1139-30-6

Basic information

• Product Name: CARYOPHYLLENE OXIDE
• Synonyms: (-)-5-Oxatricyclo[8.2.0.0(4,6)]dodecane,4,12,12-trimethyl-9-methylene-, [1R-(1R*,4R*,6R*,10S*)]-;(-)-beta-Caryophyllene epoxide;(-)-beta-caryophylleneepoxid;(-)-beta-caryophylleneepoxide;(-)-Epoxydihydrocaryophyllene;(1r-(1r*,4r*,6r*,10s*))-4,12,12-trimethyl-9-methylene-5-oxatricyclo(8.2.0.04,6)dodecane;(1r-(1r,4r,6r,10s))-4,12,12-trimethyl;(1r-(1r,4r,6r,10s))-4,12,12-trimethyl-9-methylene-5-oxatricyclo(8.2.0.04,6)dodecane
• CAS NO: 1139-30-6
• Molecular Formula: C₁₅H₂₄O
• Molecular Weight: 220.35
• EINECS: 214-519-7
• Product Categories: Alphabetical Listings;C-D;Flavors and Fragrances;Inhibitors;Sesquiterpenoids
• Mol File: 1139-30-6.mol
• Article Data: 23

Chemical Properties

• Melting Point: 62-63 °C(lit.)
• Boiling Point: 301.3°C (rough estimate)
• Flash Point: >230 °F
• Appearance: White/Crystalline Powder
• Density: 0.96
• Vapor Pressure: 0.00672mmHg at 25°C
• Refractive Index: 1.4956
• Storage Temp.: 2-8°C
• Solubility: Chloroform (Slightly), Methanol (Slightly)
• BRN: 148213
• CAS DataBase Reference: CARYOPHYLLENE OXIDE(CAS DataBase Reference)
• NIST Chemistry Reference: CARYOPHYLLENE OXIDE(1139-30-6)
• EPA Substance Registry System: CARYOPHYLLENE OXIDE(1139-30-6)

Safety Data

• Hazard Codes: Xi
• Statements: 36/38
• Safety Statements: 26
• WGK Germany: 2
• RTECS: RP5530000
• F: 1-10
• Hazardous Substances Data: 1139-30-6(Hazardous Substances Data)

Usage

Description

CARYOPHYLLENE OXIDE is a natural product found in Cupania cinerea, characterized by its white crystalline powder form and a sweet fruity aroma with a woody, slightly ambergris-like odor. It is a colorless solid with medium strength odor and is the main active constituent of essential oils obtained from various plants.

Uses

Used in Flavor and Fragrance Industry:
CARYOPHYLLENE OXIDE is used as a flavoring agent for its sweet fruity aroma and as a fragrance component for its woody, slightly ambergris-like odor.
Used in Pharmaceutical Industry:
CARYOPHYLLENE OXIDE is used as a butyrylcholinesterase inhibitor, which has potential applications in the development of drugs targeting this enzyme.
Used in Microbial Transformation:
CARYOPHYLLENE OXIDE is used in microbial transformation processes, which can lead to the production of various bioactive compounds.
Occurrence:
CARYOPHYLLENE OXIDE has been reported to be found in various plant oils, such as Nepeta betonicifolia C.A. Meyer oil from Turkey (39.20%), geranium rose-scented oil (Pelargonium spp.) from Cuba (14.70%), melissa oil (9.99%), and guava leaf oil from Cuba (8.20%).

Safety Profile

Low toxicity by ingestion and skin contact. A skin irritant. When heated to decomposition it emits acrid smoke and irritating fumes.

Purification Methods

Purify the oxide by TLC on silica gel with EtOAc/pet ether (b 60-80o) (15:85), and recrystallise it from MeOH or *C6H6. [NMR: Warnhoff Can J Chem 42 1664 1964, Ramage & Whitehead J Chem Soc 4336 1954, Beilstein 17 IV 392.]

InChI:InChI=1/C15H24O/c1-10-5-6-13-15(4,16-13)8-7-12-11(10)9-14(12,2)3/h11-13H,1,5-9H2,2-4H3/t11-,12-,13-,15+/m0/s1

Synthetic route

Methyltriphenylphosphonium bromide (1779-49-3) + (1R,4R,6R,10S)-4,12,12-trimethyl-5-oxatricyclo[8.2.0.04,6]dodcan-9-one (10306-22-6, 10306-31-7, 24173-71-5, 34175-71-8) → caryophyllene oxide (1139-30-6)

Conditions	Yield
Stage #1: Methyltriphenylphosphonium bromide With n-butyllithium In tetrahydrofuran at -78 - 0℃; for 0.166667h; Stage #2: (1R,4R,6R,10S)-4,12,12-trimethyl-5-oxatricyclo[8.2.0.04,6]dodcan-9-one In tetrahydrofuran at -78 - 20℃; for 24h;	74%

β-caryophyllene (87-44-5) → caryophyllene oxide (1139-30-6)

Conditions	Yield
With 4-methyloxetan-2-one; CpLIP2 Y179F (ipase/acyltransferase) from Candida parapsilosis; dihydrogen peroxide In aq. phosphate buffer; water at 20℃; for 24h; pH=6.5; Reagent/catalyst; Enzymatic reaction;	67%
With sodium hydrogencarbonate; 3-chloro-benzenecarboperoxoic acid In dichloromethane at 20℃; for 2h;	66%
With peracetic acid; sodium acetate In dichloromethane
With 3-chloro-benzenecarboperoxoic acid In dichloromethane at 0℃; for 0.5h;	75 % Chromat.

Perbenzoic acid (93-59-4) + β-caryophyllene (87-44-5) → caryophyllene oxide (1139-30-6)

Conditions	Yield
With chloroform

monoperoxyphthalic acid (2311-91-3) + β-caryophyllene (87-44-5) → caryophyllene oxide (1139-30-6)

Conditions	Yield
With diethyl ether

β-caryophyllene (87-44-5) → (1R,4R,5R,9S,11R)-4,5-epoxy-12-nor-8(14)-caryophyllene-11-ol (118122-82-0) + (1R,4R,5R,9S,11R)-4,5-epoxy-caryophyll-8(14)-en-12-oic acid (108525-13-9) + 15-hydroxycaryophyllene oxide (73510-14-2) + caryophyllene oxide (1139-30-6)

Conditions	Yield
for 72h; Diplodia gossypina ATCC 10936; Further byproducts given;	A 220 mg B 900 mg C 300 mg D 65 mg

β-caryophyllene (87-44-5) → caryophyllene oxide (1139-30-6) + (5S,6S)-5,6-epoxy-5,6-dihydrocaryophyllene (103475-43-0)

Conditions	Yield
With peracetic acid; sodium acetate In dichloromethane at 0℃; Yield given. Yields of byproduct given;
With 3-chloro-benzenecarboperoxoic acid In dichloromethane for 2h; Title compound not separated from byproducts;	A 81 % Spectr. B 19 % Spectr.
With peracetic acid; sodium acetate In dichloromethane at 0℃; Yield given. Yields of byproduct given. Title compound not separated from byproducts;

β-caryophyllene (87-44-5) → caryophyllene oxide (1139-30-6) + (2R,5R,6R)-2,12:5,6-diepoxycaryophyllane (60444-80-6) + (1R,4R,6R,9S,10S)-4,12,12-trimethylspiro(5-oxatricyclo[8.2.0.04,6]dodecane-9,2'-oxirane) (60479-10-9)

Conditions	Yield
With 3-chloro-benzenecarboperoxoic acid In dichloromethane at 0℃; for 0.5h; Product distribution; effect of stoichiometry, temperature, reaction time;	A 52 % Chromat. B 21 % Chromat. C 21 % Chromat.

5,6-epoxy-2-hydroxymethyl-6,10,10-trimethyl-bicyclo[7.2.0]undecan-2-ol (10577-25-0, 60479-11-0, 60479-16-5, 60479-18-7, 123808-25-3) → caryophyllene oxide (1139-30-6)

Conditions	Yield
Multi-step reaction with 2 steps 1.1: sodium periodate / water; methanol / 4.33 h / 20 °C / Inert atmosphere 2.1: n-butyllithium / tetrahydrofuran / 0.17 h / -78 - 0 °C 2.2: 24 h / -78 - 20 °C View Scheme

caryophyllene oxide (1139-30-6) → 1,5,5,8-tetramethyl-[1R-(1R*,3E,7E,11R*)]-12-oxabicyclo[9.1.0]dodeca-3,7-diene (19888-34-7, 67737-67-1, 90820-79-4, 108101-44-6)

Conditions	Yield
With phenylsilane In benzene for 2h;	100%
With (+/-)-trans-Co(III)-salen-Cl; phenylsilane In benzene for 2h;	100%
With C32H46ClCoN2O2; phenylsilane In benzene at 22℃; for 5h; Inert atmosphere;	95%

caryophyllene oxide (1139-30-6) → (-)-humulene epoxide II

Conditions	Yield
With (+/-)-trans-Co(III)-salen-Cl; phenylsilane In benzene for 2h;	100%

caryophyllene oxide (1139-30-6) → (1R,4R,6R,10S)-4,12,12-trimethyl-5-oxatricyclo[8.2.0.04,6]dodcan-9-one (10306-22-6, 10306-31-7, 24173-71-5, 34175-71-8)

Conditions	Yield
Stage #1: caryophyllene oxide With ozone In dichloromethane at -78℃; Stage #2: With acetic acid; zinc In dichloromethane; water at 20℃; for 18h; Inert atmosphere;	98%
With ruthenium trichloride; sodium periodate In water; ethyl acetate; acetonitrile for 6h;	61%
With ruthenium trichloride; sodium periodate; water In ethyl acetate; acetonitrile for 6h;	61%

6-(trimethylsilyl)hex-5-yn-1-yl 2-cyano-2-diazoacetate (1361382-43-5) + caryophyllene oxide (1139-30-6) → C27H41NO3Si

Conditions	Yield
With Rh2(esp)2 In dichloromethane at 22℃; for 4h; Inert atmosphere; diastereoselective reaction;	94%

caryophyllene oxide (1139-30-6) → 1R,5S,9S-11,11-dimethyl-4,8-bismethylenebicyclo<7.2.0>undecan-5-ol (19431-79-9)

Conditions	Yield
With n-butyllithium; diisopropylamine In tetrahydrofuran; hexane Heating;	90%
With n-butyllithium In diethyl ether
With ethenetetracarbonitrile; lithium bromide In acetone
With ethenetetracarbonitrile; lithium bromide In acetone

caryophyllene oxide (1139-30-6) → ((1R,4R,6R,9S,10S)-4,12,12-trimethyl-5-oxatricyclo[8.2.0.04,6]dodecan-9-yl)methanol

Conditions	Yield
Stage #1: caryophyllene oxide With 9-bora-bicyclo[3.3.1]nonane In tetrahydrofuran for 8h; Inert atmosphere; Cooling with ice; Stage #2: With dihydrogen peroxide; sodium hydroxide In tetrahydrofuran at 20℃; for 2h;	90%

caryophyllene oxide (1139-30-6) + thioacetic acid (507-09-5) → ({(1R,4R,6R,9R,10S)-4,12,12-trimethyl-5-oxatricyclo[8.2.0.04,6]dodec-9-yl}methyl)ethanethioate

Conditions	Yield
With silica gel regioselective reaction;	89%

caryophyllene oxide (1139-30-6) → 5,6-epoxy-2-hydroxymethyl-6,10,10-trimethyl-bicyclo[7.2.0]undecan-2-ol (10577-25-0, 60479-11-0, 60479-16-5, 60479-18-7, 123808-25-3)

Conditions	Yield
With osmium(VIII) oxide; 4-methylmorpholine N-oxide In water; tert-butyl alcohol at 20℃; for 70h;	82%

2-bromo-1,3-thiazole (3034-53-5) + caryophyllene oxide (1139-30-6) → 2-(((1S,11S,Z)-7,7,11-trimethyl-12-oxabicyclo[9.1.0]dodec-4-en-4-yl)methyl)thiazole

Conditions	Yield
With formic acid; tributyl-amine; tris[2-phenylpyridinato-C2,N]iridium(III) In acetonitrile at 45℃; for 19h; Inert atmosphere; Irradiation; Sealed tube; diastereoselective reaction;	71%

caryophyllene oxide (1139-30-6) → (1R,2S,5R,8S,9R)-1,4,4,8-tetramethyltricyclo[6.3.0.02,5]undecan-9-ol (122621-21-0) + (1S,2S,5R,8R,9R)-1,4,4,8-tetramethyltricyclo[6.3.0.02,5]undecan-9-ol (122571-86-2)

Conditions	Yield
With 2,4,6-trimethyl-pyridine; manganese; chloro-trimethyl-silane; bis(cyclopentadienyl)titanium dichloride In tetrahydrofuran at 20℃; for 0.666667h;	A 65% B 30%

caryophyllene oxide (1139-30-6) + 2-methylpropan-2-thiol (75-66-1) → clovanediol (2649-64-1) + (1S,2S,5S,8R,9R)-2-tert-butylsulfanyl-4,4,8-trimethyltricyclo[6.3.1.01,5]dodecan-9-ol + 4,10,10-trimethyl-7-methylene-1β,8α-bicyclo[6.2.0]decene-4-carboxaldehyde (475285-25-7)

Conditions	Yield
With zinc(II) chloride In dichloromethane Reflux;	A 6% B 63% C 7%

Iodoethanol (624-76-0) + caryophyllene oxide (1139-30-6) → 2β-(2-iodoethoxy)clovan-9α-ol (1112901-60-6)

Conditions	Yield
With ethenetetracarbonitrile at 25℃;	62%

caryophyllene oxide (1139-30-6) → 4,9,12,12-tetramethyl-5-oxatricyclo[8.2.0.04,6]dodecan-9-ol (103189-78-2)

Conditions	Yield
With iron(III)-acetylacetonate; methyl 4-nitrobenzenesulfonate; phenylsilane; sodium hydrogencarbonate In methanol at 0 - 20℃; for 12h; Schlenk technique; Inert atmosphere; diastereoselective reaction;	62%

caryophyllene oxide (1139-30-6) → (1R,5S,8R,9R)-4,4,8-trimethylbicyclo<6.3.1.01,5>dodeca-2-en-9-ol (92760-17-3)

Conditions	Yield
With bithmuth(III) triflate hydrate In dichloromethane for 0.166667h; Wagner-Meerwein rearrangement; Reflux;	60%
With methanol; fluorosulfonylchloride; fluorosulphonic acid 1.) -100 deg C, 2.) diethyl ether; Yield given. Multistep reaction;

caryophyllene oxide (1139-30-6) + phenylmethanethiol (100-53-8) → (1S,2S,6S,9R)-2-(benzylsulfanyl)-6,2,10,10-tetramethylbicyclo[7.2.0]undecan-5-one + (1S,2S,5S,8R)-2-(benzylsulfanyl)-4,4,8-trimethyltricyclo[6.3.1.01,5]dodec-9-ene + (1S,2S,5S,8R,9R)-2,9-bis(benzylsulfanyl)-4,4,8-trimethyltricyclo[6.3.1.01,5]dodecane

Conditions	Yield
With boron trifluoride diethyl etherate In chloroform for 5h; Reflux;	A 21% B 25% C 51%

caryophyllene oxide (1139-30-6) + 2-methylpropan-2-thiol (75-66-1) → caryophylla-2(12),6(13)-dien-5β-ol (19431-76-6) + clovanediol (2649-64-1) + (1S,2S,5S,8R)-2-tert-butylsulfanyl-4,4,8-trimethyltricyclo[6.3.1.01,5]dodec-9-ene + (1S,2S,5S,8R,9R)-2,9-bistert-butylsulfanyl-4,4,8-trimethyltricyclo[6.3.1.01,5]dodecane

Conditions	Yield
With boron trifluoride diethyl etherate In dichloromethane Reflux;	A 10% B 7% C 35% D 48%

caryophyllene oxide (1139-30-6) + aniline (62-53-3) + acetonitrile (75-05-8) → 2β-phenylaminoclovan-9α-ol + N-(9α-hydroxyclovan-2β-yl)-N'-phenyl acetamidine

Conditions	Yield
With tin(II) trifluoromethanesulfonate at 80℃; for 24h;	A 5% B 47%

caryophyllene oxide (1139-30-6) → caryophylla-2(12),6(13)-dien-5β-ol (19431-76-6) + 1R,5S,9S-11,11-dimethyl-4,8-bismethylenebicyclo<7.2.0>undecan-5-ol (19431-79-9) + isocaryolan-9-one

Conditions	Yield
With ethenetetracarbonitrile In dimethyl sulfoxide for 96h; Ambient temperature;	A 46% B 19% C 2%

caryophyllene oxide (1139-30-6) + phenylmethanethiol (100-53-8) → (1S,2S,5S,8R,9R)-2-(benzylsulfanyl)-4,4,8-trimethyltricyclo[6.3.1.01,5]dodecan-9-ol + (1S,2S,6S,9R)-2-(benzylsulfanyl)-6,2,10,10-tetramethylbicyclo[7.2.0]undecan-5-one + (1S,2S,5R,9S)-7-(benzylsulfanyl)-1,4,4,8-tetramethyl-12-oxatricyclo[7.2.1.02,5]dodecane

Conditions	Yield
With boron trifluoride diethyl etherate In chloroform at 20℃; for 2h;	A 46% B 13% C 26%

caryophyllene oxide (1139-30-6) → (+)-(6R,7R)-6,7-epoxy-6,7-dihydro-β-farnesene

Conditions	Yield
at 550℃; under 0.5 Torr;	45%
at 550℃; under 0.1 - 2 Torr; for 0.000277778h; Product distribution; Thermodynamic data; flash vacuum thermolysis; further stereoisomers; variation of temperature; activation energy;	43%

caryophyllene oxide (1139-30-6) + phenylmethanethiol (100-53-8) → 4α,11,11-trimethyl-8-methylene-1β,9α-bicyclo[7.2.0]undecan-5-one (68263-68-3) + clovanediol (2649-64-1) + C15H24O + (1S,2S,5S,8R,9R)-2-(benzylsulfanyl)-4,4,8-trimethyltricyclo[6.3.1.01,5]dodecan-9-ol

Conditions	Yield
With zinc(II) chloride In chloroform for 5h; Reflux;	A 12% B 26% C 10% D 45%

caryophyllene oxide (1139-30-6) + 2-methylpropan-2-thiol (75-66-1) → 4α,11,11-trimethyl-8-methylene-1β,9α-bicyclo[7.2.0]undecan-5-one (68263-68-3) + clovanediol (2649-64-1) + (1S,2S,5S,8R,9R)-2-tert-butylsulfanyl-4,4,8-trimethyltricyclo[6.3.1.01,5]dodecan-9-ol + 4,10,10-trimethyl-7-methylene-1β,8α-bicyclo[6.2.0]decene-4-carboxaldehyde (475285-25-7)

Conditions	Yield
With zinc(II) chloride In dichloromethane at 20℃; Catalytic behavior;	A 8% B 21% C 44% D 7%

caryophyllene oxide (1139-30-6) + 2-bromoethanol (540-51-2) → 2β-(2-bromoethoxy)clovan-9α-ol (357186-68-6)

Conditions	Yield
With ethenetetracarbonitrile at 25℃;	43%

methanol (67-56-1) + caryophyllene oxide (1139-30-6) → caryophylla-2(12),6(13)-dien-5β-ol (19431-76-6) + 9α-hydroxy-2β-methoxyclovane (127156-29-0) + isocaryolan-9-one + (1S,5R,6R,9R)-6-Methoxy-10,10-dimethyl-2-methylene-bicyclo[7.2.0]undecan-5-ol

Conditions	Yield
With ethenetetracarbonitrile for 24h; Ambient temperature; Further byproducts given;	A 20% B 42% C 11% D 6%

methanol (67-56-1) + caryophyllene oxide (1139-30-6) → caryophylla-2(12),6(13)-dien-5β-ol (19431-76-6) + 9α-hydroxy-2β-methoxyclovane (127156-29-0) + (Z)-(1R,5R,8R,9S)-8-Methoxy-4,8,11,11-tetramethyl-bicyclo[7.2.0]undec-3-en-5-ol + (1S,5R,6R,9R)-6-Methoxy-10,10-dimethyl-2-methylene-bicyclo[7.2.0]undecan-5-ol

Conditions	Yield
With ethenetetracarbonitrile for 24h; Ambient temperature; Further byproducts given;	A 20% B 42% C 3% D 6%

caryophyllene oxide (1139-30-6) → caryophylla-2(12),6(13)-dien-5β-ol (19431-76-6) + 9α-hydroxy-2β-methoxyclovane (127156-29-0) + isocaryolan-9-one + (1S,5R,6R,9R)-6-Methoxy-10,10-dimethyl-2-methylene-bicyclo[7.2.0]undecan-5-ol

Conditions	Yield
With ethenetetracarbonitrile In methanol for 24h; Ambient temperature; Further byproducts given;	A 20% B 42% C 11% D 6%

caryophyllene oxide (1139-30-6) + 4-methoxy-aniline (104-94-9) + acetonitrile (75-05-8) → 2β-(p-methoxyphenylamino)clovan-9α-ol + N-((3S,3aS,6R,7R,9aS)-6-Hydroxy-1,1,7-trimethyl-decahydro-3a,7-methano-cyclopentacycloocten-3-yl)-N'-(4-methoxy-phenyl)-acetamidine

Conditions	Yield
With tin(II) trifluoromethanesulfonate at 80℃; for 24h;	A 2% B 42%

caryophyllene oxide (1139-30-6) + acetonitrile (75-05-8) + 4-bromo-aniline (106-40-1) → N-(4-Bromo-phenyl)-N'-((3S,3aS,6R,7R,9aS)-6-hydroxy-1,1,7-trimethyl-decahydro-3a,7-methano-cyclopentacycloocten-3-yl)-acetamidine

Conditions	Yield
With tin(II) trifluoromethanesulfonate at 80℃; for 24h;	39%

Upstream product

• 87-44-5 β-caryophyllene 
• 3691-12-1 (1S,4S,7R)-7-Isopropenyl-1,4-dimethyl-1,2,3,4,5,6,7,8-octahydro-azulene 
• 64-19-7 acetic acid 
• 93-59-4 Perbenzoic acid 
• 2311-91-3 monoperoxyphthalic acid 
• 10577-25-0 5,6-epoxy-2-hydroxymethyl-6,10,10-trimethyl-bicyclo[7.2.0]undecan-2-ol 
• 1779-49-3 Methyltriphenylphosphonium bromide 
• 10306-22-6 (1R,4R,6R,10S)-4,12,12-trimethyl-5-oxatricyclo[8.2.0.0^4,6]dodcan-9-one 
• 87-44-5 β-caryophyllene 
• 61824-50-8 (Z)-(1R,9S)-4,11,11-Trimethyl-8-methylene-bicyclo[7.2.0]undec-3-en-5-one 

Downstream Products

• 10306-22-6 (1R,4R,6R,10S)-4,12,12-trimethyl-5-oxatricyclo[8.2.0.0^4,6]dodcan-9-one 
• 2649-64-1 clovanediol 
• 155485-76-0 (β,9β)-caryolane-1,9-diol 
• 92760-17-3 (1R,5S,8R,9R)-4,4,8-trimethylbicyclo<6.3.1.0^1,5>dodeca-2-en-9-ol 
• 122571-87-3 (1R,2S,5R,8S,9S)-1,4,4,8-tetramethyltricyclo[6.3.0.0^2,5]undec-9-yl acetate 
• 86834-01-7 4,5-dihydrocaryophyllen-4β-ol 
• 92174-64-6 Acetic acid (1S,5S,6S,9R)-6,10,10-trimethyl-2-methylene-bicyclo[7.2.0]undec-5-yl ester 
• 92174-64-6 1R,4R,5S,9S-4,5-dihydrocaryophyllen-5-ol acetate 
• 62346-22-9 buddledin C 
• 88514-10-7 ((1S,8R)-4,10,10-Trimethyl-7-methylene-bicyclo[6.2.0]dec-4-yl)-methanol 
• 19431-76-6 caryophyllenol-I 
• 19431-79-9 (1S,5S,9R)-10,10-Dimethyl-2,6-dimethylene-bicyclo[7.2.0]undecan-5-ol 
• 60444-80-6 (2R,5R,6R)-2,12:5,6-diepoxycaryophyllane 
• 99881-55-7 1R,5R,9S-5-acetoxy-11,11-dimethyl-4,8-bismethylenebicyclo<7.2.0>undecane 

Relevant articles and documents

A further step to sustainable palladium catalyzed oxidation: Allylic oxidation of alkenes in green solvents

The palladium catalyzed oxidation of alkenes with molecular oxygen is a synthetically important reaction which employs palladium catalysts in solution; therefore, a solvent plays a critical role for the process. In this study, we have tested several green solvents as a reaction medium for the allylic oxidation of a series of alkenes. Dimethylcarbonate, methyl isobutyl ketone, and propylene carbonate, solvents with impressive sustainability ranks and very scarcely exploited in palladium catalyzed oxidations, were proved to be excellent alternatives for the solvents conventionally employed in these processes, such as acetic acid. Palladium acetate alone or in the combination with p-benzoquinone efficiently operates as the catalyst for the oxidation of alkenes by dioxygen under 5–10 atm. For most substrates, the systems in green solvents showed better selectivity for allylic oxidation products as compared to pure acetic acid; moreover, the reactions in propylene carbonate solutions occurred even faster than in acetic acid.

PROCESS FOR PREPARING CARYOPHYLLENE OXIDE

The present invention relates to a method for oxidizing beta-caryophyllene with oxygen, in particular atmospheric oxygen, which avoids the use of catalysts, enzymes and solvents. Furthermore, the present invention provides a mixture comprising certain caryophyllene oxides as well as their use as a flavor and/or fragrance. The present invention also relates to products and semi-finished products comprising the mixture according to the invention.

Tailoring chemoenzymatic oxidation: Via in situ peracids

Epoxidation chemistry often suffers from the challenging handling of peracids and thus requires in situ preparation. Here, we describe a two-phase enzymatic system that allows the effective generation of peracids and directly translate their activity to the epoxidation of olefins. We demonstrate the approach by application to lipid and olefin epoxidation as well as sulfide oxidation. These methods offer useful applications to synthetic modifications and scalable green processes.