23986-74-5

Basic information

• Product Name: germacreneD,1-methyl-5-methylene-8-(1-methylethyl)-1,6-cyclodecadiene
• Synonyms: (1E,6E,8S)-1-Methyl-5-methylene-8-isopropyl-1,6-cyclodecadiene;(E,E)-1-Methyl-5-methylene-8-(1-methylethyl)-1,6-cyclodecadiene;germacreneD,1-methyl-5-methylene-8-(1-methylethyl)-1,6-cyclodecadiene;1,6-Cyclodecadiene, 1-methyl-5-methylene-8-(1-methylethyl)-, (1E,6E,8S)-
• CAS NO: 23986-74-5
• Molecular Formula: C₁₅H₂₄
• Molecular Weight: 204.35
• Mol File: 23986-74-5.mol
• Article Data: 8

Chemical Properties

• Boiling Point: 279.7°C at 760 mmHg
• Flash Point: 111.9°C
• Appearance: /
• Density: 0.85g/cm³
• Vapor Pressure: 0.00673mmHg at 25°C
• Refractive Index: 1.482
• Storage Temp.: Amber Vial, Refrigerator, Under inert atmosphere
• Solubility: Chloroform (Slightly), Methanol (Slightly)
• Stability: Light Sensitive
• CAS DataBase Reference: germacreneD,1-methyl-5-methylene-8-(1-methylethyl)-1,6-cyclodecadiene(CAS DataBase Reference)
• NIST Chemistry Reference: germacreneD,1-methyl-5-methylene-8-(1-methylethyl)-1,6-cyclodecadiene(23986-74-5)
• EPA Substance Registry System: germacreneD,1-methyl-5-methylene-8-(1-methylethyl)-1,6-cyclodecadiene(23986-74-5)

Safety Data

• Hazardous Substances Data: 23986-74-5(Hazardous Substances Data)

Usage

Description

Germacrene D, also known as 1-methyl-5-methylene-8-(1-methylethyl)-1,6-cyclodecadiene, is a naturally occurring sesquiterpene found in various plants. It is characterized by its unique chemical structure, which contributes to its distinct properties and applications. Germacrene D is known for its insect-repellent properties and is used in the design of analogs of olfactory ligands.

Uses

Used in Insect Repellent Applications:
Germacrene D is used as a plant-derived insect repellent, particularly effective against a variety of insects. Its natural origin and repellent properties make it a preferred choice for eco-friendly pest control solutions.
Used in Fragrance and Flavor Industry:
Germacrene D is used as a key component in the synthesis of various fragrances and flavors due to its unique olfactory properties. It contributes to the development of new and innovative scents for the perfume and food industries.
Used in Essential Oil Extraction:
Germacrene D is present in the extraction of essential oils from plants, where it plays a significant role in the overall aroma and therapeutic properties of the oil. It is often found in essential oils used for aromatherapy and in the production of natural products for various applications.
Used in Pharmaceutical Research:
Due to its unique chemical structure and biological activity, germacrene D is also used in pharmaceutical research as a potential lead compound for the development of new drugs, particularly in the areas of insect repellency and olfactory research.

InChI:InChI=1/C15H24/c1-12(2)15-10-8-13(3)6-5-7-14(4)9-11-15/h7-8,10,12,15H,3,5-6,9,11H2,1-2,4H3/b10-8+,14-7+/t15-/m0/s1

Synthetic route

Farnesol (106-28-5) → germacrene D (23986-74-5)

Conditions	Yield
With sodium carbonate; magnesium chloride In terpene synthase buffer at 25℃; for 18h; pH=10; Enzymatic reaction;	91.1%

Farnesol (106-28-5) → delta-cadinene (483-76-1, 13061-82-0, 16729-01-4, 20085-20-5, 60305-17-1, 73365-79-4) + germacrene D (23986-74-5)

Conditions	Yield
With sodium acetate; magnesium chloride In terpene synthase buffer at 25℃; for 18h; pH=5; Enzymatic reaction;	A 12.32% B 84.3%

Farnesol (106-28-5) → β-cubebene + cubebol + delta-cadinene (483-76-1, 13061-82-0, 16729-01-4, 20085-20-5, 60305-17-1, 73365-79-4) + germacrene D (23986-74-5) + β-copaene

Conditions	Yield
With potassium chloride In terpene synthase buffer at 25℃; for 18h; pH=8; Enzymatic reaction;	A 10.7% B 34.2% C 15% D 19.4% E 10.3%

Farnesol (106-28-5) → sativene (3650-28-0, 6813-05-4, 16641-59-1, 22338-87-0, 29642-51-1, 149884-32-2) + β-cubebene + cubebol + delta-cadinene (483-76-1, 13061-82-0, 16729-01-4, 20085-20-5, 60305-17-1, 73365-79-4) + germacrene D (23986-74-5) + β-copaene

Conditions	Yield
With potassium chloride In terpene synthase buffer at 37℃; for 18h; pH=8; Enzymatic reaction;	A 5.3% B 7.1% C 22.3% D 13.3% E 22.3% F 12.3%

farnesyl pyrophosphate (372-97-4, 13058-04-3, 25744-33-6, 27248-37-9, 27248-38-0, 40716-68-5) → germacrene D (23986-74-5)

Conditions	Yield
With germacradienol synthase SC9B1.20; 2-hydroxyethanethiol In pentane at 30℃; for 24h;	1.6 mg
With (S)-germacrene D synthase; 3-[(3-cholamidopropyl)dimethylammonio]propanesulfonate; glycerol; 2-amino-2-hydroxymethyl-1,3-propanediol; 2-hydroxyethanethiol; magnesium chloride In chloroform-d1; water at 25℃; for 24h; pH=7.5; Enzymatic reaction;
With Y406F-GDS-His6 In pentane at 20℃; for 120h; pH=7.5; Kinetics; Enzymatic reaction;

(2E,6E)-<1,1-2H2>-farnesyl diphosphate (118655-72-4) → C12H18(2)H2 + C15H25(2)HO + C12H19(2)H3O + germacrene D (23986-74-5)

Conditions	Yield
With Streptomyces coelicolor germacradienol synthase; Tris-Cl; magnesium chloride In water-d2 at 30℃; Enzymatic reaction;

farnesyl pyrophosphate (372-97-4, 13058-04-3, 25744-33-6, 27248-37-9, 27248-38-0, 40716-68-5) → (1S,4aS)-1,4a-Dimethyl-1,2,3,4,4a,5,6,8a-octahydro-naphthalene + (-)-geosmin (19700-21-1) + germacrene D (23986-74-5) + (–)-(4S,7R)-germacra-(1(10)E,5E)-dien-11-ol

Conditions	Yield
With Streptomyces coelicolor germacradienol synthase; Tris-Cl; magnesium chloride In water at 30℃; for 4h; Enzymatic reaction;

farnesyl pyrophosphate (372-97-4, 13058-04-3, 25744-33-6, 27248-37-9, 27248-38-0, 40716-68-5) → 4α-hydroxygermacra-1(10),5-diene (207221-31-6) + alloaromadendrene (25246-27-9) + germacrene D (23986-74-5) + (+)-bicyclogermacrene (41437-00-7, 67650-49-1, 67650-90-2, 79951-53-4, 100762-45-6, 100762-46-7, 100762-48-9, 100762-49-0, 133005-43-3, 24703-35-3)

Conditions	Yield
With recombinant (His)8-tagged Medicago truncatula MtTPS5 sesquiterpene synthase Y526F mutant; water; magnesium chloride In pentane at 30℃; for 1.5h; pH=7.5; Mechanism; aq. buffer; Enzymatic reaction; optical yield given as %ee; stereospecific reaction;

farnesyl pyrophosphate (372-97-4, 13058-04-3, 25744-33-6, 27248-37-9, 27248-38-0, 40716-68-5) → δ-cadinol (19435-97-3) + (+)-copan-3-ol + germacrene D (23986-74-5) + (-)-(1R,4S,5R,6R,7S,10R)-7-isopropyl-4,10-dimethyl-tricyclo[4.4.0.01,5]decane-4-ol (23445-02-5)

Conditions	Yield
With recombinant (His)8-tagged Medicago truncatula MtTPS5 sesquiterpene synthase; water; magnesium chloride In pentane at 30℃; for 1.5h; pH=7.5; Mechanism; aq. buffer; Enzymatic reaction; optical yield given as %ee; stereospecific reaction;

3-methyl-2-buten-1-ol (556-82-1) → germacrene D (23986-74-5)

Conditions

Yield

Multi-step reaction with 3 steps 1: Escherichia coli hydroxyethylthiazole kinase; ATP; pyruvate kinase / aq. buffer / 16 h / 20 °C / pH 8 / Enzymatic reaction 2: isopentenyl phosphate kinase from Methanocaldococcus jannaschii; ATP; pyruvate kinase / aq. buffer / 16 h / 20 °C / pH 8 / Enzymatic reaction 3: (2E,6E)-FDP synthase from Geobacillus stearothermophilus; (-)-germacrene D synthase from Solidago canadensis; 1,4-dithio-L-threitol; magnesium chloride / aq. buffer / 16 h / 20 °C / pH 8 / Enzymatic reaction View Scheme

2-methyl-1-buten-4-ol (763-32-6) → germacrene D (23986-74-5)

Conditions

Yield

Multi-step reaction with 3 steps 1: Escherichia coli hydroxyethylthiazole kinase; ATP; pyruvate kinase / aq. buffer / 16 h / 20 °C / pH 8 / Enzymatic reaction 2: isopentenyl phosphate kinase from Methanocaldococcus jannaschii; ATP; pyruvate kinase / aq. buffer / 16 h / 20 °C / pH 8 / Enzymatic reaction 3: (2E,6E)-FDP synthase from Geobacillus stearothermophilus; (-)-germacrene D synthase from Solidago canadensis; 1,4-dithio-L-threitol; magnesium chloride / aq. buffer / 16 h / 20 °C / pH 8 / Enzymatic reaction View Scheme

3-methylbut-2-enyl hydrogen phosphate (10379-43-8) → germacrene D (23986-74-5)

Conditions

Yield

Multi-step reaction with 2 steps 1: isopentenyl phosphate kinase from Methanocaldococcus jannaschii; ATP; pyruvate kinase / aq. buffer / 16 h / 20 °C / pH 8 / Enzymatic reaction 2: (2E,6E)-FDP synthase from Geobacillus stearothermophilus; (-)-germacrene D synthase from Solidago canadensis; 1,4-dithio-L-threitol; magnesium chloride / aq. buffer / 16 h / 20 °C / pH 8 / Enzymatic reaction View Scheme

phosphoric acid mono(3-methylbut-3-enyl) ester (4936-73-6) → germacrene D (23986-74-5)

Conditions

Yield

Multi-step reaction with 2 steps 1: isopentenyl phosphate kinase from Methanocaldococcus jannaschii; ATP; pyruvate kinase / aq. buffer / 16 h / 20 °C / pH 8 / Enzymatic reaction 2: (2E,6E)-FDP synthase from Geobacillus stearothermophilus; (-)-germacrene D synthase from Solidago canadensis; 1,4-dithio-L-threitol; magnesium chloride / aq. buffer / 16 h / 20 °C / pH 8 / Enzymatic reaction View Scheme

dimethylallyl diphosphate (358-72-5) + isopentenyl diphosphate (358-71-4) → germacrene D (23986-74-5)

Conditions	Yield
With 1,4-dithio-L-threitol; (-)-germacrene D synthase from Solidago canadensis; (2E,6E)-FDP synthase from Geobacillus stearothermophilus; magnesium chloride In aq. buffer at 20℃; for 16h; pH=8; Enzymatic reaction;

germacrene D (23986-74-5) → (-)-Mintsulfide (72445-42-2)

Conditions	Yield
With hydrocarbon solvent; sulfur Irradiation;	50%

germacrene D (23986-74-5) → (1S,3aS,4S,7aR)-4-Bromo-3a-methyl-7-methylene-1-(2-methyl-propenyl)-octahydro-indene (105986-38-7) + ((3R,3aS,8S,8aS)-8-Bromo-3-isopropyl-8a-methyl-1,2,3,3a,6,7,8,8a-octahydro-azulen-5-yl)-methanol (105986-40-1) + 1-((1S,3aR,4R,7aS)-4-Bromo-3a-methyl-7-methylene-octahydro-inden-1-yl)-2-methyl-propan-1-ol (105986-36-5) + (1R,4R,4aS,8aS)-6-Bromomethyl-4-isopropyl-1-methyl-1,2,3,4,4a,7,8,8a-octahydro-naphthalen-1-ol (105986-39-8, 106035-58-9)

Conditions	Yield
With N-Bromosuccinimide In tetrahydrofuran; water for 0.5h; Ambient temperature; Further byproducts given;	A 4.2% B 11% C 13.3% D 7.2%

germacrene D (23986-74-5) → ((3R,3aS,8S,8aS)-8-Bromo-3-isopropyl-8a-methyl-1,2,3,3a,6,7,8,8a-octahydro-azulen-5-yl)-methanol (105986-40-1) + 1-((1S,3aR,4R,7aS)-4-Bromo-3a-methyl-7-methylene-octahydro-inden-1-yl)-2-methyl-propan-1-ol (105986-36-5) + 1-((1R,3aR,4R,7aS)-4-Bromo-3a-methyl-7-methylene-octahydro-inden-1-yl)-2-methyl-propan-2-ol (105986-37-6) + (1R,4R,4aS,8aS)-6-Bromomethyl-4-isopropyl-1-methyl-1,2,3,4,4a,7,8,8a-octahydro-naphthalen-1-ol (105986-39-8, 106035-58-9)

Conditions	Yield
With N-Bromosuccinimide In tetrahydrofuran; water for 0.5h; Ambient temperature; Further byproducts given;	A 11% B 13.3% C 2.7% D 7.2%

germacrene D (23986-74-5) → ((3R,3aS,8S,8aS)-8-Bromo-3-isopropyl-8a-methyl-1,2,3,3a,6,7,8,8a-octahydro-azulen-5-yl)-methanol (105986-40-1) + 1-((1S,3aR,4R,7aS)-4-Bromo-3a-methyl-7-methylene-octahydro-inden-1-yl)-2-methyl-propan-1-ol (105986-36-5) + (1S,2S,4aR,5R,8aS)-5-Bromo-2-isopropyl-4a-methyl-8-methylene-decahydro-naphthalen-1-ol (82731-91-7, 106035-57-8, 117465-31-3) + (1R,4R,4aS,8aS)-6-Bromomethyl-4-isopropyl-1-methyl-1,2,3,4,4a,7,8,8a-octahydro-naphthalen-1-ol (105986-39-8, 106035-58-9)

Conditions	Yield
With N-Bromosuccinimide In tetrahydrofuran; water for 0.5h; Ambient temperature; Further byproducts given;	A 11% B 13.3% C 4.9% D 7.2%

germacrene D (23986-74-5) → ((3R,3aS,8S,8aS)-8-Bromo-3-isopropyl-8a-methyl-1,2,3,3a,6,7,8,8a-octahydro-azulen-5-yl)-methanol (105986-40-1) + 1-((1S,3aR,4R,7aS)-4-Bromo-3a-methyl-7-methylene-octahydro-inden-1-yl)-2-methyl-propan-1-ol (105986-36-5) + (1S,4R,4aS,8aS)-6-Bromomethyl-4-isopropyl-1-methyl-1,2,3,4,4a,7,8,8a-octahydro-naphthalen-1-ol (105986-39-8, 106035-58-9) + (1R,4R,4aS,8aS)-6-Bromomethyl-4-isopropyl-1-methyl-1,2,3,4,4a,7,8,8a-octahydro-naphthalen-1-ol (105986-39-8, 106035-58-9)

Conditions	Yield
With N-Bromosuccinimide In tetrahydrofuran; water for 0.5h; Ambient temperature; Further byproducts given;	A 11% B 13.3% C 7% D 7.2%
With N-Bromosuccinimide In tetrahydrofuran; water for 0.5h; Ambient temperature; Further byproducts given;	A 11% B 13.3% C 7% D 7.2%

diazomethane (186581-53-3, 908094-01-9) + germacrene D (23986-74-5) → (+/-)-2-isopropyl-4-acetyl-butyric acid methyl ester (1842-56-4)

Conditions	Yield
(i) O3, (ii) /BRN= 102415/; Multistep reaction;

germacrene D (23986-74-5) → D-germacrene (645-10-3)

Conditions	Yield
(hydrogenation);

germacrene D (23986-74-5) → (8R)-Isopropyl-(1,5Ξ)-dimethyl-cyclodeca-1-trans,6-trans-dien (10171-91-2)

Conditions	Yield
With hydrogen; palladium on barium sulfate In ethanol

germacrene D (23986-74-5) → γ-muurolene (24268-39-1)

germacrene D (23986-74-5) → (+)-γ-cadinene (39029-41-9)

germacrene D (23986-74-5) → (1S,3aS,3bR,6aS,6bR)-1-Isopropyl-3a-methyl-6-methylene-decahydro-cyclobutadicyclopentene (5208-59-3, 13828-08-5, 68036-15-7, 78148-76-2, 92998-16-8, 119903-95-6, 135355-71-4)

Conditions	Yield
(photolysis);

germacrene D (23986-74-5) → α-bourbonene (5208-58-2, 13828-07-4, 14912-45-9)

Conditions	Yield
(photolysis);

germacrene D (23986-74-5) → (-)-germacrene D (64141-33-9, 91278-65-8)

Conditions	Yield
With hydrogen; palladium on barium sulfate In ethanol

germacrene D (23986-74-5) → 1,10.4,5-Didehydrogermacran

Conditions	Yield
With hydrogen; palladium on barium sulfate In ethanol

germacrene D (23986-74-5) → β-Copaen

Conditions	Yield
(photolysis);

germacrene D (23986-74-5) → ω-cadinene (17627-21-3)

germacrene D (23986-74-5) → torilensulfat (121711-38-4)

Conditions	Yield
With sulfuric acid In diethyl ether at 0℃; for 0.333333h;	450 mg

germacrene D (23986-74-5) → Nerolidol

Conditions	Yield
With manganese(IV) oxide In diethyl ether for 1h;	5 mg

germacrene D (23986-74-5) → (E)-(1R,4S,10R)-4-Isopropyl-1-methyl-7-methylene-11-oxa-bicyclo[8.1.0]undec-5-ene (70560-77-9)

Conditions	Yield
With 3-chloro-benzenecarboperoxoic acid In diethyl ether at -10 - -4℃;	150 mg
With 3-chloro-benzenecarboperoxoic acid In diethyl ether at -5 - 0℃; for 1h;

germacrene D (23986-74-5) → (1R,7S,E)-7-isopropyl-4,10-dimethylenecyclodec-5-enol (81968-62-9)

Conditions	Yield
With 3-chloro-benzenecarboperoxoic acid; lithium diisopropyl amide Multistep reaction;
Multi-step reaction with 2 steps 1: m-chloroperoxybenzoic acid / diethyl ether / 1 h / -5 - 0 °C 2: 14.8 g / LDA / cyclohexane; diethyl ether / 1) -60 deg C -> room temperature, 2) room temperature, 10 h View Scheme
Multi-step reaction with 2 steps 1: 150 mg / m-CPBA / diethyl ether / -10 - -4 °C 2: 17 mg / lithium diisopropylamide / diethyl ether / 1.) 1 h, -74 deg C, 2.) 2 h, r.t. View Scheme

germacrene D (23986-74-5) → germacra-4(15),5,10(14)-trien-1-one (84002-60-8)

Conditions	Yield
Multi-step reaction with 3 steps 1: m-chloroperoxybenzoic acid / diethyl ether / 1 h / -5 - 0 °C 2: 14.8 g / LDA / cyclohexane; diethyl ether / 1) -60 deg C -> room temperature, 2) room temperature, 10 h 3: 39 percent / tert-butyl hydroperoxide, SeO2 / H2O; CH2Cl2 / 24 h / 30 - 35 °C View Scheme
Multi-step reaction with 2 steps 1: 1.) MCPBA, 2.) LDA 2: 30 percent / TBHP, SeO2 View Scheme

germacrene D (23986-74-5) → (E)-(7S,9S)-9-Hydroxy-7-isopropyl-4,10-dimethylene-cyclodec-5-enone (189359-16-8)

Conditions	Yield
Multi-step reaction with 3 steps 1: m-chloroperoxybenzoic acid / diethyl ether / 1 h / -5 - 0 °C 2: 14.8 g / LDA / cyclohexane; diethyl ether / 1) -60 deg C -> room temperature, 2) room temperature, 10 h 3: 21 percent / tert-butyl hydroperoxide, SeO2 / H2O; CH2Cl2 / 24 h / 30 - 35 °C View Scheme
Multi-step reaction with 2 steps 1: 1.) MCPBA, 2.) LDA 2: 21 percent / TBHP, SeO2 View Scheme

Upstream product

• 372-97-4 farnesyl pyrophosphate 
• 106-28-5 Farnesol 
• 358-72-5 dimethylallyl diphosphate 
• 358-71-4 isopentyl pyrophosphate 
• 4936-73-6 phosphoric acid mono(3-methylbut-3-enyl) ester 
• 10379-43-8 3-methylbut-2-enyl hydrogen phosphate 
• 763-32-6 2-methyl-1-buten-4-ol 
• 556-82-1 3-methyl-2-buten-1-ol 
• 118655-72-4 (2E,6E)-<1,1-²H2>-farnesyl diphosphate 

Downstream Products

• 78094-94-7 (1S,3aR,4R,8aR)-1-Isopropyl-3a,7-dimethyl-4-phenylmethanesulfinyl-1,2,3,3a,4,5,6,8a-octahydro-azulene 
• 472-07-1 junenol 
• 123163-72-4 (-)-periplanone C 
• 81968-62-9 (1R,7S,E)-7-isopropyl-4,10-dimethylenecyclodec-5-enol 
• 72445-42-2 mintsulfide 
• 5208-58-2 α-bourbonene 
• 5208-59-3 (1S,3aS,3bR,6aS,6bR)-1-Isopropyl-3a-methyl-6-methylene-decahydro-cyclobutadicyclopentene 
• 24268-39-1 γ-muurolene 
• 645-10-3 Germacran 

Relevant articles and documents

Mechanism and Stereochemistry of the Germacradienol/Germacrene D Synthase of Streptomyces coelicolor A3(2)

Incubation of farnesyl diphosphate (1, FPP) with recombinant germacradienol synthase from Streptomyces coelicolor A3(2) gave, in addition to (4S,7R)-germacra-1(10)E,5E-diene-11-ol (2), 15% of (?)-germacrene D (5). Incubations of [1,1-2HM2]FPP (1a), (1R)-[1-2H]FPP (1b), and (1S)-[1-2H]FPP (1c) with germacradienol/germacrene D synthase and analysis of the resulting samples of germacradienol (2) and germacrene D (5) by a combination of 1H, 2H, and 13C NMR and mass spectrometry established that it is H-1si of FPP that is lost in the formation of germacradienol (2) and that undergoes 1,3-hydride transfer in the formation of (?)-germacrene D (5). The proportion of the two products was also sensitive to isotopic labeling, with cyclization of (1S)-[1-2H]FPP (1c) giving an increased proportion (35%) of 5. These results could be explained by a mechanism involving partitioning of a common helminthogermacradienyl cation intermediate 7. Copyright

Chemoenzymatic preparation of germacrene analogues

A small library of novel germacrenes was generated using a combination of two plant enzymes, germacrene A synthase, and D synthase and modified farnesyl diphosphate (FDP) analogues. This chemoenzymatic approach allows the preparation of potentially valuable volatiles for biological studies. The Royal Society of Chemistry 2012.

OLFACTORY LIGANDS

The invention provides analogues of (S)-germacrene D analogue which have improved insect repellent properties compared to (S)-germacrene D analogue or which have insect attractant properties.