphere; Irradiation; | 44 Photocatalyzed Oxidative [3+2] Cycloaddition Prepared according to a modified literature procedure (T. P. Yoon, et al., Angew. Chem. Int. Ed. 2014, 53, 11056). To a mixture of trans -anet ol (19.3 mg, 130 μιηο), ammonium peroxydisulfate (45.6 mg, 200 μηιο) photocatalyst (2.5 mol%, see table below, ) in MeCN (3.0 mL) was added /?-hydroxyanisole (12.4 mg, 100 μιηο) and was degassed by a stream of argon for 10 min. The reaction was performed under argon atmosphere with the light on for 40 h. The reaction mixture was filtered over silica gel and rinsed with EtOAc. The filtrate was concentrated in vacuo, dissolved in CH2CI2, mixed with silica gel (1 g), concentrated in vacuo and the residue was column chromatographed over silica gel with cyclohexane: EtOAc 50: 1- 50:3 afforded cycloadducts in the yields indicated in the table below. (0723) (±)-5-Methoxy-2-(4-methoxyphenyl)-3-methyl-2,3-dihydrobenzofuran (0724) R/ 0.29 (n hexane:EtOAc 5: 1); 1H NMR (500 MHz, CDC13): δ = 7.35-7.37 (2H, m, C2'H, C6'H), 6.90-6.92 (2H, m, C3'H, C5'H), 6.72-6.76 (1H, m, C4H), 6.69-6.72 (2H, m, C6H, C7H), 5.08 (1H, d, 3J 9.0, C1H), 3.82 (3H, s, C4'OCH3), 3.78 (3H, s, C50CH3), 3.38-3.44 (1H, m, C2H), 1.38 (3H, d, 3J 6.8, CH3); 13C NMR (125 MHz, CDC13): δ = 159.6 (C4 '), 154.4 (C5), 153.3 (C8), 133.1 (C3), 132.7 {CI '), 127.7 (C2 C6'), 114.0 (C3 C5 '), 112.9 (C6), 110.0 (C7), 109.4 (C4), 92.6 (CI), 56.1 (C4'OCH3), 55.3 (C50CH3), 45.7 (C2), 17.6 (CH3); Analytical data is in agreement with literature (T. P. Yoon, et al, Angew. Chem. Int. Ed. 2014, 53, 11056). |
76% | With μ-Oxo-I,I'-bis(trifluoroacetato-O)-I,I'-diphenyldiiodine(III) In acetonitrile at 0 - 20℃; | Typical procedure for the oxidative coupling of phenols 1 with styrenes 2 using the PIFA dimer leading to dihydrobenzofurans 3 General procedure: To an ice-cooled solution of equimolar phenol 1a (24.8 mg, 0.20 mmol) and styrene 2a (27.6 mg, 0.20mmol) in MeCN (0.5 mL), the PIFA dimer (65.0 mg, 0.10 mmol) was added in one portion at room temperature. The reaction mixture was stirred for 30 min and then it was quenched with solid sodium hydrogen carbonate. After filtration, solvent was removed in vacuo and the residue was purified by column chromatography on silica-gel to give 2-aryldihydrobenzofuran 3aa (40.1 mg, 0.152 mmol) in 76% yield. |
64% | With di-tert-butyl peroxide; iron(III) chloride hexahydrate In 1,2-dichloro-ethane at 60℃; for 2h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With tris(2,2’--bipyrazyl)ruthenium(II) bis(tetrakis(3,5-bis(trifluoromethyl)phenyl)borate) In dichloromethane at 20℃; for 1h; Irradiation; regioselective reaction; | |
98% | With iron perchlorate hexahydrate In acetonitrile at 20℃; for 24h; regioselective reaction; | |
98% | With iron(III) chloride In acetonitrile at 20℃; for 1h; |
95% | With Fe(3,4,7,8-tetramethyl-1,10-phenanthroline)<SUB>3</SUB>(PF<SUB>6</SUB>)<SUB>3</SUB> In 2,2,2-trifluoroethanol; 1,2-dichloro-ethane at 0℃; for 2h; | |
88% | With 9-(2-trifluoromethylphenyl)-1,3,6,8-tetramethoxythioxanthylium trifluoromethanesulfonate In nitromethane at 20℃; for 0.25h; UV-irradiation; | General procedure for [4+2] cycloaddition with photocatalyst under visible light irradiation General procedure: The alkene (1)(0.50 mmol), diene(2) (1.5 mmol),TXT1 (1.0 mol%) andCH3NO2 (8.0 mL) wereadded intoa 10 ml recovery flask. The resulting solution was stirred at room temperature under air and green LEDirradiation. After the reaction was completed (checked byTLC), the desired cycloadduct3was isolated bycolumn chromatography on silica gel (hexane/ethylacetate = 100/1). |
88% | With 9-(2-trifluoromethylphenyl)-1,3,6,8-tetramethoxythioxanthylium trifluoromethanesulfonate In nitromethane at 20℃; for 3h; Irradiation; | |
86% | With [Cr(bathophenanthroline)3](BF4)3 In nitromethane for 24h; UV-irradiation; | |
80% | With tris-(4-bromophenyl)aminium hexachloroantimonate In dichloromethane at 0℃; | |
55.2% | With 2,6-di-tert-butyl-pyridine; tris-(4-bromophenyl)aminium hexachloroantimonate In dichloromethane at 0℃; for 0.166667h; | |
With C26H18N10Ru(2+)*2C32H12BF24(1-) In dichloromethane at 20℃; for 3h; Inert atmosphere; Irradiation; | ||
96 %Spectr. | In nitromethane at 20℃; Electrochemical reaction; | |
95 %Spectr. | With lithium perchlorate In nitromethane at 10℃; for 4.5h; UV-irradiation; | |
71 %Spectr. | With lithium perchlorate In nitromethane at 20℃; for 2h; UV-irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With ammonium peroxydisulfate In nitromethane for 12h; Irradiation; Inert atmosphere; | |
96% | With tetrabutylammonium tetrafluoroborate In acetonitrile Electrolysis; | |
96% | With tetrabutylammonium tetrafluoroborate In acetonitrile Electrolysis; |
92% | With ammonium peroxydisulfate; tris(2,2′-bipyrazine-N1,N1′)ruthenium(II) hexafluorophosphate In acetonitrile for 12h; Irradiation; Schlenk technique; | |
64% | With lithium perchlorate; acetic acid In acetonitrile for 3h; Ambient temperature; electrolysis, platinum electrodes; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With tris(2,2’--bipyrazyl)ruthenium(II) bis(tetrakis(3,5-bis(trifluoromethyl)phenyl)borate) In dichloromethane at 20℃; for 1h; Irradiation; regioselective reaction; | |
98% | With lithium perchlorate In nitromethane at 20℃; Electrolysis; | General procedure for bulk electrolysis General procedure: To a solution of lithium perchlorate (1.06 g, 10.0 mmol) in nitromethane (10 mL) stirred at rt was added trans-anethole (1) (150 L, 1.0 mmol) and isoprene (2) (303 L, 3.0 mmol). The resulting reaction mixture was electrolyzed at rt using carbon felt electrodes (2 cm × 2 cm) in an undivided cell with stirring at aconstant potential of 1.0 V vs Ag/AgCl. After completion (monitored by TLC and GC-MS), the reaction mixture was diluted with CH2Cl2 and washed with brine. The organic layer was dried over MgSO4, filtered, and concentrated in vacuo to give a crude product as a yellow oil. Silica gel column chromatography (EtOAc/Hex = 1:30) gave the title compound (211.6 mg, 98%). 1H NMR (CDCl3, 600 MHz) δ 7.08 (2H, d, J= 8.5 Hz), 6.84 (2H, d, J = 8.5 Hz), 5.44 (1H, br. s), 3.79 (3H, s), 2.32-2.27 (1H, m), 2.24-2.10 (2H, m), 2.06(1H, dd, J = 17.2, 4.5 Hz), 1.93-1.85 (1H, m), 1.83-1.76 (1H, m), 1.69 (3H, s), 0.70 (3H, d, J = 6.8 Hz); 13CNMR (150 MHz, CDCl3) 157.7, 138.2, 133.8, 128.5, 120.9, 113.7, 55.2, 46.9, 39.8, 35.3, 34.0, 23.4, 20.3. |
98% | With iron perchlorate hexahydrate In acetonitrile at 20℃; for 24h; regioselective reaction; |
98% | With Fe(3,4,7,8-tetramethyl-1,10-phenanthroline)<SUB>3</SUB>(PF<SUB>6</SUB>)<SUB>3</SUB> In 2,2,2-trifluoroethanol; 1,2-dichloro-ethane at 20℃; for 3h; | |
94% | With 9-(2-trifluoromethylphenyl)-1,3,6,8-tetramethoxythioxanthylium trifluoromethanesulfonate In nitromethane at 20℃; for 0.25h; UV-irradiation; | General procedure for [4+2] cycloaddition with photocatalyst under visible light irradiation General procedure: The alkene (1)(0.50 mmol), diene(2) (1.5 mmol),TXT1 (1.0 mol%) andCH3NO2 (8.0 mL) wereadded intoa 10 ml recovery flask. The resulting solution was stirred at room temperature under air and green LEDirradiation. After the reaction was completed (checked byTLC), the desired cycloadduct3was isolated bycolumn chromatography on silica gel (hexane/ethylacetate = 100/1). |
94% | With 9-(2-trifluoromethylphenyl)-1,3,6,8-tetramethoxythioxanthylium trifluoromethanesulfonate In nitromethane at 20℃; for 0.25h; Irradiation; | |
88% | With [Cr(bathophenanthroline)3](BF4)3 In nitromethane for 27h; UV-irradiation; | |
81% | With lithium perchlorate; titanium(IV) oxide In nitromethane at 20℃; for 2h; UV-irradiation; | |
21.8% | With 2,6-di-tert-butyl-pyridine; tris-(4-bromophenyl)aminium hexachloroantimonate In dichloromethane at 0℃; for 0.133333h; | |
With tris-(4-bromophenyl)aminium hexachloroantimonate In dichloromethane | ||
With Ru(bpz)<SUB>3</SUB>(PF<SUB>6</SUB>)<SUB>2</SUB> In nitromethane at 20℃; for 3h; Inert atmosphere; Irradiation; | ||
98 %Spectr. | In nitromethane at 20℃; Electrochemical reaction; | |
With acetic acid In nitromethane at 20℃; Electrolysis; | ||
98 %Spectr. | With lithium perchlorate In nitromethane at 10℃; for 4.5h; UV-irradiation; | |
97 %Spectr. | With bis(trifluoromethane)sulfonimide lithium In methyl cyclohexane at 20℃; Electrochemical reaction; | |
89 %Spectr. | With 2,3,5,6-tetrafluoro-1,4-benzoquinone; C80H48N8Pd2 In dichloromethane-d2 at 26.84℃; for 1h; | |
98 %Spectr. | With lithium perchlorate In nitromethane Electrolysis; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
32% | With methyl magnesium iodide | |
23% | With magnesium; methyl iodide In diethyl ether at 165℃; for 3h; Inert atmosphere; | |
22% | With potassium hydroxide In ethanol at 160℃; for 1.5h; microwave oven; | 39.A Trans-anethole (0.5mL, 3.34mmol), potassium hydroxide (4g, 71mmol) and ethanol (6mL) were mixed and sealed in a microwave tube. The reaction mixture was heated at 160 °C in microwave oven at very high setting for 3 x 30 minutes. The reaction was quenched with saturated citric acid. The aqueous phase was extracted by ethyl acetate (3 x lOmL). The combined organic layers were dried over MgS04, filtered and concentrated to give a yellow crude product. The crude product was purified via column chromatography on silica gel with a gradient of 0%→ 50% of ethyl acetate in hexanes to afford the title product (0.10 g, 22% yield): XH NMR (400 MHz, CDC13) δ 7.23 (m, 2 H), 6.80 (m, 2 H), 6.36 (dd, J = 15.7, 1.8 Hz, 1 H), 6.11 (dq, J = 15.7, 6.6 Hz, 1 H), 5.12 (s, 1 H), 1.89 (m, 3 H); LCMS (ESI) mle 133.1 [(M - H)-, calcd for C9HuO 133.2]. |
13% | With methyl magnesium iodide |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With oxone||potassium monopersulfate triple salt; water; sodium hydrogencarbonate In acetone; acetonitrile at 0℃; for 1.5h; diastereoselective reaction; | |
38% | With 3-chloro-benzenecarboperoxoic acid In dichloromethane | |
99 % Chromat. | With dihydrogen peroxide In tert-Amyl alcohol at 20℃; for 12h; |
95 % Chromat. | With urea hydrogen peroxide adduct In tert-Amyl alcohol at 20℃; for 3h; | |
Multi-step reaction with 2 steps 1: 100 percent / HOBr / dioxane / 0.5 h / 20 °C 2: 93 percent / methanolic KOH / 0.25 h / 5 °C | ||
With Oxone; sodium hydrogencarbonate In water; acetone; acetonitrile at 0℃; for 5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With AD-mix-β In water; <i>tert</i>-butyl alcohol at 20℃; for 24h; | |
With potassium permanganate; N-benzyl-N,N,N-triethylammonium chloride In dichloromethane | ||
61 mg | With pyridine; osmium(VIII) oxide for 1.41667h; Ambient temperature; |
Multi-step reaction with 3 steps 1: 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione / 12 h / 20 °C / Inert atmosphere 2: potassium carbonate; methanol 3: zinc; acetic acid / tetrahydrofuran; water | ||
Multi-step reaction with 3 steps 1: 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione / 12 h / 20 °C / Inert atmosphere 2: potassium carbonate; methanol 3: zinc; acetic acid / tetrahydrofuran; water | ||
Multi-step reaction with 3 steps 1: 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione / 12 h / 20 °C / Inert atmosphere 2: zinc / tetrahydrofuran; water 3: potassium carbonate; methanol | ||
Multi-step reaction with 3 steps 1: 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione / 12 h / 20 °C / Inert atmosphere 2: zinc / tetrahydrofuran; water 3: potassium carbonate; methanol | ||
Multi-step reaction with 3 steps 1: 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione / 12 h / 20 °C / Inert atmosphere 2: zinc / tetrahydrofuran; water 3: potassium carbonate; methanol | ||
Multi-step reaction with 3 steps 1: 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione / 12 h / 20 °C / Inert atmosphere 2: zinc / tetrahydrofuran; water 3: potassium carbonate; methanol |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With polymer-bound bis(azido)iodate(I) In dichloromethane at 20℃; for 16h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | Stage #1: E-1-(4'-methoxyphenyl)prop-1-ene With benzo[1,3,2]dioxaborole In toluene at 20℃; for 2h; Stage #2: With sodium hydroxide; water; dihydrogen peroxide In toluene at 20℃; for 2h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | In acetonitrile at 20℃; for 66h; | |
92% | With 3ClO4(1-)*Fe(3+)*Al2O3 In acetonitrile at 20℃; for 66h; | |
68% | With iron perchlorate hexahydrate In acetonitrile at 40℃; for 24h; diastereoselective reaction; |
35% | With lithium perchlorate In nitromethane at 20℃; Electrolysis; | General procedure for bulk electrolysis General procedure: To a solution of lithium perchlorate (1.06 g, 10.0 mmol) in nitromethane (10 mL) stirred at rt was added trans-anethole (1) (150 L, 1.0 mmol). The resulting reaction mixture was electrolyzed at rt using carbon felt electrodes (2 cm × 2 cm) in an undivided cell with stirring at a constant potential of 1.0 V vs Ag/AgCl. After the passage of 0.4 F/mol, the reaction mixture was diluted with CH2Cl2 and washed with brine. The organic layer was dried over MgSO4, filtered, and concentrated in vacuo to give crude product as a yellow oil. Silica gel column chromatography (EtOAc/Hex = 1:30) gave the title compound (103.5 mg, 35%). Analytical data are in agreement with the literature.1 |
With graphitic carbon nitride; magnesium sulfate In nitromethane for 2.5h; Irradiation; | ||
34 %Spectr. | With 2,3,5,6-tetrafluoro-1,4-benzoquinone; C80H48N8Pd2 In dichloromethane-d2 at 26.84℃; for 1h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With indium(III) chloride In dichloromethane at 20℃; for 5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With sodium tetrahydroborate; oxygen In tetrahydrofuran at 30℃; for 40h; | A Typical Procedure of Olefin Hydration with NaBH4. General procedure: NCI-Co (Co: 1.0mol%) was added to a CarouselTM tube anddried with heat gun in vacuo. NaBH4 (22.7 mg, 0.6mmol),olefin 1 (0.3mmol) and THF (0.9 mL) were added to theCarousel tube. The mixture was stirred for 40 h under 1 bar ofO2 atmosphere at 30 °C. If necessary, anisole (2530mg) as aninternal standard was added to the mixture, and an aliquot ofthe reaction mixture (0.02 mL) was filtered through a silicagel packed disposable Pasteur pipette and washed with ethylacetate to prepare for GC analysis. Ethyl acetate was added tothe mixture and the solid catalyst was removed by filtration.After that, the solvents were removed in vacuo and 1HNMRanalysis of the crude mixture was conducted with tetrachloroethaneas an internal standard. The residue was purified bypreparative TLC to afford the corresponding alcohol 2. |
1.5 g | Stage #1: E-1-(4'-methoxyphenyl)prop-1-ene With mercury(II) diacetate In tetrahydrofuran; water at 20℃; for 1h; Stage #2: With sodium hydroxide; sodium tetrahydroborate In tetrahydrofuran; water at 20℃; for 3h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride; acrylic acid methyl ester In dichloromethane for 2h; Reflux; Inert atmosphere; | |
90% | With C33H43Cl2N3O3RuS In toluene at 110℃; for 2h; Inert atmosphere; | 1.1 Preparation of compound 1 The zhan catalyst (commercially available from the supplier Sigma USA under the reference 762261) (44 mg, 0.061 mmol, 0.01 eq.) is added to a solution of commercial anethole (298 mg, 2.0 mmol) in anhydrous toluene. The reaction mixture is heated at 110°C under an inert atmosphere (N2) for 2 hours. After cooling to room temperature, the toluene is evaporated off under reduced pressure and the residue is purified by column chromatography on silica gel (5/1 hexane/dichloromethane) to isolate the intermediate in the form of a white solid after evaporating off the solvents (433 mg, 90% yield). |
74% | With silica-supported Hoveyda-Grubbs II catalyst In hexane at 70℃; for 14h; Inert atmosphere; Glovebox; |
90 % Turnov. | In toluene at 85℃; for 2h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With dihydrogen peroxide In tert-Amyl alcohol at 20℃; for 12h; | 21 In a typical experiment, the ruthenium complex [Ru(2,2':6',2-terpyridine)(pyridine-2,6-dicarboxylate)] (VI-1) (0.0025 mmol) is stirred in tert-amyl alcohol (9 ml) at room temperature and the olefin of the formula (III) (0.5 mmol) is added. A solution of 30% strength hydrogen peroxide (1.5 mmol) in t-amyl alcohol (0.83 ml) is metered into this mixture over a period of 12 hours. The reaction is then quenched by addition of water (10 ml) and Na2SO3 (0.5 g) and the mixture is extracted with ethyl acetate (20 ml). After the organic phase has been dried, aliquots are analysed by means of gas chromatography. To isolate the epoxides, the solvent is removed by distillation and the product is, if appropriate, purified by column chromatography. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
50% | With sulfur In N,N-dimethyl-formamide for 8h; Heating; | 3; 6 Anethole (1) (32.5 g; 0.21 mol) and sulphur (45 g; 1.40 mol) were heated in dimethylformamide (250 ml) for 8 hr; the residue after removal of solvent was almost completely soluble in toluene. An attempt to extract the toluene liquors with 2N-aqueous sodium hydroxide, gave a precipitate of an orange solid (8.5 g). m.p. over 300° C. This product was dissolved in boiling water and gave an orange precipitate (2) after addition of hydrochloric acid (Yield 50%), m.p. 188-189° C. 1H NMR (DMSO) δ 6.86 (d, 2H), 7.68 (s, 1H), 7.75 (d, 2H), 10.51 (s, -OH); MS (ESI), m/z 225(M-). |
50% | Stage #1: E-1-(4'-methoxyphenyl)prop-1-ene With sulfur In N,N-dimethyl-formamide for 8h; Heating / reflux; Stage #2: With sodium hydroxide; water In toluene Stage #3: With hydrogenchloride; water at 100℃; | 3; 6 EXAMPLE 3General synthetic procedure of:4- or 5-Amino-2-hydroxy-benzoic acid 4-(5-thioxo-5H-[1,2]dithiol-3-yl)-phenyl ester(4)4- or 5-nmlno salicylic acidSynthesis of5-p-hydroxyphenyl-1,2-dithione-3-thione (ADT-OH)Anethole 1 (32.5 g; 0.21 mol) and sulphur (45 g; 1.40 mol) were heated in dimethylformamide (250 ml) for 8 hr; the residue after removal of solvent was almost completely soluble in toluene. An attempt to extract the toluene liquors with 2N- aqueous sodium hydroxide, gave a precipitate of an orange solid (8.5 g). m.p. over 3000C. This product was dissolved in boiling water and gave an orange precipitate 2 after addition of hydrochloric acid (Yield 50%), m.p. 188-189 0C. 1H NMR (DMSO) δ6.86 (d, 2H), 7.68 (s, 1 H), 7.75 (d, 2H), 10.51 (s, -OH); MS (ESI), m/z 225{W).; EXAMPLE 6General synthetic procedure of:4-or 5-Amino-2-[4-(5-thioxo-5H-[1,2]dithiol-3-yl)-phenoxycarbonyloxy]-benzoic acid (15)2-Hydroxy-4-or 5-[4-(5-thioxo-5H-[1,2]dithiol-3-yl)-phenoxycarbonylamino]- benzoic acid (16) EPO EPO Synthesis of 5-p-hydroxyphenyl-t ,2-dithione-3-thione (ADT-OH)Anetholβ 1 (32.5 g; 0.21 mol) and sulphur (45 g; 1.40 mol) were heated in dimethylformamide (250 ml) for 8 hr; the residue after removal of solvent was almost completely soluble in toluene. An attempt to extract the toluene liquors with 2 N- aqueous sodium hydroxide, gave a precipitate of an orange solid (8.5 g). m.p. over 3000C. This product was dissolved in boiling water and gave an orange precipitate 2 after addition of hydrochloric acid (Yield 50%), m.p. 188-189 0C. 1H NMR (DMSO) δ 6.86 (d, 2H), 7.68 (s, 1 H), 7.75 (d, 2H), 10.51 (s, -OH); MS (ESI), m/z225(M"). |
50% | Stage #1: E-1-(4'-methoxyphenyl)prop-1-ene With sulfur In N,N-dimethyl-formamide for 8h; Heating / reflux; Stage #2: In toluene Stage #3: at 100℃; | 3; 6 EXAMPLE 3General synthetic procedure of:4- or 5-Amino-2-hydroxy-benzoic acid 4-(5-thioxo-5H-[1,2]dithiol-3-yl)-phenyl ester(4)4- or 5-nmlno salicylic acidSynthesis of5-p-hydroxyphenyl-1,2-dithione-3-thione (ADT-OH)Anethole 1 (32.5 g; 0.21 mol) and sulphur (45 g; 1.40 mol) were heated in dimethylformamide (250 ml) for 8 hr; the residue after removal of solvent was almost completely soluble in toluene. An attempt to extract the toluene liquors with 2N- aqueous sodium hydroxide, gave a precipitate of an orange solid (8.5 g). m.p. over 3000C. This product was dissolved in boiling water and gave an orange precipitate 2 after addition of hydrochloric acid (Yield 50%), m.p. 188-189 0C. 1H NMR (DMSO) δ6.86 (d, 2H), 7.68 (s, 1 H), 7.75 (d, 2H), 10.51 (s, -OH); MS (ESI), m/z 225{W).; EXAMPLE 6General synthetic procedure of:4-or 5-Amino-2-[4-(5-thioxo-5H-[1,2]dithiol-3-yl)-phenoxycarbonyloxy]-benzoic acid (15)2-Hydroxy-4-or 5-[4-(5-thioxo-5H-[1,2]dithiol-3-yl)-phenoxycarbonylamino]- benzoic acid (16) EPO EPO Synthesis of 5-p-hydroxyphenyl-t ,2-dithione-3-thione (ADT-OH)Anetholβ 1 (32.5 g; 0.21 mol) and sulphur (45 g; 1.40 mol) were heated in dimethylformamide (250 ml) for 8 hr; the residue after removal of solvent was almost completely soluble in toluene. An attempt to extract the toluene liquors with 2 N- aqueous sodium hydroxide, gave a precipitate of an orange solid (8.5 g). m.p. over 3000C. This product was dissolved in boiling water and gave an orange precipitate 2 after addition of hydrochloric acid (Yield 50%), m.p. 188-189 0C. 1H NMR (DMSO) δ 6.86 (d, 2H), 7.68 (s, 1 H), 7.75 (d, 2H), 10.51 (s, -OH); MS (ESI), m/z225(M"). |
13% | Stage #1: E-1-(4'-methoxyphenyl)prop-1-ene With sulfur In N,N-dimethyl-formamide for 8h; Heating / reflux; Stage #2: With sodium hydroxide In water; toluene Stage #3: With hydrogenchloride In water Heating / reflux; | 1 Synthesis of 5-p-hydroxyphenyl-1,2-dithiole-3-thione (2; ADT-OH) Synthesis of 5-p-hydroxyphenyl-1,2-dithiole-3-thione (2; ADT-OH) Anethole (31 g, 0.21 mol) and sulfur (44.8 g, 1.40 mol) were heated in N,N-dimethylformamide (250 ml) for 8 hrs; after removal of solvent, the residue was almost completely soluble in toluene. An attempt to extract the toluene liquors with 2N-aqueous sodium hydroxide, gave an orange solid precipitate (8.5 g; m.p. over 300° C.). This product was dissolved in boiling water and, after addition of hydrochloric acid, gave 2 as an orange precipitate (6.2 g, yield 13%) m.p. 188-189° C. 1H NMR (DMSO-d6) δ 6.86 (d, 2H), 7.68 (s, 1H), 7.75 (d, 2H), 10.51 (s, -OH); MS (ESI), m/z 225 (M-). |
Multi-step reaction with 2 steps 1: sulfur / N,N-dimethyl acetamide / 6 h / Reflux 2: pyridine hydrochloride / 0.33 h / 160 °C / Microwave irradiation |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With sodium t-butanolate In toluene under N2; diborane reacted with alkene in toluene in presence of Cu complex (3 mol%), NaO-t-Bu and MeOH at 22°C for 10 min; detd. by (1)H NMR spectra; one stereoisomer (>98% stereoselectivity) obtained; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | Stage #1: bis(pinacol)diborane With CuCl(SIMes); sodium t-butanolate In toluene for 0.166667h; Inert atmosphere; Stage #2: E-1-(4'-methoxyphenyl)prop-1-ene With methanol In toluene at 22℃; for 0.166667h; Inert atmosphere; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | Stage #1: ethyltriphenylphosphonium bromide With n-butyllithium In tetrahydrofuran at -78 - 0℃; Inert atmosphere; Stage #2: 4-methoxy-benzaldehyde In tetrahydrofuran at -78 - 25℃; for 3.83333h; Inert atmosphere; Stage #3: With dichloro bis(acetonitrile) palladium(II) In chloroform at 25℃; for 72h; | |
67.2% | With potassium <i>tert</i>-butylate; tetrabutylammomium bromide In N,N-dimethyl-formamide at 0 - 95℃; for 4.5h; Inert atmosphere; | 4.1.2 General procedure B General procedure: To a stirred mixture of alkyl triphenylphosphonium bromide (9.0mmol), t-BuOK (2.7g, 24.0mmol), and TBAB (0.1g, 0.3mmol) in dry DMF (10mL) was added the corresponding methoxybenzaldehyde derivative (6.0mmol) under the protection of nitrogen at 0-5°C and stirring was continued at room temperature (RT) for 0.5h. The reaction mixture was heated at 90-95°C for 4h. After completing the reaction (TLC monitoring), the reaction mixture was quenched with 70mL H2O. Then the mixture was extracted three times with 70mL EtOAc. The organic phase was collected, dried over anhydrous MgSO4, filtered, and concentrated in reduced pressure. The residue was purified using silica gel chromatography (Pet. Ether/EtOAc, v/v=40-20:1). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
43.8% | Stage #1: tert-butyl carbazate With sodium hydroxide In propan-1-ol; water at 20℃; for 0.0833333h; Stage #2: With 1,3-dichloro-5,5-dimethylhydantoin In propan-1-ol; water at 20℃; for 0.166667h; Stage #3: E-1-(4'-methoxyphenyl)prop-1-ene With potassium osmate(VI) dihydrate; hydroquinidein 1,4-phthalazinediyl diether; sodium hydroxide In propan-1-ol; water at 0℃; | 8.A Tert-butyl carbamate (3.1 equiv., 4.54 g, 38.75 mmol) was dissolved in 50 mL of 1-propanol and 99 mL of a 0.38 M aqueous NaOH was added. The reaction was stirred for 5 minutes at ambient temperature and 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione (1.535 equiv., 3.78 g, 19.2 mmol) were added and the reaction was stirred for 10 minutes at ambient temperature. The reaction was cooled down to 0° C. and (DHQ)2PHAL (0.06 equiv., 0.585 g, 0.75 mmol) dissolved in 50 mL 1-propanol were added. After that 1 equiv. of the trans-anethole (1.85 g, 1.875 mL, 12.5 mmol) dissolved in 100 mL of 1-propanol were added followed by potassium osmate dihydrate (0.04 equiv., 0.184 g, 0.5 mmol) suspended in 1 mL 0.38 M aqueous NaOH. The reaction was stirred at 0° C. until complete consumption of the trans-anethole (TLC control). 85 mL of water was added and the reaction mixture was extracted three times by means of 150 mL ethyl acetate. Saturated aqueous sodium chloride solution had to be added until phase separation was observed. The combined organic layer was washed with brine, dried over sodium sulfate, filtrated and the solvents were removed under reduced pressure. The product was purified by FPLC using a heptane-ethyl acetate gradient (0→30%). The product elutes at about 25% of ethyl acetate. Yield: 1.54 g (43.8%) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With potassium carbonate In water; isopropyl alcohol at 120℃; for 0.5h; Inert atmosphere; Microwave irradiation; | 1 In this example, (E)-Anethol is prepared by the following procedure: Potassium allyltrifluoroborate (148.0 mg, 1.0 mmol), 4-bromoianisole (32 L, 0.25 mmol), (a 4:1 ratio of potassium allyltrifluoroborate and 4-bromoanisole respectively), K2CO3 (104.0 mg, 0.75 mmol) and PdCl2(dtbpf) (5.0 mg, 0.0075 mmol, 3 mol %) were placed in an argon flushed pyrex tube. The pyrex tube was capped with a rubber septum, flushed with argon and 2.5 mL of isopropanol/water (2:1) was added. The resulting mixture in the pyrex tube was placed in a CEM microwave unit and allowed to irradiate at 120° C. for 30 minutes. As an example, preparation of (E)-Anethol by this method is set forth in FIG. 1.After standard work-up by adding ammonium chloride and ethyl ether, the ether layer was separated. The reaction mixture was adsorbed in a silica gel plate for preparative TLC with hexane as the eluent and the developed TLC plate was exposed to a UV lamp and the intense spot for the product was marked. The collected compound adsorbed in the silica gel was washed with ethyl ether, filtered, dried the filtrate to get the desired product. The pure product (E)-Anethol was isolated in 97% yield. In another aspect, the preparative TLC the product can also be purified by subjected to silica gel chromatography using hexane as an eluent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With Hoveyda-Grubbs catalyst first generation In 1,2-dichloro-ethane at 70℃; Schlenk technique; Inert atmosphere; Glovebox; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | With [bis(acetoxy)iodo]benzene In dichloromethane at 20℃; for 0.833333h; Irradiation; regioselective reaction; | 1 4.2. General procedure for the one-pot, three-component synthesis of dihydrofurans 3 General procedure: A solution of 1,3-cyclohexanedione 1 (1.00-2.00 mmol), iodobenzene diacetate (1.00-2.00 mmol) and alkene 2 (4.05-14.71 mmol) in dichloromethane (10 mL) was irradiated (250 W) at room temperature for 40-360 min. The solvent was evaporated under reduced pressure, and the residue was purified by flash chromatography to afford fused dihydrofuran 3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With oxygen In aq. buffer at 21℃; for 24h; Enzymatic reaction; | 2.2.8. Biotransformations General procedure: For the determination of the conversion, a previous procedure [25], [26] and [27] was adapted. Lyophilized cells (30 mg) were resuspended in Bis-Tris buffer (1 mL, 50 mM, pH 6.0). The cells were ultrasonicated (1 s pulse on, 4 s pulse off for a total time of 100 s, 50% amplitude) and centrifuged (4 °C, 8000 rpm, 20,000 × g, 20 min). The supernantant was used for the assay performed in 48 well RP plates. Each sample was tested in duplicates. The reaction mixture contained the cell free extract (900 μL) and t-anethole (5 μL, 4.94 mg, 33 μmol). In case of other tested substrates, an additional co-solvent (DMSO, 100 μL, 10%, v/v final concentration) was also added to improve solubility [28]. The reaction was run under oxygen pressure (2 bar) and shaken (170 rpm, GFL 3015 orbital shaker) at 21 °C. After 24 h, the samples were extracted with ethyl acetate (2× 500 μL) and analysed by GC. | |
With alkene cleaving enzyme AlkCE from Trametes hirsuta FCC047; oxygen; manganese triacetate In aq. buffer at 21℃; Enzymatic reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
42% | With iron(III)-acetylacetonate; di-tert-butyl peroxide In dimethyl sulfoxide at 130℃; for 12h; Inert atmosphere; Schlenk technique; | 4.2 General procedure for iron-catalyzed decarboxylative methylation of cinnamic acid General procedure: A mixture of cinnamic acid (0.3mmol), DTBP (0.6mmol), FeCl3 (20mol%), and DMSO (2mL) in a Schlenk tube was stirred under an argon atmosphere at 130°C for 12h. After that the mixture was poured into ethyl acetate, then washed with water, extracted with ethyl acetate, dried by anhydrous Na2SO4, then filtered, and evaporated under vacuum, the residue was purified by flash column chromatography (petroleum ether or petroleum ether/ethyl acetate) to afford the corresponding coupling products. |
32% | With ferrocene; di-tert-butyl peroxide at 120℃; for 24h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
49% | With ammonium acetate; acetic acid; malononitrile In acetonitrile at 80℃; for 8h; | 2 Example 2: (£ -l-Methoxy-4-(prop-l-en-l-yl) benzene ( 1-a) Example 1: Preparation of (E)-5-(hex-l-en-l-yl)-l,2,3-trimethoxybenzene: (1-g) To a mixture of 3,4,5-trimethoxybenzaldehyde (0.784 g, 0.004 mol), hexanal (0.5 g, 0.005 mol) and malononitrile (0.66 g, 0.01 mol), was added 30 ml of acetonitrile followed by the addition of glacial acetic acid (0.42 ml 0.0075 mol). The reaction mixture was stirred for 10 min and then ammonium acetate (0.385 g, 0.005 mol) was added. The reaction was stirred at 80 °C for 8 h. The mixture was then allowed to come to room temperature, filtered through Whatmann filter paper and the filtrate was concentrated on rotavapor. The residual oil was then partitioned between water and ethyl acetate and the organic extract was dried over sodium sulfate, concentrated and purified over silica gel using ethyl acetate - pet ether (3% ethyl acetate in pet ether) as an eluent to give (E)-5-(hex-l-en-l- yl)-l,2,3-trimethoxybenzene as a colourless liquid (0.6 g, 60%); IR (chloroform): 810, 925, 1377, 1506, 1582, 1651, 2929, 2989 cm-1. 1H NMR (200 MHz, CDC13) : δ 0.93 (t, J - 7Hz, 3H), 1.30-1.56 (m, 4H), 2.27 (q, J = 7Hz, 2H), 3.84 (s, 3H), 3.88 (s, 6H), 6.14 (dt, J = 16, 7 Ηζ,ΙΗ), 6.32 (d, J = 16 Hz, 1H), 6.58 (s, 2H); l3C NMR (50 MHz, CDC13): δ 13.7, 22.0, 31.3, 32.4, 55.7 (2C), 60.6, 102.6 (2C), 129.4, 130.5, 133.5, 136.9, 153.0 (2C); HRMS (ESI) m/z calcd for [C15H2203 + Na]+: 273.1461, found 273.1462; [Ci5H2203 + H]+: 251.1642, found 251.1642. This compound was prepared from anisaldehyde and propionaldehyde following the procedure similar to the one described in Example 1. Colorless liquid; Yield: 49 %; IR (Neat): 1036, 1 175, 1282, 1509, 1608, 2835, 2957, 3023 cm"1. 1H NMR (200 MHz, CDC13) : δ 1.89 (d, J = 6 Hz, 3H), 3.82 (s, 3H), 6.12 (dq, J = 16, 6 Hz, 1H), 6.38 (d, J = 16 Hz, 1H), 6.86 (d, J = 8 Hz, 2H), 7.29 (d, J = 8 Hz, 2H); I3C NMR (50 MHz, CDC13): δ 18.3, 55.0, 1 13.7 (2C), 123.2, 126.7 (2C), 130.2, 130.6, 158.4. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
36 % de | With [((NH2)salhex)Cu]; dihydrogen peroxide In water; acetone at 40℃; for 24h; | 2.5 Procedure for catalytic sulfoxidation of thioanisole General procedure: The catalytic experiments were carried out at atmospheric pressure at set constant temperatures in a glass batch reactor, equipped with magnetic stirrer, thermometer and condenser. In a typical run, the solid catalyst and thioanisole (1.0 mmol) were dissolved in the appropriate solvent (4mL). Then the oxidant (1.2-1.5 mmol), hydrogen peroxide (30% w/v aqueous solution) was added to the mixture. Control experiments were also carried out the in absence of catalyst. |
43 % de | With dihydrogen peroxide; copper(II) acetate monohydrate In water; acetone at 40℃; for 24h; | 2.5 Procedure for catalytic sulfoxidation of thioanisole General procedure: The catalytic experiments were carried out at atmospheric pressure at set constant temperatures in a glass batch reactor, equipped with magnetic stirrer, thermometer and condenser. In a typical run, the solid catalyst and thioanisole (1.0 mmol) were dissolved in the appropriate solvent (4mL). Then the oxidant (1.2-1.5 mmol), hydrogen peroxide (30% w/v aqueous solution) was added to the mixture. Control experiments were also carried out the in absence of catalyst. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
18% de | With [((NH2)salhex)Cu]; dihydrogen peroxide In methanol; water at 40℃; for 24h; | 2.5 Procedure for catalytic sulfoxidation of thioanisole General procedure: The catalytic experiments were carried out at atmospheric pressure at set constant temperatures in a glass batch reactor, equipped with magnetic stirrer, thermometer and condenser. In a typical run, the solid catalyst and thioanisole (1.0 mmol) were dissolved in the appropriate solvent (4mL). Then the oxidant (1.2-1.5 mmol), hydrogen peroxide (30% w/v aqueous solution) was added to the mixture. Control experiments were also carried out the in absence of catalyst. |
33 % de | With dihydrogen peroxide; copper(II) acetate monohydrate In methanol; water at 40℃; for 24h; | 2.5 Procedure for catalytic sulfoxidation of thioanisole General procedure: The catalytic experiments were carried out at atmospheric pressure at set constant temperatures in a glass batch reactor, equipped with magnetic stirrer, thermometer and condenser. In a typical run, the solid catalyst and thioanisole (1.0 mmol) were dissolved in the appropriate solvent (4mL). Then the oxidant (1.2-1.5 mmol), hydrogen peroxide (30% w/v aqueous solution) was added to the mixture. Control experiments were also carried out the in absence of catalyst. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
42% | With iron(III) chloride In dimethyl sulfoxide at 130℃; for 12h; Inert atmosphere; Schlenk technique; | 8 4.2. General procedure for iron-catalyzed decarboxylative methylation of cinnamic acid General procedure: A mixture of cinnamic acid (0.3 mmol), DTBP (0.6 mmol), FeCl3 (20 mol %), and DMSO (2 mL) in a Schlenk tube was stirred under an argon atmosphere at 130 °C for 12 h. After that the mixture was poured into ethyl acetate, then washed with water, extracted with ethyl acetate, dried by anhydrous Na2SO4, then filtered, and evaporated under vacuum, the residue was purified by flash column chromatography (petroleum ether or petroleum ether/ethyl acetate) to afford the corresponding coupling products. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In water at 25℃; for 24h; | 2.3. Preparation of solid inclusion complexes and physical mixtures General procedure: Solid inclusion complexes were prepared via the freeze-drying method. CDs and AN were mixed in an aqueous solution in a 1:1 M ratio at a concentration of 10 mM. The mixtures were agitated using a laboratory shaker at 300 rpm for 24 h at 25 °C. Then, solutions were filtered, frozen and lyophilized at 85 °C and 0 Pa in a Christ Alpha 2-4 LD Freeze dryer for approximately 48 h or until all moisture had been sublimated. | |
at 25℃; for 24h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride In toluene at 70℃; for 4h; Inert atmosphere; Glovebox; | |
With Hoveyda-Grubbs catalyst second generation In 1,2-dichloro-ethane Inert atmosphere; Glovebox; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With μ-Oxo-I,I'-bis(trifluoroacetato-O)-I,I'-diphenyldiiodine(III) In dichloromethane at 0 - 20℃; for 3h; | Procedure for the oxidative coupling of aniline 1f with alkenes 2d and 2g using the PIFA dimer leading to indoline 3fd and it derivatives General procedure: To a stirred solution of anilide 1f (27.7 mg, 0.10 mmol) and anethole 2d (44.5 mg, 0.30 mmol) or cyclicenamide 2g (66.9 mg, 0.30 mmol) in CH2Cl2 (10 mL) was added dropwise a solution of the PIFA dimer(82 mg, 0.125 mmol) in CH2Cl2 (10 mL) over 2 h by the syringe pump at room temperature. The reaction mixture was then stirred for additional 1 h. The solvent was evaporated in vacuo and the residue was purified by column chromatography on silica-gel to give pure indoline 3fd (44.0 mg, 0.093 mmol) or pyrroloindoline 4 (11.0 mg, 0.022 mmol), respectively. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With iron perchlorate hexahydrate In acetonitrile at 20℃; for 24h; regioselective reaction; | |
88% | With C26H18N10Ru(2+)*2C32H12BF24(1-) In dichloromethane for 1.5h; Irradiation; | |
84% | With 9-(2-trifluoromethylphenyl)-1,3,6,8-tetramethoxythioxanthylium trifluoromethanesulfonate In nitromethane at 20℃; for 1h; UV-irradiation; | General procedure for [4+2] cycloaddition with photocatalyst under visible light irradiation General procedure: The alkene (1)(0.50 mmol), diene(2) (1.5 mmol),TXT1 (1.0 mol%) andCH3NO2 (8.0 mL) wereadded intoa 10 ml recovery flask. The resulting solution was stirred at room temperature under air and green LEDirradiation. After the reaction was completed (checked byTLC), the desired cycloadduct3was isolated bycolumn chromatography on silica gel (hexane/ethylacetate = 100/1). |
76% | With iron(III) chloride In dichloromethane; acetonitrile at 0℃; for 3h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With aluminium(III) triflate; palladium diacetate; triphenylphosphine; In 5,5-dimethyl-1,3-cyclohexadiene; at 95℃; under 26252.6 Torr; for 4h;Catalytic behavior; | General procedure: Al(OTf)3 (10 mol%), Ph3P (20 mol%), xylene (0.5 g), and the appropriate alkene (4 mmol) were added together in the Parr reactor and dissolved in MeOH (6 mL). The reactor was degassed and allowed to heat up to 95 C. Pd(OAc)2 (5 mol%) dissolved in MeOH (2 mL) was injected, whereafter the pressure was set to 35 bar of CO. Conversions, yields, and product ratios were determined utilizing a Shimadzu 2010 GC instrument with xylene as the internal standard (Tables 2-4). Where applicable, the products were directly purified by flash column chromatography [100 g Merck Kieselgel 60 (230-400 mesh) per gram of crude mixture] with the eluent as indicated. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With tris(2,2’--bipyrazyl)ruthenium(II) bis(tetrakis(3,5-bis(trifluoromethyl)phenyl)borate) In dichloromethane at 20℃; for 2h; Irradiation; regioselective reaction; | |
91% | With lithium perchlorate; titanium(IV) oxide In nitromethane at 20℃; for 2h; UV-irradiation; | |
73 %Spectr. | In nitromethane at 20℃; Electrochemical reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
38% | With [Ru(η5-C5Me5)(CH3CN){P(OEt)3}2]BPh4 In water at 95℃; for 18h; | 2.3. Catalytic procedure General procedure: In a 3 mL vial were introduced the surfactant followed by water(1 mL). The mixture was stirred until complete dissolution and formation of a clear solution. To this, catalyst 1 (0.005 mmol) was added and the mixture was stirred for 10 min, followed by allylbenzene(50 eq. with respect to 1). The mixture was heated at 95 C under stirring at 750 rpm. After 18 h the aqueous reaction mixture was extracted two times with ethyl acetate and the organic phase was analyzed by GC and GC-MS. The structure ofthe isomerized products were confirmed by GC-MS and 1H NMR. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 77.3% 2: 45.1% | With silica gel In water at 400℃; Inert atmosphere; | 5 Preparation of 1-methoxy-4-(1-propenyl)benzene (anethole) from 1,1-bis(4-methoxy-phenyl)propane (examples 1-6) Preparation of 1-methoxy-4-(1-propenyl)benzene (anethole) from 1,1-bis(4-methoxy-phenyl)propane (examples 1-6) (0052) Several cleavage experiments to cleave 1,1-bis(4-methoxyphenyl)propane (Dimer1) to anisole and anethole were conducted. The reactor used was a gas phase oven with an internal diameter of 4 cm and electric heating. The latter was filled first with quartz rings for a distance of 15 cm and then with catalyst strands having a strand diameter of 3 mm for a distance of 20 cm. The part of the gas phase oven filled with quartz rings serves as evaporator zone for the 1,1-bis(4-methoxyphenyl)propane supplied in trickle mode and any solvent added. The carrier gas used was nitrogen. The reaction product was condensed at a temperature of 5° C. in the bottom and in a downstream cooler. When a solvent was used, water in this case, it was run into the evaporator zone together with 1,1-bis(4-methoxyphenyl)propane in two separate feeds. The analysis of the organic products was effected in the experiments after removal and discarding of the aqueous phase. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
27.2% | With 10% phosphoric acid on silica In water at 350℃; Inert atmosphere; | 5 Preparation of 1-methoxy-4-(1-propenyl)benzene (anethole) from 1,1-bis(4-methoxy-phenyl)propane (examples 1-6) General procedure: Preparation of 1-methoxy-4-(1-propenyl)benzene (anethole) from 1,1-bis(4-methoxy-phenyl)propane (examples 1-6) (0052) Several cleavage experiments to cleave 1,1-bis(4-methoxyphenyl)propane (Dimer1) to anisole and anethole were conducted. The reactor used was a gas phase oven with an internal diameter of 4 cm and electric heating. The latter was filled first with quartz rings for a distance of 15 cm and then with catalyst strands having a strand diameter of 3 mm for a distance of 20 cm. The part of the gas phase oven filled with quartz rings serves as evaporator zone for the 1,1-bis(4-methoxyphenyl)propane supplied in trickle mode and any solvent added. The carrier gas used was nitrogen. The reaction product was condensed at a temperature of 5° C. in the bottom and in a downstream cooler. When a solvent was used, water in this case, it was run into the evaporator zone together with 1,1-bis(4-methoxyphenyl)propane in two separate feeds. The analysis of the organic products was effected in the experiments after removal and discarding of the aqueous phase. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With 1,1,1,3',3',3'-hexafluoro-propanol; Pentafluorobenzoic acid In dichloromethane at 20℃; for 1h; regioselective reaction; | Typical procedure for the coupling of QMA 4a with alkene nucleophiles 2 leading to benzodifurans5. General procedure: To a stirred solution of QMA 4a (242 mg, 1.0 mmol) and alkene nucleophile 2a (208 mg, 2.0 mmol) inthe mixture of HFIP (2.5 mL) and dichloromethane (2.5 mL), pentafluorobenzoic acid (212 mg, 1.0mmol) was added in one portion at room temperature. The reaction mixture was stirred for 1 h, thensolvent as removed in vacuo. The residue was purified by column chromatography on silica-gel(hexane/EtOAc = 10/1) to give 2,6-diphenyl-2,3,6,7-tetrahydrobenzo[1,2-b:4,5-b’]difuran 5aa (286 mg,0.91 mmol) in 91% yield. The product 5aa was obtained as the mixture of two diastereomers. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
67% | With cerium(IV) sulfate tetrahydrate; magnesium sulfate In toluene at 20℃; for 24h; | General procedure for the Ce(SO4)2•4H2O oxidative cyclization of benzoquinonewith olefin General procedure: Method A: To a reaction tube 32.4 mg (0.3 mmol) BQ was added in. Then 363.9 mg (0.9 mmol) Ce(SO4)2•4H2O and 216.7 mg (1.8 mmol) MgSO4 were added in the tube. After adding 3 mLtoluene, 2.1 mmol of olefin was added in the tube. The reaction tube was stirred for 24 h at room temperature. When the reaction was finished the reaction mixture was filtered using a sand core funnel. The pure product was obtained by flash column chromatography on silica gel (petroleum and acetic ether). The yields were determined by isolated yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With cerium(IV) sulfate tetrahydrate; magnesium sulfate In toluene at 20℃; for 24h; | General procedure for the Ce(SO4)2•4H2O oxidative cyclization of[1,4]naphthoquinone with olefin General procedure: Method B: To a reaction tube 47.4 mg (0.3 mmol) BQ was added in. Then 363.9 mg (0.9 mmol) Ce(SO4)2•4H2O and 216.7 mg (1.8 mmol) MgSO4 were added in the tube. After adding 3 mLtoluene, 2.1 mmol of olefin was added in the tube. The reaction tube was stirred for 24 h at room temperature. When the reaction was finished the reaction mixture was filtered using a sand corefunnel. The pure product was obtained by flash column chromatography on silica gel (petroleum and acetic ether). The yields were determined by isolated yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With conjugated microporous poly(benzothiadiazole) In nitromethane at 20℃; for 8h; UV-irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With 9-(2-methylphenyl)-1,3,6,8-tetramethoxythioxanthylium trifluoromethanesulfonate In nitromethane at 20℃; for 2h; Irradiation; regioselective reaction; | |
88% | With iron perchlorate hexahydrate In ethyl acetate at 40℃; for 24h; diastereoselective reaction; | |
88% | With iron perchlorate hexahydrate In ethyl acetate at 40℃; for 24h; | 1 Example 1 In a 10 mL round bottom flask, styrene (583 μL, 5.0 mmol) was dissolved in 3 mL of ethyl acetate, then Fe(ClO4)3.6Η2Ο (35.4 mg, 10 mol%) was added, and finally trans-anethole was added (162 mg, 1.0 mmol) dissolved in 1 mL of ethyl acetate and added dropwise to the above solution at a rate of 2 mL/h by microinjection of the pump. The reaction was stirred at 40 °C for 24 hours under atmospheric conditions. After the reaction was completed, it was rotated. The solvent was evaporated to dryness on an evaporator, and then purified by silica gel column chromatography, eluted with chloroform and petroleum ether as eluent to give 1-methoxy-4-[(1RS, 2SR, 4RS) as a colorless oil. 2-methyl-4-phenylcyclobutyl)benzene 222 mg, yield 88%. |
86% | With Fe(3,4,7,8-tetramethyl-1,10-phenanthroline)<SUB>3</SUB>(PF<SUB>6</SUB>)<SUB>3</SUB> In 2,2,2-trifluoroethanol; 1,2-dichloro-ethane at 20℃; for 3h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With 9-(2-methylphenyl)-1,3,6,8-tetramethoxythioxanthylium trifluoromethanesulfonate In nitromethane at 20℃; for 2h; Irradiation; regioselective reaction; | |
78% | With Fe(3,4,7,8-tetramethyl-1,10-phenanthroline)<SUB>3</SUB>(PF<SUB>6</SUB>)<SUB>3</SUB> In 2,2,2-trifluoroethanol; 1,2-dichloro-ethane at 20℃; for 3h; | |
75% | With iron perchlorate hexahydrate In ethyl acetate at 40℃; for 24h; diastereoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With 9-(2-methylphenyl)-1,3,6,8-tetramethoxythioxanthylium trifluoromethanesulfonate In nitromethane at 20℃; for 3h; Irradiation; regioselective reaction; | |
88% | With iron perchlorate hexahydrate In ethyl acetate at 40℃; for 24h; diastereoselective reaction; | |
85% | With Fe(3,4,7,8-tetramethyl-1,10-phenanthroline)<SUB>3</SUB>(PF<SUB>6</SUB>)<SUB>3</SUB> In 2,2,2-trifluoroethanol; 1,2-dichloro-ethane at 0℃; for 3h; |
80% | With iron(III) chloride; 2,5-Dimethyl-2,4-hexadiene In acetonitrile at 0℃; for 24h; | |
24 %Spectr. | With 2,3,5,6-tetrafluoro-1,4-benzoquinone; C80H48N8Pd2 In dichloromethane-d2 at 26.84℃; for 1h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With iron(III) trifluoromethanesulfonate; 2,5-Dimethyl-2,4-hexadiene In acetonitrile at 20℃; for 5h; | |
85% | With Fe(3,4,7,8-tetramethyl-1,10-phenanthroline)<SUB>3</SUB>(PF<SUB>6</SUB>)<SUB>3</SUB> In 2,2,2-trifluoroethanol; 1,2-dichloro-ethane at 20℃; for 6h; | |
70% | With iron perchlorate hexahydrate In ethyl acetate at 40℃; for 24h; diastereoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
55% | With iron perchlorate hexahydrate In ethyl acetate at 40℃; for 24h; diastereoselective reaction; | |
55% | With iron perchlorate hexahydrate In ethyl acetate at 40℃; for 24h; | 14 Example 14 In 10mL round-bottomed flask, β- methylstyrene (583μL, 5.0mmol) was dissolved in 3mL of ethyl acetate, thenadded of Fe (ClO. 4). 3.6H2O (35.4 mg, 10 mol%), and finally trans-anethole (148mg, 1.0mmol) was dissolved in 1mLof ethyl acetate by syringe pump at a rate of 2mL h / added dropwise to the solution and the reaction was stirred at 40 atmospheric conditionsstirred for 24 hours, the reaction was complete after The solvent was evaporated to dryness on a rotary evaporator, and then purified by silica gel column chromatography, eluted with chloroform andpetroleum ether as eluent to give the product as a colorless oil 1-[(1RS, 2SR, 3SR, 4RS)-2 , 3-dimethyl-4-phenylcyclobutyl]-4-methoxybenzene 146 mg, yield 55%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With [Ir(2-(2,4-difluorophenyl)-4-(trifluoromethyl)pyridine)2(5,5'-bis(trifluoromethyl)-2,2'-bipyridine)]PF6; Potassium benzoate In N,N-dimethyl-formamide at 23℃; Irradiation; diastereoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With [Ir(2-(2,4-difluorophenyl)-4-(trifluoromethyl)pyridine)2(5,5'-bis(trifluoromethyl)-2,2'-bipyridine)]PF6; Potassium benzoate In N,N-dimethyl-formamide at 23℃; Irradiation; diastereoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With [Ir(2-(2,4-difluorophenyl)-4-(trifluoromethyl)pyridine)2(5,5'-bis(trifluoromethyl)-2,2'-bipyridine)]PF6; Potassium benzoate In N,N-dimethyl-formamide at 23℃; Irradiation; diastereoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
39% | Stage #1: 2-amino-phenol With nitrosyl hexafluorophosphate In acetonitrile at 0℃; for 2h; Stage #2: E-1-(4'-methoxyphenyl)prop-1-ene With tris-(dibenzylideneacetone)dipalladium(0); zinc(II) carbonate In acetonitrile at 20℃; for 20h; | 4.2.8. Heck oxyarylation (general procedure H) General procedure: One-pot diazotization and Heck oxyarylation between 12a-cand 2a-h was performed using optimized reaction conditions reportedin literature [27,56]. In brief, the corresponding o-aminophenol(1 mmol) was dissolved in ACN (9 mL) and cooled to 0 C.Then, NOPF6 (1 mmol) was added in one portion. Immediate formationof brown gas was observed. After 2 h of stirring at thattemperature, ZnCO3 (2 mmol), Pd2(dba)3 (5 mol%) and phenylpropenederivative (1.2 mmol) were added. The resulting darkened mixturewas stirred at rt for 20 h and then 10% NaHCO3 (30 mL)wasadded. The mixture was filtered over a Celite pad and the filtrateextracted with EtOAc (3x). The combined organic layers were driedover anhydrous Na2SO4 and the solvent removed under reducedpressure. The product was purified by chromatography asindicated. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | Stage #1: 2,2'-dipyridyldisulphide With bromine In dichloromethane at 20℃; for 0.5h; Stage #2: E-1-(4'-methoxyphenyl)prop-1-ene In dichloromethane at 20℃; for 24h; regioselective reaction; | trans-3-(4-Methoxyphenyl)-2-methyl-2H,3H-thiazolo[3,2-]pyridin-4-ium bromide(13) A solution of bromine (0.122 g, 0.76 mmol) in methylene chloride (8 mL) was added dropwise to a solution of di(2-pyridine) disulfide (0.168 g, 0.76 mmol) in methylene chloride (8 mL) and the mixture was stirred for 30 min at room temperature. A solution of trans-anethole (0.225 g, 1.52 mmol) in methylene chloride (8 mL) was added dropwise and the reaction mixture stirred for 24 h at room temperature. The mixture was filtered and the solvent was removed by rotary evaporator. The residue was dried in vacuum giving the product (0.411 g, 80% yield) as a light yellow oil.1H-NMR (400 MHz, D2O): δ 1.57-1.58 (m, 3H, CH3), 3.88 (s, 3H, CH3), 4.51-4.58 (m, 1H, SCH), 5.91 (d,J= 10.6 Hz, 1H, NCH), 7.13-7.15 (m, 2H, Ar), 7.47-7.49 (m, 2H, Ar), 7.58-7.60 (m, 1H, Py), 7.99-8.01 (m, 1H, Py), 8.12-8.14 (m, 1H, Py), 8.26-8.30 (m, 1H, Py).13C-NMR (101 MHz, D2O): δ 15.98 (H3), 49.50 (SCH), 55.54 (H3), 81.15 (N+CH), 115.26 (6H4), 122.77 (Py), 123.48 (Py), 125.00 (6H4), 130.31 (6H4), 141.29 (Py), 144.79 (Py), 159.80 (NCS, Py), 160.66 (H3, 6H4). Anal. Calcd for C15H16NBrOS: 53.26, H 4.77, N 4.14, Br 23.62, S 9.48. Found: 53.58, H 4.90, N 4.32, Br 23.92, S 9.71. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | Stage #1: pyridin-2-yl sulfenyl chloride With sulfuryl dichloride In dichloromethane at 20℃; for 0.166667h; Stage #2: E-1-(4'-methoxyphenyl)prop-1-ene In dichloromethane at 20℃; for 20h; regioselective reaction; | 2-[(3,4-dimethoxyphenyl)methyl]-2H,3H-[1,3]thiazolo[3,2-]pyridin-4-ium chloride(5) General procedure: A solution of sulfuryl chloride (0.068 g, 0.5 mmol) in methylene chloride (7 mL) was added dropwise to a solution of di(2-pyridine) disulfide (0.109 g, 0.5 mmol) in methylene chloride (7 mL) and the mixture was stirred for 10 min at room temperature. A solution of methyl eugenol (0.178 g, 1 mmol) in methylene chloride (7 mL) was added dropwise and the reaction mixture was stirred for 20 h at room temperature. The solvent was removed by rotary evaporator (RE-52AA, Xi’an Heb Biotechnology Co., Xi’an, China) and the residue was dried in vacuum giving the product (0.324 g, quantitative yield) as a light yellow oil. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | Stage #1: 2,2'-dipyridyldiselenide With sulfuryl dichloride In chloroform at 20℃; for 0.333333h; Stage #2: E-1-(4'-methoxyphenyl)prop-1-ene In chloroform at 20℃; for 5h; Reflux; regioselective reaction; | trans-3-(4-Methoxyphenyl)-2-methyl-2H,3H-selenazolo[3,2-]pyridin-4-ium chloride(12) A solution of sulfuryl chloride (0.122 g, 0.9 mmol) in chloroform (10 mL) was added dropwise to a solution of di(2-pyridine) diselenide (0.28 g, 0.9 mmol) in chloroform (20 mL) and the mixture was stirred for 20 min at room temperature. A solution of trans-anethole (0.266 g, 1.8 mmol) in chloroform (10 mL) was added dropwise and the reaction mixture stirred for 1 h at room temperature and 4 h at reflux temperature. The solvent was removed by rotary evaporator and the residue was dried in vacuum giving the product (0.613 g) in quantitative yield as a yellowish powder, mp 141-143 °C.1H-NMR (400 MHz, D2O): δ 1.67 (d,J= 6.6 Hz, 3H, CH3,), 3.83 (s, 3H, CH3), 4.60 (qd,J= 13.4, 6.6 Hz, 1H, SeCH), 5.97 (d, 1H,J= 9.4 Hz, NCH), 7.12 (dd,J= 9.0, 2.5 Hz, 2H, Ar), 7.41 (dd,J= 9.0, 2.5 Hz, 2H, Ar), 7.63-7.66 (m, 1H, Py), 8.16-8.26 (m, 3H, Py).13C-NMR (101 MHz, D2O): δ 17.54 (H3), 45.62 (SeCH), 55.69 (H3), 83.78 (NCH), 115.37 (Ar), 123.60 (Py), 126.10 (Ar), 127.76 (Py), 130.05 (Ar), 142.96 (Py), 144.21 (Py), 158.58 (NCSe, Py), 160.61 (H3, Ar). Anal. Calcd for C15H16NclOSe: 52.88, H 4.73, N 4.11, Cl 10.41, Se 23.18. Found: 53.11, H 4.93, N 4.36, Cl 10.60, Se 23.40. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | Stage #1: 2,2'-dipyridyldiselenide With bromine In chloroform at 20℃; for 0.333333h; Stage #2: E-1-(4'-methoxyphenyl)prop-1-ene In chloroform at 20℃; for 6h; Reflux; regioselective reaction; | trans-3-(4-Methoxyphenyl)-2-methyl-2H,3H-[1,3]selenazolo[3,2-]pyridin-4-ium bromide(16) A solution of bromine (0.051 g, 0.32 mmol) in chloroform (10 mL) was added dropwise to a solution of di(2-pyridine) diselenide (0.1 g, 0.32 mmol) in chloroform (10 mL) and the mixture was stirred for 20 min at room temperature. A solution of trans-anethole (0.095 g, 0.64 mmol) in chloroform (10 mL) was added dropwise and the reaction mixture stirred for 1 h at room temperature and 5 h at reflux temperature. The mixture was filtered and the solvent was removed by rotary evaporator. The residue was dried in vacuum giving the product (0.234 g, 95% yield) as a light orange oil.1H-NMR (400 MHz, D2O): δ 1.62 (d,J= 6.5 Hz, 3H, CH3,), 3.85 (s, 3H, CH3), 4.57-4.61 (m, 1H, SeCH), 5.91 (d, 1H,J= 9.7 Hz, NCH), 7.10 (d,J= 8.3 Hz, 2H, Ar), 7.39 (d,J= 8.3 Hz, 2H, Ar), 7.59-7.60 (m, 1H, Py), 8.11-8.20 (m, 3H, Py).13C-NMR (101 MHz, D2O): δ 17.19 (H3), 45.48 (SeCH), 55.56 (H3), 83.68 (NCH), 115.25 (Ar), 123.41 (Py), 125.84 (Ar), 127.61 (Py), 130.05 (Ar), 142.85 (Py), 144.02 (Py), 158.47 (NCSe, Py), 160.52 (H3, Ar). Anal. Calcd for C15H16NbrOSe: 46.78, H 4.19, N 3.64, Br 20.75, Se 20.50. Found: 48.02, H 4.48, N 3.98, Br 21.03, Se 20.21. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
50% | With 1,1,1,3',3',3'-hexafluoro-propanol; crithmene In acetonitrile at 20℃; Electrochemical reaction; | 6.2. General procedure A Alkene (1.0 equiv., 2.0 mmol), together with amine (5.0 equiv., 10.0 mmol), hexafluoroisopropanol(HFIP, 5.0 equiv., 10.0 mmol, 1.05 mL) and γ-terpinene (0.5 equiv., 1.0 mmol, 0.16 mL) were dissolvedin acetonitrile using a 20 mL volumetric flask (0.1M). The mixture was swirled until homogeneous andplaced in a 20 ml disposable syringe. The solution was pumped through the electrochemical setup witha fixed flowrate of 0.15 mL/min to give a residence time of 5 minutes in the active part of the reactor,equipped with a graphite anode, steel cathode divided by a 0.25 mm thick Teflon gasket. The firstfraction was discarded after which a constant current (selected on the basis of the voltammogramsrecorded) was applied. The reaction mixture was collected in a vial cooled at 0°C for 67 minutes, whichcorresponds to 1.0 mmol scale. The crude mixture was concentrated under vacuum at roomtemperature, to prevent decomposition of the product and directly purified by flash columnchromatography on silica gel. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | With 1,1,1,3',3',3'-hexafluoro-propanol; crithmene In acetonitrile at 20℃; Electrochemical reaction; | 6.2. General procedure A Alkene (1.0 equiv., 2.0 mmol), together with amine (5.0 equiv., 10.0 mmol), hexafluoroisopropanol(HFIP, 5.0 equiv., 10.0 mmol, 1.05 mL) and γ-terpinene (0.5 equiv., 1.0 mmol, 0.16 mL) were dissolvedin acetonitrile using a 20 mL volumetric flask (0.1M). The mixture was swirled until homogeneous andplaced in a 20 ml disposable syringe. The solution was pumped through the electrochemical setup witha fixed flowrate of 0.15 mL/min to give a residence time of 5 minutes in the active part of the reactor,equipped with a graphite anode, steel cathode divided by a 0.25 mm thick Teflon gasket. The firstfraction was discarded after which a constant current (selected on the basis of the voltammogramsrecorded) was applied. The reaction mixture was collected in a vial cooled at 0°C for 67 minutes, whichcorresponds to 1.0 mmol scale. The crude mixture was concentrated under vacuum at roomtemperature, to prevent decomposition of the product and directly purified by flash columnchromatography on silica gel. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
41% | With 1,1,1,3',3',3'-hexafluoro-propanol; crithmene In acetonitrile at 20℃; Electrochemical reaction; | 6.2. General procedure A Alkene (1.0 equiv., 2.0 mmol), together with amine (5.0 equiv., 10.0 mmol), hexafluoroisopropanol(HFIP, 5.0 equiv., 10.0 mmol, 1.05 mL) and γ-terpinene (0.5 equiv., 1.0 mmol, 0.16 mL) were dissolvedin acetonitrile using a 20 mL volumetric flask (0.1M). The mixture was swirled until homogeneous andplaced in a 20 ml disposable syringe. The solution was pumped through the electrochemical setup witha fixed flowrate of 0.15 mL/min to give a residence time of 5 minutes in the active part of the reactor,equipped with a graphite anode, steel cathode divided by a 0.25 mm thick Teflon gasket. The firstfraction was discarded after which a constant current (selected on the basis of the voltammogramsrecorded) was applied. The reaction mixture was collected in a vial cooled at 0°C for 67 minutes, whichcorresponds to 1.0 mmol scale. The crude mixture was concentrated under vacuum at roomtemperature, to prevent decomposition of the product and directly purified by flash columnchromatography on silica gel. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
45% | With 1,1,1,3',3',3'-hexafluoro-propanol; crithmene In acetonitrile at 20℃; Electrochemical reaction; | 6.2. General procedure A Alkene (1.0 equiv., 2.0 mmol), together with amine (5.0 equiv., 10.0 mmol), hexafluoroisopropanol(HFIP, 5.0 equiv., 10.0 mmol, 1.05 mL) and γ-terpinene (0.5 equiv., 1.0 mmol, 0.16 mL) were dissolvedin acetonitrile using a 20 mL volumetric flask (0.1M). The mixture was swirled until homogeneous andplaced in a 20 ml disposable syringe. The solution was pumped through the electrochemical setup witha fixed flowrate of 0.15 mL/min to give a residence time of 5 minutes in the active part of the reactor,equipped with a graphite anode, steel cathode divided by a 0.25 mm thick Teflon gasket. The firstfraction was discarded after which a constant current (selected on the basis of the voltammogramsrecorded) was applied. The reaction mixture was collected in a vial cooled at 0°C for 67 minutes, whichcorresponds to 1.0 mmol scale. The crude mixture was concentrated under vacuum at roomtemperature, to prevent decomposition of the product and directly purified by flash columnchromatography on silica gel. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
53% | With 1,1,1,3',3',3'-hexafluoro-propanol; crithmene In acetonitrile at 20℃; Electrochemical reaction; | 6.2. General procedure A Alkene (1.0 equiv., 2.0 mmol), together with amine (5.0 equiv., 10.0 mmol), hexafluoroisopropanol(HFIP, 5.0 equiv., 10.0 mmol, 1.05 mL) and γ-terpinene (0.5 equiv., 1.0 mmol, 0.16 mL) were dissolvedin acetonitrile using a 20 mL volumetric flask (0.1M). The mixture was swirled until homogeneous andplaced in a 20 ml disposable syringe. The solution was pumped through the electrochemical setup witha fixed flowrate of 0.15 mL/min to give a residence time of 5 minutes in the active part of the reactor,equipped with a graphite anode, steel cathode divided by a 0.25 mm thick Teflon gasket. The firstfraction was discarded after which a constant current (selected on the basis of the voltammogramsrecorded) was applied. The reaction mixture was collected in a vial cooled at 0°C for 67 minutes, whichcorresponds to 1.0 mmol scale. The crude mixture was concentrated under vacuum at roomtemperature, to prevent decomposition of the product and directly purified by flash columnchromatography on silica gel. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | With 1,1,1,3',3',3'-hexafluoro-propanol; crithmene In acetonitrile at 20℃; Electrochemical reaction; | 6.2. General procedure A Alkene (1.0 equiv., 2.0 mmol), together with amine (5.0 equiv., 10.0 mmol), hexafluoroisopropanol(HFIP, 5.0 equiv., 10.0 mmol, 1.05 mL) and γ-terpinene (0.5 equiv., 1.0 mmol, 0.16 mL) were dissolvedin acetonitrile using a 20 mL volumetric flask (0.1M). The mixture was swirled until homogeneous andplaced in a 20 ml disposable syringe. The solution was pumped through the electrochemical setup witha fixed flowrate of 0.15 mL/min to give a residence time of 5 minutes in the active part of the reactor,equipped with a graphite anode, steel cathode divided by a 0.25 mm thick Teflon gasket. The firstfraction was discarded after which a constant current (selected on the basis of the voltammogramsrecorded) was applied. The reaction mixture was collected in a vial cooled at 0°C for 67 minutes, whichcorresponds to 1.0 mmol scale. The crude mixture was concentrated under vacuum at roomtemperature, to prevent decomposition of the product and directly purified by flash columnchromatography on silica gel. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62% | With 1,1,1,3',3',3'-hexafluoro-propanol; crithmene In acetonitrile at 20℃; Electrochemical reaction; | 6.2. General procedure A Alkene (1.0 equiv., 2.0 mmol), together with amine (5.0 equiv., 10.0 mmol), hexafluoroisopropanol(HFIP, 5.0 equiv., 10.0 mmol, 1.05 mL) and γ-terpinene (0.5 equiv., 1.0 mmol, 0.16 mL) were dissolvedin acetonitrile using a 20 mL volumetric flask (0.1M). The mixture was swirled until homogeneous andplaced in a 20 ml disposable syringe. The solution was pumped through the electrochemical setup witha fixed flowrate of 0.15 mL/min to give a residence time of 5 minutes in the active part of the reactor,equipped with a graphite anode, steel cathode divided by a 0.25 mm thick Teflon gasket. The firstfraction was discarded after which a constant current (selected on the basis of the voltammogramsrecorded) was applied. The reaction mixture was collected in a vial cooled at 0°C for 67 minutes, whichcorresponds to 1.0 mmol scale. The crude mixture was concentrated under vacuum at roomtemperature, to prevent decomposition of the product and directly purified by flash columnchromatography on silica gel. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
57% | With 1,1,1,3',3',3'-hexafluoro-propanol; crithmene In acetonitrile at 20℃; Electrochemical reaction; | 6.2. General procedure A Alkene (1.0 equiv., 2.0 mmol), together with amine (5.0 equiv., 10.0 mmol), hexafluoroisopropanol(HFIP, 5.0 equiv., 10.0 mmol, 1.05 mL) and γ-terpinene (0.5 equiv., 1.0 mmol, 0.16 mL) were dissolvedin acetonitrile using a 20 mL volumetric flask (0.1M). The mixture was swirled until homogeneous andplaced in a 20 ml disposable syringe. The solution was pumped through the electrochemical setup witha fixed flowrate of 0.15 mL/min to give a residence time of 5 minutes in the active part of the reactor,equipped with a graphite anode, steel cathode divided by a 0.25 mm thick Teflon gasket. The firstfraction was discarded after which a constant current (selected on the basis of the voltammogramsrecorded) was applied. The reaction mixture was collected in a vial cooled at 0°C for 67 minutes, whichcorresponds to 1.0 mmol scale. The crude mixture was concentrated under vacuum at roomtemperature, to prevent decomposition of the product and directly purified by flash columnchromatography on silica gel. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With 1,1,1,3',3',3'-hexafluoro-propanol; crithmene In acetonitrile at 20℃; Electrochemical reaction; | 6.2. General procedure A Alkene (1.0 equiv., 2.0 mmol), together with amine (5.0 equiv., 10.0 mmol), hexafluoroisopropanol(HFIP, 5.0 equiv., 10.0 mmol, 1.05 mL) and γ-terpinene (0.5 equiv., 1.0 mmol, 0.16 mL) were dissolvedin acetonitrile using a 20 mL volumetric flask (0.1M). The mixture was swirled until homogeneous andplaced in a 20 ml disposable syringe. The solution was pumped through the electrochemical setup witha fixed flowrate of 0.15 mL/min to give a residence time of 5 minutes in the active part of the reactor,equipped with a graphite anode, steel cathode divided by a 0.25 mm thick Teflon gasket. The firstfraction was discarded after which a constant current (selected on the basis of the voltammogramsrecorded) was applied. The reaction mixture was collected in a vial cooled at 0°C for 67 minutes, whichcorresponds to 1.0 mmol scale. The crude mixture was concentrated under vacuum at roomtemperature, to prevent decomposition of the product and directly purified by flash columnchromatography on silica gel. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | With aluminum(III) fluoride; nickel(II) tetrafluoroborate hexahydrate; trimethoxysilane; (3aS,3'aS,8aR,8'aR)-8,8a,8',8'a-tetrahydro-3aH,3'aH-2,2'-biindeno[1,2-d]oxazole; sodium iodide; zinc In toluene at 0℃; for 24h; Inert atmosphere; Glovebox; enantioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
56% | With aluminum(III) fluoride; nickel(II) tetrafluoroborate hexahydrate; trimethoxysilane; (3aS,3'aS,8aR,8'aR)-8,8a,8',8'a-tetrahydro-3aH,3'aH-2,2'-biindeno[1,2-d]oxazole; sodium iodide; zinc In toluene at 15℃; for 24h; Inert atmosphere; Glovebox; enantioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
50% | With cobalt(II) tetrafluoroborate hexahydrate; N-isopropyl-N,2-dimethylpropan-2-amine In water; N,N-dimethyl-formamide at 80℃; for 24h; Schlenk technique; | b-Fluoroalkyl Alcohols 3-1-3-38; General Procedure General procedure: To a 50-mL of Schlenk flask were added sequentially Co(BF4)2·6H2O(0.1 mmol, 0.1 equiv), CH3CN (4 mL), RfBr (1.5 mmol, 1.5 equiv),alkene (1 mmol), N-isopropyl-N-methyl-tert-butylamine (4 mmol, 4equiv), and water (75 L). Then the flask was equipped with an airballoon and stirred at 65 °C for 24 h. The mixture was cooled to rt andfiltered through a pad of Celite. The filtrate was concentrated, and theresidue was purified by silica gel chromatography. |
Tags: 4180-23-8 synthesis path| 4180-23-8 SDS| 4180-23-8 COA| 4180-23-8 purity| 4180-23-8 application| 4180-23-8 NMR| 4180-23-8 COA| 4180-23-8 structure
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H305 | May be harmful if swallowed and enters airways |
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H311 | Toxic in contact with skin |
H312 | Harmful in contact with skin |
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H315 | Causes skin irritation |
H316 | Causes mild skin irritation |
H317 | May cause an allergic skin reaction |
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H319 | Causes serious eye irritation |
H320 | Causes eye irritation |
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H332 | Harmful if inhaled |
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H335 | May cause respiratory irritation |
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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 |
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