6902-91-6

Basic information

• Product Name: (3Z,7Z)-3,7-Dimethyl-10-propan-2-ylidene-cyclodeca-3,7-dien-1-one
• Synonyms: GerMacrol (obsol;(E,E)-GerMacrone;(3E,7E)-10-Isopropylidene-3,7-diMethyl-3,7-cyclodecadien-1-one;(3E,7E)-3,7-DiMethyl-10-(propan-2-ylidene)cyclodeca-3,7-dienone;(3z,7z)-3,7-dimethyl-10-propan-2-ylidene-cyclodeca-3,7-dien-1-one;(E,E)-Germacra-3,7(11),9-trien-6-one;(E,E)-3,7-Dimethyl-10-(1-methylethylidene)-3,7-cyclodecadien-1-one;3,7-Cyclodecadien-1-one, 3,7-dimethyl-10-(1-methylethylidene)-, (E,E)-
• CAS NO: 6902-91-6
• Molecular Formula: C₁₅H₂₂O
• Molecular Weight: 218.33458
• Product Categories: chemical reagent;pharmaceutical intermediate;phytochemical;reference standards from Chinese medicinal herbs (TCM).;standardized herbal extract;Inhibitors
• Mol File: 6902-91-6.mol

Chemical Properties

• Melting Point: 55-58 °C
• Boiling Point: 330.274 °C at 760 mmHg
• Flash Point: 148.419 °C
• Appearance: /
• Density: 0.916 g/cm³
• Vapor Pressure: 0.000168mmHg at 25°C
• Refractive Index: 1.485
• Storage Temp.: 2-8°C
• Solubility: Chloroform (Slightly), Ethyl Acetate (Slightly), Methanol (Slightly)
• Stability: Light Sensitive
• BRN: 2047453
• CAS DataBase Reference: (3Z,7Z)-3,7-Dimethyl-10-propan-2-ylidene-cyclodeca-3,7-dien-1-one(CAS DataBase Reference)
• NIST Chemistry Reference: (3Z,7Z)-3,7-Dimethyl-10-propan-2-ylidene-cyclodeca-3,7-dien-1-one(6902-91-6)
• EPA Substance Registry System: (3Z,7Z)-3,7-Dimethyl-10-propan-2-ylidene-cyclodeca-3,7-dien-1-one(6902-91-6)

Safety Data

• Safety Statements: 23-24/25
• RTECS: GU2210000
• Hazardous Substances Data: 6902-91-6(Hazardous Substances Data)

Usage

Uses

1. Used in Pharmaceutical Industry:
(3Z,7Z)-3,7-Dimethyl-10-propan-2-ylidene-cyclodeca-3,7-dien-1-one can be used as an active pharmaceutical ingredient (API) for the development of new drugs targeting various diseases. Its unique structure may allow it to interact with specific biological targets, potentially leading to novel therapeutic effects.
2. Used in Chemical Research:
(3Z,7Z)-3,7-Dimethyl-10-propan-2-ylidene-cyclodeca-3,7-dien-1-one can serve as a starting material or intermediate in the synthesis of other complex organic molecules. Researchers in the field of organic chemistry may utilize it to explore new reaction pathways, develop innovative synthetic methods, or create new compounds with specific properties.
3. Used in Material Science:
The unique structure of (3Z,7Z)-3,7-Dimethyl-10-propan-2-ylidene-cyclodeca-3,7-dien-1-one may endow it with special physical or chemical properties that could be harnessed in the development of new materials. For example, it could be used in the creation of advanced polymers, coatings, or other materials with specific characteristics.
4. Used in Agrochemical Industry:
(3Z,7Z)-3,7-Dimethyl-10-propan-2-ylidene-cyclodeca-3,7-dien-1-one may also have potential applications in the agrochemical industry, possibly as a component in the development of new pesticides, herbicides, or other agricultural chemicals. Its specific mode of action and target pests or weeds would need to be determined through further research and development.
5. Used in Fragrance Industry:
Given the complex structure of (3Z,7Z)-3,7-Dimethyl-10-propan-2-ylidene-cyclodeca-3,7-dien-1-one, it may possess unique olfactory properties that could be of interest to the fragrance industry. It could potentially be used as a component in the creation of new perfumes, colognes, or other scented products.

Synthesis Reference(s)

Tetrahedron Letters, 24, p. 3489, 1983 DOI: 10.1016/S0040-4039(00)86020-7

Safety Profile

A poison by ingestion. When heated to decomposition it emits acrid smoke and irritating vapors.

InChI:InChI=1/C15H22O/c1-11(2)14-9-8-12(3)6-5-7-13(4)10-15(14)16/h7-8H,5-6,9-10H2,1-4H3/b12-8+,13-7+

Synthetic route

(3E,7E)-1-Hydroxy-10-isopropylidene-3,7-dimethyl-cyclodeca-3,7-dienecarbonitrile (87920-50-1) → germacrone (6902-91-6)

Conditions	Yield
With sodium hydroxide In diethyl ether for 0.333333h; Yield given;

8-hydroxygeranyl acetate (37905-03-6) → germacrone (6902-91-6)

Conditions

Yield

Multi-step reaction with 13 steps 2: 65 percent / triphenylphosphine / palladium acetate / tetrahydrofuran / 5 h / Heating 3: 95 percent / sodium hydride / diethyl ether / 0 °C 4: 70 percent / diethyl ether / -10 °C 5: 90 percent / triphenylphosphine, carbon tetrachloride / 12 h / Heating 6: diisobutylaluminium hydride / tetrahydrofuran / -40 °C 7: manganese dioxide / hexane / Ambient temperature 8: KCN, 18-crown-6 / 1 h / 0 °C 9: trimethylbenzylammonium fluoride / tetrahydrofuran; H2O / 0 °C 11: 79 percent / sodium bis(trimethylsilyl)amide / tetrahydrofuran / 0.5 h / 56 °C 12: p-toluenesulfonic acid / methanol / 1 h / 0 °C 13: 2percent aqueous sodium hydroxide / diethyl ether / 0.33 h View Scheme

(4E,8E)-10-Chloro-2-isopropylidene-5,9-dimethyl-deca-4,8-dien-1-ol (87920-44-3) → germacrone (6902-91-6)

Conditions	Yield
Multi-step reaction with 7 steps 1: manganese dioxide / hexane / Ambient temperature 2: KCN, 18-crown-6 / 1 h / 0 °C 3: trimethylbenzylammonium fluoride / tetrahydrofuran; H2O / 0 °C 5: 79 percent / sodium bis(trimethylsilyl)amide / tetrahydrofuran / 0.5 h / 56 °C 6: p-toluenesulfonic acid / methanol / 1 h / 0 °C 7: 2percent aqueous sodium hydroxide / diethyl ether / 0.33 h View Scheme

(4E,8E)-10-Chloro-2-isopropylidene-5,9-dimethyl-deca-4,8-dienal (87920-45-4) → germacrone (6902-91-6)

Conditions	Yield
Multi-step reaction with 6 steps 1: KCN, 18-crown-6 / 1 h / 0 °C 2: trimethylbenzylammonium fluoride / tetrahydrofuran; H2O / 0 °C 4: 79 percent / sodium bis(trimethylsilyl)amide / tetrahydrofuran / 0.5 h / 56 °C 5: p-toluenesulfonic acid / methanol / 1 h / 0 °C 6: 2percent aqueous sodium hydroxide / diethyl ether / 0.33 h View Scheme

(4E,8E)-10-Hydroxy-2-isopropylidene-5,9-dimethyl-deca-4,8-dienoic acid methyl ester (87920-42-1) → germacrone (6902-91-6)

Conditions

Yield

Multi-step reaction with 9 steps 1: 90 percent / triphenylphosphine, carbon tetrachloride / 12 h / Heating 2: diisobutylaluminium hydride / tetrahydrofuran / -40 °C 3: manganese dioxide / hexane / Ambient temperature 4: KCN, 18-crown-6 / 1 h / 0 °C 5: trimethylbenzylammonium fluoride / tetrahydrofuran; H2O / 0 °C 7: 79 percent / sodium bis(trimethylsilyl)amide / tetrahydrofuran / 0.5 h / 56 °C 8: p-toluenesulfonic acid / methanol / 1 h / 0 °C 9: 2percent aqueous sodium hydroxide / diethyl ether / 0.33 h View Scheme

(4E,8E)-10-Chloro-2-isopropylidene-5,9-dimethyl-deca-4,8-dienoic acid methyl ester (87920-43-2) → germacrone (6902-91-6)

Conditions

Yield

Multi-step reaction with 8 steps 1: diisobutylaluminium hydride / tetrahydrofuran / -40 °C 2: manganese dioxide / hexane / Ambient temperature 3: KCN, 18-crown-6 / 1 h / 0 °C 4: trimethylbenzylammonium fluoride / tetrahydrofuran; H2O / 0 °C 6: 79 percent / sodium bis(trimethylsilyl)amide / tetrahydrofuran / 0.5 h / 56 °C 7: p-toluenesulfonic acid / methanol / 1 h / 0 °C 8: 2percent aqueous sodium hydroxide / diethyl ether / 0.33 h View Scheme

(5E,9E)-11-Chloro-2-hydroxy-3-isopropylidene-6,10-dimethyl-undeca-5,9-dienenitrile (87920-47-6) → germacrone (6902-91-6)

Conditions	Yield
Multi-step reaction with 4 steps 2: 79 percent / sodium bis(trimethylsilyl)amide / tetrahydrofuran / 0.5 h / 56 °C 3: p-toluenesulfonic acid / methanol / 1 h / 0 °C 4: 2percent aqueous sodium hydroxide / diethyl ether / 0.33 h View Scheme

(5E,9E)-11-Chloro-3-isopropylidene-6,10-dimethyl-2-trimethylsilanyloxy-undeca-5,9-dienenitrile (87920-46-5) → germacrone (6902-91-6)

Conditions	Yield
Multi-step reaction with 5 steps 1: trimethylbenzylammonium fluoride / tetrahydrofuran; H2O / 0 °C 3: 79 percent / sodium bis(trimethylsilyl)amide / tetrahydrofuran / 0.5 h / 56 °C 4: p-toluenesulfonic acid / methanol / 1 h / 0 °C 5: 2percent aqueous sodium hydroxide / diethyl ether / 0.33 h View Scheme

(4E,8E)-2-Acetyl-10-(1-ethoxy-ethoxy)-5,9-dimethyl-deca-4,8-dienoic acid methyl ester (87920-40-9) → germacrone (6902-91-6)

Conditions

Yield

Multi-step reaction with 11 steps 1: 95 percent / sodium hydride / diethyl ether / 0 °C 2: 70 percent / diethyl ether / -10 °C 3: 90 percent / triphenylphosphine, carbon tetrachloride / 12 h / Heating 4: diisobutylaluminium hydride / tetrahydrofuran / -40 °C 5: manganese dioxide / hexane / Ambient temperature 6: KCN, 18-crown-6 / 1 h / 0 °C 7: trimethylbenzylammonium fluoride / tetrahydrofuran; H2O / 0 °C 9: 79 percent / sodium bis(trimethylsilyl)amide / tetrahydrofuran / 0.5 h / 56 °C 10: p-toluenesulfonic acid / methanol / 1 h / 0 °C 11: 2percent aqueous sodium hydroxide / diethyl ether / 0.33 h View Scheme

(5E,9E)-11-Chloro-2-(1-ethoxy-ethoxy)-3-isopropylidene-6,10-dimethyl-undeca-5,9-dienenitrile (87920-48-7) → germacrone (6902-91-6)

Conditions	Yield
Multi-step reaction with 3 steps 1: 79 percent / sodium bis(trimethylsilyl)amide / tetrahydrofuran / 0.5 h / 56 °C 2: p-toluenesulfonic acid / methanol / 1 h / 0 °C 3: 2percent aqueous sodium hydroxide / diethyl ether / 0.33 h View Scheme

(3E,7E)-1-(1-Ethoxy-ethoxy)-10-isopropylidene-3,7-dimethyl-cyclodeca-3,7-dienecarbonitrile (87920-49-8) → germacrone (6902-91-6)

Conditions	Yield
Multi-step reaction with 2 steps 1: p-toluenesulfonic acid / methanol / 1 h / 0 °C 2: 2percent aqueous sodium hydroxide / diethyl ether / 0.33 h View Scheme

(4E,8E)-2-[1-(Diethoxy-phosphoryloxy)-eth-(E)-ylidene]-10-hydroxy-5,9-dimethyl-deca-4,8-dienoic acid methyl ester (87920-41-0) → germacrone (6902-91-6)

Conditions

Yield

Multi-step reaction with 10 steps 1: 70 percent / diethyl ether / -10 °C 2: 90 percent / triphenylphosphine, carbon tetrachloride / 12 h / Heating 3: diisobutylaluminium hydride / tetrahydrofuran / -40 °C 4: manganese dioxide / hexane / Ambient temperature 5: KCN, 18-crown-6 / 1 h / 0 °C 6: trimethylbenzylammonium fluoride / tetrahydrofuran; H2O / 0 °C 8: 79 percent / sodium bis(trimethylsilyl)amide / tetrahydrofuran / 0.5 h / 56 °C 9: p-toluenesulfonic acid / methanol / 1 h / 0 °C 10: 2percent aqueous sodium hydroxide / diethyl ether / 0.33 h View Scheme

Acetic acid (2E,6E)-8-(1-ethoxy-ethoxy)-3,7-dimethyl-octa-2,6-dienyl ester (87064-43-5) → germacrone (6902-91-6)

Conditions

Yield

Multi-step reaction with 12 steps 1: 65 percent / triphenylphosphine / palladium acetate / tetrahydrofuran / 5 h / Heating 2: 95 percent / sodium hydride / diethyl ether / 0 °C 3: 70 percent / diethyl ether / -10 °C 4: 90 percent / triphenylphosphine, carbon tetrachloride / 12 h / Heating 5: diisobutylaluminium hydride / tetrahydrofuran / -40 °C 6: manganese dioxide / hexane / Ambient temperature 7: KCN, 18-crown-6 / 1 h / 0 °C 8: trimethylbenzylammonium fluoride / tetrahydrofuran; H2O / 0 °C 10: 79 percent / sodium bis(trimethylsilyl)amide / tetrahydrofuran / 0.5 h / 56 °C 11: p-toluenesulfonic acid / methanol / 1 h / 0 °C 12: 2percent aqueous sodium hydroxide / diethyl ether / 0.33 h View Scheme

germacrone (6902-91-6) → (3E,7E)-3,7-dimethyl-10-(1-methylethylidene)-3,7-cyclodecanedien-1-ol (90988-53-7)

Conditions	Yield
With methanol; sodium tetrahydroborate at 0℃; for 4h; Sealed tube;	98.3%
With lithium aluminium tetrahydride In tetrahydrofuran at -10℃; for 0.166667h; Inert atmosphere;	94%
With sodium tetrahydroborate In methanol at 4℃; for 1h;	83%

germacrone (6902-91-6) → (4S)-trans-β-elemenone (20303-60-0)

Conditions	Yield
With bis(benzonitrile)palladium(II) dichloride In toluene for 1h; Cope rearrangement; Reflux; Inert atmosphere;	98%

germacrone (6902-91-6) → C15H22O (1443277-02-8)

Conditions	Yield
With sulfuric acid In chloroform at 20℃; for 1h; Temperature; Time; Inert atmosphere;	94%

germacrone (6902-91-6) → isogermacrone (5975-50-8)

Conditions	Yield
With sodium ethanolate at 20℃; for 48h; Inert atmosphere;	86%

germacrone (6902-91-6) → germacrone-1,10-epoxide + (4S,5S)-(+)-germacrone 4,5-epoxide (32179-17-2, 70680-71-6, 92691-35-5)

Conditions	Yield
With 3-chloro-benzenecarboperoxoic acid In dichloromethane for 6h; Inert atmosphere;	A 19% B 79%

germacrone (6902-91-6) → selina-4(14),7(11)-dien-8-one (54707-47-0) + C15H22O (1443277-02-8) + eudesma-4,7(11)-dien-8-one (97530-59-1)

Conditions	Yield
With sulfuric acid In chloroform at 25℃; for 0.5h; Inert atmosphere;	A 5% B 78% C 10%

germacrone (6902-91-6) → 1,10-epoxygermacrone (52061-45-7, 106862-05-9, 142794-64-7) + (+/-)-germacrone-4,5-epoxide (32179-17-2, 70680-71-6, 92691-35-5)

Conditions	Yield
With 3-chloro-benzenecarboperoxoic acid In dichloromethane at 20℃;	A 19% B 72%

germacrone (6902-91-6) → C15H21BrO (1443277-03-9) + C15H21BrO (1443277-04-0)

Conditions	Yield
With N-Bromosuccinimide In dichloromethane at 20℃; for 0.25h; Inert atmosphere;	A 53% B 19%

germacrone (6902-91-6) → selina-4(14),7(11)-dien-8-one (54707-47-0) + C15H22O (1443277-02-8) + eudesma-4,7(11)-dien-8-one (97530-59-1) + eudesm-3,7(11)-diene-8-one

Conditions	Yield
With sulfuric acid In chloroform at 25℃; for 0.0833333h; Inert atmosphere;	A 5% B 21% C 42% D 24%

germacrone (6902-91-6) → isogermacrone <(2Z,7E)-3,7-dimethyl-10-(1-methylethylidene)-2,7-cyclodecadien-1-one> (5975-50-8, 92465-08-2, 92465-09-3, 108667-42-1, 116713-46-3) + C15H22O2

Conditions	Yield
With dihydrogen peroxide; sodium hydroxide In ethanol at 20℃; for 960h;	A 41% B 20%

germacrone (6902-91-6) + 1-Nitropropane (108-03-2) → 1,5,5,11-tetramethyltricyclo[6.2.1.0(4,11)]undec-3-en-6-one + 1,4-dimethyl-8-isopropylidenespiro[4.5]dec-1-en-7-one + 1,7-dimethyl-4-isopropylidenebicyclo[5.3.0]dec-9-en-3-one + 10-(1-chloropropylideneaminooxy)-1,7-dimethyl-4-isopropylidenebicyclo[5.3.0]decan-3-one + 9-(1-chloropropylideneaminooxy)-1,7-dimethyl-4-isopropylidenebicyclo[5.3.0]decan-3-one

Conditions	Yield
With chlorosulfonic acid at -78℃; for 1h; Inert atmosphere;	A 39% B 27% C 9% D 4% E 1%
With chlorosulfonic acid at -78℃; for 0.166667h; Inert atmosphere;	A 16% B 16% C 5% D 21% E 15%

Phenylselenyl chloride (5707-04-0) + germacrone (6902-91-6) → C21H26OSe (1443277-05-1) + C21H26OSe (1443277-06-2) + C21H26OSe (1443277-08-4) + C21H26OSe (1443277-09-5) + C21H26OSe (1443277-07-3)

Conditions	Yield
In dichloromethane at 20℃; for 0.5h; Inert atmosphere;	A 37% B 20% C 14% D 6% E 7%

germacrone (6902-91-6) → C15H21ClO + C15H21ClO (1443277-11-9) + C15H21ClO (1443277-12-0)

Conditions	Yield
With N-chloro-succinimide In dichloromethane at 20℃; for 30h; Inert atmosphere;	A 35% B 6% C 31%

germacrone (6902-91-6) → C15H22O + C15H22O + C15H22O

Conditions	Yield
With chlorosulfonic acid at -78℃; for 0.166667h; Inert atmosphere;	A 24% B 35% C 8%

germacrone (6902-91-6) → eudesma-4,7(11),dien-8-one + 6-isopropylidene-4,8aβ-dimethyl-trans-1,2,5,6,8,8a-hexahydronaphthalene-7-(4aH)-one (54707-46-9, 73788-48-4, 130466-24-9)

Conditions	Yield
With gallium(III) trichloride In dichloromethane at 20℃; for 0.666667h;	A 15% B 24%

germacrone (6902-91-6) + lead(IV) tetraacetate (546-67-8) → (1R,3aR,8aR)-7-Isopropylidene-1-methoxy-1-methyl-4-methylene-octahydro-azulen-6-one (115857-52-8) + 4,7-Diacetyl-2-isopropylidene-cyclooctanone (115842-60-9) + (1S,3aR,4R,8aS)-7-Isopropylidene-1,4-dimethoxy-1,4-dimethyl-octahydro-azulen-6-one (115842-59-6, 115939-29-2) + (1S,3aS,4S,8aS)-7-Isopropylidene-1,4-dimethoxy-1,4-dimethyl-octahydro-azulen-6-one (115842-59-6, 115939-29-2)

Conditions	Yield
In methanol for 0.833333h; Ambient temperature;	A 40 mg B 20% C 20 mg D 60 mg

germacrone (6902-91-6) → 2-isopropylidene-5,9-dimethyl-cyclodecanone (69239-69-6)

Conditions	Yield
With hydrogen; platinum(IV) oxide

germacrone (6902-91-6) → 10-isopropylidene-3,7-dimethyl-cyclodeca-3t,7t-dienone (32663-53-9)

Conditions	Yield
With acetophenone In diethyl ether Irradiation;
With acetophenone Irradiation;

germacrone (6902-91-6) → 3,7-dimethyl-10-isopropylidene-3(Z),7(E)-cyclodecadien-1-one (32663-51-7)

Conditions	Yield
With acetophenone In diethyl ether Irradiation;
With acetophenone Irradiation;

germacrone (6902-91-6) → (+/-)-4r-isopropenyl-2-isopropylidene-5c-methyl-5t-vinyl-cyclohexanone (470-19-9, 20303-60-0, 30824-86-3, 32663-57-3, 52153-83-0)

Conditions	Yield
at 140 - 148℃;

methanol (67-56-1) + germacrone (6902-91-6) → (1R,3aR,8aR)-7-Isopropylidene-1-methoxy-1-methyl-4-methylene-octahydro-azulen-6-one (115857-52-8) + 4,7-Diacetyl-2-isopropylidene-cyclooctanone (115842-60-9) + (1S,3aR,4R,8aS)-7-Isopropylidene-1,4-dimethoxy-1,4-dimethyl-octahydro-azulen-6-one (115842-59-6, 115939-29-2) + (1S,3aS,4S,8aS)-7-Isopropylidene-1,4-dimethoxy-1,4-dimethyl-octahydro-azulen-6-one (115842-59-6, 115939-29-2)

Conditions	Yield
With lead(IV) acetate for 0.833333h; Ambient temperature;	A 40 mg B 40 mg C 20 mg D 60 mg

diiodomethane (75-11-6) + germacrone (6902-91-6) → 4,5-cyclopropane-8-oxo-germacrene B (96235-08-4) + 1,10-cyclopropane-8-oxo-germacrene B (96235-09-5)

Conditions	Yield
With copper(l) chloride; zinc In diethyl ether at 30℃; for 24h;

germacrone (6902-91-6) + lead(IV) tetraacetate (546-67-8) → 2-hydroxy-4-methyl-ω,ω-dichloroacetophenone (116046-02-7) + Acetic acid (1R,8aR)-7-isopropylidene-1,4-dimethyl-6-oxo-1,2,3,5,6,7,8,8a-octahydro-azulen-1-yl ester (115842-58-5) + Acetic acid (3aR,4R)-7-isopropylidene-1,4-dimethyl-6-oxo-2,3,3a,4,5,6,7,8-octahydro-azulen-4-yl ester (115842-51-8) + Acetic acid (1S,3aS,4S,8aS)-1-acetoxy-7-isopropylidene-1,4-dimethyl-6-oxo-decahydro-azulen-4-yl ester (98644-26-9, 115936-78-2)

Conditions	Yield
In acetic acid for 2h; Ambient temperature; Further byproducts given;	A 50 mg B 25 mg C 25 mg D 16 mg

germacrone (6902-91-6) + lead(IV) tetraacetate (546-67-8) → (3aR,3bR,7aS)-6-Isopropylidene-1,3b-dimethyl-3,3a,3b,4,6,7-hexahydro-cyclopenta[1,3]cyclopropa[1,2]benzen-5-one (115842-54-1) + (3aS,8aS)-5-Isopropylidene-3-methyl-8-methylene-3a,4,5,7,8,8a-hexahydro-1H-azulen-6-one (115842-48-3) + (3aS,8aS)-5-Isopropylidene-3,8-dimethyl-3a,4,5,8a-tetrahydro-1H-azulen-6-one (115842-47-2) + Acetic acid (3aR,4R,8aR)-7-isopropylidene-1,4-dimethyl-6-oxo-3,3a,4,5,6,7,8,8a-octahydro-azulen-4-yl ester (115842-49-4)

Conditions	Yield
In benzene for 18h; Ambient temperature; Further byproducts given;	A 3 mg B 15 mg C 18 mg D 75 mg

germacrone (6902-91-6) + lead(IV) tetraacetate (546-67-8) → (3aS,8aS)-5-Isopropylidene-3-methyl-8-methylene-3a,4,5,7,8,8a-hexahydro-1H-azulen-6-one (115842-48-3) + (3aS,8aS)-5-Isopropylidene-3,8-dimethyl-3a,4,5,8a-tetrahydro-1H-azulen-6-one (115842-47-2) + Acetic acid (4aR,8aS)-6-isopropylidene-4,8a-dimethyl-7-oxo-1,2,4a,5,6,7,8,8a-octahydro-naphthalen-1-yl ester (115842-52-9) + Acetic acid (3aR,4R,8aR)-7-isopropylidene-4-methyl-1-methylene-6-oxo-decahydro-azulen-4-yl ester (115842-50-7) + Acetic acid (3aR,4R,8aR)-7-isopropylidene-1,4-dimethyl-6-oxo-3,3a,4,5,6,7,8,8a-octahydro-azulen-4-yl ester (115842-49-4) + Acetic acid (3aR,4R)-7-isopropylidene-1,4-dimethyl-6-oxo-2,3,3a,4,5,6,7,8-octahydro-azulen-4-yl ester (115842-51-8)

Conditions	Yield
In benzene for 18h; Mechanism; Product distribution; Ambient temperature; different solvents, reaction time;	A 15 mg B 18 mg C 9 mg D 12 mg E 75 mg F 9 mg

germacrone (6902-91-6) + lead(IV) tetraacetate (546-67-8) → (3aS,8aS)-5-Isopropylidene-3-methyl-8-methylene-3a,4,5,7,8,8a-hexahydro-1H-azulen-6-one (115842-48-3) + (3aS,8aS)-5-Isopropylidene-3,8-dimethyl-3a,4,5,8a-tetrahydro-1H-azulen-6-one (115842-47-2) + Acetic acid (4aR,8aS)-6-isopropylidene-4,8a-dimethyl-7-oxo-1,2,4a,5,6,7,8,8a-octahydro-naphthalen-1-yl ester (115842-52-9) + Acetic acid (3aR,4R,8aR)-7-isopropylidene-1,4-dimethyl-6-oxo-3,3a,4,5,6,7,8,8a-octahydro-azulen-4-yl ester (115842-49-4)

Conditions	Yield
In benzene for 18h; Ambient temperature; Further byproducts given;	A 15 mg B 18 mg C 9 mg D 75 mg

germacrone (6902-91-6) + lead(IV) tetraacetate (546-67-8) → (3aS,8aS)-5-Isopropylidene-3-methyl-8-methylene-3a,4,5,7,8,8a-hexahydro-1H-azulen-6-one (115842-48-3) + (3aS,8aS)-5-Isopropylidene-3,8-dimethyl-3a,4,5,8a-tetrahydro-1H-azulen-6-one (115842-47-2) + Acetic acid (3aR,4R,8aR)-7-isopropylidene-4-methyl-1-methylene-6-oxo-decahydro-azulen-4-yl ester (115842-50-7) + Acetic acid (3aR,4R,8aR)-7-isopropylidene-1,4-dimethyl-6-oxo-3,3a,4,5,6,7,8,8a-octahydro-azulen-4-yl ester (115842-49-4)

Conditions	Yield
In benzene for 18h; Ambient temperature; Further byproducts given;	A 15 mg B 18 mg C 12 mg D 75 mg

germacrone (6902-91-6) + lead(IV) tetraacetate (546-67-8) → (3aS,8aS)-5-Isopropylidene-3-methyl-8-methylene-3a,4,5,7,8,8a-hexahydro-1H-azulen-6-one (115842-48-3) + (3aS,8aS)-5-Isopropylidene-3,8-dimethyl-3a,4,5,8a-tetrahydro-1H-azulen-6-one (115842-47-2) + Acetic acid (3aR,4R,8aR)-7-isopropylidene-1,4-dimethyl-6-oxo-3,3a,4,5,6,7,8,8a-octahydro-azulen-4-yl ester (115842-49-4) + Acetic acid (2E,6E)-(1S,5S)-5-acetoxy-8-isopropylidene-1,5-dimethyl-9-oxo-cyclodeca-2,6-dienyl ester (115842-56-3)

Conditions	Yield
In benzene for 18h; Ambient temperature; Further byproducts given;	A 15 mg B 18 mg C 75 mg D 3 mg

germacrone (6902-91-6) + lead(IV) tetraacetate (546-67-8) → (3aS,8aS)-5-Isopropylidene-3-methyl-8-methylene-3a,4,5,7,8,8a-hexahydro-1H-azulen-6-one (115842-48-3) + Acetic acid (3aR,4R,8aR)-7-isopropylidene-1,4-dimethyl-6-oxo-3,3a,4,5,6,7,8,8a-octahydro-azulen-4-yl ester (115842-49-4) + Acetic acid (1R,8aR)-7-isopropylidene-1,4-dimethyl-6-oxo-1,2,3,5,6,7,8,8a-octahydro-azulen-1-yl ester (115842-58-5) + Acetic acid (3aR,4R)-7-isopropylidene-1,4-dimethyl-6-oxo-2,3,3a,4,5,6,7,8-octahydro-azulen-4-yl ester (115842-51-8)

Conditions	Yield
In acetic acid for 2h; Ambient temperature; Further byproducts given;	A 16 mg B 50 mg C 25 mg D 25 mg

germacrone (6902-91-6) + lead(IV) tetraacetate (546-67-8) → Acetic acid (1R,3aR,8aR)-7-isopropylidene-1-methyl-4-methylene-6-oxo-decahydro-azulen-1-yl ester (115842-57-4) + Acetic acid (3aR,4R,8aR)-7-isopropylidene-1,4-dimethyl-6-oxo-3,3a,4,5,6,7,8,8a-octahydro-azulen-4-yl ester (115842-49-4) + Acetic acid (1R,8aR)-7-isopropylidene-1,4-dimethyl-6-oxo-1,2,3,5,6,7,8,8a-octahydro-azulen-1-yl ester (115842-58-5) + Acetic acid (3aR,4R)-7-isopropylidene-1,4-dimethyl-6-oxo-2,3,3a,4,5,6,7,8-octahydro-azulen-4-yl ester (115842-51-8)

Conditions	Yield
In acetic acid for 2h; Ambient temperature; Further byproducts given;	A 16 mg B 50 mg C 25 mg D 25 mg

Upstream product

• 87920-50-1 (3E,7E)-1-Hydroxy-10-isopropylidene-3,7-dimethyl-cyclodeca-3,7-dienecarbonitrile 
• 37905-03-6 8-hydroxygeranyl acetate 
• 87920-44-3 (4E,8E)-10-Chloro-2-isopropylidene-5,9-dimethyl-deca-4,8-dien-1-ol 
• 87920-45-4 (4E,8E)-10-Chloro-2-isopropylidene-5,9-dimethyl-deca-4,8-dienal 
• 87920-42-1 (4E,8E)-10-Hydroxy-2-isopropylidene-5,9-dimethyl-deca-4,8-dienoic acid methyl ester 
• 87920-43-2 (4E,8E)-10-Chloro-2-isopropylidene-5,9-dimethyl-deca-4,8-dienoic acid methyl ester 
• 87920-47-6 (5E,9E)-11-Chloro-2-hydroxy-3-isopropylidene-6,10-dimethyl-undeca-5,9-dienenitrile 
• 87920-46-5 (5E,9E)-11-Chloro-3-isopropylidene-6,10-dimethyl-2-trimethylsilanyloxy-undeca-5,9-dienenitrile 
• 87920-40-9 (4E,8E)-2-Acetyl-10-(1-ethoxy-ethoxy)-5,9-dimethyl-deca-4,8-dienoic acid methyl ester 
• 87920-48-7 (5E,9E)-11-Chloro-2-(1-ethoxy-ethoxy)-3-isopropylidene-6,10-dimethyl-undeca-5,9-dienenitrile 
• 87920-49-8 (3E,7E)-1-(1-Ethoxy-ethoxy)-10-isopropylidene-3,7-dimethyl-cyclodeca-3,7-dienecarbonitrile 
• 87920-41-0 (4E,8E)-2-[1-(Diethoxy-phosphoryloxy)-eth-(E)-ylidene]-10-hydroxy-5,9-dimethyl-deca-4,8-dienoic acid methyl ester 
• 87064-43-5 Acetic acid (2E,6E)-8-(1-ethoxy-ethoxy)-3,7-dimethyl-octa-2,6-dienyl ester 

Downstream Products

• 470-19-9 (+/-)-4r-isopropenyl-2-isopropylidene-5c-methyl-5t-vinyl-cyclohexanone 
• 116046-02-7 2-hydroxy-4-methyl-ω,ω-dichloroacetophenone 
• 115842-58-5 Acetic acid (1R,8aR)-7-isopropylidene-1,4-dimethyl-6-oxo-1,2,3,5,6,7,8,8a-octahydro-azulen-1-yl ester 
• 115842-51-8 Acetic acid (3aR,4R)-7-isopropylidene-1,4-dimethyl-6-oxo-2,3,3a,4,5,6,7,8-octahydro-azulen-4-yl ester 
• 98644-26-9 Acetic acid (1S,3aS,4S,8aS)-1-acetoxy-7-isopropylidene-1,4-dimethyl-6-oxo-decahydro-azulen-4-yl ester 
• 68984-95-2 curcumenone 
• 142717-57-5 dihydrocurcumenone 
• 142717-58-6 1α,4β-dihydroxyeudesm-7(11)-en-8-one 
• 32179-17-2 (4S,5S)-epoxy-(+)-4,5-dihydrogermacrone 
• 68984-97-4 isozedoarondiol 
• 69010-39-5 Procurcumenol 
• 116425-34-4 isozedoarondiol 
• 52061-45-7 germacrone 1,10-epoxide 
• 32179-17-2 (+/-)-germacrone-4,5-epoxide 

Relevant articles and documents

A FIRST TOTAL SYNTHESIS OF GERMACRONE BY INTRAMOLECULAR ALKYLATION OF PRETECTED CYANOHYDRIN

A total synthesis of Germacrone by the intramolecular alkylation of a carbanion generated from protected cyanohydrin is presented.