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CAS No. : | 100-86-7 | MDL No. : | MFCD00004465 |
Formula : | C10H14O | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | RIWRBSMFKVOJMN-UHFFFAOYSA-N |
M.W : | 150.22 | Pubchem ID : | 7531 |
Synonyms : |
|
Num. heavy atoms : | 11 |
Num. arom. heavy atoms : | 6 |
Fraction Csp3 : | 0.4 |
Num. rotatable bonds : | 2 |
Num. H-bond acceptors : | 1.0 |
Num. H-bond donors : | 1.0 |
Molar Refractivity : | 47.03 |
TPSA : | 20.23 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) : | -5.68 cm/s |
Log Po/w (iLOGP) : | 2.17 |
Log Po/w (XLOGP3) : | 2.16 |
Log Po/w (WLOGP) : | 2.0 |
Log Po/w (MLOGP) : | 2.49 |
Log Po/w (SILICOS-IT) : | 2.37 |
Consensus Log Po/w : | 2.24 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 2.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -2.4 |
Solubility : | 0.593 mg/ml ; 0.00395 mol/l |
Class : | Soluble |
Log S (Ali) : | -2.22 |
Solubility : | 0.91 mg/ml ; 0.00606 mol/l |
Class : | Soluble |
Log S (SILICOS-IT) : | -3.03 |
Solubility : | 0.14 mg/ml ; 0.000931 mol/l |
Class : | Soluble |
PAINS : | 0.0 alert |
Brenk : | 0.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 1.0 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P264-P270-P301+P312+P330-P501 | UN#: | N/A |
Hazard Statements: | H302 | Packing Group: | N/A |
GHS Pictogram: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With aluminum (III) chloride; triphenylphosphine; In nitromethane; at 80℃; for 2h; | General procedure: In a typical reaction, alcohol (0.4 mmol) was mixed with AlCl3 (0.02 mmol, 5 mol%) and triphenylphosphine (PPh3, 0.02 mmol, 5 mol%) in nitromethane (1.0 mL). Thereafter the mixture was stirred at 80 C for 2 h. After the reaction, the mixture was cooled to room temperature, and the product was isolated using preparative thin layer chromatography (TLC, eluting solution: petroleum ether/ethyl acetate, 5/1 (v/v)). Tests for substrate scope were all performed with an analogous procedure. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With SiO2 coated on magnetic CoFe2O4 nanoparticle immobilized N-propyldiethylenetriamine sulfamic acid; at 80℃; for 4h;Green chemistry; | General procedure: A mixture of alcohol (1 mmol), nitrile (1 mmol),CoFe2O4SiO2-DASA (0.1 g) was heated at 80C under solvent-free conditions. The reaction process was monitored by thin layerchromatography (TLC). After completion of the reaction, the reaction mixture was cooled to room temperature and ethyl acetate(5 mL) was added. The catalyst was removed by using a magnetand washed with ethyl acetate. The combined organic layers weredried over anhydrous MgSO4, and the solvent was evaporated under reduced pressure. The pure product was obtained by column chromatography on silica gel using hexane/ethyl acetate as eluent. |
To a mixture of <strong>[100-86-7]2-methyl-1-phenyl-2-propanol</strong> (1.5 g, 10 mmol) and acetonitrile (3 mL) in acetic acid (15 mL) was added concentrated sulfuric acid (3 mL) dropwise at room temperature. The mixture was stirred at 65 C. for 3 hours and then poured into ice-water (ca. 200 mL). The aqueous solution was basified with saturated aqueous sodium hydroxide until pH>11. The suspension was stirred for further 0.5 hour, and then the precipitated solid was filtered and washed with water. The white solid was air-dried to give N-(2-methyl-1-phenylpropan-2-yl)acetamide (1.5 g, 78% yield), which was used for the next step without further purification.A mixture of N-(2-methyl-1-phenylpropan-2-yl)acetamide (191 mg, 1.00 mmol) and potassium hydroxide (1 g) in ethylene glycol (10 mL) was refluxed for 8 hours. The mixture was diluted with ice-water and extracted with ethyl acetate. The combined organic fractions were washed with water, dried over anhydrous sodium sulfate and concentrated in vacuo to give crude 2-methyl-1-phenylpropan-amine (200 mg) as a brown oil, which was used for the next step without further purification.Compound A14 was synthesized according to the procedure for compound A22, substituting the crude 2-methyl-1-phenylpropan-amine in place of 1-(4-fluorophenyl)-2-methylpropan-2-amine. The product was purified by preparative HPLC to give compound A14 (30 mg, 13% yield for 2 steps) as a white solid: 96.4% purity (HPLC); MS m/z: 480.3 (M+1); 1H NMR (CDCl3, 500 MHz) delta 8.39 (d, J=7.5 Hz, 1H), 7.90 (d, J=7.5 Hz, 1H), 7.65 (t, JHF=54.0 Hz, 1H), 7.42 (m, 2H), 7.28 (m, 3H), 7.16-7.10 (m, 2H), 5.15 (s, 1H), 4.01-3.75 (m, 8H), 3.22 (s, 2H), 1.49 (s, 6H) ppm. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | With phosphoric acid; dihydrogen peroxide; In water; at 45℃; for 5h;Inert atmosphere; | 1-phenyl-2-methyl-2-propanol (3.1 mL, 20 mmol, 1 equiv), hydrogen peroxide (50 v/v % H2O, 2.3 mL, 40 mmol, 2 equiv), and phosphoric acid (85%, 5.8 mL, 100 mmol, 5 equiv) were combined in a round-bottom flask backfilled with nitrogen. The reaction was heated to 45 C. for 5 h at which point the reaction was deemed complete by disappearance of starting material (TLC). The reaction mixture was cooled to room temperature and diluted with hexanes (150 mL). The separated organic layer was washed with deionized water (2×10 mL) and brine (1×10 mL), dried over sodium sulfate, and concentrated in vacuo. The resulting thick and dark oil was purified by silica column chromatography (1.9×30.5 cm) with 5% EA in hexanes to furnish, following concentration in vacuo, 2.192 g (66%) of the hydroperoxide as a light yellow oil. Rf: 0.40 (10% EA/Hex); IR (thin film): 3399 (br), 2981 (m), 1453 (s) cm-1; 1H NMR: delta 1.22 (s, 6H), 2.90 (s, 2H), 7.24 (br m, 5H); 13C NMR: delta 24.0, 44.6, 83.2, 126.4, 128.1, 130.6, 137.7. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With toluene-4-sulfonic acid In dichloromethane for 5h; Ambient temperature; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With ethanol; water at 45℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
B) 1,1,3-Trimethyl-3,4-dihydroisoquinoline To a solution of ethyl cyanoacetate (4.14 g, 33.3 mmol) in dry benzene (85 ml) is added concentrated sulfuric acid keeping the temperature below 5C. After 30 minutes a solution of 2-methyl-1 -phenyl-propan-2-ol in benzene (55 ml) is added over a period of 30 minutes.. The reaction mixture is refluxed for 2.5 h and poured onto ice.. The organic layer is separated and neutralized with concentrated ammonia, extracted with ether, dried and concentrated.. Purification by chromatography (40% ethyl acetate/hexanes) gives the title compound as light yellow oil. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With sulfuric acid; at 5 - 20℃; for 5.08333h; | 100.6 ml of concentrated sulfuric acid (9.4 eq.) are placed in a 500 ml three-necked flask equipped with a condenser and a thermometer, followed by cooling to a temperature in the region of 5- 10C. A mixture containing 30 g of methyl- 1 -phenyl-2-propanol (1 eq.) and 9.83 g of acetonitrile (1 eq.) is added dropwise. The mixture is stirred for 5 minutes at a temperature in the region of 5-10C and then for 5 hours at room temperature (monitoring by TLC, 95/5 CH2Cl2/MeOH). (0210) The mixture is then poured into 1 litre of water and extracted with 100 ml of toluene. The aqueous phase is basified to pH 8.5 with ammonium carbonate and then extracted twice with 500 ml of MTBE (methyl tert-butyl ether). The organic phase is dried over Na2S04, filtered, evaporated to dryness and then dried under vacuum over P205. 27 g (78% yield) of compound (a) are obtained in the form of a yellow liquid. (0211) The NMR and mass analyses are in accordance with the expected structure. |
74% | With sulfuric acid; at 0 - 20℃; for 1h; | Example 2: This example illustrates the preparation of 3,3-dimethyl-1 -pyrrolo[1 ,2-b]pyridazin- 3-yl-4H-isoquinolinea) Preparation of 1 ,3,3-trimethyl-4H-isoquinolineAcetonitrile (1.5 g, 37 mmol) was slowly added to 98% sulfuric acid (50 g, 0.5 mol) at 0 00. Then 2-methyl-i -phenyl-propan-2-ol (5.0 g, 33 mmol) was added to this solution at 0 00 The reaction mixture was allowed to reach room temperature, stirred for 1 h at this temperature and poured on aqueous sodium hydroxide solution of pH 9. The mixture was extracted withethyl acetate, the organic layer washed with water and brine, dried over sodium sulfate and evaporated under reduced pressure to obtain 1 ,3,3-trimethyl-4H-isoquinoline (4.3 g, 25 mmol, 74 %), which was pure enough to be directly used in the next step. 1H-NMR (400 MHz, 0D013): oe (ppm) = 1.20 (s, 6H), 2.37 (s, 3H), 2.69 (s, 2H), 7.14 (d, 1H), 7.27-7.36 (m, 2H), 7.48 (d, 1H). |
With sulfuric acid; In benzene; at 20℃; for 24h; | REFERENCE EXAMPLE 2 1,3,3-trimethyl-3,4-dihydroisoquinolin To conc. sulfuric acid (10 ml) was added a solution of 2-methyl-1-phenylpropan-2-ol (7.0 g) and acetonitrile (1.62 ml) in benzene (7.0 ml) dropwise and the mixture was stirred for 24 hours at room temperature.The mixture was neutralized by adding to a mixture of ice and a saturated aqueous solution of sodium bicarbonate dropwise, and it was extracted with ethyl acetate twice.The extract was dried over anhydrous magnesium sulfate and was concentrated under reduced pressure.The residue was dissolved in ether and was extracted with 1 N hydrochloric acid and 2N hydrochloric acid.The extract was washed with ether and to the mixture was added 5N aqueous solution of sodium hydroxide and was extracted with ether twice.The extract was washed with water and a saturated aqueous solution of sodium chloride successively, and dried over anhydrous magnesium sulfate and was concentrated under reduced pressure to give the title compound (2.53 g) having the following physical data. TLC: Rf 0.22 (hexane:ethyl acetate=2:1); NMR (CDCl3): delta 7.48 (dd, J=7.5, 1.5 Hz, 1H), 7.35 (dt, J=1.5, 7.5 Hz, 1H), 7.30-7.25 (m, 1H), 7.14 (d, J=7.5 Hz, 1H), 2.69 (s, 2H), 2.38 (s, 3H), 1.20 (s, 6H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Methyllithium (1.45M in THF, 49.4 mL, 72.1 mmol) was added slowly to a -78 C. solution of titanium tetrachloride (7.93 mL, 72.1 mmol) in Et2O (250 mL). After the addition was complete, the purple-black solution was warmed to -30 C. and a solution of 1-phenyl-2-propanone (8.64 g, 64.4 mmol) in Et2O (50 mL) was added over 10 min. The solution was warmed to RT and stirring was continued for 4 h before it was quenched with the careful addition of 100 mL of water. The reaction mixture was extracted with Et2O (3*200 mL) and the combined organic extracts were washed with brine (3*100 mL), dried over MgSO4 and evaporated in vacuo to a light yellow liquid, which was used directly in the next step. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With tetrabutyl ammonium fluoride In various solvent(s) for 16h; Ambient temperature; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | 171 g (1 mol) of benzyl bromide was slowly added into 36.5 g (1.5 mol) of magnesium powder in 500 g of dry THF to form a first mixture. The first mixture was gently heated to 50 C. and stirred for 1 hour, and then 69.7 g (1.2 mol) of anhydrous acetone was slowly added to form a second mixture. The second mixture was heated to reflux for 8 hours. After cooling to room temperature, 1000 g of 10% hydrochloric acid was added, and the resulting mixture was extracted with 500 g of dichloromethane twice. Upon separation of the phases, the organic layer was dried with a desiccant (magnesium sulfate). A colorless liquid, 2-methyl-1-phenylpropan-2-ol, with a yield of 95% was obtained after the removal of desiccant and solvent from the organic layer. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With sulfuric acid In benzene at 60℃; for 1h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With sodium hydroxide; In methanol; dichloromethane; at 20℃; for 3.5h; | General procedure: To a solution of the ester (1 mmol) in CH2Cl2 (9 mL) was added a methanolicsolution of 3 N NaOH (1 mL, 3 mmol), with the final concentration of the alkali being 0.3 N, and the solventmixture CH2Cl2/CH3OH (9:1, v/v, 10 mL). Esters bearing more than one ester moiety needed more equivalentsof NaOH (Table 1). After stirring, the solution became cloudy and the sodium salt of the carboxylic acid beganto precipitate. The progress of the reaction was monitored by thin layer chromatography (TLC). The mixturewas stirred until the ester was consumed (Table 1), the solvents were then removed under vacuum, theresidue was diluted with water (10 mL) and extracted with ethyl acetate or diethyl ether (2x20 mL) to isolatethe water-insoluble alcohol, and/or to remove unreacted ester. The aqueous phase was cooled, acidified to pH~2 with dilute HCl and extracted with AcOEt (2x20 mL). The combined organic layers were dried (Na2SO4) andthe solvent removed to afford the acid. Alternatively, the RCOONa precipitated during the reaction can beisolated by filtration, washed with CH2Cl2 (10 mL), dried and weighed (Yields: 80-96%). |
95% | With sodium hydroxide; In methanol; at 20℃; for 24h; | A two-necked reaction flask containing a magnetic stirring bar was charged with1,1-dimethyl-2-phenylethyl acetate (2c, 95.0 mg, 0.49 mmol), NaOH (62.7 mg, 1.57 mmol), andMeOH (3 mL). The reaction mixture was stirred at room temperature for 24 h. The reaction wasneutralized with HCl aq. (2 M), and the mixture was extracted with EtOAc (3 × 20 mL). Thecollected organic layers were dried over Na2SO4. The solution was concentrated under reducedpressure to give the crude product, which was analyzed by 1H NMR spectroscopy using1,1,2,2-tetrachloroethane as an internal standard. Purification by flash column chromatography onsilica gel (hexane/ethyl acetate = 85:15) gave the product as a colorless liquid (70.5 mg, 95% yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With polyvinylpolypyrrolidone-bound boron trifluoride In acetonitrile at 20℃; for 2.5h; | |
93% | With o-benzenedisulfonimide at 20℃; for 0.0833333h; | |
92% | With saccharin sulfonic acid In dichloromethane for 1h; Reflux; |
92% | With silica-sulfuric acid nanoparticles In neat (no solvent) at 20℃; for 0.5h; | |
90% | With magnesium bis(trifluoromethane solfonyl)imide at 20℃; for 1h; | |
90% | With [SnIV(TNH2PP)(OTf)2]*CMP In acetonitrile at 20℃; for 0.133333h; | |
85% | With iodine at 25℃; for 0.166667h; | |
84% | With supported L-pyrrolidine-2-carboxylic acid-4-hydrogen sulfate on Silica Gel at 20℃; for 5h; Green chemistry; | |
81% | With p-toluenesulfonyl chloride at 20℃; for 3h; neat (no solvent); | |
78% | In acetonitrile at 20℃; for 6h; | |
60% | With benzyltriphenylphosphonium tribromide In chloroform for 1h; Reflux; | |
98 % Chromat. | With bismuth(lll) trifluoromethanesulfonate In tetrahydrofuran at 25℃; for 2h; | |
27 % Chromat. | In dimethyl sulfoxide at 50℃; for 24h; | |
95 %Chromat. | With [tetrabutylammonium]8 5,10,15,20-tetrakis(4-hexamolybdato)-porphyrinatotin(IV) chloride In acetonitrile at 20℃; for 0.116667h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
> 99% | quinoline-2-carboxylic acid; cyclopentadienylruthenium(II) trisacetonitrile hexafluorophosphate; In methanol; at 30℃; for 3h;Conversion of starting material; | Table 1 shows the results of the deallylation reaction of the ally ethers represented by general formula (I) given above in the case of using a [CpRu(CH3CN)3]PF6-quinaldic acid composite system as the CpRu(II) complex of the present invention. The reaction was carried out in methanol at 30 C. under the condition of [[CpRu(II)(CH3CN)3]PF6]=[quinaldic acid]=1 mM unless otherwise specified. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With hydrogenchloride In 1,4-dioxane; N,N-dimethyl acetamide at 20℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With 1,3-disulfonic acid imidazolium hydrogen sulfate; In neat (no solvent); at 20℃; for 0.0833333h;Green chemistry; | 2.5.1 (1,1-Dimethyl-2-phenyl-ethoxy)-trimethylsilyl ether IR (neat): nu = 2950, 1450, 1255, 1095, 838, 740, 693 cm-1; 1H NMR (400 MHz, CDCl3): delta = 0.148 (s, 9H), 1.292 (s, 6H), 2.802 (s, 2H), 7.272-7.356 (m, 5H) ppm; MS (EI, 70 eV) m/z: 222 [M+], 207 [M+-CH3], 133 [M+-OTMS]; Anal. calcd for C13H22OSi: C, 70.27; H, 9.90. Found: C, 70.25; H, 9.87. |
93% | With [nano-MCM-41(at)(CH2)3-1-methylimidazole]Br3; In dichloromethane; at 20℃; for 0.5h; | General procedure: To a mixture of alcohol or phenol (1 mmol) and HMDS (2 mmol) in CH2Cl2 (5 ml) was added 10 mmol of [nano-MCM-41(at)(CH2)3-1-methylimidazole]Br3 with stirring at room temperature for the appropriate time (Table3). The progress of the reaction was monitored by TLC. At the end of the reaction, the solvent was evaporated, Et2O (10 mL) was added, and the catalyst was filtered. The filtrates were washed with brine, dried over Na2SO4, and concentrated under reduced pressure to afford the crude product. |
82% | For the tetrahydropyanylation or trimethylsilylation of alcohols, to solution of the DHP(1 mmol) or HMDS(1 mmol) in CH3CN (5ml) were added {K*18-crown-6]Br3}n (0.001 mmol). The solution was stirred at room temperature for 1 min. Then alcohol(1 mmol for THP and 2 mmolf for TMS) was stirred at room temperature for an appropriate time (Table 2). After completion of the reaction, CH3CN was removed by water bath distillation. To the residue was added n-hexane or ethyl acetate(5 ml) and the mixture was filtered (the catalyst is insoluble in n-hexane and ethyl acetate). The filtrate was wahed with n-hexane or ethyl acetate (10 ml*2). The solvent was removed by distillation to yield pure products. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77 % Chromat. | In water at 200℃; for 0.00275h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: 78 percent / AcOH; H2SO4 / 5 h / 20 °C 2: thiourea; AcOH / ethanol / 10 h / Heating | ||
Multi-step reaction with 3 steps 1: 79 percent / H2SO4, AcOH / Ambient temperature; The reagents were added at 0 gradC, then stirring overnight at room temperature. 2: 1. 20percent NaOH, 2. HCl gas / 1.220 gradC, 24h; 3: by neutralization | ||
Multi-step reaction with 2 steps 1: 15.2 g / H2SO4 / acetic acid / 12 h / Ambient temperature 2: aq. KOH / 24 h / 200 °C |
Multi-step reaction with 2 steps 1: acetic acid; sulfuric acid 2: aq. NaOH solution | ||
Multi-step reaction with 2 steps 1.1: sulfuric acid; acetic acid / 20 - 65 °C 1.2: pH > 11 2.1: potassium hydroxide / ethylene glycol / 8 h / Reflux | ||
Multi-step reaction with 2 steps 1: trifluoroacetic acid / 9 h / 50 °C 2: thiourea; acetic acid / ethanol / 10 h / 80 °C | ||
Multi-step reaction with 2 steps 1: sulfuric acid; acetic acid / 0 - 20 °C 2: acetic acid; thiourea / ethanol / 10 h / Reflux | ||
With potassium cyanide; sulfuric acid; acetic acid In water at 0 - 80℃; | 1 Example 1 : 2-Methyl-1-phenyl-propan-2-amine A suspension of potassium cyanide (0.135 g, 1 .997 mmol) in acetic acid (0.22 mL, 3.861 mmol) was prepared and cooled with an ice/water bath to 0-10°C. In the meanwhile a mixture of sulfuric acid (0.255 mL, 4.527 mmol) and acetic acid (0.22 mL, 3.861 mmol) was prepared. A strong exothermic effect was observed. Then the acidic solution was added dropwise to the suspension over 5 min. The reaction mixture changed into a milky suspension. 2-methyl-1-phenyl-propan-2-ol (0.2 g, 1 .331 mmol) was added drop wise to the suspension over 5 min and the reaction mixture was heated to 80°C. After 3h stirring at this temperature water (0.240 mL, 13.314 mmol) was added in one portion and it was stirred over night at 80°C.The cooled down reaction mixture was poured slowly on cold sat. Na2C03-solution. A gas formation could be observed during the addition as expected. It was extracted 3x with fe/ -butyl methyl ether. The organic layers were combined, washed once with brine and dried over Na2S04. It was filtered and evaporated to obtain 2-methyl-1-phenyl-propan-2-amine with a purity of 93.0 % and 89.2 % chemical yield. NMR (400 MHz, CDCb) d ppm 1.15 (s, 6 H) 1.49 (br s, 2 H) 2.69 (s, 2 H) 7.19 - 7.36 (m, 5 H) | |
Multi-step reaction with 2 steps 1: sulfuric acid / acetonitrile / 3 h / 65 °C / Inert atmosphere 2: potassium hydroxide / 1,2-dimethoxyethane / 8 h / Reflux |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: red phosphorus; iodine; aqueous HI 2: concentrated H2SO4; aqueous HNO3 / 0 - 3 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
36% | With trifluorormethanesulfonic acid; In dichloromethane; at -10℃; for 0.5h; | 10,8 g of trifluoromethane sulfonic acid was added dropwise to a mixture of 2 g (10 mmol) 2-chloropyridine-3-carbonitrile and 2,17 g (10 mmol) 2-methyl-1-phenyl-propan-2-ol in 40 ml dichloromethane at -10C. After 30 minutes the reaction mixture was poured onto sodium hydrogencarbonate solution, the organic layer was separated and the aqueous layer was extracted twice with dichloromethane. The combined organic extracts were evaporated and the residue was purified via silica gel chromatography with heptane/ethyl acetate mixtures to yield 1,42 g (36 %) of the title compound as a colorless solid. 1H-NMR(CDCI3, delta in ppm): 8,5 (s, broad, 1 H); 7,75 (d, 1 H); 7,4 (m, 2H); 7,2 (m, 2H); 6,85 (d, 1 H); 2,9 (s, very broad, 2H); 1 ,4 (s, very broad, 3H); 1 ,3 (s, very broad, 3H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With methanol; 1,3-disulfonic acid imidazolium hydrogen sulfate; at 20℃; for 0.0833333h;Green chemistry; | General procedure: A mixture of the substrate (1 mmol), ionic liquid [Dsim]HSO4 (6.5 mg, ?0.02 mmol) in methanol (2 mL) was stirred at room temperature. After completion of the reaction (monitored by TLC), solvent was evaporated, water (1 mL) was added to the mixture, and stirred vigorously. Decantation of the mixture gave almost pure product(s). The products were characterized by comparison of their IR and NMR data. The ionic liquid was dried at 65 ?C under vacuum to remove moisture, and then reused. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | Under ice-cold conditions, 2.80 g (15.0 mmol) of 3-bromo-5-cyanopyridine was added to 15mL of concentrated sulfuric acid, and a further 2.76 g (17.7 mmol) of 2-methyl-3-phenyl-2-propanol was dropped into the mixture slowly followed by stirring for 2 hours at room temperature. The reaction solution was poured into ice water and neutralized with sodium carbonate followed by extraction with ethyl acetate. The organic layer was washed with water and dried by addition of anhydrous magnesium sulfate followed by distilling off the solvent under reduced pressure. The resulting residue was purified by silica gel column chromatography (developing solvent: n-hexane:ethyl acetate = 9:1 (volume ratio)) to obtain 3.2 g (yield: 68%) of the target compound. The obtained compound was amorphous. 1H-NMR data of the compound are shown below. 1 H-NMR(300MHz, CDCl3)deltappm; 1.28(6H, s), 2.82(2H, s), 7.14(1H, d, J=7.2Hz), 7.2-7.3(2H, m), 7.3-7.5(1H, m), 8.07(1H, m), 8.70(1H, d, J=1.8Hz), 8.73(1H, d, J=2.1Hz) |
Yield | Reaction Conditions | Operation in experiment |
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80% | With Fe/SWCNTs at 20℃; for 1h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85.8% | With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In N,N-dimethyl-formamide; at 20℃;Cooling with ice; | Example 2: Synthesis of peptide acid using 1,1-dimethyl-2-phenyl-ethyl (Bpr) group; Synthesis of Fmoc-Val-Gly-Pro-OBpr (1) Z-Pro-OBpr To a solution of Z-Pro (19.4 g, 77.7 mmol) in DMF (200 ml) were added 2-methyl-1-phenyl-propan-2-ol (12.5 ml, 81.5 mmol) and 4-(dimethylamino)pyridine (DMAP) (2.85 g, 23.3 mmol), EDC HCl (15.6 g, 81.5 mmol) was added under ice-cooling, and the mixture was stirred for 30 min under ice-cooling and further at room temperature overnight. EDC HCl (7.45 g, 38.9 mmol) was added, and the mixture was stirred at room temperature for 4 hr. The reaction mixture was concentrated under reduced pressure, the residue was dissolved in ethyl acetate (400 ml), and the mixture was washed successively with 10% aqueous citric acid solution, water, saturated aqueous sodium hydrogen carbonate solution and water. The organic layer was dried over magnesium sulfate, and concentrated under reduced pressure to give the title compound as a pale-yellow oil (25.4 g, 85.8%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With N-ethyl-N,N-diisopropylamine; sodium iodide; at 150℃; for 1h;Inert atmosphere; Neat (no solvent); | General procedure: Benzylation of sterically hindered alcohols, such as menthol (21) and 1,1-dimethylphenylethanol (22) that were otherwise slow under the standard reaction condition were activated by a catalytic amount of NaI. Menthol (1 mmol) or 1,1-dimethylphenylethanol (1 mmol) were added to the reaction vessel containing DIPEA (1.6 mmol), then 1.5 equiv of alkyl halide (R2-X) and 10 mol % of NaI added. The mixture was stirred for 1 h at 150 C. Upon cooling, to the resulting mixture ethyl acetate (5 mL) and 10% aqueous sodium bisulphate (5 mL) were added and the organic phase extracted by three potions of EtOAc. Combined organic layer was dried over magnesium sulfate and the solvent evaporated in vacuo. Further purification was carried out by silica gel column chromatography. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
58% | With bis(1,5-cyclooctadiene)diiridium(I) dichloride; sodium carbonate; In toluene; at 100℃; for 5h;Inert atmosphere; | General procedure: A two-necked, 500-mL round bottom flask was equipped with a magnetic stirring bar and a three-way stopcock, of which one way was connected to an argon flow line and the other was connected to a vacuum line. The apparatus was flame-dried in vacuum, and allowed to cool to room temperature under an argon purge. To a solution of [IrCl(cod)]2 (1 mol%) in dry toluene triethylene glycol monomethyl ether, vinyl acetate (2.0 equiv), and Na2CO3 (0.60 equiv) were added and the mixture was stirred at 100 C for 3 h. After the reaction, the resulting salts were removed and washed with Et2O. The solvent was removed under reduced pressure. Purification of the residue by vacuum distillation (2 times distillation with CaH2) gave the product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With triethylamine; In dichloromethane; at 20℃; for 0.0833333h; | 50mL egg-shaped flask was added N - saccharin trifluoromethylthio group 1 (110mg, 0.39mmol), 2- methyl-3-phenyl propanol (45.0mg, 0.3mmol), 96muL triethylamine (0.69mmol), in dichloromethane (5 mL), at room temperature for 5min.After completion of the reaction, the reaction solution rapidly by about 6 millimeters silica gel column, the column with the amount of methylene chloride and washed twice, and the combined organic liquid, spin dry to give trifluoromethyl - (2-benzyl) isopropyl thio peroxide (62mg, 83% isolated yield).Purity by NMR identified more than 95%.Trifluoromethyl - (2-benzyl-yl) thio-isopropyl peroxy (((2-Methyl-1-phenylpropan-2-YL) Oxy) (trifluoromethyl) sulfane): |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 43 %Chromat. 2: 41 %Chromat. 3: 9 %Chromat. 4: 5 %Chromat. | With 1H-imidazole; (1,2-dimethyl-4(1H)-pyridinone-3-olate)2MnCl In acetonitrile at 4℃; for 24h; | Typical reaction procedure: General procedure: Complex 1 (0.04 mmol), thesubstrate (4 mmol, 100 equivalents), imidazole (0.16 mmol, 4equivalents) were solubilised in acetonitrile (10 mL) at 0C and leftto stir for a few minutes. Then, 6 mmol (150 equivalents) of oxidantwere added (except H2O2: 18 mmol, 450 equivalents were used).The mixture was then incubated at 4C for 24 h, after which it wasdiluted with 10 mL water and extracted once with 10 mL diethylether. Bromobenzene was then added to the organic phase and themixture was analysed by GC/MS. All reported conversions are anaverage of at least 3 repeats. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With sulfuric acid; In cyclohexane; at 0 - 68℃; for 2.5h; | General procedure: To cooled (0 C) 95% sulfuric acid (10 ml) and undermagnetic stirring, was added dropwise a benzonitrile (1.25eq). Then (500 mg, 3.33mmol) of tertiary alcohol1,1-dimethyl-2-phenylethanol (1, commercial product) in cyclohexane (10 ml) was added to the solution. Afterreturn to room temperature, the resulting mixture was stirred under reflux for 2.5 hours. Then, the solution iscooled at room temperature and versed on ice-cold water under magnetic stirring. The solution is alkalizedwith ammonia. The organic layer was extracted with dichloromethane (100 ml), washed with a saturatedaqueous NaCl solution, dried over sodium sulfate and filtered. The solvent was removed in vacuo and thecrude material was then purified by chromatography (silicia gel) to afford the imine as pure compound. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With sulfuric acid; In hexane; at 68℃; for 2.5h;Cooling; | To a cooled (0 C) solution (7.5 mL) of sulfuric acid H2SO4 (95 %), 2mL of trichloroacetonitrile in 28 mL of hexane was added dropwise and under magnetic stirring. Then, (1.5 g, 9.98 mmol) of tertiary alcohol 1 (commercial product) in 15 mL of hexane was added to the solution. After a return to room temperature, the resulting mixture was stirred under reflux for 2.5 h. Then, the solution was cooled at room temperature and versed on ice-cold water (50 mL) under magnetic stirring. The solution is alkalized with ammonia. The organic layer was extracted with dichloromethane (100mL), washed with a saturated aqueous NaCl solution, dried over sodium sulfate, and filtered. The solvent was removed in vacuo and the crude material was then purified by chromatography (silica gel, eluent dichloromethane/methanol 95:5) to afford the imine 6 as pure compound. Yield: 90%. Mp: 74 C. 1H NMR (CDCl3, 300 MHz): delta(ppm) 1.27 (s, 6H, 2-CH3), 2.74 (s, 2H, CH2), 7.22 (d, J=8.7 Hz, 1H), 7.30(m, 1H), 7.38 (m, 1H), 8.11 (d, J=7.8 Hz, 1H). 13C NMR (CDCl3, 75 MHz): delta 26.75 (2C), 39.02, 55.74, 97.67, 122.79, 126.16, 127.60, 128.70, 131.20, 138.31, 157.90. IR (KBr): upsilon 2970 cm -1 (CH3), 1690 cm -1 (C=N), 1618 cm -1 (Ar). HRMS-ES [M+Na]+ calc. for C12H12NCl3 Na 297.9933; found 297.9929. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | With 4-methyl-morpholine; In dichloromethane; at 20℃; | General procedure: To a solution of the corresponding alcohol (1.0 mmol) in CH2Cl2 (3 mL) were added N-methylmorpholine (101 mg, 1.0 mmol) and ethyl propiolate (108 mg, 1.1 mmol). The reaction mixture was stirred at r.t., and the progress of the reaction was monitored by TLC. After completion of the reaction, the solvent was removed on a rotary evaporator and the residue was extracted with EtOAc (3 × 10 mL). The combined organic extracts were washed with brine (30 mL), and dried over anhyd Na2SO4. The solvent was removed on a rotary evaporator, and the crude product was purified by silica gel column chromatography using EtOAc and hexane as eluents. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With trifluorormethanesulfonic acid; In dichloromethane; at -5℃; for 0.5h; | 5,49 g of trifluoromethane sulfonic acid was added dropwise to a mixture of 1,2 g (7,3 mmol) 5,6-dimethoxy-pyridine-3-carbonitrile an6 1,1 g (7,3 mmol) ) 2-methyl-1-phenyl-propan-2-ol in 50 ml dichloromethane at -5C. After 30 minutes the reaction mixture was poured onto sodium hydrogencarbonate solution, the organic layer was separated and the aqueous layer was extracted twice with dichloromethane. The combined organic extracts were evaporated and the residue was purified via silica gel chromatography with heptane/ethyl acetate mixtures to yield 1.8 g (83 %) of the title compound as a yellow oil. 1H-NMR(CDCI3, delta in ppm): 7.9 (d, 1 H); 7,4 (m, 1 H); 7,35 (d, 1 H); 7,25 (m, 3H); 4,1 (s, 3H); 3,95 (s, 3H); 2,8 (s, 2H); 1,3 (s, 6H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With hydrogen bromide; dihydrogen peroxide; In 1,2-dichloro-ethane; at 60℃; for 12h;Irradiation; | 112 g (0.745 mol) of 2-methyl-1-phenylpropan-2-ol and 127 g (1.86 mol) of 50% hydrogen peroxide were mixed in 1000 g of DCE to form a mixture. 63 g (0.373 mol) of hydrobromic acid was slowly added to the mixture at 60 C., and then mixture was irradiated by a visible light lamp (with a wavelength of about 400 nm) for 12 hours to form a crude product (in an organic layer). After extracted the curde product with DCE and brine and evaporated to remove the solvent, 2-hydroxy-2-methyl-1-phenylpropan-1-one was obtained with a yield of 85%. (bp. 102-103 C./4 mmHg) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
61% | With sulfuric acid; In benzene; at 60 - 70℃; for 0.25h; | General procedure: Cyanacetohydrazide 1 (9.9 g, 0.1 mol) was dissolved in 2-propanol(150 ml) while heating to 60-70, and benzaldehyde(10.6 ml, 0.11 mol) was added. Precipitate of N'-benzylidene-2-cyanacetohydrazide 2 started to form after 5-10 min as large, colorless crystals. The solution was left for 2 h at room temperature and then cooled to 0 C. The product was filtered off and washed with anhydrous ether (20 ml).The hydrazone was obtained in quantitative yield and after drying for 1 h, was used in the next step without additional purification. A mixture of hydrazone 2 (3.74 g, 21 mmol)and carbinol 6 (3 ml, 20 mmol) in anhydrous benzene(50 ml) was vigorously stirred and treated by dropwise addition of concd H2SO4 (8 ml). The stirring was continuedfor 15 min at 60-70, the reaction mixture was cooled to 20C, poured into ice water (200 ml), while keeping the temperature at or below 25 C. The benzene layer was separated, the aqueous phase was neutralized with aqueous 25% ammonia solution while cooling with ice andmaintaining the mixture at 20 C. The precipitate thatformed was filtered off, dried, and recrystallized. Yield2.68 g (42%), colorless crystals, mp 169-170 C(2-propanol |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62% | With sulfuric acid; In benzene; at 60 - 70℃; for 0.25h; | General procedure: Cyanacetohydrazide 1 (9.9 g, 0.1 mol) was dissolved in 2-propanol(150 ml) while heating to 60-70, and benzaldehyde(10.6 ml, 0.11 mol) was added. Precipitate of N'-benzylidene-2-cyanacetohydrazide 2 started to form after 5-10 min as large, colorless crystals. The solution was left for 2 h at room temperature and then cooled to 0 C. The product was filtered off and washed with anhydrous ether (20 ml).The hydrazone was obtained in quantitative yield and after drying for 1 h, was used in the next step without additional purification. A mixture of hydrazone 2 (3.74 g, 21 mmol)and carbinol 6 (3 ml, 20 mmol) in anhydrous benzene(50 ml) was vigorously stirred and treated by dropwise addition of concd H2SO4 (8 ml). The stirring was continuedfor 15 min at 60-70, the reaction mixture was cooled to 20C, poured into ice water (200 ml), while keeping the temperature at or below 25 C. The benzene layer was separated, the aqueous phase was neutralized with aqueous 25% ammonia solution while cooling with ice andmaintaining the mixture at 20 C. The precipitate thatformed was filtered off, dried, and recrystallized. Yield2.68 g (42%), colorless crystals, mp 169-170 C(2-propanol |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
64% | With sulfuric acid; In benzene; at 60 - 70℃; for 0.5h; | General procedure: Cyanacetohydrazide 1 (9.9 g, 0.1 mol) was dissolved in 2-propanol(150 ml) while heating to 60-70, and benzaldehyde(10.6 ml, 0.11 mol) was added. Precipitate of N'-benzylidene-2-cyanacetohydrazide 2 started to form after 5-10 min as large, colorless crystals. The solution was left for 2 h at room temperature and then cooled to 0 C. The product was filtered off and washed with anhydrous ether (20 ml).The hydrazone was obtained in quantitative yield and after drying for 1 h, was used in the next step without additional purification. A mixture of hydrazone 2 (3.74 g, 21 mmol)and carbinol 6 (3 ml, 20 mmol) in anhydrous benzene(50 ml) was vigorously stirred and treated by dropwise addition of concd H2SO4 (8 ml). The stirring was continuedfor 15 min at 60-70, the reaction mixture was cooled to 20C, poured into ice water (200 ml), while keeping the temperature at or below 25 C. The benzene layer was separated, the aqueous phase was neutralized with aqueous 25% ammonia solution while cooling with ice andmaintaining the mixture at 20 C. The precipitate thatformed was filtered off, dried, and recrystallized. Yield2.68 g (42%), colorless crystals, mp 169-170 C(2-propanol |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
220 mg | With sulfuric acid In toluene at 0 - 20℃; for 3h; | 35.B Step B: 6-(3 ,3-dimethyl-3 ,4-dihydroisoquinolin- I -yl)quinoxaline To a stirred solution of quinoxaline-6-carbonitriie (0.259 g, 1.669 mrnol) in toluene (10 ml) wasadded 2-methyl-i -phenylpropan-2-ol (0.300 g, 1.997 mmol) followed by the addition of H2S04(1.779 ml, 33.4 mmol) at 0 °C. The reaction mixture was allowed to stir at room temperature for 3h. The reaction mixture was concentrated under reduced pressure and crude was neutralized by saturated sodium bicarbonate solution and extracted with ethyl acetate (2 x 1 50rn1). A combined organic layer was concentrated under reduced pressure and the crude was purified by reverse phaseHPLC to afford desired 6-(3,3-dimethyi-3,4-dihydroisoquinoiin-i-yi)quinoxaiine (220mg) as a sticky solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With sulfuric acid; In toluene; at 0 - 20℃; | i-oxo-1,3-dihydroisohenzofuran-5-carhonitrile (0.2 g, 1.257 mmoi) was taken in tolune (8 ml), 2-methyl-i-phenylpropan-2-oi (0.245 g, 1,634 mmol) was added followed by H2S04 (1.340 ml, 25.1 mmol) dropwise at 0 °C. Reaction mixture was allowed to stir at RT for overnight. Reaction mixture was neutralized by sodium bicarbonate and extracted with ethyl acetate. organic portion was washed with brine, dried with anhydrous sodium sulfate and evaporated to give crude which was purified by Reverse phase Prep.HJL.C to give pure5-(3,3-dimethyi-3.4-dihvdroisoquinoiin.-i-yi)isobenzofurani(3H)one (300 mg, 1030 mmoi, 32 percent). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
26% | In 1,2-dichloro-ethane at 0 - 20℃; Acidic conditions; | 1.A.1.1 1 .1 1 -(5,6-dibromo-3-pyridyl)-3,3-dimethyl-4H-isoquinoline 1 .1 1 -(5,6-dibromo-3-pyridyl)-3,3-dimethyl-4H-isoquinoline |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With sulfuric acid; In cyclohexane; at 0 - 68℃; for 2.5h; | General procedure: To cooled (0 C) 95% sulfuric acid (10 ml) and undermagnetic stirring, was added dropwise a benzonitrile (1.25eq). Then (500 mg, 3.33mmol) of tertiary alcohol1,1-dimethyl-2-phenylethanol (1, commercial product) in cyclohexane (10 ml) was added to the solution. Afterreturn to room temperature, the resulting mixture was stirred under reflux for 2.5 hours. Then, the solution iscooled at room temperature and versed on ice-cold water under magnetic stirring. The solution is alkalizedwith ammonia. The organic layer was extracted with dichloromethane (100 ml), washed with a saturatedaqueous NaCl solution, dried over sodium sulfate and filtered. The solvent was removed in vacuo and thecrude material was then purified by chromatography (silicia gel) to afford the imine as pure compound.3,3-Dimethyl-1-phenyl-3,4-dihydroisoquinoline (imine 2). Reaction of benzonitrile (429 mg, 1.25eq) accordingto the general procedure afforded 2 of (83%), isolated as a white solid, mp 69-71 C; 1H NMR (CDCl3, 400MHz):delta (ppm) 1.34 (s, 6H, 2-CH3), 2.86 (2H, CH2), 7.23-7.61 (m, 9H). 13C NMR (CDCl3, 75MHz): delta27.64 (2C), 38.8, 54.5,126.4, 127.9, 128.0, 128.1, 128.2, 128.8, 128.95, 130.7, 137.5, 139.3, 164.5. HRMS (ESI) [M + H]+ calc. ForC17H18N 236.1433; found 236.1424. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | With sulfuric acid; In cyclohexane; at 0 - 68℃; for 2.5h; | General procedure: To cooled (0 C) 95% sulfuric acid (10 ml) and undermagnetic stirring, was added dropwise a benzonitrile (1.25eq). Then (500 mg, 3.33mmol) of tertiary alcohol1,1-dimethyl-2-phenylethanol (1, commercial product) in cyclohexane (10 ml) was added to the solution. Afterreturn to room temperature, the resulting mixture was stirred under reflux for 2.5 hours. Then, the solution iscooled at room temperature and versed on ice-cold water under magnetic stirring. The solution is alkalizedwith ammonia. The organic layer was extracted with dichloromethane (100 ml), washed with a saturatedaqueous NaCl solution, dried over sodium sulfate and filtered. The solvent was removed in vacuo and thecrude material was then purified by chromatography (silicia gel) to afford the imine as pure compound. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With sulfuric acid; In cyclohexane; at 15℃; for 0.25h; | At 15C a solution of 380 g (2,53 mol) 2-methyl-1-phenyl-propan-2 -ol and 426 g (4,3 mol) ethyl cyanoformate in 500 ml cyclohexane has been added to a mixture of 500 ml cyclohexane and 1899 g (19 mol) concentrated sulfuric acid upon stirring. After ca. 15 min the reaction mixture was poured onto an ice/water mixture and cautiously basified upon addition of concentrated NaOH-solution. The phases were separated and the aqeous layer was extracted twice with me- thyl-t-butylether. The combined organic phases were dried over sodium sulfate and ant volatiles were evaporated to yield 584 g (99 %) ethyl 3,3-dimethyl-4H-isoquinoline-1-carboxylate as a yellow oil.1H-NMR (CDCIs, din ppm):7,55 (d, 1 H); 7,4 (t, 1 H); 7,3 (t, 1 H); 7,18 (d, 1 H); 4,45 (q, 2H); 2,75 (s, 2H); 1 ,4 (t,3H); 1 ,28 (s, 6H) |
99% | With sulfuric acid; In cyclohexane; at 15℃; for 0.25h; | At 15C a solution of 380 g (2,53 mol) 2-methyl-1 -phenyl-propan-2 -ol and 426 g (4,3 mol) ethyl cyanoformate in 500 ml cyclohexane has been added to a mixture of 500 ml cyclohexane and 1899 g (19 mol) concentrated sulfuric acid upon stirring. After ca. 15 min the reaction mixture was poured onto an ice/water mixture and cautiously basified upon addition of concentrated NaOH-solution. The phases were separated and the aqeous layer was extracted twice with me- thyl-t-butylether. The combined organic phases were dried over sodium sulfate and ant volatiles were evaporated to yield 584 g (99 %) ethyl 3,3-dimethyl-4H-isoquinoline-1-carboxylate as a yellow oil. 1H-NMR (CDCIs, d in ppm): 7,55 (d, 1 H); 7,4 (t, 1 H); 7,3 (t, 1 H); 7,18 (d, 1 H); 4,45 (q, 2H); 2,75 (s, 2H); 1 ,4 (t, 3H); 1 ,28 (s, 6H) |
99% | With sulfuric acid; In cyclohexane; at 15℃; for 0.25h; | At 15C a solution of 380 g (2,53 mol) 2-methyl-1 -phenyl-propan-2 -ol and 426 g (4,3 mol) ethyl cyanoformate in 500 ml cyclohexane has been added to a mixture of 500 ml cyclohexane and 1899 g (19 mol) concentrated sulfuric acid upon stirring. After ca. 15 min the reaction mixture was poured onto an ice/water mixture and cautiously basified upon addition of concentrated NaOH-solution. The phases were separated and the aqeous layer was extracted twice with me- thyl-t-butylether. The combined organic phases were dried over sodium sulfate and ant volatiles were evaporated to yield 584 g (99 %) ethyl 3,3-dimethyl-4H-isoquinoline-1-carboxylate as a yellow oil. 1H-NMR (CDCIs, d in ppm): 7,55 (d, 1H); 7,4 (t, 1H); 7,3 (t, 1H); 7,18 (d, 1H); 4,45 (q, 2H); 2,75 (s, 2H); 1,4 (t, 3H); 1,28 (s, 6H) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With dichloro[1,1'-bis(di-t-butylphosphino)ferrocene]palladium(II); sodium t-butanolate; In neat (no solvent); at 100℃; for 1h;Inert atmosphere; Microwave irradiation; | General procedure: The reaction methods used for all the reactions shown in Tables2-4 are the same except for cholesterol, 1e where 1.0 mL of 1,4-dioxane was added. An oven dry clean microwave vial is loadedwith 1.0 mmol of NaOtBu (100.0 mg), 0.0025 mmol of PdCl2(dtbpf)(2.0 mg), capped with air-tight silicon septa and flushed withargon. Then 0.5 mmol of aroyl chloride was added as limiting reagentvia micro syringe, and tertiary alcohol (1.0 mL) was added via drysyringe. The resulting reaction mixture was then microwaved(CEM Explorer 24, 300 W) at 100 C for 60 min. Crude reaction productin reaction tube was diluted with dichloromethane and transferredinto a separating funnel. Water was then added to the funneland, after standard extraction, excess alcohol was completely misciblewith water. The bottom organic layer was collected in a smallErlenmeyer flask over anhydrous Na2SO4. The dichloromethanelayer was filtered through sintered funnel and filtrate, collectedin a round bottom flask, and completely dried by rotary evaporator and under reduced pressure in vacuo. In case of cholesterol 1e,0.5 mmol of aroyl chloride, 1.0 mmol of cholesterol, and 1.0 mLof 1,4-dioxane were used. The desired ester product was confirmedby 1H NMR, 13C NMR, and 19F NMR. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | With sulfuric acid; In toluene; at 60 - 70℃; for 0.333333h; | General procedure: Concentrated H2SO4 (8 ml) wasadded dropwise with vigorous stirring to a mixture ofnitrile 2b-h (21 mmol) and carbinol 1- (20 mmol) inanhydrous PhMe (50 ml). Stirring was continued for20 min at 60-70. The mixture was then cooled to 20,poured into ice water (200 ml) at such a rate as to not allowthe temperature of the mixture to exceed 25. The organicphase was separated, the aqueous phase was neutralizedwith 25% aqueous NH4OH cooling with ice, alsocontrolling the addition as to not let the temperature exceed20. The formed precipitate was filtered off, dried, andrecrystallized. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | With sulfuric acid; In toluene; at 60 - 70℃; for 0.333333h; | General procedure: Concentrated H2SO4 (8 ml) wasadded dropwise with vigorous stirring to a mixture ofnitrile 2b-h (21 mmol) and carbinol 1- (20 mmol) inanhydrous PhMe (50 ml). Stirring was continued for20 min at 60-70. The mixture was then cooled to 20,poured into ice water (200 ml) at such a rate as to not allowthe temperature of the mixture to exceed 25. The organicphase was separated, the aqueous phase was neutralizedwith 25% aqueous NH4OH cooling with ice, alsocontrolling the addition as to not let the temperature exceed20. The formed precipitate was filtered off, dried, andrecrystallized. |
Tags: 100-86-7 synthesis path| 100-86-7 SDS| 100-86-7 COA| 100-86-7 purity| 100-86-7 application| 100-86-7 NMR| 100-86-7 COA| 100-86-7 structure
[ 530-91-6 ]
1,2,3,4-Tetrahydronaphthalen-2-ol
Similarity: 0.89
[ 22436-06-2 ]
(S)-2-Methyl-3-phenylpropan-1-ol
Similarity: 0.85
[ 530-91-6 ]
1,2,3,4-Tetrahydronaphthalen-2-ol
Similarity: 0.89
[ 22436-06-2 ]
(S)-2-Methyl-3-phenylpropan-1-ol
Similarity: 0.85
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P380 | Evacuate area. |
P381 | Eliminate all ignition sources if safe to do so. |
P390 | Absorb spillage to prevent material damage. |
P391 | Collect spillage. Hazardous to the aquatic environment |
P301 + P310 | IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician. |
P301 + P312 | IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell. |
P301 + P330 + P331 | IF SWALLOWED: Rinse mouth. Do NOT induce vomiting. |
P302 + P334 | IF ON SKIN: Immerse in cool water/wrap in wet bandages. |
P302 + P350 | IF ON SKIN: Gently wash with plenty of soap and water. |
P303 + P361 + P353 | IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower. |
P304 + P312 | IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell. |
P304 + P340 | IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing. |
P304 + P341 | IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P305 + P351 + P338 | IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. |
P306 + P360 | IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes. |
P307 + P311 | IF exposed: call a POISON CENTER or doctor/physician. |
P308 + P313 | IF exposed or concerned: Get medical advice/attention. |
P309 + P311 | IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician. |
P332 + P313 | IF SKIN irritation occurs: Get medical advice/attention. |
P333 + P313 | IF SKIN irritation or rash occurs: Get medical advice/attention. |
P335 + P334 | Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages. |
P337 + P313 | IF eye irritation persists: Get medical advice/attention. |
P342 + P311 | IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician. |
P370 + P376 | In case of fire: Stop leak if safe to Do so. |
P370 + P378 | In case of fire: |
P370 + P380 | In case of fire: Evacuate area. |
P370 + P380 + P375 | In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion. |
P371 + P380 + P375 | In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion. |
Storage | |
Code | Phrase |
P401 | |
P402 | Store in a dry place. |
P403 | Store in a well-ventilated place. |
P404 | Store in a closed container. |
P405 | Store locked up. |
P406 | Store in corrosive resistant/ container with a resistant inner liner. |
P407 | Maintain air gap between stacks/pallets. |
P410 | Protect from sunlight. |
P411 | |
P412 | Do not expose to temperatures exceeding 50 oC/ 122 oF. |
P413 | |
P420 | Store away from other materials. |
P422 | |
P402 + P404 | Store in a dry place. Store in a closed container. |
P403 + P233 | Store in a well-ventilated place. Keep container tightly closed. |
P403 + P235 | Store in a well-ventilated place. Keep cool. |
P410 + P403 | Protect from sunlight. Store in a well-ventilated place. |
P410 + P412 | Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF. |
P411 + P235 | Keep cool. |
Disposal | |
Code | Phrase |
P501 | Dispose of contents/container to ... |
P502 | Refer to manufacturer/supplier for information on recovery/recycling |
Physical hazards | |
Code | Phrase |
H200 | Unstable explosive |
H201 | Explosive; mass explosion hazard |
H202 | Explosive; severe projection hazard |
H203 | Explosive; fire, blast or projection hazard |
H204 | Fire or projection hazard |
H205 | May mass explode in fire |
H220 | Extremely flammable gas |
H221 | Flammable gas |
H222 | Extremely flammable aerosol |
H223 | Flammable aerosol |
H224 | Extremely flammable liquid and vapour |
H225 | Highly flammable liquid and vapour |
H226 | Flammable liquid and vapour |
H227 | Combustible liquid |
H228 | Flammable solid |
H229 | Pressurized container: may burst if heated |
H230 | May react explosively even in the absence of air |
H231 | May react explosively even in the absence of air at elevated pressure and/or temperature |
H240 | Heating may cause an explosion |
H241 | Heating may cause a fire or explosion |
H242 | Heating may cause a fire |
H250 | Catches fire spontaneously if exposed to air |
H251 | Self-heating; may catch fire |
H252 | Self-heating in large quantities; may catch fire |
H260 | In contact with water releases flammable gases which may ignite spontaneously |
H261 | In contact with water releases flammable gas |
H270 | May cause or intensify fire; oxidizer |
H271 | May cause fire or explosion; strong oxidizer |
H272 | May intensify fire; oxidizer |
H280 | Contains gas under pressure; may explode if heated |
H281 | Contains refrigerated gas; may cause cryogenic burns or injury |
H290 | May be corrosive to metals |
Health hazards | |
Code | Phrase |
H300 | Fatal if swallowed |
H301 | Toxic if swallowed |
H302 | Harmful if swallowed |
H303 | May be harmful if swallowed |
H304 | May be fatal if swallowed and enters airways |
H305 | May be harmful if swallowed and enters airways |
H310 | Fatal in contact with skin |
H311 | Toxic in contact with skin |
H312 | Harmful in contact with skin |
H313 | May be harmful in contact with skin |
H314 | Causes severe skin burns and eye damage |
H315 | Causes skin irritation |
H316 | Causes mild skin irritation |
H317 | May cause an allergic skin reaction |
H318 | Causes serious eye damage |
H319 | Causes serious eye irritation |
H320 | Causes eye irritation |
H330 | Fatal if inhaled |
H331 | Toxic if inhaled |
H332 | Harmful if inhaled |
H333 | May be harmful if inhaled |
H334 | May cause allergy or asthma symptoms or breathing difficulties if inhaled |
H335 | May cause respiratory irritation |
H336 | May cause drowsiness or dizziness |
H340 | May cause genetic defects |
H341 | Suspected of causing genetic defects |
H350 | May cause cancer |
H351 | Suspected of causing cancer |
H360 | May damage fertility or the unborn child |
H361 | Suspected of damaging fertility or the unborn child |
H361d | Suspected of damaging the unborn child |
H362 | May cause harm to breast-fed children |
H370 | Causes damage to organs |
H371 | May cause damage to organs |
H372 | Causes damage to organs through prolonged or repeated exposure |
H373 | May cause damage to organs through prolonged or repeated exposure |
Environmental hazards | |
Code | Phrase |
H400 | Very toxic to aquatic life |
H401 | Toxic to aquatic life |
H402 | Harmful to aquatic life |
H410 | Very toxic to aquatic life with long-lasting effects |
H411 | Toxic to aquatic life with long-lasting effects |
H412 | Harmful to aquatic life with long-lasting effects |
H413 | May cause long-lasting harmful effects to aquatic life |
H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
Sorry,this product has been discontinued.
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