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CAS No. : | 150-84-5 | MDL No. : | MFCD00015039 |
Formula : | C12H22O2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | JOZKFWLRHCDGJA-UHFFFAOYSA-N |
M.W : | 198.30 | Pubchem ID : | 9017 |
Synonyms : |
|
Num. heavy atoms : | 14 |
Num. arom. heavy atoms : | 0 |
Fraction Csp3 : | 0.75 |
Num. rotatable bonds : | 7 |
Num. H-bond acceptors : | 2.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 60.61 |
TPSA : | 26.3 Ų |
GI absorption : | High |
BBB permeant : | Yes |
P-gp substrate : | No |
CYP1A2 inhibitor : | No |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -4.33 cm/s |
Log Po/w (iLOGP) : | 3.29 |
Log Po/w (XLOGP3) : | 4.48 |
Log Po/w (WLOGP) : | 3.32 |
Log Po/w (MLOGP) : | 3.04 |
Log Po/w (SILICOS-IT) : | 3.14 |
Consensus Log Po/w : | 3.46 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 1.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -3.43 |
Solubility : | 0.0737 mg/ml ; 0.000372 mol/l |
Class : | Soluble |
Log S (Ali) : | -4.75 |
Solubility : | 0.00351 mg/ml ; 0.0000177 mol/l |
Class : | Moderately soluble |
Log S (SILICOS-IT) : | -2.88 |
Solubility : | 0.261 mg/ml ; 0.00132 mol/l |
Class : | Soluble |
PAINS : | 0.0 alert |
Brenk : | 1.0 alert |
Leadlikeness : | 2.0 |
Synthetic accessibility : | 2.69 |
Signal Word: | Danger | Class: | 9 |
Precautionary Statements: | P501-P273-P260-P270-P264-P280-P391-P314-P337+P313-P305+P351+P338-P301+P312+P330 | UN#: | 3082 |
Hazard Statements: | H302-H319-H372-H410 | Packing Group: | Ⅲ |
GHS Pictogram: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With ozone In ethyl acetate | ||
Multi-step reaction with 2 steps 1.1: oxygen / dichloromethane / 0.5 h / -78 °C 1.2: 2 h / 25 °C 2.1: 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; disodium hydrogenphosphate; sodium hypochlorite; sodium chloride / acetonitrile; water / 3 h / 35 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With N-methyl-2-indolinone In water; acetone; <i>tert</i>-butyl alcohol at 20℃; for 36h; | |
67% | With ruthenium trichloride; sodium periodate In water; ethyl acetate; acetonitrile at 0℃; for 0.05h; | |
67% | With ruthenium trichloride; sodium periodate In ethyl acetate; acetonitrile for 0.05h; |
With tert.-butylhydroperoxide; osmium(VIII) oxide; tetraethylammonium chloride; sodium acetate In acetone; <i>tert</i>-butyl alcohol |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
40% | With tert.-butylhydroperoxide; dipyridinium dichromate In benzene at 25℃; for 11h; | |
(i) tBuOH, CrO3, CCl4, (ii) /BRN= 1723886/, Ac2O, AcOH; Multistep reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With aluminium trichloride In benzene |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In benzene |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium periodate 1.) CCl4, CH3CN, H2O, 0.5h, 25 deg C, 2.) Et2O; Yield given. Multistep reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With diphenyl diselenide; magnesium sulfate at 66 - 68℃; electrolysis under a constant current 6.7 mA/cm2; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 65% 2: 20% | With triethylsilane; lithium perchlorate at 20℃; for 48h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98.5% | With dimethylaluminum chloride In n-heptane; dichloromethane at 0℃; for 1h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
45% | With ethylaluminum dichloride In n-heptane; benzene at 25℃; for 72h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
57% | With tin(ll) chloride In water; acetic acid for 17h; Ambient temperature; | |
With Pichia kluyveri NBRC 1165; S-acetyl coenzyme A In decane for 288h; | 2.6. Transacetylation of citronellol with P. kluyveri NBRC 1165 Microbial transacetylation of citronellol by acetyl-CoA produced viaglucose metabolism was compared between the S-L IBR and L-L IBRtac.P. kluyveri NBRC 1165 was cultivated in 25 ml of the CA-medium at30 °C with rotation (200 rpm) for 1 day as a seed broth.Concerning the S-L IBR, 150 μl of the 1-day seed broth was inoculatedon the CA-agar plate prepared in a glass vial (50 ml; 30mmi.d.) and stationary precultivation was done at 30 °C for 1 day. The samefour reactors were constructed. Three ml of a 10 or 20% solution ofcitronellol in n-decane was added onto a biofilm formed on the agarplate, and incubation was continued for 12 days. The products accumulatedin the organic phase were directly determined by the GLC |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
61% | With boron trifluoride diethyl etherate at 25℃; for 1h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
30% | In methanol; chloroform; acetonitrile |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With (NMe4)(Co-ortho-phenylenebis(N'-methyloxamidate)*2H2O*CH3CN; oxygen; pivalaldehyde In fluorobenzene for 1.25h; Ambient temperature; | |
95% | With sodium acetate; bis[3,5-bis(trifluoromethyl)diphenyl] diselenide In 2,2,2-trifluoroethanol at 20℃; for 0.5h; | |
90% | With <NMe4>2<Ni(Me2opba)>*4H2O; oxygen; pivalaldehyde In fluorobenzene for 2.5h; |
65% | With sodium chlorite; edetate disodium In water; acetonitrile at 55 - 65℃; for 15h; | |
55% | With dihydrogen peroxide In water at 20℃; for 6h; Green chemistry; | |
94.5 % Chromat. | With oxygen; isobutyraldehyde In 1,2-dichloro-ethane for 3h; Ambient temperature; | |
95 % Chromat. | With Ni(dmp)2; oxygen; isobutyraldehyde In 1,2-dichloro-ethane for 24h; Ambient temperature; | |
90 % Turnov. | With <Fe3O(piv)3(MeOH)3>Cl; oxygen at 60℃; for 20h; | |
81 % Chromat. | With <N,N'-bis(salicylidene-γ-iminopropyl)methylaminato>cobalt (II); oxygen; 2-Methylcyclohexanone at 75℃; for 6h; | |
86 % Chromat. | With 1,1-diethoxypropane; bis(3-methyl-2,4-pentanedionato)cobalt(II); 4 A molecular sieve; oxygen at 45℃; for 20h; | |
With oxygen; isobutyraldehyde In 1,2-dichloro-ethane for 7h; Ambient temperature; Yield given; | ||
82 % Chromat. | With 1,1-diethoxypropane; bis(3-methyl-2,4-pentanedionato)cobalt(II); 4 A molecular sieve; oxygen at 45℃; for 20h; | |
Multi-step reaction with 2 steps 1: 1.) I2, 4 angstroem molecular sieves, 2.) pyridinium chloride / 1.) dry CH2Cl2, room temp, 30 min, 2.) 3 h 2: 70 percent / Al2O3 | ||
With 3-chloro-benzenecarboperoxoic acid In dichloromethane at 20℃; | ||
With [((S,S)-N,N′-bis(2-pyridylmethyl)-(S,S)-2,2′-bipyrrolidine)FeII(OTf)2]; dihydrogen peroxide; acetic acid In water; acetonitrile at 0℃; Inert atmosphere; chemospecific reaction; | ||
With ferredoxin reductase; [2Fe–2S] ferredoxin; cytochrome P450 enzyme CYP101C1 In aq. buffer Enzymatic reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 40% 2: 40% | With potassium permanganate; water; copper(II) sulfate; <i>tert</i>-butyl alcohol In dichloromethane at 25℃; for 2h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 1% 2: 90% | With triethylsilane; lithium perchlorate; trifluoroacetic acid In various solvent(s) at 20℃; for 22h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With ozone In dichloromethane at -78℃; | |
90% | With ozone In dichloromethane at -78℃; | |
88% | Stage #1: citronellyl-acetate With oxygen In dichloromethane at -78℃; for 0.5h; Stage #2: With dimethylsulfide In dichloromethane at 25℃; for 2h; | 45 PREPARATION 45: 3-methyl-6-oxohexyl acetate A solution of 3,7-dimethyloct-6-en-1-yl acetate (6 g, 30.26 mmol) in DCM (50 mL) was purged with ozone at -78°C for 30 minutes and then with O2 until there was no ozone observed in the off-gas. Next, Me2S (10.63 g, 171.08 mmol, 12.57 mL) was added and the mixture was stirred at 25°C for 2 hours. TLC (petroleum ether/EtOAc = 5:1, Rf =0.4) indicated the starting material was consumed and one major new spot with larger polarity was detected. The reaction mixture was concentrated under reduced pressure and purified by column chromatography (SiO2) using a gradient of petroleum ether/EtOAc (10:1 to 5:1) to give the title compound as a yellow oil (4.6 g, 88%).1H NMR (CDCl3) δ ppm 9.68 - 9.73 (m, 1H), 3.99 - 4.07 (m, 2H), 2.28 - 2.47 (m, 2H), 1.97 (s, 3H), 1.56 - 1.67 (m, 2H), 1.49 - 1.55 (m, 1H), 1.37 - 1.47 (m, 2H), 0.86 (d, J = 6.4 Hz, 2H), 0.84 (br s, 1H). |
88% | Stage #1: citronellyl-acetate With oxygen In dichloromethane at -78℃; for 0.5h; Stage #2: With dimethylsulfide In dichloromethane at 25℃; for 2h; | 45 PREPARATION 45: 3-methyl-6-oxohexyl acetate A solution of 3,7-dimethyloct-6-en-1-yl acetate (6 g, 30.26 mmol) in DCM (50 mL) was purged with ozone at -78°C for 30 minutes and then with O2 until there was no ozone observed in the off-gas. Next, Me2S (10.63 g, 171.08 mmol, 12.57 mL) was added and the mixture was stirred at 25°C for 2 hours. TLC (petroleum ether/EtOAc = 5:1, Rf =0.4) indicated the starting material was consumed and one major new spot with larger polarity was detected. The reaction mixture was concentrated under reduced pressure and purified by column chromatography (SiO2) using a gradient of petroleum ether/EtOAc (10:1 to 5:1) to give the title compound as a yellow oil (4.6 g, 88%).1H NMR (CDCl3) δ ppm 9.68 - 9.73 (m, 1H), 3.99 - 4.07 (m, 2H), 2.28 - 2.47 (m, 2H), 1.97 (s, 3H), 1.56 - 1.67 (m, 2H), 1.49 - 1.55 (m, 1H), 1.37 - 1.47 (m, 2H), 0.86 (d, J = 6.4 Hz, 2H), 0.84 (br s, 1H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | With hydrogenchloride In acetic acid at 0℃; for 1h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With sodium chloride In dichloromethane; water for 4h; Ambient temperature; electrolysis by using Pt foils at constant current (50 mA); | |
84% | With sodium chloride In dichloromethane; water at 25℃; for 0.3h; electrolysis: ruthenium oxide: anode; titanium cylinder: cathode; I = 0.94 A; | |
67% | With chlorine In tetrachloromethane at 0℃; for 0.583333h; |
In dichloromethane; water at 25℃; for 0.3h; influence of concentration of electrolyte NaCl and reaction time on the product yield; | ||
With hypochloric acid In dichloromethane | ||
Multi-step reaction with 2 steps 1: 95 percent / LiClO4 / CH2Cl2 / 0 °C 2: 70 percent / BnEt3NCl / CHCl3 / 7 h / Heating |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With pyridine; sulfuryl dichloride In dichloromethane at -60℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With selenium oxychloride In dichloromethane at -20℃; for 0.75h; Yield given. Yields of byproduct given. Title compound not separated from byproducts; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With 3-chloro-benzenecarboperoxoic acid In dichloromethane at 0℃; for 2h; Yield given. Yields of byproduct given. Title compound not separated from byproducts; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With 3-chloro-benzenecarboperoxoic acid In chloroform 1.) 0 deg C, 2.) 24 h, room temp.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With diphenyl diselenide; water; magnesium sulfate In acetonitrile at 66 - 68℃; electrolysis under a constant current 6.7 mA/cm2; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
53% | Stage #1: citronellyl-acetate With tert.-butylhydroperoxide; selenium(IV) oxide In dichloromethane Stage #2: With sodium tetrahydroborate | |
With tert.-butylhydroperoxide; sodium tetrahydroborate; selenium(IV) oxide 1.) CH2Cl2, 22 deg C, 2.) MeOH; Yield given. Multistep reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With lithium perchlorate In dichloromethane at 0℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | In dichloromethane at 0℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With thionyl chloride; triethylamine In dichloromethane at 25℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
46 % Chromat. | With tert.-butylhydroperoxide; cetyltrimethylammonium chlorochromate In benzene at 80℃; for 2h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With tert.-butylhydroperoxide; selenium(IV) oxide; silica gel In dichloromethane for 0.166667h; Irradiation; | |
60% | With tert.-butylhydroperoxide In dichloromethane; water at 20℃; for 24h; | (E)-3,7-Dimethyl-8-oxooct-6-enyl acetate (4) To a stirred suspension of 5 wt% SeO2 on silica (15.0 g, 6.75 mmol) in CH2Cl2 (135 mL) was added aq 70 wt% tBuOOH (4.9 mL, 34.1 mmol) as a bolus followed by a solution of citronellyl acetate (3.0 mL, 2.7 g, 13.5 mmol) in CH2Cl2 (12.5 mL) added over a period of 15 min. The resulting suspension was stirred vigorously open to the atmosphere for 24 h, and then filtered through a frit. The filtrate was concentrated in vacuo to yield a yellow oil (3.58 g), which was purified by Kugelrohr distillation (130 °C oven temperature/2 Torr) to afford aldehyde 4 (2.86 g, 60%) as a pale yellow oil comprised of a 96:4 mixture of E-and Z-isomers. The E-isomer can be isolated using column chromatography (30% Et2O/hexane) to give analytically pure material with spectroscopic data identical to those reported in the literature. |
With tert.-butylhydroperoxide; selenium(IV) oxide In toluene for 120h; Ambient temperature; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With pyridine In dichloromethane at 20℃; | |
99% | With C12H8N2*2CH4O3S at 60℃; for 3h; | |
98% | With iodine at 25℃; for 0.0166667h; |
96% | With silica-supported phosphomolybdic acid at 20℃; for 0.133333h; | |
95% | With lanthanum(III) nitrate at 20℃; for 0.166667h; | |
95% | With N-ethyl-N,N-diisopropylamine In dichloromethane at 20℃; for 16h; | 44 PREPARATION 44: 3,7-dimethyloct-6-en-1-yl acetate To a solution of 3,7-dimethyloct-6-en-1-ol (10 g, 63.99 mmol) in DCM (100 mL) were added DIPEA (24.81 g, 191.98 mmol, 33.44 mL) and Ac2O (7.19 g, 70.39 mmol, 6.59 mL). The mixture was stirred at 20°C for 16 hours. TLC (petroleum ether/EtOAc = 10:1, Rf =0.79) indicated the starting material was consumed and one major new spot with lower polarity was detected. The reaction mixture was concentrated under reduced pressure and purified by column chromatography (SiO2) using a gradient of petroleum ether/EtOAc (1:0 to 100:1) to give the title compound as a colorless oil (12 g, 95%).1H NMR (CDCl3) δ ppm 5.06 - 5.10 (m, 1H), 4.06 - 4.13 (m, 2H), 2.03 (s, 3H), 1.68 - 1.95 (m, 2H), 1.64 - 1.65 (m, 1H), 1.53 - 1.60 (m, 4H), 1.44 - 1.45 (m, 3H), 1.34 - 1.42 (m, 1H), 1.17 - 1.19 (m, 2H), 0.92 - 1.17 (d, 1H), 0.90 (d, 3H). |
95% | With N-ethyl-N,N-diisopropylamine In dichloromethane at 20℃; for 16h; | 44 PREPARATION 44: 3,7-dimethyloct-6-en-1-yl acetate To a solution of 3,7-dimethyloct-6-en-1-ol (10 g, 63.99 mmol) in DCM (100 mL) were added DIPEA (24.81 g, 191.98 mmol, 33.44 mL) and Ac2O (7.19 g, 70.39 mmol, 6.59 mL). The mixture was stirred at 20°C for 16 hours. TLC (petroleum ether/EtOAc = 10:1, Rf =0.79) indicated the starting material was consumed and one major new spot with lower polarity was detected. The reaction mixture was concentrated under reduced pressure and purified by column chromatography (SiO2) using a gradient of petroleum ether/EtOAc (1:0 to 100:1) to give the title compound as a colorless oil (12 g, 95%).1H NMR (CDCl3) δ ppm 5.06 - 5.10 (m, 1H), 4.06 - 4.13 (m, 2H), 2.03 (s, 3H), 1.68 - 1.95 (m, 2H), 1.64 - 1.65 (m, 1H), 1.53 - 1.60 (m, 4H), 1.44 - 1.45 (m, 3H), 1.34 - 1.42 (m, 1H), 1.17 - 1.19 (m, 2H), 0.92 - 1.17 (d, 1H), 0.90 (d, 3H). |
92% | With nickel dichloride at 20℃; for 0.416667h; Neat (no solvent); | |
92% | In pyridine at 0 - 30℃; for 12h; | |
90% | at 20℃; for 6h; | |
62% | With nickel dichloride for 0.133333h; microwave irradiation; | |
With pyridine; dmap | ||
With pyridine | ||
With triethylamine In dichloromethane at 20℃; for 16h; | ||
With immobilized enzyme Novozym 435<SUP>®</SUP> at 150℃; Enzymatic reaction; | ||
93.1 %Spectr. | With sulfonated biochar at 20.1℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With Mucor miehei lipase at 55 - 60℃; for 8h; | ||
100 %Spectr. | With Candida rugosa lipase In toluene at 40℃; for 96h; Enzymatic reaction; | |
With immobilized enzyme Novozym 435<SUP>®</SUP> at 50℃; for 0.133333h; Enzymatic reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
61% | Stage #1: citronellyl-acetate With ozone In dichloromethane at -78℃; Stage #2: 1,1-dibromomethane With diethylamine In dichloromethane at -78 - 55℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99.9% | With Candida antarctica lipase B at 50℃; for 4h; Molecular sieve; Ionic liquid; Green chemistry; Enzymatic reaction; | |
95% | With ZrCl4-Mg(ClO4)2 composite In neat (no solvent) at 20℃; for 0.133333h; | Typical experimental procedure for the onepotsynthesis of benzyl acetate General procedure: A mixture of 4-methoxy benzyl alcohol (1b, 1 mmol),acetic acid (3 mmol), 2 mol% ZrCl4-Mg(ClO4)2 catalyst was stirred at room temperature for the time specified inTable 5. After completion of reaction (monitored by TLC),the solid or liquid product was filtered and washed with25 ml diethyl ether and water. The organic layer wassuccessively washed with saturated NaHCO3 solution. Theorganic layer was dried over anhydrous sodium sulfateand evaporated of the solvent under reduced pressure toprovide a residue which was passed through a short padof silica gel (60-120 mesh) using hexane as eluent to providethe analytically pure acylated product (please seeAppendix S1).Note that as we know that esterification is a reversiblereaction, to avoid this reversible we used every time activatedmolecular sieves as dehydrating agent/waterabsorbing agent. We have not mentioned it in our actualexperimental procedure. |
90% | With cetyltrimethylammonium chloride; potassium hexacyanoferrate(III) at 80℃; for 1h; |
With molecular sieve at 120℃; for 8h; | ||
With tin(II) chloride dihdyrate In acetonitrile at 24.84℃; for 6h; | ||
With N,N′,N′′,N′′′-hexadecyltrimethylammonium bis(trifluoromethylsulfonyl)imide; Novozym 435 (immobilized Candida antarctica lipase B) at 50℃; for 4h; Green chemistry; Enzymatic reaction; | Lipase-catalyzed synthesis of flavour esters in sponge-like ionic liquid (SLILs) Three mmol of citronellol, geraniol, nerol or anisyl alcohol, and 1, 2 or 3mmol of acetic acid were added to 3mL screw-capped vials with teflon-lined septa. Then, the corresponding amount of [C16tma][NTf2] was added to reach a final IL concentration of 60 or 70% (w/w) with respect to the mass substrates. Reaction mixtures were pre-incubated at 50°C for 10min, resulting in fully clear monophasic systems. Then, 80mg of MS13× per mmol of carboxylic acid were also added. The reaction was started by adding Novozym 435 (40mg/mmol of carboxylic acid) and the reaction was incubated for 4h at 50°C while shaking (300rpm), or under 4W microwave irradiation (which provided a 50°C constant temperature). For products analysis, aliquots (20μL) were taken at selected times and suspended in 500μL octane, and the resulting biphasic mixture was shaken to extract the products. The resulting mixture was centrifuged at 14,000rpm for 10min. Finally, 300μL of the octane extract were added to 100μL of a 100mM ethyl propionate (internal standard) solution in octane, and the final solution was analyzed by CG. For full recovery of the flavour ester products at 4h, the reaction mixtures were consecutively centrifuged four times at 14,000rpm (15min) and at room temperature, 21, 10 and 4°C, which resulted in a top liquid phase of flavour ester and a bottom solid phase containing the SLIL. For the case of anisyl acetate, the reaction mixture was cooled in an ice bath for 3h, and the resulting solid mixture was placed in a centrifugal filter, then centrifuged at 16,000rpm (10min) and at 0°C. This resulted in a top SLIL solid phase, which was retained inside the filter, and a bottom liquid phase of anisyl acetate. For all cases, a sample (10μL) of the resulting flavour ester phase was dissolved in 1mL acetone-δ6, then analyzed by 300MHz 1H NMR and 282MHz 19F NMR, in a Brucker AC 300E spectrometer for SLIL detection. All experiments were carried out in duplicate. | |
With Iron(III) nitrate nonahydrate In acetonitrile at 64.84℃; for 3h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With potassium fluoride on basic alumina In toluene for 1h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | Stage #1: citronellyl-acetate; 2,2,2-trichloroethyl sulfamate With tetra(trifluoroacetamidato)dirhodium(II); magnesium oxide In benzene at 0℃; Stage #2: With [bis(acetoxy)iodo]benzene In benzene at 0 - 25℃; for 8h; Further stages.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With selenium(IV) oxide; urea-hydrogen peroxide In water; isopropyl alcohol for 0.0111111h; microwave irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
44% | With (triphenylphosphine)gold(I) chloride; silver trifluoromethanesulfonate In toluene at 85℃; for 48h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 4 steps 1.1: SeO2; tBuOOH / CH2Cl2 1.2: 53 percent / NaBH4 2.1: 95 percent / pyridine / CH2Cl2 / 5 h / 20 °C 3.1: 63 percent / Li2CuCl4 / tetrahydrofuran / 3.5 h / -78 - 4 °C 4.1: 87 percent / H2 / 10 percent Pd/C / ethanol / 24 h / 20 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 8 steps 1.1: SeO2; tBuOOH / CH2Cl2 1.2: 53 percent / NaBH4 2.1: 95 percent / pyridine / CH2Cl2 / 5 h / 20 °C 3.1: 63 percent / Li2CuCl4 / tetrahydrofuran / 3.5 h / -78 - 4 °C 4.1: 87 percent / H2 / 10 percent Pd/C / ethanol / 24 h / 20 °C 5.1: pyridine / CH2Cl2 / 17 h / 4 °C 6.1: 3.33 g / NaI / dimethylformamide / 2 h / 50 °C 7.1: 99 percent / n-butyllithium; HMPA / tetrahydrofuran; hexane / -78 - 0 °C 8.1: 83 percent / lithium; EtNH2 / tetrahydrofuran / 2 h / -60 - -50 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 4 steps 1.1: SeO2; tBuOOH / CH2Cl2 1.2: 53 percent / NaBH4 2.1: 95 percent / pyridine / CH2Cl2 / 5 h / 20 °C 3.1: 70 percent / Li2CuCl4 / tetrahydrofuran / 3.5 h / -78 - 4 °C 4.1: 90 percent / H2 / 10 percent Pd/C / ethanol / 24 h / 20 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 6 steps 1.1: SeO2; tBuOOH / CH2Cl2 1.2: 53 percent / NaBH4 2.1: 95 percent / pyridine / CH2Cl2 / 5 h / 20 °C 3.1: 63 percent / Li2CuCl4 / tetrahydrofuran / 3.5 h / -78 - 4 °C 4.1: 87 percent / H2 / 10 percent Pd/C / ethanol / 24 h / 20 °C 5.1: pyridine / CH2Cl2 / 17 h / 4 °C 6.1: 3.33 g / NaI / dimethylformamide / 2 h / 50 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 6 steps 1.1: SeO2; tBuOOH / CH2Cl2 1.2: 53 percent / NaBH4 2.1: 95 percent / pyridine / CH2Cl2 / 5 h / 20 °C 3.1: 70 percent / Li2CuCl4 / tetrahydrofuran / 3.5 h / -78 - 4 °C 4.1: 90 percent / H2 / 10 percent Pd/C / ethanol / 24 h / 20 °C 5.1: pyridine / CH2Cl2 / 17 h / 4 °C 6.1: 1.80 g / NaI / dimethylformamide / 2 h / 50 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 5 steps 1.1: SeO2; tBuOOH / CH2Cl2 1.2: 53 percent / NaBH4 2.1: 95 percent / pyridine / CH2Cl2 / 5 h / 20 °C 3.1: 63 percent / Li2CuCl4 / tetrahydrofuran / 3.5 h / -78 - 4 °C 4.1: 87 percent / H2 / 10 percent Pd/C / ethanol / 24 h / 20 °C 5.1: pyridine / CH2Cl2 / 17 h / 4 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 5 steps 1.1: SeO2; tBuOOH / CH2Cl2 1.2: 53 percent / NaBH4 2.1: 95 percent / pyridine / CH2Cl2 / 5 h / 20 °C 3.1: 70 percent / Li2CuCl4 / tetrahydrofuran / 3.5 h / -78 - 4 °C 4.1: 90 percent / H2 / 10 percent Pd/C / ethanol / 24 h / 20 °C 5.1: pyridine / CH2Cl2 / 17 h / 4 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 8 steps 1.1: SeO2; tBuOOH / CH2Cl2 1.2: 53 percent / NaBH4 2.1: 95 percent / pyridine / CH2Cl2 / 5 h / 20 °C 3.1: 70 percent / Li2CuCl4 / tetrahydrofuran / 3.5 h / -78 - 4 °C 4.1: 90 percent / H2 / 10 percent Pd/C / ethanol / 24 h / 20 °C 5.1: pyridine / CH2Cl2 / 17 h / 4 °C 6.1: 1.80 g / NaI / dimethylformamide / 2 h / 50 °C 7.1: 85 percent / n-butyllithium; HMPA / tetrahydrofuran; hexane / -78 - 0 °C 8.1: 81 percent / lithium; EtNH2 / tetrahydrofuran / 2 h / -60 - -50 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 7 steps 1.1: SeO2; tBuOOH / CH2Cl2 1.2: 53 percent / NaBH4 2.1: 95 percent / pyridine / CH2Cl2 / 5 h / 20 °C 3.1: 63 percent / Li2CuCl4 / tetrahydrofuran / 3.5 h / -78 - 4 °C 4.1: 87 percent / H2 / 10 percent Pd/C / ethanol / 24 h / 20 °C 5.1: pyridine / CH2Cl2 / 17 h / 4 °C 6.1: 3.33 g / NaI / dimethylformamide / 2 h / 50 °C 7.1: 99 percent / n-butyllithium; HMPA / tetrahydrofuran; hexane / -78 - 0 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 7 steps 1.1: SeO2; tBuOOH / CH2Cl2 1.2: 53 percent / NaBH4 2.1: 95 percent / pyridine / CH2Cl2 / 5 h / 20 °C 3.1: 70 percent / Li2CuCl4 / tetrahydrofuran / 3.5 h / -78 - 4 °C 4.1: 90 percent / H2 / 10 percent Pd/C / ethanol / 24 h / 20 °C 5.1: pyridine / CH2Cl2 / 17 h / 4 °C 6.1: 1.80 g / NaI / dimethylformamide / 2 h / 50 °C 7.1: 85 percent / n-butyllithium; HMPA / tetrahydrofuran; hexane / -78 - 0 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: SeO2, t-BuOOH / toluene / 120 h / Ambient temperature 2: LiAlH4 / diethyl ether / 1 h |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: SeO2, t-BuOOH / toluene / 120 h / Ambient temperature 2: 81 percent / aq. K2CO3 / methanol / 1 h |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: SeO2, t-BuOOH / toluene / 120 h / Ambient temperature 2: NaBT4 / ethanol / 1 h 3: aq. K2CO3 / methanol / 1 h |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: SeO2, t-BuOOH / toluene / 120 h / Ambient temperature 2: LiAlH4 / diethyl ether / 1 h 3: 1.) (COCl)2, DMSO, 2.) Et3N / 1.) CH2Cl2, -78 deg C, 10 min, 2.) CH2Cl2, from -78 deg C to RT |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: SeO2, t-BuOOH / toluene / 120 h / Ambient temperature 2: NaBT4 / ethanol / 1 h |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 10 steps 1: 1.) SeO2, t-BuOOH, 2.) NaBH4 / 1.) CH2Cl2, 22 deg C, 2.) MeOH 2: 95 percent / imidazole / dimethylformamide / 0 °C 3: 95 percent / LiOH / methanol / 22 °C 4: 85 percent / PCC / CH2Cl2 / 1 h / 22 °C 5: 73 percent / LDA / tetrahydrofuran / 2 h / -78 - 20 °C 6: 89 percent / Dibal / CH2Cl2 / 0.17 h / -78 °C 7: LiH, SO3, pyridine / 2 h / 22 °C 8: LiAlH4 / 16 h / 22 °C 9: 96 percent / n-Bu4N(+)F(-) / tetrahydrofuran / 22 °C 10: 82 percent / PCC / CH2Cl2 / 1 h / 22 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 9 steps 1: 1.) SeO2, t-BuOOH, 2.) NaBH4 / 1.) CH2Cl2, 22 deg C, 2.) MeOH 2: 95 percent / imidazole / dimethylformamide / 0 °C 3: 95 percent / LiOH / methanol / 22 °C 4: 85 percent / PCC / CH2Cl2 / 1 h / 22 °C 5: 73 percent / LDA / tetrahydrofuran / 2 h / -78 - 20 °C 6: 89 percent / Dibal / CH2Cl2 / 0.17 h / -78 °C 7: LiH, SO3, pyridine / 2 h / 22 °C 8: LiAlH4 / 16 h / 22 °C 9: 96 percent / n-Bu4N(+)F(-) / tetrahydrofuran / 22 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: 1.) SeO2, t-BuOOH, 2.) NaBH4 / 1.) CH2Cl2, 22 deg C, 2.) MeOH 2: 95 percent / imidazole / dimethylformamide / 0 °C 3: 95 percent / LiOH / methanol / 22 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 4 steps 1: 1.) SeO2, t-BuOOH, 2.) NaBH4 / 1.) CH2Cl2, 22 deg C, 2.) MeOH 2: 95 percent / imidazole / dimethylformamide / 0 °C 3: 95 percent / LiOH / methanol / 22 °C 4: 85 percent / PCC / CH2Cl2 / 1 h / 22 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 8 steps 1: 1.) SeO2, t-BuOOH, 2.) NaBH4 / 1.) CH2Cl2, 22 deg C, 2.) MeOH 2: 95 percent / imidazole / dimethylformamide / 0 °C 3: 95 percent / LiOH / methanol / 22 °C 4: 85 percent / PCC / CH2Cl2 / 1 h / 22 °C 5: 73 percent / LDA / tetrahydrofuran / 2 h / -78 - 20 °C 6: 89 percent / Dibal / CH2Cl2 / 0.17 h / -78 °C 7: LiH, SO3, pyridine / 2 h / 22 °C 8: LiAlH4 / 16 h / 22 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 6 steps 1: 1.) SeO2, t-BuOOH, 2.) NaBH4 / 1.) CH2Cl2, 22 deg C, 2.) MeOH 2: 95 percent / imidazole / dimethylformamide / 0 °C 3: 95 percent / LiOH / methanol / 22 °C 4: 85 percent / PCC / CH2Cl2 / 1 h / 22 °C 5: 73 percent / LDA / tetrahydrofuran / 2 h / -78 - 20 °C 6: 89 percent / Dibal / CH2Cl2 / 0.17 h / -78 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: 1.) SeO2, t-BuOOH, 2.) NaBH4 / 1.) CH2Cl2, 22 deg C, 2.) MeOH 2: 95 percent / imidazole / dimethylformamide / 0 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 5 steps 1: 1.) SeO2, t-BuOOH, 2.) NaBH4 / 1.) CH2Cl2, 22 deg C, 2.) MeOH 2: 95 percent / imidazole / dimethylformamide / 0 °C 3: 95 percent / LiOH / methanol / 22 °C 4: 85 percent / PCC / CH2Cl2 / 1 h / 22 °C 5: 73 percent / LDA / tetrahydrofuran / 2 h / -78 - 20 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 7 steps 1: 1.) SeO2, t-BuOOH, 2.) NaBH4 / 1.) CH2Cl2, 22 deg C, 2.) MeOH 2: 95 percent / imidazole / dimethylformamide / 0 °C 3: 95 percent / LiOH / methanol / 22 °C 4: 85 percent / PCC / CH2Cl2 / 1 h / 22 °C 5: 73 percent / LDA / tetrahydrofuran / 2 h / -78 - 20 °C 6: 89 percent / Dibal / CH2Cl2 / 0.17 h / -78 °C 7: LiH, SO3, pyridine / 2 h / 22 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 13 steps 1: 1.) SeO2, t-BuOOH, 2.) NaBH4 / 1.) CH2Cl2, 22 deg C, 2.) MeOH 2: 95 percent / imidazole / dimethylformamide / 0 °C 3: 95 percent / LiOH / methanol / 22 °C 4: 85 percent / PCC / CH2Cl2 / 1 h / 22 °C 5: 73 percent / LDA / tetrahydrofuran / 2 h / -78 - 20 °C 6: 89 percent / Dibal / CH2Cl2 / 0.17 h / -78 °C 7: LiH, SO3, pyridine / 2 h / 22 °C 8: LiAlH4 / 16 h / 22 °C 9: 96 percent / n-Bu4N(+)F(-) / tetrahydrofuran / 22 °C 10: 82 percent / PCC / CH2Cl2 / 1 h / 22 °C 11: 72 percent / potassium tert-butoxide / tetrahydrofuran / 4 h 12: 2.) LDA / 1.) o-dichlorobenzene, reflux, 5 min, 2.) THF, -78, 20 min 13: 60 percent / boron trichloride / CH2Cl2 / 0.02 h / -78 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 12 steps 1: 1.) SeO2, t-BuOOH, 2.) NaBH4 / 1.) CH2Cl2, 22 deg C, 2.) MeOH 2: 95 percent / imidazole / dimethylformamide / 0 °C 3: 95 percent / LiOH / methanol / 22 °C 4: 85 percent / PCC / CH2Cl2 / 1 h / 22 °C 5: 73 percent / LDA / tetrahydrofuran / 2 h / -78 - 20 °C 6: 89 percent / Dibal / CH2Cl2 / 0.17 h / -78 °C 7: LiH, SO3, pyridine / 2 h / 22 °C 8: LiAlH4 / 16 h / 22 °C 9: 96 percent / n-Bu4N(+)F(-) / tetrahydrofuran / 22 °C 10: 82 percent / PCC / CH2Cl2 / 1 h / 22 °C 11: 72 percent / potassium tert-butoxide / tetrahydrofuran / 4 h 12: 2.) LDA / 1.) o-dichlorobenzene, reflux, 5 min, 2.) THF, -78, 20 min |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 11 steps 1: 1.) SeO2, t-BuOOH, 2.) NaBH4 / 1.) CH2Cl2, 22 deg C, 2.) MeOH 2: 95 percent / imidazole / dimethylformamide / 0 °C 3: 95 percent / LiOH / methanol / 22 °C 4: 85 percent / PCC / CH2Cl2 / 1 h / 22 °C 5: 73 percent / LDA / tetrahydrofuran / 2 h / -78 - 20 °C 6: 89 percent / Dibal / CH2Cl2 / 0.17 h / -78 °C 7: LiH, SO3, pyridine / 2 h / 22 °C 8: LiAlH4 / 16 h / 22 °C 9: 96 percent / n-Bu4N(+)F(-) / tetrahydrofuran / 22 °C 10: 82 percent / PCC / CH2Cl2 / 1 h / 22 °C 11: 72 percent / potassium tert-butoxide / tetrahydrofuran / 4 h |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 12 steps 1: 1.) SeO2, t-BuOOH, 2.) NaBH4 / 1.) CH2Cl2, 22 deg C, 2.) MeOH 2: 95 percent / imidazole / dimethylformamide / 0 °C 3: 95 percent / LiOH / methanol / 22 °C 4: 85 percent / PCC / CH2Cl2 / 1 h / 22 °C 5: 73 percent / LDA / tetrahydrofuran / 2 h / -78 - 20 °C 6: 89 percent / Dibal / CH2Cl2 / 0.17 h / -78 °C 7: LiH, SO3, pyridine / 2 h / 22 °C 8: LiAlH4 / 16 h / 22 °C 9: 96 percent / n-Bu4N(+)F(-) / tetrahydrofuran / 22 °C 10: 82 percent / PCC / CH2Cl2 / 1 h / 22 °C 11: 72 percent / potassium tert-butoxide / tetrahydrofuran / 4 h 12: 1,2-dichloro-benzene / 0.08 h / Heating |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 12 steps 1: 1.) SeO2, t-BuOOH, 2.) NaBH4 / 1.) CH2Cl2, 22 deg C, 2.) MeOH 2: 95 percent / imidazole / dimethylformamide / 0 °C 3: 95 percent / LiOH / methanol / 22 °C 4: 85 percent / PCC / CH2Cl2 / 1 h / 22 °C 5: 73 percent / LDA / tetrahydrofuran / 2 h / -78 - 20 °C 6: 89 percent / Dibal / CH2Cl2 / 0.17 h / -78 °C 7: LiH, SO3, pyridine / 2 h / 22 °C 8: LiAlH4 / 16 h / 22 °C 9: 96 percent / n-Bu4N(+)F(-) / tetrahydrofuran / 22 °C 10: 82 percent / PCC / CH2Cl2 / 1 h / 22 °C 11: 72 percent / potassium tert-butoxide / tetrahydrofuran / 4 h 12: 1,2-dichloro-benzene / 0.08 h / Heating |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: 98.5 percent / Me2AlCl / heptane; CH2Cl2 / 1 h / 0 °C 2: 95 percent / pyridine / 25 °C 3: 87 percent / NaI / acetone / 11 h / Heating |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: 98.5 percent / Me2AlCl / heptane; CH2Cl2 / 1 h / 0 °C 2: 95 percent / pyridine / 25 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: 95 percent / 85percent m-Chloroperoxybenzoic acid / CHCl3 / 1.) 0 deg C, 2.) 24 h, room temp. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: 95 percent / 85percent m-Chloroperoxybenzoic acid / CHCl3 / 1.) 0 deg C, 2.) 24 h, room temp. 3: Et3N, methanesulfonyl chloride |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75.2% | 5 Example 5 There were thus obtained 4.46 g of (E)-7-hydroperoxy-3,7-dimethyl-5-octen-1-yl acetate in a purity of 95%; nD23 =1.460; yield 75.2% based on reacted citronellol acetate. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With water; dihydrogen peroxide Potassium phosphate 50 mM; Potassium chloride 20 mM; | 2 Determination of Perhydrolysis (OPD Assay)The perhydrolytic activity assay described below was used to determine the amount of peracid formed in the reaction. In these assays, the solution comprised 50 mM potassium phosphate pH 7.5, 10 mM ester substrate, 29 mM hydrogen peroxide, 20 mM potassium chloride, and 10 mM O-phenylenediamine.When using water insoluble ester as the acyl donor, an ester adsorbed fabric swatch was used as the substrate, prepared as described above (“Preparation of Substrate”).Perhydrolytic activity was measured by monitoring the absorbance increase at 458 nm of oxidized O-phenylenediamine (OPD) by peracid generated with the enzyme. The perhydrolytic activity assay solution was prepared in the same manner as the hydrolytic activity assay solution, except that OPD was added to the assay solution to a final concentration of 10 mM. The OPD solution was prepared immediately before conducting the assay by dissolving 72 mg OPD (Sigma-Aldrich, dihydrochloride) in 19.94 mL of the same buffer and the pH was adjusted by slowly adding 60 μL of 13.5 M potassium hydroxide. The pH was measured and if needed, small quantities of potassium hydroxide were added to return the pH to the original pH of the buffer. Then, 495 μL of this OPD solution were added with the other assay components to a final assay volume of 0.990 mL. An assay quenching solution was also prepared by dissolving 36 mg OPD in 20 mL 100 mM citric acid and 70% ethanol.The assay was typically conducted at 25° C. The assay was started by pipetting 100 μL of assay solution before the addition of the enzyme into 200 μL of quenching solution to determine the amount of perhydrolytic components and background absorbance in the assay solution at time 0. Then, 10 μL of enzyme were added to the assay solution to a desired final concentration which produced approximately 10 nanomoles of peracid per minute. A timer was started and 100 μL aliquots were taken from the assay solution and added to 200 μL of quenching solution at various times, typically 2, 5, 10, 15, 25, 40, and 60 minutes, after adding the enzyme. The quenched assay solutions were incubated for 30 minutes to allow any remaining peracid to oxidize the OPD. Then, 100 μL of each quenched assay solution was transferred to a 96-well microtiter plate (Costar) and the absorbance of the solution was measured at 458 nm by a spectrophotometric plate reader (Molecular Devices, SpectraMAX 250). The amount of peracid in each quenched sample was calculated using a standard curve generated under the above conditions with peracetic acid at varying concentrations in the assay solution (without enzyme).Perhydrolysis/Hydrolysis Ratio:Perhydrolysis/Hydrolysis ratio=Perhydrolysis measured in the Perhydrolysis assay/(Total acid detected in the hydrolysis assay-Perhydrolysis measured in the perhydrolysis assay)The results of these experiments are provided in FIGS. 7, 10 and FIG. 11. FIG. 7 provides a graph which shows the ratio of perbutyric acid to butyric acid generated by various enzymes from 10 mM tributyrin and 29 mM hydrogen peroxide in 40 minutes. FIG. 10 shows the ratio of perbutyric acid to butyric acid generated by various enzymes from 10 mM tributyrin and 29 mM hydrogen peroxide in 4, 10, and 30 minutes. FIG. 11 shows the ratio of peracetic acid to acetic acid generated by various enzymes from 10 mM triacetin and 29 mM hydrogen peroxide in 4 and 10 minutes. The results obtained in these experiments indicated that M. smegmatis perhydrolase homologues exhibited a ratio above 1 in the OPD/GC assays described above, while other classes of enzymes exhibited ratios significantly below 1.Table 2-1 provides data showing the perhydrolysis activity of various homologues described herein on triacetin, as compared to the wild-type M. smegmatis perhydrolase. The results provided in Table 2-2 indicate that the perhydrolase has activity over a broad range of substrates. In addition to the results provided in these Tables, FIGS. 8 and 9 provide data showing that the perhydrolase of the present invention has broad pH and temperature range activiti |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With pyridine; toluene-4-sulfonic acid In dichloromethane |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
43% | With [1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene][2-isopropoxy-5-(2,2,2-trifluoroacetamido)benzylidene]ruthenium(II) dichloride In ethyl acetate at 80℃; for 1h; Inert atmosphere; | |
43% | In ethyl acetate at 80℃; for 1h; Inert atmosphere; | 1 [0061] Example 1[0062] The reactivity of different terpenoids compounds, using different olefins in the presence of catalyst Cla according to Scheme 1, was investigated. S6 S7Citronellol acetate DihydromyrcenolScheme 1 : Screening of terpenoids in olefin cross-metathesis catalyzed by catalyst Cla[0063] The reaction was run in ethylacetate solvent and the results are summarized in Table 1.[0064] Table 1 : Screening of terpenoid compounds S6-S7 in olefin cross-metathesis[0065] Terpenoid compounds having only one double bond were reacted. When citronellol acetate S6 was reacted with n-butyl acrylate (2 eq.) Ol in AcOEt in the presence of 1 mol% of catalyst Cla, the expected product P4 was obtained in 43% isolated yield. [0066] Terpenoid compounds having two double bonds were reacted. The second double bond was masked, for instance as the hydrated form. The reactivity of dihydromyrcenol S7 was evaluated. S7 can be considered as a derivative of citronellene where one double bond is masked as a hydroxyl group. The double bond could be regenerated later from the alcohol through a simple elimination reaction. When S7 was reacted 17h at 60°C with n- butyl acrylate (2 eq.) Ol and in the presence of 1 mol% of catalyst Cla, the expected olefin cross-metathesis product P5 was obtained in an isolated yield of 71%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride; toluene-4-sulfonic acid In water at 22℃; for 12h; Sealed vial; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride; toluene-4-sulfonic acid In water at 22℃; for 12h; Sealed vial; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94 %Chromat. | With steapsin lipase In hexane at 55℃; for 24h; Enzymatic reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | With bis(dimethyl-di-n-octylammonium) molybdate; dihydrogen peroxide In cyclohexane; water at 25℃; for 6.6h; | Typical catalytic experiments General procedure: [DiC8]2[MoO4] (11.1 mg, 15.8 mol), C8E4 (211.1 mg,0.689 mmol), H2O (1.0 g), cyclohexane (1.0 g) were added consecutively to prepare the microemulsion in a reaction tube. Then-terpinene (50 mg, 0.367 mmol) was added into the mixture and kept at 30C (Winsor IV), the H2O2 (50 wt.%, 17 M) was added stepwise (10 L, each 20 min). The conversion was complete afterthe addition of 6× 10 L (1.02 mmol). Then the reaction tube was kept still at 5C for 3 h, the oil phase was separated and themicroemulsion phase was washed with cyclohexane (1 mL) at 5C, the organic phases were combined and cyclohexane was removed by evaporation, the crude product was purified by asmall chromatography on silica gel (cyclohexane/AcOEt = 5:1) and pure colorless oil was obtained |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
51 %Spectr. | With trityl tetrafluoroborate In dichloromethane at -20℃; for 135h; diastereoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
47% | With trityl tetrafluoroborate In dichloromethane at -20℃; for 135h; diastereoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
26% | With trityl tetrafluoroborate In dichloromethane at -20℃; for 135h; diastereoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
45% | With potassium <i>tert</i>-butylate In 1,4-dioxane at 120℃; for 65h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With zinc(II) oxide at 120℃; for 3h; | 3 The sec-butyl acetate and citronellol were added to the reactor in a reactor at a molar ratio of 3: 1,And 2 parts by weight of zinc oxide was added as a catalyst to 100 parts by weight of the amount of citronelly, and reacted at 120 ° C for 3 hours under normal pressure. After the completion of the reaction, the obtained product was fed to a separation column, and the reflux temperature of the column top gas phase was controlled at 100C to remove the azeotrope of sec-butyl acetate and sec-butyl alcohol, and then the distillation was carried out under reduced pressure , Collecting citronellyl acetate. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 4 steps 1.1: ; tert.-butylhydroperoxide / dichloromethane; water / 24 h / 20 °C 2.1: n-butyllithium / tetrahydrofuran; hexane / 2.5 h / 0 °C / Inert atmosphere 2.2: -78 - 20 °C / Inert atmosphere 3.1: potassium carbonate / methanol / 2 h / 20 °C / Inert atmosphere 4.1: 2,6-di-tert-butyl-4-methyl-phenol; 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione / <i>tert</i>-butyl alcohol / 0.42 h / Inert atmosphere; Reflux |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 5 steps 1.1: ; tert.-butylhydroperoxide / dichloromethane; water / 24 h / 20 °C 2.1: n-butyllithium / tetrahydrofuran; hexane / 2.5 h / 0 °C / Inert atmosphere 2.2: -78 - 20 °C / Inert atmosphere 3.1: potassium carbonate / methanol / 2 h / 20 °C / Inert atmosphere 4.1: 2,6-di-tert-butyl-4-methyl-phenol; 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione / <i>tert</i>-butyl alcohol / 0.42 h / Inert atmosphere; Reflux 5.1: diisopropylamine; n-butyllithium / tetrahydrofuran / 1 h / -78 °C / Inert atmosphere 5.2: 0.45 h / -78 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 6 steps 1.1: ; tert.-butylhydroperoxide / dichloromethane; water / 24 h / 20 °C 2.1: n-butyllithium / tetrahydrofuran; hexane / 2.5 h / 0 °C / Inert atmosphere 2.2: -78 - 20 °C / Inert atmosphere 3.1: potassium carbonate / methanol / 2 h / 20 °C / Inert atmosphere 4.1: 2,6-di-tert-butyl-4-methyl-phenol; 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione / <i>tert</i>-butyl alcohol / 0.42 h / Inert atmosphere; Reflux 5.1: diisopropylamine; n-butyllithium / tetrahydrofuran / 1 h / -78 °C / Inert atmosphere 5.2: 0.45 h / -78 °C / Inert atmosphere 6.1: 2,6-di-tert-butyl-4-methyl-phenol; 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione / ethyl acetate / 0.83 h / Inert atmosphere; Reflux |
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3,7-Dimethyloct-6-en-1-yl propionate
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3,7-Dimethyloct-6-en-1-yl butyrate
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[ 68922-10-1 ]
3,7-Dimethyloct-6-en-1-yl 3-methylbutanoate
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[ 97-89-2 ]
3,7-Dimethyloct-6-en-1-yl isobutyrate
Similarity: 0.88
[ 85409-36-5 ]
2,3,7-Trimethyloct-6-en-1-yl butyrate
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[ 141-14-0 ]
3,7-Dimethyloct-6-en-1-yl propionate
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[ 141-16-2 ]
3,7-Dimethyloct-6-en-1-yl butyrate
Similarity: 0.91
[ 68922-10-1 ]
3,7-Dimethyloct-6-en-1-yl 3-methylbutanoate
Similarity: 0.91
[ 97-89-2 ]
3,7-Dimethyloct-6-en-1-yl isobutyrate
Similarity: 0.88
[ 85409-36-5 ]
2,3,7-Trimethyloct-6-en-1-yl butyrate
Similarity: 0.88