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[ CAS No. 87-44-5 ] {[proInfo.proName]}

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Cat. No.: {[proInfo.prAm]}
Chemical Structure| 87-44-5
Chemical Structure| 87-44-5
Structure of 87-44-5 * Storage: {[proInfo.prStorage]}
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Product Details of [ 87-44-5 ]

CAS No. :87-44-5 MDL No. :MFCD00075925
Formula : C15H24 Boiling Point : -
Linear Structure Formula :- InChI Key :-
M.W : 204.35 Pubchem ID :-
Synonyms :
(-)-(E)-Caryophyllene;(−)-trans-Caryophyllene;E-Caryophyllene;CCRIS 8094;AI3-36121;Caryophyllene;NSC 11906;(−)-β-caryophyllene

Calculated chemistry of [ 87-44-5 ]

Physicochemical Properties

Num. heavy atoms : 15
Num. arom. heavy atoms : 0
Fraction Csp3 : 0.73
Num. rotatable bonds : 0
Num. H-bond acceptors : 0.0
Num. H-bond donors : 0.0
Molar Refractivity : 68.78
TPSA : 0.0 Ų

Pharmacokinetics

GI absorption : Low
BBB permeant : No
P-gp substrate : No
CYP1A2 inhibitor : No
CYP2C19 inhibitor : Yes
CYP2C9 inhibitor : Yes
CYP2D6 inhibitor : No
CYP3A4 inhibitor : No
Log Kp (skin permeation) : -4.44 cm/s

Lipophilicity

Log Po/w (iLOGP) : 3.29
Log Po/w (XLOGP3) : 4.38
Log Po/w (WLOGP) : 4.73
Log Po/w (MLOGP) : 4.63
Log Po/w (SILICOS-IT) : 4.19
Consensus Log Po/w : 4.24

Druglikeness

Lipinski : 1.0
Ghose : None
Veber : 0.0
Egan : 0.0
Muegge : 1.0
Bioavailability Score : 0.55

Water Solubility

Log S (ESOL) : -3.87
Solubility : 0.0278 mg/ml ; 0.000136 mol/l
Class : Soluble
Log S (Ali) : -4.1
Solubility : 0.0164 mg/ml ; 0.0000801 mol/l
Class : Moderately soluble
Log S (SILICOS-IT) : -3.77
Solubility : 0.0349 mg/ml ; 0.000171 mol/l
Class : Soluble

Medicinal Chemistry

PAINS : 0.0 alert
Brenk : 1.0 alert
Leadlikeness : 2.0
Synthetic accessibility : 4.51

Safety of [ 87-44-5 ]

Signal Word:Warning Class:N/A
Precautionary Statements:P264-P270-P273-P301+P312-P330 UN#:N/A
Hazard Statements:H302-H413 Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 87-44-5 ]

* 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.

  • Downstream synthetic route of [ 87-44-5 ]

[ 87-44-5 ] Synthesis Path-Downstream   1~75

  • 4
  • [ 87-44-5 ]
  • [ 1139-30-6 ]
YieldReaction ConditionsOperation in experiment
66% With sodium hydrogencarbonate; 3-chloro-benzenecarboperoxoic acid; In dichloromethane; at 20℃; for 2h; Compound 1beta-caryophyllene (5.5 mL, 5 g, 24.45 mol) was dissolved in dry dichloromethane solution (35 mL).Add 15% NaHCO3 (68ml) at room temperature.After mixing well, add mCPBA (7.4g, 36.675mmol) slowly.After stirring for two hours, the reaction was quenched with 15% NaOH solution (100 ml).The organic phase was washed with saturated brine (100 ml x 3) and the resulting organic phase was dried over anhydrous sodium sulfate.Recrystallization gave 3.48 g (compound 7) as a white solid in 66% yield.
  • 9
  • [ 87-44-5 ]
  • [ 62560-57-0 ]
  • [ 58404-89-0 ]
  • [ 131717-65-2 ]
  • (3aR,7aR)-3a,7a-dimethyl-4-(2-methyl-1-propenyl)-2,3,3a,6,7,7a-hexahydro-1H-indene [ No CAS ]
  • 11
  • [ 87-44-5 ]
  • [ 58404-89-0 ]
  • [ 131717-65-2 ]
  • [ 118-65-0 ]
  • [ 56633-28-4 ]
  • 12
  • [ 87-44-5 ]
  • [ 58404-89-0 ]
  • [ 131717-65-2 ]
  • [ 136296-35-0 ]
  • (3aR,7aR)-3a,7a-dimethyl-4-(2-methyl-1-propenyl)-2,3,3a,6,7,7a-hexahydro-1H-indene [ No CAS ]
  • 13
  • [ 87-44-5 ]
  • [ 58404-89-0 ]
  • [ 131717-65-2 ]
  • [ 136296-37-2 ]
  • (3aR,7aR)-3a,7a-dimethyl-4-(2-methyl-1-propenyl)-2,3,3a,6,7,7a-hexahydro-1H-indene [ No CAS ]
  • 14
  • [ 87-44-5 ]
  • [ 58404-89-0 ]
  • [ 131717-65-2 ]
  • [ 136296-36-1 ]
  • (3aR,7aR)-3a,7a-dimethyl-4-(2-methyl-1-propenyl)-2,3,3a,6,7,7a-hexahydro-1H-indene [ No CAS ]
  • 15
  • [ 87-44-5 ]
  • [ 58404-89-0 ]
  • [ 131717-65-2 ]
  • [ 56684-96-9 ]
  • (3aR,7aR)-3a,7a-dimethyl-4-(2-methyl-1-propenyl)-2,3,3a,6,7,7a-hexahydro-1H-indene [ No CAS ]
  • 16
  • [ 87-44-5 ]
  • [ 58404-89-0 ]
  • [ 131717-65-2 ]
  • [ 56684-96-9 ]
  • (1Z,5Z,9S)-2,6,10,10-tetramethylbicyclo<7.2.0>undeca-1,5-diene [ No CAS ]
  • 17
  • [ 87-44-5 ]
  • [ 58404-89-0 ]
  • [ 131717-65-2 ]
  • [ 80374-27-2 ]
  • (1S,2R,5Z,9R)-2,6,10,10-tetramethyltricyclo<7.2.0.02,5>undec-5-ene [ No CAS ]
  • 18
  • [ 87-44-5 ]
  • [ 58404-89-0 ]
  • [ 131717-65-2 ]
  • (3aR,7aR)-3a,7a-dimethyl-4-(2-methyl-1-propenyl)-2,3,3a,6,7,7a-hexahydro-1H-indene [ No CAS ]
  • (1S,2R,5R,6Z,9R)-2,6,10,10-tetramethyltricyclo<7.2.0.02,5>undec-6-ene [ No CAS ]
  • 19
  • [ 87-44-5 ]
  • [ 469-92-1 ]
  • (1S,2R,5Z,9R)-2,6,10,10-tetramethyltricyclo<7.2.0.02,5>undec-5-ene [ No CAS ]
  • [ 169220-03-5 ]
  • 20
  • (E)-caryophyll-4-en-8-yl p-nitrobenzoate [ No CAS ]
  • [ 87-44-5 ]
  • [ 169220-06-8 ]
  • [ 60269-12-7 ]
  • 21
  • [ 87-44-5 ]
  • [ 95-48-7 ]
  • (1R,2S,5R,8S)-2-methyl-4-(4,4,8-trimethyltricyclo[6.3.1.02,5]dodec-1-yl)phenol [ No CAS ]
  • 22
  • [ 87-44-5 ]
  • [ 108-46-3 ]
  • (1R,2S,5R,8S)-4-(4,4,8-trimethyltricyclo[6.3.1.02,5]dodec-1-yl)benzene-1,3-diol [ No CAS ]
  • 23
  • [ 67-56-1 ]
  • [ 87-44-5 ]
  • [ 101927-11-1 ]
  • 24
  • [ 87-44-5 ]
  • [ 101979-01-5 ]
  • 25
  • [ 87-44-5 ]
  • oxygen [ No CAS ]
  • [ 131830-35-8 ]
  • 26
  • [ 87-44-5 ]
  • oxygen [ No CAS ]
  • [ 169220-06-8 ]
  • 27
  • [ 87-44-5 ]
  • oxygen [ No CAS ]
  • [ 169129-20-8 ]
  • 28
  • [ 87-44-5 ]
  • oxygen [ No CAS ]
  • [ 169220-05-7 ]
  • 29
  • [ 87-44-5 ]
  • oxygen [ No CAS ]
  • 3',5'-dinitrobenzoic acid (1S,2R,5R,6S,9R)-2,6,10,10-tetramethyltricyclo<7.2.0.02,5>undec-6-yl ester [ No CAS ]
  • 30
  • [ 87-44-5 ]
  • oxygen [ No CAS ]
  • 3',5'-dinitrobenzoic acid (1S,2R,5R,6R,9R)-2,6,10,10-tetramethyltricyclo<7.2.0.02,5>undec-6-yl ester [ No CAS ]
  • 31
  • [ 60362-44-9 ]
  • [ 1779-49-3 ]
  • [ 87-44-5 ]
YieldReaction ConditionsOperation in experiment
48% To methyltriphenylphosphonium bromide (0.173 g, 0.50 mmol) in THF (1.0 mL) under nitrogen at -78C was added n-BuLi (0.29 mL, 0.40 mmol, 1.4M in THF) dropwise. The resulting mixture was stirred at 0C for 10 min, then cooled to -78C before adding caryophyllene ketone 10 (0.05 g, 0.24 mmol) in THF (1 mL) dropwise. The mixture was warmed to room temperature and stirred for a further 24 h. Water (5 mL) was slowly added, and the resulting mixture extracted with diethyl ether (25 mL). The organic layer was washed with 2M HCl (5 mL), then 4M NaOH (5 mL). The combined basic aqueous washes were further extracted with diethyl ether (3 x 20 mL). The combined organic extracts were dried (MgSO4) and the solvent was removed in vacuo. The crude product was purified using flash chromatography (petroleum ether) to give the title product 13 (0.071g, 48%) as a clear colourless oil.
  • 32
  • [ 87-44-5 ]
  • palladium dichloride [ No CAS ]
  • di-μ-chloro(exo-η(3)-carophyllenyl)dipalladium(II) [ No CAS ]
  • 33
  • [ 528-43-8 ]
  • [ 87-44-5 ]
  • [ 130756-35-3 ]
  • [ 133056-11-8 ]
  • 34
  • [ 87-44-5 ]
  • [ 31056-66-3 ]
YieldReaction ConditionsOperation in experiment
With hydrogen;5% Pd(II)/C(eggshell); In ethanol; at 50℃; under 25877.6 Torr; for 2h; An 18.5 wt % solution of caryophyllene (Sigma-Aldrich; St. Louis, Mo.; purchased as beta-caryophyllene) in absolute ethanol was prepared. GC-MS and NMR analysis of the caryophyllene indicated that it was a mixture of both the alpha- (13.31) and beta- (86.7%) isomers (MW 204).This solution was hydrogenated using ESCAT-142 (Engelhard, Iselin, N.J.; 5% Pd/C powder catalyst) using 10% powdered catalyst by weight relative to the beta caryophellene; the reaction was carried out for 2 hours at 50 C. and 3.45 MPa hydrogen pressure. GC-MS and NMR analysis of the hydrogenated solution indicated that alpha-caryophyllene (alpha-humulene) was not hydrogenated, and beta-caryophyllene was converted to dihydro-beta-caryophyllene.
  • 35
  • [ 87-44-5 ]
  • [ 4396-13-8 ]
  • [ 100-52-7 ]
  • psidial A [ No CAS ]
  • [ 1219603-97-0 ]
  • guajadial [ No CAS ]
  • 36
  • [ 87-44-5 ]
  • [ 24844-34-6 ]
YieldReaction ConditionsOperation in experiment
With sulfuric acid; In diethyl ether; Example 15 In a 3 L four-necked flask was placed 680 mL of diethyl ether, to which 360 g of concentrated sulfuric acid and 920 g of beta-caryophyllene (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were slowly added dropwise at 0 C. After 20 hours, the reaction mixture was washed with aqueous sodium hydroxide solution and collected by steam distillation. This was then separated by silica gel chromatography. The fractional distillation of the product gave 100 g of an isomerization product of beta-caryophyllene. This was diluted with 300 mL of hexane and charged in a 1 L autoclave together with 9 g of a palladium-carbon hydrogenation catalyst and subjected to hydrogenation (hydrogen pressure: 6 MPa, reaction temperature: 100 C., reaction time: 1 hour). After completion of the reaction, the catalyst was removed by filtration. The filtrate was distilled under reduced pressure to obtain 95 g of desired 4,7a,9,9-tetramethyl-octahydro-1,3a-ethano-indene (Fluid 7). The results of the measurements of the properties and the traction coefficient are shown in Table 1.
  • 37
  • [ 87-44-5 ]
  • [ 1332835-53-6 ]
  • [ 122-51-0 ]
  • [ 1332835-54-7 ]
  • 38
  • [ 87-44-5 ]
  • [ 3691-12-1 ]
  • [ 18374-76-0 ]
  • [ 60594-22-1 ]
YieldReaction ConditionsOperation in experiment
Composition (%w/w) of the starting olefinic mixture according to GC-MS analysis : &eiemene (0.3), beta-patchoulene (5.6), beta-elemene (3), cycloseychellene (1.75), beta-caryophyllene (7), a- guaiene (27), a-patchoulene (10), seychellene (14), delta-patchoulene (5.5), ^patchoulene (0.45), a-humulene (1), aciphyllene (4), a-bulnesene (18).A mixture of alpha-guaiene rich olefinic fraction (200 g), 1 M KH2PO4/K2HPO4 pH 7.5 buffer solution (200 ml), DeniUte II S laccase (20 g; from Novozymes), and water (1600 ml) was stirred vigorously while a slow flow of air was bubbled through the sintered glass end of a gas introduction tube, and heated at 40C for 46 hours. Air-bubbling was stopped and NaOH (20 g, 1 0.5 mol) was added into the mixture that was heated to reflux under vigorous stirring and N - bubbling for 9.5 h while the colour of the mixture turned from yellow to brown The resulting mixture was cooled to 25, poured into H20 (750 ml), and extracted twice with MTBE (750 and 350 ml). The joined organic phases were washed twice with H20 (250 ml) and once with aqueous saturated NaCI solution (250 ml), and dried with MgS04. Filtration and evaporation of the solvent led to 188 g of crude material. Short-path distillation led to 55.5 g (28 % yield based on 200 g olefinic mixture) of olfactorily pure material (fractions 8-15, 104-153C/0.10 mbar, oil bath temperature 125-175C).GC-analysis: 7.0% caryophyllene oxide, 2.9% (1R,3S,5f?,8S)-3,8-dimethyl-5-(prop-1-en-2-yl)- 1, 2,3,4,5,6, 7,8-octahydroazulen-1-ol, 3.1% (1 S,3S,5R,8S)-epimer, 4.2% 3-patchoulenone, 7.2% rotundone, 0.3% ct-bulnesenone, 0.5% (1f?,3S,3aS,5R)-3,8-dimethyl-5-(prop-1-en-2-yl)- 1 ,2,3,3a,4,5,6,7-octahydroazulen-1-ol (compound of formula I), 0.9% (1 S,3S,3aS,5R)-3,8- dimethyl-5-(prop-1-en-2-yl)-1 ,2,3,3a,4,5,6,7-octahydroazulen-1-ol (compound of formula I).Odour description of the mixture (fraction 8-15): woody, floral, tobacco, reminiscent of some aspects of patchouli and pepper.
  • 39
  • [ 87-44-5 ]
  • [ 3691-12-1 ]
  • [ 1139-30-6 ]
  • [ 1353713-25-3 ]
  • [ 18374-76-0 ]
YieldReaction ConditionsOperation in experiment
Composition (% wfw)) of the starting olefinic mixture according to GC-MS analysis: delta-elemene (0.14), beta-patchoulene (3.8), cycloseychellene (2.3), beta-caryophyllene (12), cc-guaiene (49), a- patchouiene (11), seychel.ene (14.5), aciphyllene (0.2), a-buinesene (0.4).A mixture of alpha-guaiene rich olefinic fraction (500 g), M KH2PO4/K2HPO4 pH 7.5 buffer solution (200 ml), DeniLite II S laccase (20 g), and water ( 300 ml) was stirred vigorously while a slow flow of air was bubbled through the sintered glass end of a gas introduction tube, and heated at 40C for 69 hours. Air-bubbling was stopped and NaOH (20 g, 0.5 mol) was added into the mixture that was heated to reflux under vigorous stirring and N2-bubbling for 8 h while the colour of the mixture turned from yellow to brown The resulting mixture was cooled to 25, poured into H20 (1500 ml), and extracted twice with TBE (1500 and 1000 ml). The joined organic phases were washed twice with H20 (500 ml) and once with aqueous saturated NaCI solution (500 ml), and dried with MgS04. Filtration and evaporation of the solvent led to 493 g of crude material. Short-path distillation led to 140 g (28 % yield based on 500 g olefinic mixture) of olfactorily pure material (fractions 6-13, 105-147C/0.05 mbar, oil bath temperature 130- 80C). GC-analysis: 15.0% caryophyllene oxides, 5.4% ( R,3S,5 8S)-3,8-dimethyl-5-(prop-1-en-2- yl)-1 ,2,3,4,5,6,7,8-octahydroazulen-1-ol, 4.5% (1 S,3S,5R,8S)-epimer, 2.7% ?-patchoulenone, 2.9% rotundone.Odour description of the mixture (fraction 6-13): woody, floral, tobacco, reminiscent of some aspects of patchouli and pepper.
  • 40
  • [ 87-44-5 ]
  • C8H8N3O3Pol [ No CAS ]
  • [ 1350541-06-8 ]
  • 41
  • [ 87-44-5 ]
  • [ 69842-07-5 ]
YieldReaction ConditionsOperation in experiment
With 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone; sodium tetrahydroborate; ruthenium(III) trichloride hydrate; In water; at 0℃; for 1h; General procedure: To a 15-mL 1-neck reaction flask fitted with a glass stopper [Note: A larger-scale reaction may require the use of a pressure vessel and/or addition of NaBH4 in small portions.] were added a small spin bar, 0.18-0.20 mmol of substrate, 0.60 mL of 5:1 (v/v) [10:1 (v/v) in Table 1, entry 3] liquid amide(s)/H2O, and 7.0 mg (0.034 mmol) of ruthenium(III) chloride hydrate (Sigma-Aldrich Catalog No. 206229). After cooling the latter mixture to 0 C (external ice-H2O bath), 9.0 mg (0.24 mmol) of NaBH4 powder was added in one portion; and the mixture was subsequently stirred at 0 C for 60 min. The reaction was then quenched by addition of 2.0 mL of 2 M aqueous HCl to the reaction flask, followed by 1.0 mL of pentane and subsequent stirring of the mixture at 0 C for 15 min. The product was then isolated by dilution of the reaction mixture with 10 mL of 4:1 (v/v) pentane/dichloromethane; and solid material was removed by filtration through a small pad of Hyflo Super-Cel filtering aid. After dilution of the filtrate with 10 mL of pentane, removal of the liquid amide(s) was accomplished by washing the filtrate with 10% (w/v) aqueous NaCl (4 15 mL portions). The organic layer was subsequently dried over anhydrous MgSO4, filtered, and the volatile organic solvents were removed by evaporation at reduced pressure.
  • 42
  • [ 87-44-5 ]
  • [ 92720-79-1 ]
  • C17H28F3NO3S [ No CAS ]
  • 43
  • [ 201230-82-2 ]
  • [ 87-44-5 ]
  • C16H26O [ No CAS ]
YieldReaction ConditionsOperation in experiment
With methoxy(cyclooctadiene)rhodium(I) dimer; hydrogen; triphenylphosphine; In ethanol; at 60℃; under 60804.1 Torr; for 6h;Inert atmosphere; Autoclave;Catalytic behavior; General procedure: The commercially acquired chemicals were used without an additional treatment except indicated cases. beta-<strong>[87-44-5]Caryophyllene</strong>[(-)-trans caryophyllene] (purity of ca. 90%) and tris(2,4-di-tert-butylphenyl) phosphite, (2,4-di-tbuPhO)3P were purchased from Sigma-Aldrich. [Rh(COD)(OMe)]2(COD = 1,5-cyclooctadiene) was synthesized as described in [34]. Tris(2-tbutylphenyl)phosphite,(2-tbuPhO)3P was prepared as described in [35] and purified using column chromatography (silica gel 60) and a mixture of hexane and chloroform as eluents. Toluene was refluxed for 8 h in the presence of sodium lumps and benzophenone and then distilled under argon. Ethanol was refluxed for 6 h in the presence of magnesium turnings and solid iodine and then distilled under argon. Hydroformylation reactions were performed in a homemade stainless steal autoclave equipped with a magnetic stirrer. The reaction solution was periodically sampled using a valved dip tube and analyzed by gas chromatography (GC) on a GC- Shimadzu GC2010equipment using a Rtx-5MS capillary column and a FID detector. Conversion and selectivity were calculated based on the substrate converted; dodecane was used as an internal standard. The difference in the reaction mass balance, if any, was attributed to the formation of high-boiling products non-detectable by GC. Initial turnover frequencies (TOFs) were determined at conversions of upto 20-30%. In a typical run, a toluene or ethanol (20.0 mL) solution of [Rh(COD)(OMe)]2(5.0 mol), phosphorus ligand (0-0.30 mmol), -caryophyllene (4 mmol), and dodecane (2 mmol) was added under inert atmosphere (Ar) into the autoclave, which was pressurized to 40-80 atm (CO/H2= 1/3-3/1). The reaction temperature (60-80C) was attained using an oil bath and then an intensive stirring was started. At the end of the run, the autoclave was cooled to ambient temperature; the gas mixture from the autoclave was allowed slowly vent out.
  • 44
  • [ 201230-82-2 ]
  • [ 87-44-5 ]
  • C16H26O [ No CAS ]
  • C17H28O2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
With methoxy(cyclooctadiene)rhodium(I) dimer; hydrogen; triphenylphosphine; In ethanol; at 60℃; under 60804.1 Torr; for 24h;Inert atmosphere; Autoclave;Catalytic behavior; General procedure: The commercially acquired chemicals were used without an additional treatment except indicated cases. beta-<strong>[87-44-5]Caryophyllene</strong>[(-)-trans caryophyllene] (purity of ca. 90%) and tris(2,4-di-tert-butylphenyl) phosphite, (2,4-di-tbuPhO)3P were purchased from Sigma-Aldrich. [Rh(COD)(OMe)]2(COD = 1,5-cyclooctadiene) was synthesized as described in [34]. Tris(2-tbutylphenyl)phosphite,(2-tbuPhO)3P was prepared as described in [35] and purified using column chromatography (silica gel 60) and a mixture of hexane and chloroform as eluents. Toluene was refluxed for 8 h in the presence of sodium lumps and benzophenone and then distilled under argon. Ethanol was refluxed for 6 h in the presence of magnesium turnings and solid iodine and then distilled under argon. Hydroformylation reactions were performed in a homemade stainless steal autoclave equipped with a magnetic stirrer. The reaction solution was periodically sampled using a valved dip tube and analyzed by gas chromatography (GC) on a GC- Shimadzu GC2010equipment using a Rtx-5MS capillary column and a FID detector. Conversion and selectivity were calculated based on the substrate converted; dodecane was used as an internal standard. The difference in the reaction mass balance, if any, was attributed to the formation of high-boiling products non-detectable by GC. Initial turnover frequencies (TOFs) were determined at conversions of upto 20-30%. In a typical run, a toluene or ethanol (20.0 mL) solution of [Rh(COD)(OMe)]2(5.0 mol), phosphorus ligand (0-0.30 mmol), -caryophyllene (4 mmol), and dodecane (2 mmol) was added under inert atmosphere (Ar) into the autoclave, which was pressurized to 40-80 atm (CO/H2= 1/3-3/1). The reaction temperature (60-80C) was attained using an oil bath and then an intensive stirring was started. At the end of the run, the autoclave was cooled to ambient temperature; the gas mixture from the autoclave was allowed slowly vent out.
  • 45
  • [ 201230-82-2 ]
  • [ 87-44-5 ]
  • C16H26O [ No CAS ]
  • C17H28O2 [ No CAS ]
  • C20H36O2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
With methoxy(cyclooctadiene)rhodium(I) dimer; hydrogen; triphenylphosphine; In ethanol; at 60℃; under 60804.1 Torr; for 24h;Inert atmosphere; Autoclave;Catalytic behavior; General procedure: The commercially acquired chemicals were used without an additional treatment except indicated cases. beta-<strong>[87-44-5]Caryophyllene</strong>[(-)-trans caryophyllene] (purity of ca. 90%) and tris(2,4-di-tert-butylphenyl) phosphite, (2,4-di-tbuPhO)3P were purchased from Sigma-Aldrich. [Rh(COD)(OMe)]2(COD = 1,5-cyclooctadiene) was synthesized as described in [34]. Tris(2-tbutylphenyl)phosphite,(2-tbuPhO)3P was prepared as described in [35] and purified using column chromatography (silica gel 60) and a mixture of hexane and chloroform as eluents. Toluene was refluxed for 8 h in the presence of sodium lumps and benzophenone and then distilled under argon. Ethanol was refluxed for 6 h in the presence of magnesium turnings and solid iodine and then distilled under argon. Hydroformylation reactions were performed in a homemade stainless steal autoclave equipped with a magnetic stirrer. The reaction solution was periodically sampled using a valved dip tube and analyzed by gas chromatography (GC) on a GC- Shimadzu GC2010equipment using a Rtx-5MS capillary column and a FID detector. Conversion and selectivity were calculated based on the substrate converted; dodecane was used as an internal standard. The difference in the reaction mass balance, if any, was attributed to the formation of high-boiling products non-detectable by GC. Initial turnover frequencies (TOFs) were determined at conversions of upto 20-30%. In a typical run, a toluene or ethanol (20.0 mL) solution of [Rh(COD)(OMe)]2(5.0 mol), phosphorus ligand (0-0.30 mmol), -caryophyllene (4 mmol), and dodecane (2 mmol) was added under inert atmosphere (Ar) into the autoclave, which was pressurized to 40-80 atm (CO/H2= 1/3-3/1). The reaction temperature (60-80C) was attained using an oil bath and then an intensive stirring was started. At the end of the run, the autoclave was cooled to ambient temperature; the gas mixture from the autoclave was allowed slowly vent out.
  • 46
  • [ 201230-82-2 ]
  • [ 87-44-5 ]
  • C16H26O [ No CAS ]
  • C20H36O2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
With methoxy(cyclooctadiene)rhodium(I) dimer; tris(2,4-di-tert-butylphenyl)phosphite; hydrogen; In ethanol; at 60℃; under 60804.1 Torr; for 6h;Inert atmosphere; Autoclave;Catalytic behavior; General procedure: The commercially acquired chemicals were used without an additional treatment except indicated cases. beta-<strong>[87-44-5]Caryophyllene</strong>[(-)-trans caryophyllene] (purity of ca. 90%) and tris(2,4-di-tert-butylphenyl) phosphite, (2,4-di-tbuPhO)3P were purchased from Sigma-Aldrich. [Rh(COD)(OMe)]2(COD = 1,5-cyclooctadiene) was synthesized as described in [34]. Tris(2-tbutylphenyl)phosphite,(2-tbuPhO)3P was prepared as described in [35] and purified using column chromatography (silica gel 60) and a mixture of hexane and chloroform as eluents. Toluene was refluxed for 8 h in the presence of sodium lumps and benzophenone and then distilled under argon. Ethanol was refluxed for 6 h in the presence of magnesium turnings and solid iodine and then distilled under argon. Hydroformylation reactions were performed in a homemade stainless steal autoclave equipped with a magnetic stirrer. The reaction solution was periodically sampled using a valved dip tube and analyzed by gas chromatography (GC) on a GC- Shimadzu GC2010equipment using a Rtx-5MS capillary column and a FID detector. Conversion and selectivity were calculated based on the substrate converted; dodecane was used as an internal standard. The difference in the reaction mass balance, if any, was attributed to the formation of high-boiling products non-detectable by GC. Initial turnover frequencies (TOFs) were determined at conversions of upto 20-30%. In a typical run, a toluene or ethanol (20.0 mL) solution of [Rh(COD)(OMe)]2(5.0 mol), phosphorus ligand (0-0.30 mmol), -caryophyllene (4 mmol), and dodecane (2 mmol) was added under inert atmosphere (Ar) into the autoclave, which was pressurized to 40-80 atm (CO/H2= 1/3-3/1). The reaction temperature (60-80C) was attained using an oil bath and then an intensive stirring was started. At the end of the run, the autoclave was cooled to ambient temperature; the gas mixture from the autoclave was allowed slowly vent out.
  • 47
  • [ 87-44-5 ]
  • 1-[(1R,4R/S,8S)-10,10-dimethyl-7-methylene-4-bicyclo[6.2.0]decanyl]ethanone [ No CAS ]
  • [ 475285-25-7 ]
YieldReaction ConditionsOperation in experiment
40%Chromat.; 10%Chromat. With dinitrogen monoxide; In toluene; at 230℃; under 52505.3 - 56255.6 Torr; for 3h;Autoclave; Production examples: Example 11.1 Oxidation of beta-caryophyllene in toluene at 230C with N20 (40 bar) A 300 mL autoclave is charged with 30.0 g beta-caryophyllene (88 wt.-% obtained from Aldrich Chemicals) in 70.0 g toluene and flushed 3 times with N2 (50 bar). The vessel is then pressurized with N2O (40 bar) at room temperature. The magnetic stirring is turned on and the autoclave heated to the reaction temperature (230C) for 3 hours. During reaction the pressure in the autoclave was about 70-75 bar. After cooling to room temperature and slow depressurization, the solution was analyzed with quantitative GC using dioxane as the internal standard (HP-5 column: 60 m (Length), 0.32 mm (ID), 1 .0 mupiiota (Film)/ 100C to 225C in 5C/min, 10 minutes at 225C, 225C to until 280C in 5C/min.). The conversion of beta-caryophyllene was 97%. The yields of (I), (II), (III), (IV) and (V) where found to be 40%, 10%, 3%, 1 % and 2% respectively.
  • 48
  • [ 87-44-5 ]
  • C13H20O [ No CAS ]
  • 1-[(1R,4R,8S)-10,10-dimethyl-7-methylene-4-bicyclo[6.2.0]decanyl]ethanone [ No CAS ]
  • 1-[(1R,4S,8S)-10,10-dimethyl-7-methylene-4-bicyclo[6.2.0]decanyl]ethanone [ No CAS ]
  • [ 475285-25-7 ]
YieldReaction ConditionsOperation in experiment
8%Chromat.; 15%Chromat. With dinitrogen monoxide; at 210℃; under 52505.3 - 56255.6 Torr; for 3h;Autoclave; Example II.2: Oxidation of beta-caryophyllene at 210C with N2O (40 bar) without added solvent A 300 mL autoclave is charged with 100 g beta-caryophyllene (88 wt.-% obtained from Aldrich Chemicals) and flushed 3 times with N2 (50 bar). The vessel is then pressurized with N2O (40 bar) at room temperature. The magnetic stirring is turned on and the autoclave heated to the reaction temperature (210C) for 3 hours. During reaction the pressure in the autoclave was about 70 to 75 bar. After cooling to room temperature and slow depressurization, the solution was analyzed with quantitative GC using dioxane as the internal standard (HP-5 column: 60 m (Length), 0.32 mm (ID), 1.0 muetaeta (Film)/ 100C to 225C in 5C/min, 10 minutes at 225C, 225C to until 280C in 5C/min.). The conversion of beta-caryophyllene was 58% and the selectivity of (I), (II), (III) and (IV) where found to be 59%, 15%, 8% and 2% respectively. The 4R/4S- diastereomeric ratio of 1 -[(1 R,4R,8S)-10,10-dimethyl-7-methylene-4- bicyclo[6.2.0]decanyl]ethanone in the crude product was 64 : 36.
  • 49
  • [ 87-44-5 ]
  • [ 60362-44-9 ]
  • 1-((1R,8S)-10,10-dimethyl-7-methylene-4-bicyclo(6.2.0)decanyl)ethanone [ No CAS ]
  • [ 475285-25-7 ]
YieldReaction ConditionsOperation in experiment
40%; 10% With dinitrogen monoxide; In toluene; at 230℃; under 52505.3 - 56255.6 Torr; for 3h;Autoclave; A 300 mL autoclave is charged with 30.0 g beta-caryophyllene (88 wt.-% obtained from Aldrich Chemicals) in 70.0 g toluene and flushed 3 times with N2 (50 bar). The vessel is then pressurized with N20 (40 bar) at room temperature. The magnetic stirring is turned on and the autoclave heated to the reaction temperature (230C) for 3 hours.During reaction the pressure in the autoclave was about 70-75 bar. After cooling to room temperature and slow depressurization, the solution was analyzed with quantitative GC using dioxane as the internal standard (HP-S column: 60 m (Length), 0.32 mm (ID), 1.0 pm (Film) 100C to 225C in 5C/mm, 10 minutes at 225C, 225C to until 280C in 5C/mm.). The conversion of beta-caryophyllene was 97%. The yieldsof (l.b), (II), (Ill), (IV) and (V) where found to be 40%, 10%, 3%, 1% and 2% respectively.
  • 50
  • [ 87-44-5 ]
  • norisoleptospermone [ No CAS ]
  • hyperjapone C [ No CAS ]
  • hyperjapone E [ No CAS ]
  • 51
  • [ 87-44-5 ]
  • 3,5-dihydroxy-4,6,6-trimethyl-2-(2-methyl-1-oxopropyl)-2,4-cyclohexadiene-1-one [ No CAS ]
  • hyperjapone B [ No CAS ]
  • hyperjapone D [ No CAS ]
  • 52
  • [ 87-44-5 ]
  • [ 158611-70-2 ]
  • (1S,5E,9R)-6,10,10-trimethyl-4’-[4-(trifluoromethyl)phenyl]-3’H-spiro[bicyclo[7.2.0]undecane-2,2’-[1,5]oxazole]-5-ene [ No CAS ]
  • (1’S,4’R,7’S,11’R)-1’,5’,5’-trimethyl-4-12’-bis[4-(trifluoromethyl)phenyl]-3H-14’-oxa-13’-azaspiro[1,5-oxazole-2,8-tricyclo[9.3.0.04,7]tetradecan]-12’-ene [ No CAS ]
YieldReaction ConditionsOperation in experiment
45%; 30% In dichloromethane; at 20℃; General procedure: 4-Trifluoromethylbenzonitrile oxide (4) was generated asfollows: a solution of the corresponding chloroxime (0.25 g,1.12 mmol) in dry dichloromethane was passed through anAmberlyst-21 column and added dropwise over 30 min tothe solution of a dipolarophile in dry dichloromethane, andthe solution was stirred overnight at room temperature. Waterwas added, organic layer was separated and the aqueousone extracted with dichloromethane. The combined organiclayers were dried (MgSO4) and the product was purified byflash column chromatography.
  • 53
  • [ 87-44-5 ]
  • [ 61565-12-6 ]
  • myrtucommulone O [ No CAS ]
  • myrtucommulone N [ No CAS ]
  • (2aR,4aR,10R,10aS,13aS)-10-isopropyl-2,2,4a,6,6,8,8-heptamethyl-13-methylene-1,2,2a,3,4,4a,10,10a,11,12,13,13a-dodecahydrocyclobuta[6,7]cyclonona[1,2-b]chromene-7,9(6H,8H)-dione [ No CAS ]
YieldReaction ConditionsOperation in experiment
42%; 10%; 25% In neat (no solvent); at 80℃; for 6h;Inert atmosphere; (-)-b-caryophyllene (0.6 ml, 0.49 mmol)was added dropwise toisobutylidenesyncarpic acid (34 mg, 0.14 mmol) under Ar, then themixture was heated to 80 C for 6 h. Directly purification by flashchromatography on SiO2 (petrol/EtOAc, 60:1 / 32:1 as eluent)gave myrtucommulone N (6.4 mg, 10%) as a white solid and thecolorless oil which was puried by Semi-Preparative HPLC Chromatography(MeOH/H2O 9:1) affording myrtucommulone K(16 mg, 25%), myrtucommulone O (27 mg, 42%).Myrtucommulone O: colorless blocks; m.p. 130e132 C;[a]D20 32 (c 0.5, CHCl3); IR(neat, cm1) n 3405, 2959, 2925, 2856,1714, 1645, 1605, 1459, 1384, 1261, 1070, 1026, 856, 800, 759, 679,667. HRESIMS m/z 441.3365 [M H] (calcd for C29H45O3:441.3363).Myrtucommulone N: colorless blocks; m.p. 140e142 C;[a]D20 42 (c 0.5, CHCl3); IR (neat, cm1) n 3409, 2954, 2931, 2870,1717, 1652, 1632, 1466, 1383, 1286, 1180, 1117, 1051, 887, 860, 778,733; 1H NMR (CDCl3, 400 MHz) d 4.89 (s, 1H), 4.82 (s, 1H), 2.33 (m,3H), 2.11 (m, 1H), 2.02 (m, 3H), 1.86 (m, 2H), 1.55 (m, 3H), 1.37 (m,1H), 1.32 (s, 3H), 1.28 (s, 3H), 1.24 (s, 6H), 0.99 (s, 3H), 0.95 (s, 3H),0.93 (s, 3H), 0.82 (d, J 7.0 Hz, 3H), 0.72 (d, J 7.0 Hz, 3H). 13C NMR(CDCl3, 100 MHz) d 213.9, 197.4, 171.0, 152.4, 114.6, 111.1, 83.5, 55.3,53.9, 47.6, 42.1, 40.6, 38.6, 38.5, 36.1, 35.5, 35.3, 33.6, 31.8, 30.5, 25.1,25.1, 24.6, 24.0, 22.4, 21.8, 21.3, 20.3, 19.6. HRESIMS m/z 441.3361[M H] (calcd for C29H45O3: 441.3363).Myrtucommulone K: colorless blocks; m.p. 151e152 C;[a]D20 126 (c 0.5, CHCl3); IR (neat, cm1) n 3405, 2952, 2932, 2869,1712, 1645, 1611, 1460, 1380, 1292, 1187, 1117, 1037, 958, 889, 864,814, 735; 1H NMR (CDCl3, 400 MHz) d 4.92 (s, 1H), 4.91 (s, 1H), 2.71(dd, J 4.8, 3.4 Hz, 1H), 2.43 (m, 2H), 2.17 (m, 1H), 2.07 (m, 2H), 1.76(m, 5H), 1.55 (m, 5H), 1.39 (s, 3H), 1.37 (s, 3H), 1.35 (s, 3H), 1.34 (s,6H), 1.17 (d, J 6.8 Hz, 3H), 0.98 (s, 3H), 0.95 (s, 3H), 0.69 (d,J 7.0 Hz, 3H). 13C NMR (CDCl3,100 MHz) d 214.2,198.3,170.4,151.2,112.7, 111.1, 85.7, 57.0, 55.3, 48.0, 44.2, 41.9, 39.6, 36.6, 36.5, 35.7,34.5, 30.0, 26.8, 26.1, 26.0, 25.8, 25.3, 25.0, 24.4, 23.7, 23.1, 21.9, 19.9.MHRESIMS m/z 441.3361 [M H] (calcd for C29H45O3: 441.3363).
In toluene; for 3h;Reflux; The a,b-unsaturated ketone i (224 mg, 0.95 mmol)and b-caryophyllene (1.0 g, 5.0 mmol) were dissolved in drytoluene (5 mL). After being heated to reflux for 3 h under nitrogenatmosphere, the reaction was cooled to room temperature andpurified directly by flash chromatography (silica gel, hexane/ethylacetate, from 100:1 to 10:1) to give a mixture (250 mg, 60% yield)as a colorless solid. The mixture (50 mg) was further purified by semi-prep-HPLC (MeOH/H2O, 90:10, v/v, 2 mL/min) to obtain compounds1b (9.0 mg, tR = 20.0 min), 1a (10 mg, 21.0 min) and 1c(12.0 mg, tR = 27 min). 1a: [a]20D +43 (c 0.10, CHCl3), 1b: [a]20D +36 (c 0.10, CHCl3), 1c: [a]20D 27 (c 0.10, CHCl3). 1H (500 MHz) and 13C(125 MHz) NMR spectral data were the same as the natural compound.
  • 54
  • [ 87-44-5 ]
  • [ 1671-87-0 ]
  • (6aR,8aS)-4a,7,7-trimethyl-9-methylene-1,4-di(pyridin-2-yl)-4a,5,6, 6a,7,8,8a,9,10,11-decahydro-2H-cyclobuta[5,6]cyclonona[1,2-d]pyridazine [ No CAS ]
YieldReaction ConditionsOperation in experiment
96% In methanol; at 20℃; for 4h; The compound 1beta-caryophyllene (33.7 mg, 0.165 mmol) was dissolved in a dry methanol solution (3 ml) and passed to it at room temperature.Tetrazine compound 2 (35.3 mg, 0.150 mmol) was added and the mixture was stirred at room temperature for four hours and the yellow color faded, indicating that the tetrazine starting material was consumed.After depletion, stirring was continued for 3 days in methanol solution. The solvent was suspended under reduced pressure and the residue was separated by column chromatography (dichloromethane:Methanol = 20:1, v/v) to give a pale yellow solid 63.9 mg, 96% yield.
  • 55
  • [ 87-44-5 ]
  • [ 536-74-3 ]
  • (1R,4S,7R,11S)-4,13,13-trimethyl-10-methylene-6-phenyltricyclo[9.2.0.04,7]tridec-5-ene [ No CAS ]
  • 56
  • [ 74-85-1 ]
  • [ 87-44-5 ]
  • (2R,3S)-3-(hexa-1,5-dien-2-yl)-1,1-dimethyl-2-(3-methylbut-3-en1-yl)cyclobutane [ No CAS ]
YieldReaction ConditionsOperation in experiment
In dichloromethane; at 40℃; under 7500.75 Torr; for 1h;Autoclave;Catalytic behavior; Tauomicron a solution of caryophyllene (90 mg, 0.1 mL, 0.434 mmol) in methylene chloride (4 mL) 100 mu of the precatalyst solution in methylene chloride (complex volume: see table) was added. The autoclave was blown three times with ethylene, and then the reaction mixture was heated to the temperature of 40C under 1 0 bar dynamic ethylene pressure over 1 hour. After an hour, the autoclave was cooled to the temperature of 0C on ice (5 minutes). The cooled reaction mixture was quenched with SnatchCat (Apeiron) solution . After 1 5 minutes of stirring, 1 0 mL of hexane was added. The solution was filtered through a layer of silica gel, which was then washed with a solution of 25% (v/v) methylene chloride in hexane. The filtrate was evaporated. A colourless oil was obtained. The composition of the sample (product to substrate ratio) was calculated based on the ratio of the signals in the1 H NMR spectrum.
  • 57
  • [ 87-44-5 ]
  • C15H12O5 [ No CAS ]
  • guapsidial A [ No CAS ]
  • psiguajadial D [ No CAS ]
  • 58
  • [ 87-44-5 ]
  • C15H26 [ No CAS ]
  • isocaryolane [ No CAS ]
  • (1R,2R,6S,7S)-2,6,8,8-tetramethyltricyclo[5.2.2.01,6]undecane [ No CAS ]
  • (1R,3R,4S,7S,11S)-3,7,11-trimethyltricyclo[5.3.2.04,11]dodecane [ No CAS ]
  • [ 123414-62-0 ]
YieldReaction ConditionsOperation in experiment
28%; 3.1%; 2%; 11.1%; 41.7% In hexane; at 68℃; for 3h; Sulfuric acid (0.5 mL, 9.33 mmol)was added to a solution of caryophyllene 1 (50.0 mg, 0.245 mmol) in hexane (2 mL). The mixture was refluxed with vigorous stirringfor 3 h. The organic solution was separated, the residue was diluted with water (2 mL), extracted with hexane (3×1 mL) anddiethyl ether (3×1 mL). The combined organic fractions were washed with water and dried with MgSO4.
  • 59
  • [ 87-44-5 ]
  • C15H26 [ No CAS ]
  • (1R,3R,4S,7S,11S)-3,7,11-trimethyltricyclo[5.3.2.04,11]dodecane [ No CAS ]
  • [ 123414-62-0 ]
YieldReaction ConditionsOperation in experiment
35.9%; 13.9%; 38.7% With sulfuric acid; In hexane; at 68℃; for 3h; Sulfuric acid (0.5 mL, 9.33 mmol)was added to a solution of caryophyllene 1 (50.0 mg, 0.245 mmol) in hexane (2 mL). The mixture was refluxed with vigorous stirringfor 3 h. The organic solution was separated, the residue was diluted with water (2 mL), extracted with hexane (3×1 mL) anddiethyl ether (3×1 mL). The combined organic fractions were washed with water and dried with MgSO4.
  • 60
  • [ 50-00-0 ]
  • [ 87-44-5 ]
  • 3-benzoyl-2,4,6-trihydroxybenzaldehyde [ No CAS ]
  • C30H34O5 [ No CAS ]
  • C30H34O5 [ No CAS ]
YieldReaction ConditionsOperation in experiment
With sodium acetate; acetic acid; at 90℃; for 4h;Inert atmosphere; As shown in Formula 5, the resorcinol derivative (1, 1004 mg, 3.89 mmol), paraformaldehyde (2, 351.4mg, 11.7mmol) and sodium acetate (52.9mg, 0.389mmol) were moved to the reaction tube. Under the protection of argon, beta-caryophyllene (3, 3.0mL, 11.7mmol) was added to the system and 20mL dissolve the acetic acid, quickly warm to 90 C and stir for 4h; After the reaction was completed, the temperature was lowered to room temperature and concentrated under reduced pressure. The crude product was extracted with ethyl acetate. Wash with saturated NaHCO3aq. and NaCl solution, dry with anhydrous Na2SO4, The crude product was concentrated under reduced pressure again; after the crude product was coarsely divided on a silica gel column, The crude compound (about 745.6 mg, 1.57 mmol), 95% NaBH3CN (920 mg, 7.86 mmol) and 0.1 mg of methyl orange were transferred to a 100 mL round bottom flask, Add 30mL of tetrahydrofuran to the bottle under the protection of argon. The mixture was dissolved by stirring for 5min; a 2M HCl aqueous solution was added dropwise to the system to keep the pH value in the system less than 4 (the phenomenon is that the solution color is red), and stirred overnight (16h); After the reaction was completed, the mixture was concentrated under reduced pressure. The residue was extracted with ethyl acetate (3 × 20 mL), washed with saturated brine, After drying over anhydrous Na2SO4 and concentrating under reduced pressure, a crude product was obtained; The crude product was purified with a silica gel column (petroleum ether/ethyl acetate: 50/1 to 25/1) to obtain two parts containing Formula one and Formula two, respectively, preparative high-pressure liquid phase (waters column, CH3OH/H2O: 90/10, 3 mL/min) was used for separation, and Psiguajanone A and B were obtained from part of the formula.
  • 61
  • [ 50-00-0 ]
  • [ 87-44-5 ]
  • 3-benzoyl-2,4,6-trihydroxybenzaldehyde [ No CAS ]
  • C30H36O4 [ No CAS ]
  • C30H36O4 [ No CAS ]
YieldReaction ConditionsOperation in experiment
As shown in Formula 5, the resorcinol derivative (1, 1004 mg, 3.89 mmol), paraformaldehyde (2, 351.4mg, 11.7mmol) and sodium acetate (52.9mg, 0.389mmol) were moved to the reaction tube. Under the protection of argon, beta-caryophyllene (3, 3.0mL, 11.7mmol) was added to the system and 20mL dissolve the acetic acid, quickly warm to 90 C and stir for 4h; After the reaction was completed, the temperature was lowered to room temperature and concentrated under reduced pressure. The crude product was extracted with ethyl acetate. Wash with saturated NaHCO3aq. and NaCl solution, dry with anhydrous Na2SO4, The crude product was concentrated under reduced pressure again; after the crude product was coarsely divided on a silica gel column, The crude compound (about 745.6 mg, 1.57 mmol), 95% NaBH3CN (920 mg, 7.86 mmol) and 0.1 mg of methyl orange were transferred to a 100 mL round bottom flask, Add 30mL of tetrahydrofuran to the bottle under the protection of argon. The mixture was dissolved by stirring for 5min; a 2M HCl aqueous solution was added dropwise to the system to keep the pH value in the system less than 4 (the phenomenon is that the solution color is red), and stirred overnight (16h); After the reaction was completed, the mixture was concentrated under reduced pressure. The residue was extracted with ethyl acetate (3 × 20 mL), washed with saturated brine, After drying over anhydrous Na2SO4 and concentrating under reduced pressure, a crude product was obtained; The crude product was purified with a silica gel column (petroleum ether/ethyl acetate: 50/1 to 25/1) to obtain two parts containing Formula one and Formula two, respectively, preparative high-pressure liquid phase (waters column, CH3OH/H2O: 90/10, 3 mL/min) was used for separation, and Psiguajanone A and B were obtained from part of the formula.
  • 62
  • [ 57-55-6 ]
  • [ 87-44-5 ]
  • 2-((4,4,8-trimethyltricyclo[6.3.1.02,5]dodecan-1-yl)oxy)propan-1-ol [ No CAS ]
  • 1-((4,4,8-trimethyltricyclo[6.3.1.02,5]dodecan-1-yl)oxy)propan-2-ol [ No CAS ]
YieldReaction ConditionsOperation in experiment
With phosphoric acid; at 125℃; <strong>[87-44-5]Caryophyllene</strong> (500 g, 2.4 mol) and propane- l,2-diol (292 g, 3.8 mol) were charged into a reactor. Phosphoric acid (8.29 g, 85% purity) was added. The reaction mixture was heated to 125 C for 8-16 hours. The progress and completion of the reaction were monitored by gas-liquid chromatograph (GLC). The reaction was then cooled to 80 C, diluted with ethyl acetate (100 mL) and washed with sodium bicarbonate to quench phosphoric acid. The organic layer was separated, washed with brine, distilled and rushed over to provide the crude product (463 g). The crude product was further fractionated to provide a positional isomeric mixture containing major products 2-((4,4,8-trimethyltricyclo[6.3.l.02,5]dodecan-l- yl)oxy)propan-l-ol (Structure 1) (-23%) and l-((4,4,8-trimethyltricyclo[6.3.l.02,5]dodecan-l- yl)oxy)propan-2-ol (Structure 2) (-60%), and minor products 2(or l)-((l ,4,4- trimethyltricyclo[6.3.l.02,5]dodecan-8-yl)oxy)propan-l(or 2)-ol (-10%) and 2(or l)-((l , 1,7- trimethyldecahydro-3a,7-methanocyclopenta[8]annulen-3-yl)oxy)propan-l(or 2)-ol (-7%). The mixture had a boiling point of 140 C at 1.0 mmHg. Each of the isomers (where * denotes a chiral center) might further contain stereoisomers including (27?)-2(or l)-(((lS,8S)-, (27?)-2(or l)-(((lS,8tf)-, (2tf)-2(or l)-(((ltf,8tf)-, (2tf)-2(or l)-(((ltf,8S)-, (2S)-2(or l)-(((lS,8S)-, (2S)-2(or l)-(((lS,8tf)-, (2S)-2(or l)-(((ltf,8tf)-, and (2S)-2(or l)-(((ltf,8S)-4,4,8- trimethyltricyclo[6.3.1.02,5]dodecanyl)oxy)propanol. NMR (500 MHz, CDCl3) d: 3.67-3.95 (m, 1H), 2.97-3.37 (m, 2H), 2.05-2.29 (m, 1H), 1.17- 1.90 (m, 12H), 0.99-1.17 (m, 6H), 0.98 (s, 3H), 0.97 (s, 3H), 0.87 (s, 3H).The obtained mixture as well as each isomer was described as having amber, wood, cedar and dry notes. Among all the isomers, Structure 1 exhibited particularly strong and long- lasting notes.
  • 63
  • [ 87-44-5 ]
  • [ 4254-14-2 ]
  • (2R)-2-((4,4,8-trimethyltricyclo[6.3.1.02,5]dodecan-1-yl)oxy)propan-1-ol [ No CAS ]
  • (2R)-1-((4,4,8-trimethyltricyclo[6.3.1.02,5]dodecan-1-yl)oxy)propan-2-ol [ No CAS ]
  • (2R)-2-((1,1,7-trimethyldecahydro-3a,7-methanocyclopenta[8]annulen-3-yl)oxy)propan-1-ol [ No CAS ]
  • (2R)-1-((1,1,7-trimethyldecahydro-3a,7-methanocyclopenta[8]annulen-3-yl)oxy)propan-2-ol [ No CAS ]
YieldReaction ConditionsOperation in experiment
With phosphoric acid; at 125℃; General procedure: Caryophyllene (500 g, 2.4 mol) and propane- l,2-diol (292 g, 3.8 mol) were charged into a reactor. Phosphoric acid (8.29 g, 85% purity) was added. The reaction mixture was heated to 125 C for 8-16 hours. The progress and completion of the reaction were monitored by gas-liquid chromatograph (GLC). The reaction was then cooled to 80 C, diluted with ethyl acetate (100 mL) and washed with sodium bicarbonate to quench phosphoric acid. The organic layer was separated, washed with brine, distilled and rushed over to provide the crude product (463 g). The crude product was further fractionated to provide a positional isomeric mixture containing major products 2-((4,4,8-trimethyltricyclo[6.3.l.02,5]dodecan-l- yl)oxy)propan-l-ol (Structure 1) (-23%) and l-((4,4,8-trimethyltricyclo[6.3.l.02,5]dodecan-l- yl)oxy)propan-2-ol (Structure 2) (-60%), and minor products 2(or l)-((l ,4,4- trimethyltricyclo[6.3.l.02,5]dodecan-8-yl)oxy)propan-l(or 2)-ol (-10%) and 2(or l)-((l , 1,7- trimethyldecahydro-3a,7-methanocyclopenta[8]annulen-3-yl)oxy)propan-l(or 2)-ol (-7%). The mixture had a boiling point of 140 C at 1.0 mmHg. Each of the isomers (where * denotes a chiral center) might further contain stereoisomers including (27?)-2(or l)-(((lS,8S)-, (27?)-2(or l)-(((lS,8tf)-, (2tf)-2(or l)-(((ltf,8tf)-, (2tf)-2(or l)-(((ltf,8S)-, (2S)-2(or l)-(((lS,8S)-, (2S)-2(or l)-(((lS,8tf)-, (2S)-2(or l)-(((ltf,8tf)-, and (2S)-2(or l)-(((ltf,8S)-4,4,8- trimethyltricyclo[6.3.1.02,5]dodecanyl)oxy)propanol. NMR (500 MHz, CDCl3) d: 3.67-3.95 (m, 1H), 2.97-3.37 (m, 2H), 2.05-2.29 (m, 1H), 1.17- 1.90 (m, 12H), 0.99-1.17 (m, 6H), 0.98 (s, 3H), 0.97 (s, 3H), 0.87 (s, 3H).The obtained mixture as well as each isomer was described as having amber, wood, cedar and dry notes. Among all the isomers, Structure 1 exhibited particularly strong and long- lasting notes.
  • 64
  • [ 108340-61-0 ]
  • [ 87-44-5 ]
  • (2R)-2-((4,4,8-trimethyltricyclo[6.3.1.02,5]dodecan-1-yl)oxy)pentan-1-ol [ No CAS ]
  • (2R)-1-((4,4,8-trimethyltricyclo[6.3.1.02,5]dodecan-1-yl)oxy)pentan-2-ol [ No CAS ]
  • (2R)-2-((1,1,7-trimethyldecahydro-3a,7-methanocyclopenta[8]annulen-3-yl)oxy)pentan-1-ol [ No CAS ]
  • (2R)-1-((1,1,7-trimethyldecahydro-3a,7-methanocyclopenta[8]annulen-3-yl)oxy)pentan-2-ol [ No CAS ]
YieldReaction ConditionsOperation in experiment
With phosphoric acid; at 125℃; General procedure: <strong>[87-44-5]Caryophyllene</strong> (500 g, 2.4 mol) and propane- l,2-diol (292 g, 3.8 mol) were charged into a reactor. Phosphoric acid (8.29 g, 85% purity) was added. The reaction mixture was heated to 125 C for 8-16 hours. The progress and completion of the reaction were monitored by gas-liquid chromatograph (GLC). The reaction was then cooled to 80 C, diluted with ethyl acetate (100 mL) and washed with sodium bicarbonate to quench phosphoric acid. The organic layer was separated, washed with brine, distilled and rushed over to provide the crude product (463 g). The crude product was further fractionated to provide a positional isomeric mixture containing major products 2-((4,4,8-trimethyltricyclo[6.3.l.02,5]dodecan-l- yl)oxy)propan-l-ol (Structure 1) (-23%) and l-((4,4,8-trimethyltricyclo[6.3.l.02,5]dodecan-l- yl)oxy)propan-2-ol (Structure 2) (-60%), and minor products 2(or l)-((l ,4,4- trimethyltricyclo[6.3.l.02,5]dodecan-8-yl)oxy)propan-l(or 2)-ol (-10%) and 2(or l)-((l , 1,7- trimethyldecahydro-3a,7-methanocyclopenta[8]annulen-3-yl)oxy)propan-l(or 2)-ol (-7%). The mixture had a boiling point of 140 C at 1.0 mmHg. Each of the isomers (where * denotes a chiral center) might further contain stereoisomers including (27?)-2(or l)-(((lS,8S)-, (27?)-2(or l)-(((lS,8tf)-, (2tf)-2(or l)-(((ltf,8tf)-, (2tf)-2(or l)-(((ltf,8S)-, (2S)-2(or l)-(((lS,8S)-, (2S)-2(or l)-(((lS,8tf)-, (2S)-2(or l)-(((ltf,8tf)-, and (2S)-2(or l)-(((ltf,8S)-4,4,8- trimethyltricyclo[6.3.1.02,5]dodecanyl)oxy)propanol. NMR (500 MHz, CDCl3) d: 3.67-3.95 (m, 1H), 2.97-3.37 (m, 2H), 2.05-2.29 (m, 1H), 1.17- 1.90 (m, 12H), 0.99-1.17 (m, 6H), 0.98 (s, 3H), 0.97 (s, 3H), 0.87 (s, 3H).The obtained mixture as well as each isomer was described as having amber, wood, cedar and dry notes. Among all the isomers, Structure 1 exhibited particularly strong and long- lasting notes.
  • 65
  • [ 29117-54-2 ]
  • [ 87-44-5 ]
  • (2S)-2-((4,4,8-trimethyltricyclo[6.3.1.02,5]dodecan-1-yl)oxy)pentan-1-ol [ No CAS ]
  • (2S)-1-((4,4,8-trimethyltricyclo[6.3.1.02,5]dodecan-1-yl)oxy)pentan-2-ol [ No CAS ]
  • (2S)-1-((1,1,7-trimethyldecahydro-3a,7-methanocyclopenta[8]annulen-3-yl)oxy)pentan-2-ol [ No CAS ]
YieldReaction ConditionsOperation in experiment
With phosphoric acid; at 125℃; General procedure: <strong>[87-44-5]Caryophyllene</strong> (500 g, 2.4 mol) and propane- l,2-diol (292 g, 3.8 mol) were charged into a reactor. Phosphoric acid (8.29 g, 85% purity) was added. The reaction mixture was heated to 125 C for 8-16 hours. The progress and completion of the reaction were monitored by gas-liquid chromatograph (GLC). The reaction was then cooled to 80 C, diluted with ethyl acetate (100 mL) and washed with sodium bicarbonate to quench phosphoric acid. The organic layer was separated, washed with brine, distilled and rushed over to provide the crude product (463 g). The crude product was further fractionated to provide a positional isomeric mixture containing major products 2-((4,4,8-trimethyltricyclo[6.3.l.02,5]dodecan-l- yl)oxy)propan-l-ol (Structure 1) (-23%) and l-((4,4,8-trimethyltricyclo[6.3.l.02,5]dodecan-l- yl)oxy)propan-2-ol (Structure 2) (-60%), and minor products 2(or l)-((l ,4,4- trimethyltricyclo[6.3.l.02,5]dodecan-8-yl)oxy)propan-l(or 2)-ol (-10%) and 2(or l)-((l , 1,7- trimethyldecahydro-3a,7-methanocyclopenta[8]annulen-3-yl)oxy)propan-l(or 2)-ol (-7%). The mixture had a boiling point of 140 C at 1.0 mmHg. Each of the isomers (where * denotes a chiral center) might further contain stereoisomers including (27?)-2(or l)-(((lS,8S)-, (27?)-2(or l)-(((lS,8tf)-, (2tf)-2(or l)-(((ltf,8tf)-, (2tf)-2(or l)-(((ltf,8S)-, (2S)-2(or l)-(((lS,8S)-, (2S)-2(or l)-(((lS,8tf)-, (2S)-2(or l)-(((ltf,8tf)-, and (2S)-2(or l)-(((ltf,8S)-4,4,8- trimethyltricyclo[6.3.1.02,5]dodecanyl)oxy)propanol. NMR (500 MHz, CDCl3) d: 3.67-3.95 (m, 1H), 2.97-3.37 (m, 2H), 2.05-2.29 (m, 1H), 1.17- 1.90 (m, 12H), 0.99-1.17 (m, 6H), 0.98 (s, 3H), 0.97 (s, 3H), 0.87 (s, 3H).The obtained mixture as well as each isomer was described as having amber, wood, cedar and dry notes. Among all the isomers, Structure 1 exhibited particularly strong and long- lasting notes.
  • 66
  • [ 87-44-5 ]
  • [ 89401-28-5 ]
  • C25H38O2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
With phosphoric acid; at 125℃; for 8h; Preparation of (27?)-2-((4,4,8-Trimethyltricyclo[6.3.1.02 5]dodecan-l-yl)oxy)propan-l-ol (Structure la): <strong>[87-44-5]Caryophyllene</strong> (2 g, 9.4 mmol) and (R)- 1 -(Benzyloxy)propan-2-ol (1.3 g, 7.8 mol) were charged into a reactor. Phosphoric acid (40 mg, 85% purity) was added. The reaction mixture was heated to 125 C for 8 hours. The progress and completion of the reaction were monitored by GLC. The reaction was then cooled to 80 C, diluted with ethyl acetate (10 mL) and washed with sodium bicarbonate. The organic layer was separated, washed with brine and concentrated to provide a first crude product, which was purified by silica gel chromatography using a gradient of hexanes and ethyl acetate. The isolated benzylated product was hydrogenated using 5% palladium on carbon (Pd/C) at 30 C and hydrogen (100 psi) to provide a second crude product, which was concentrated and then purified by silica gel chromatography using a gradient of hexanes and ethyl acetate to afford the product (2R)-2- ((4,4,8-trimethyltricyclo[6.3.l.02?5]dodecan-l-yl)oxy)propan-l-ol (Structure la) (-99%).
  • 67
  • [ 87-44-5 ]
  • [ 107-21-1 ]
  • 2-((4,4,8-trimethyltricyclo[6.3.1.02,5]dodecan-1-yl)oxy)ethan-1-ol [ No CAS ]
  • 2-((1,1,7-trimethyldecahydro-3a,7-methanocyclopenta[8]annulen-3-yl)oxy)ethan-1-ol [ No CAS ]
YieldReaction ConditionsOperation in experiment
With phosphoric acid; at 125℃; General procedure: <strong>[87-44-5]Caryophyllene</strong> (500 g, 2.4 mol) and propane- l,2-diol (292 g, 3.8 mol) were charged into a reactor. Phosphoric acid (8.29 g, 85% purity) was added. The reaction mixture was heated to 125 C for 8-16 hours. The progress and completion of the reaction were monitored by gas-liquid chromatograph (GLC). The reaction was then cooled to 80 C, diluted with ethyl acetate (100 mL) and washed with sodium bicarbonate to quench phosphoric acid. The organic layer was separated, washed with brine, distilled and rushed over to provide the crude product (463 g). The crude product was further fractionated to provide a positional isomeric mixture containing major products 2-((4,4,8-trimethyltricyclo[6.3.l.02,5]dodecan-l- yl)oxy)propan-l-ol (Structure 1) (-23%) and l-((4,4,8-trimethyltricyclo[6.3.l.02,5]dodecan-l- yl)oxy)propan-2-ol (Structure 2) (-60%), and minor products 2(or l)-((l ,4,4- trimethyltricyclo[6.3.l.02,5]dodecan-8-yl)oxy)propan-l(or 2)-ol (-10%) and 2(or l)-((l , 1,7- trimethyldecahydro-3a,7-methanocyclopenta[8]annulen-3-yl)oxy)propan-l(or 2)-ol (-7%). The mixture had a boiling point of 140 C at 1.0 mmHg. Each of the isomers (where * denotes a chiral center) might further contain stereoisomers including (27?)-2(or l)-(((lS,8S)-, (27?)-2(or l)-(((lS,8tf)-, (2tf)-2(or l)-(((ltf,8tf)-, (2tf)-2(or l)-(((ltf,8S)-, (2S)-2(or l)-(((lS,8S)-, (2S)-2(or l)-(((lS,8tf)-, (2S)-2(or l)-(((ltf,8tf)-, and (2S)-2(or l)-(((ltf,8S)-4,4,8- trimethyltricyclo[6.3.1.02,5]dodecanyl)oxy)propanol. NMR (500 MHz, CDCl3) d: 3.67-3.95 (m, 1H), 2.97-3.37 (m, 2H), 2.05-2.29 (m, 1H), 1.17- 1.90 (m, 12H), 0.99-1.17 (m, 6H), 0.98 (s, 3H), 0.97 (s, 3H), 0.87 (s, 3H).The obtained mixture as well as each isomer was described as having amber, wood, cedar and dry notes. Among all the isomers, Structure 1 exhibited particularly strong and long- lasting notes.
  • 68
  • [ 87-44-5 ]
  • (1S,9R)-6,10,10-trimethyl-2-methylenebicyclo[7.2.0]undecan-5-ol [ No CAS ]
YieldReaction ConditionsOperation in experiment
To 6.6mL of 1M catecholborane in tetrahydrofuran, add 4.4mmol of beta-caryophyllene, reflux at 80 C for 18h, dilute with 40mL CH2Cl2 and cool, then add 20mL of 3M KOH and 20mL of 30% H2O2 in turn for 30min , Washed with saturated NaCl three times, dried, and removed the solvent to obtain a dark yellow oily liquid. Using a 100-200 mesh silica gel column mobile phase petroleum ether: ethyl acetate = 1: 7, to obtain a light yellow oily liquid C1. The reaction process is as follows:
  • 69
  • [ 60269-12-7 ]
  • [ 1176003-49-8 ]
  • [ 87-44-5 ]
  • (2aS,2a1S,4aS,7S,7aS)-2a,4,4a,7-tetramethyl-2,2a,2a1,4a,5,6,7,7a-octahydro-1H-cyclopenta[cd]indene [ No CAS ]
  • (2aS,2a1R,5S,7aR)-1,1,2a,5-tetramethyl-2,2a,2a1,3,5,6,7,7a-octahydro-1H-cyclopenta[cd]indene [ No CAS ]
  • 70
  • [ 87-44-5 ]
  • [ 4396-13-8 ]
  • [ 66-25-1 ]
  • littordial C [ No CAS ]
  • jejuguajavone B [ No CAS ]
YieldReaction ConditionsOperation in experiment
1: 40% 2: 14% Stage #1: β-caryophyllene; 2,4-diformyl 2,4,6-trihydroxybenzene; hexanal With 1,1,1,3',3',3'-hexafluoro-propanol for 0.0833333h; Inert atmosphere; Stage #2: With ethylenediaminediacetic acid at 20℃; for 4h; Inert atmosphere;
  • 71
  • [ 7648-30-8 ]
  • [ 87-44-5 ]
  • ethyl 2,2-difluoro-3-((2aR,7bS)-5-iodo-2,2,4a-trimethyldecahydro-7aH-cyclobuta[e]inden-7a-yl)propanoate [ No CAS ]
YieldReaction ConditionsOperation in experiment
90% With Potassium bicarbonate In 1,4-dioxane at 50℃; Inert atmosphere; Irradiation; 2 Preparation of (2,2-difluoro-1-((2aR,7bS)-5-iodo-2,2,4a-trimethyldecahydro-7aH-cyclobuta[e]inden-7a-yl)pentan-3-one): Add anhydrous potassium bicarbonate (0.6g, 6mmol), 2-phenol (6mg, 0.06mmol), 30ml of 1,4-dioxane to a three-necked flask protected by dry oxygen-free nitrogen.β-Caryophyllene (610 mg, 3 mmol), ethyl iododifluoroacetate (1.50 g, 6 mmol).Then the reaction flask was placed under blue light irradiation at 50°C for thorough stirring.After confirming the end of the reaction by thin layer chromatography, cool the reaction flask to room temperature,Add an appropriate amount of aqueous solution to quench the reaction, then add ethyl acetate to extract the aqueous phase,Combine the organic phases, wash the organic phases with a saturated aqueous NaCl solution, and dry with anhydrous sodium sulfate,After filtration and rotary evaporation to recover the solvent, the residue was column chromatographed with petroleum ether: ethyl acetate=1-1000:1 (volume ratio) to obtain 1.22 g of a yellow solid with a yield of 90%.
88% With 2-hydroxybromobenzene; anhydrous potassium acetate In acetonitrile at 20℃; for 12h; Irradiation; Inert atmosphere; 3. General procedure for the synthesis of difluoroalkylated protoilludanes 3a-3l. General procedure: To a 25 mL of Schlenk tube equipped with a Teflon septum were added KOAc (0.6 mmol, 2.0 equiv) under N2, followed by CH3CN (3 mL) with stirring. β-Caryophyllene 1 (0.6 mmol, 2.0 equiv), 2-bromophenol (0.03 mmol, 0.1 equiv) and iododifluoromethyl ketones 2 (0.3 mmol, 1.0 equiv) were added subsequently. The tube was then irradiated with 12 W blue LEDs (430 nm-490 nm). After stirring for 12 h, the solvent was removed and the residue was purified with silica gel chromatography to provide pure product 3. Special notes: In theory, you could get up to eight stereoisomers from the product because the product contains three new chiral centers. To confirm the structure of the compound 3, we isolated two isomers of 3a by careful column chromatography in this paper.
88% With 2-hydroxybromobenzene; anhydrous potassium acetate In acetonitrile at 20℃; for 12h; Irradiation; Inert atmosphere; 3. General procedure for the synthesis of difluoroalkylated protoilludanes 3a-3l. General procedure: To a 25 mL of Schlenk tube equipped with a Teflon septum were added KOAc (0.6 mmol, 2.0 equiv) under N2, followed by CH3CN (3 mL) with stirring. β-Caryophyllene 1 (0.6 mmol, 2.0 equiv), 2-bromophenol (0.03 mmol, 0.1 equiv) and iododifluoromethyl ketones 2 (0.3 mmol, 1.0 equiv) were added subsequently. The tube was then irradiated with 12 W blue LEDs (430 nm-490 nm). After stirring for 12 h, the solvent was removed and the residue was purified with silica gel chromatography to provide pure product 3. Special notes: In theory, you could get up to eight stereoisomers from the product because the product contains three new chiral centers. To confirm the structure of the compound 3, we isolated two isomers of 3a by careful column chromatography in this paper.
  • 72
  • [ 87-44-5 ]
  • [ 4396-13-8 ]
  • [ 1122-91-4 ]
  • bromo (+)-psiguadial B [ No CAS ]
YieldReaction ConditionsOperation in experiment
7.24% With sodium acetate; acetic acid at 80℃; for 24h; 2.2.5. Preparation of of bromo (+)-Psiguadial B (8c) To a stirred solution of diformylphloroglucinol (11, 100 mg, 0.55mmol) and sodium acetate (4.5 mg, 0.06 mmol, 0.1 equiv.) in acetic acid(4 mL), 4-bromobenzaldehyde (12c, 203 mg, 1.10 mmol, 2.0 equiv.) andβ -Caryophyllene (5, 0.37 mL, 1.65 mmol, 3.0 equiv.) were addeddropwise at 80 C, the mixture was continuingly stirred for 24 h at 80 C.Upon cooling to room temperature, brine (5 mL) and diethyl ether (20mL) were added and the layers separated. The aqueous layer was thenextracted with diethyl ether (10 mL × 3), and the combined organiclayers were washed with brine (20 mL) and dried over anhydrousNa2SO4. It was filtered and concentrated to give the crude residue,which was purified by Preparative HPLC (40-72% ACN in H2O) to giveproduct (8c) as a pale cream solid (22 mg, 7.24%). ESI LC/MS: m/zcalcd. for C30H33BrO5 [M]+: 552.15; found [M]+: 552.95 and [M + 2]+:554.90. 1H NMR (400 MHz, CDCl3) δ 13.49 (s, 1H, OH), 13.06 (s, 1H,OH), 10.07 (s, 2H, CHO), 7.37 (d, J = 8.6 Hz, 2H), 6.97 (d, J = 6.64 Hz,2H), 3.46 (d, J = 11.44 Hz, 1H), 2.14-2.06 (m, 2H), 1.93-1.78 (m, 2H),1.70-1.57 (m, 3H), 1.51-1.38 (m, 5H), 1.36-1.31 (m, 1H), 1.27-1.24(m, 1H), 1.08-1.04 (m, 1H), 1.01 (apparent d, 6H), 0.86 (s, 3H). 13CNMR (100 MHz, CDCl3) δ 192.30, 191.58, 169.48, 168.57, 163.43,142.54, 131.31 (2C), 129.56 (2C), 119.84, 105.14, 104.64, 104.15,84.12, 49.89, 47.43, 44.04, 39.95, 37.56, 36.94, 35.44, 35.09, 33.47,29.70, 29.39, 26.06, 23.86, 20.73, 20.11.
  • 73
  • [ 87-44-5 ]
  • [ 4396-13-8 ]
  • [ 100-52-7 ]
  • [ 1254173-26-6 ]
YieldReaction ConditionsOperation in experiment
5.37% With sodium acetate; acetic acid at 80℃; for 24h; 2.2.2. Preparation of (+)-Psiguadial B (8) To a stirred solution of diformylphloroglucinol (11, 100 mg, 0.549mmol) and sodium acetate (4.5 mg, 0.06 mmol, 0.1 equiv.) in acetic acid(4 mL), benzaldehyde (12, 0.11 mL, 1.10 mmol, 2.0 equiv.) and β-Caryophyllene(5, 0.37 mL, 1.65 mmol, 3.0 equiv.) were added dropwise at80 C, the mixture was continuingly stirred for 24 h at 80 C. Uponcooling to room temperature, brine (5 mL) and diethyl ether (Et2O, 20mL) were added and the layers separated. The aqueous layer was thenextracted with Et2O (10 mL × 3), and the combined organic layers werewashed with brine (20 mL) and dried over anhydrous Na2SO4. It wasfiltered and concentrated to give the crude residue, which was purifiedby preparative HPLC (40-72% ACN in H2O) to give product (8) as a palecream solid (14 mg, 5.37%). ESI LC/MS: m/z calcd. for C30H34O5 [M +H]+: 475.24; found 475.09. 1H NMR (400 MHz, CDCl3) δ 13.49 (s, 1H,OH), 13.02 (s, 1H, OH), 10.06 (s, 2H, CHO), 7.26-7.18 (m, 3H),7.17-7.09 (br m, 2H), 3.47 (d, J = 11.48 Hz, 1H), 2.15 - 2.06 (m, 2H),1.95-1.87 (m, 1H), 1.84-1.77 (m, 1H), 1.73-1.65 (m, 3H), 1.50-1.44(m, 3H), 1.42-1.29 (m, 3H), 1.26-1.23 (m, 1H), 1.06-1.02 (m, 1H), 0.99(apparent d, 6H), 0.84 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 192.36,191.53, 169.66, 168.53, 163.51, 143.42, 128.18 (3C), 126.23 (2C),105.73, 104.65, 104.15, 84.14, 50.02, 47.46, 44.04, 40.39, 37.61,36.93, 35.44, 35.09, 33.46, 30.63, 29.37, 26.09, 23.91, 20.75, 20.11.
  • 74
  • [ 87-44-5 ]
  • [ 4396-13-8 ]
  • [ 459-57-4 ]
  • fluoro (+)-psiguadial B [ No CAS ]
YieldReaction ConditionsOperation in experiment
6.66% With sodium acetate; acetic acid at 80℃; for 24h; 2.2.3. Preparation of fluoro (+)-Psiguadial B (8a) To a stirred solution of diformylphloroglucinol (11, 100 mg, 0.549mmol) and sodium acetate (4.5 mg, 0.06 mmol, 0.1 equiv.) in acetic acid(4 mL), 4-fluorobenzaldehyde (12a, 0.12 mL, 1.10 mmol, 2.0 equiv.)and β -Caryophyllene (5, 0.37 mL, 1.65 mmol, 3.0 equiv.) were addeddropwise at 80 C, the mixture was continuingly stirred for 24 h at 80 C.Upon cooling to room temperature, brine (5 mL) and diethyl ether (20mL) were added and the layers separated. The aqueous layer was thenextracted with diethyl ether (10 mL × 3), and the combined organiclayers were washed with brine (20 mL) and dried over anhydrousNa2SO4. It was filtered and concentrated to give the crude residue,which was purified by Preparative HPLC (40-72% ACN in H2O) togiveproduct (8a) as a white solid (18 mg, 6.66%). ESI LC/MS: m/z calcd.for C30H33FO5 [M + H]+: 493.24; found 493.65. 1H NMR (400 MHz, CDCl3) δ 13.50 (s, 1H, OH), 13.05 (s, 1H, OH), 10.07 (s, 2H, CHO), 7.04(br s, 2H), 6.96-6.92 (m, 2H), 3.47 (d, J = 11.48 Hz, 1H), 2.15-2.07 (m,2H), 1.95-1.78 (m, 2H), 1.70-1.57 (m, 3H), 1.51-1.38 (m, 5H),1.36-1.31 (m, 1H), 1.27-1.24 (m, 1H), 1.08-1.03 (m, 1H), 1.01(apparent d, 6H), 0.86 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 192.32,191.58, 169.58, 168.55, 163.41, 162.56, 160.13, 139.02, 138.99,128.91, 115.13, 114.92, 105.53, 104.63, 104.17, 84.15, 50.09, 47.44,44.05, 39.69, 37.59, 36.95, 35.44, 35.08, 33.48, 30.61, 29.37, 26.06,23.87, 20.73, 20.12.
  • 75
  • [ 87-44-5 ]
  • [ 4396-13-8 ]
  • [ 104-88-1 ]
  • chloro (+)-psiguadial B [ No CAS ]
YieldReaction ConditionsOperation in experiment
7.16% With sodium acetate; acetic acid at 80℃; for 24h; 2.2.4. Preparation of chloro (+)-Psiguadial B (8b) To a stirred solution of diformylphloroglucinol (11, 100 mg, 0.55mmol) and sodium acetate (4.5 mg, 0.06 mmol, 0.1 equiv.) in acetic acid(4 mL), 4-chlorobenzaldehyde (12b, 154 mg, 1.10 mmol, 2.0 equiv.) andβ -Caryophyllene (5, 0.37 mL, 1.65 mmol, 3.0 equiv.) were addeddropwise at 80 C, the mixture was continuingly stirred for 24 h at 80 C.Upon cooling to room temperature, brine (5 mL) and diethyl ether (20mL) were added and the layers separated. The aqueous layer was thenextracted with diethyl ether (10 mL × 3), and the combined organiclayers were washed with brine (20 mL) and dried over anhydrousNa2SO4. It was filtered and concentrated to give the crude residue,which was purified by Preparative HPLC (40-72% ACN in H2O) to giveproduct (8b) as a white solid (20 mg, 7.16%). ESI LC/MS: m/z calcd. forC30H33ClO5 [M]+: 509.21; found [M]+: 509.05 and [M + 2]+: 511.0. 1HNMR (400 MHz, CDCl3) δ 13.50 (s, 1H, OH), 13.06 (s, 1H, OH), 10.07 (s,2H, CHO), 7.22 (d, J = 8.68 Hz, 2H), 7.03 (d, J = 6.88 Hz, 2H), 3.47 (d, J= 11.44 Hz, 1H), 2.14-2.07 (m, 2H), 1.94-1.78 (m, 2H), 1.70-1.57 (m,3H), 1.51-1.38 (m, 5H), 1.36-1.31 (m, 1H), 1.27-1.24 (m, 1H),1.09-1.04 (m, 1H), 1.01 (apparent d, 6H), 0.86 (s, 3H). 13C NMR (100MHz, CDCl3) δ 192.30, 191.58, 169.50, 168.57, 163.42, 141.99, 131.81(3C), 128.37 (2C), 105.22, 104.64, 104.15, 84.12, 49.94, 47.43, 44.04,39.87, 37.56, 36.94, 35.44, 35.09, 33.47, 30.61, 29.39, 26.06, 23.87,20.73, 20.11.
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