475-20-7

Basic information

• Product Name: (+)-LONGIFOLENE
• Synonyms: (+)-Longifolen;(+)-Longofolene;[1S-(1alpha,3abeta,4alpha,8abeta)]-decahydro-4,8,8-trimethyl-9-methylene-1,4-Methanoazulene;[1S-(1α,3aβ,4α,8aβ)]-decahydro-9-methylene-4,8,8-trimethyl-1,4-methanoazulene;1,4-Methanoazulene, decahydro-4,8,8-trimethyl-9-methylene-;1,4-Methanoazulene, decahydro-4,8,8-trimethyl-9-methylene-, (1S,3aR,4S,8aS)-(+)-;1,4-methanoazulene,decahydro-4,8,8-trimethyl-9-methylene-,(1s,3ar,4s,8as)-(;1,4-methanoazulene,decahydro-4,8,8-trimethyl-9-methylene-,(1S,3aR,4S,8aS)-(+)-
• CAS NO: 475-20-7
• Molecular Formula: C15H24
• Molecular Weight: 204.35
• EINECS: 207-491-2
• Product Categories: Pharmaceutical Raw Materials
• Mol File: 475-20-7.mol
• Article Data: 10

Chemical Properties

• Boiling Point: 254 °C706 mm Hg(lit.)
• Flash Point: 98 °C
• Appearance: Light-yellowish oil-shaped liquid
• Density: 0.928 g/mL at 25 °C(lit.)
• Vapor Pressure: 0.0312mmHg at 25°C
• Refractive Index: n20/D 1.504(lit.)
• Storage Temp.: 2-8°C
• Water Solubility: 7.9mg/L at 24℃
• Merck: 13,5588
• CAS DataBase Reference: (+)-LONGIFOLENE(CAS DataBase Reference)
• NIST Chemistry Reference: (+)-LONGIFOLENE(475-20-7)
• EPA Substance Registry System: (+)-LONGIFOLENE(475-20-7)

Safety Data

• RIDADR: UN1230 - class 3 - PG 2 - Methanol, solution
• WGK Germany: 2
• RTECS: PB7724500
• F: 8-10-23
• Hazardous Substances Data: 475-20-7(Hazardous Substances Data)

Usage

Chemical Properties

(+)-Longifolene is a kind of natural spice extracted from heavy turpentine. It has special chemical activity and is the raw material of synthetic resin, synthetic spice, flotation agent and organic synthesis. Also Longifolene can be used in the formulation of flavors to replace some expensive flavors.

Uses

(+)-Longifolene is a tricyclic sesquiterpene, and the content in masson pine heavy turpentine is about 60%～78%. It has special chemical activity and can be used a raw material for synthetic resins, synthetic fragrances, flotation agents and organic synthesis.

Flammability and Explosibility

Notclassified

InChI:InChI=1/C15H24/c1-10-11-6-7-12-13(11)14(2,3)8-5-9-15(10,12)4/h11-13H,1,5-9H2,2-4H3/t11-,12-,13-,15-/m1/s1

Synthetic route

sodium cyanide (143-33-9) + [(1R,2S,7S,8S,9S)-3,3,7-trimethyltricyclo[5.4.0.02,9]undec-8-yl]methyl 4-methylbenzenesulfonate (4678-06-2, 4678-07-3) → [(1R,2S,7R,8S,9R)-3,3,7-trimethyltricyclo[5.4.0.02,9]undec-8-yl]acetonitrile (943033-63-4) + longifolene (475-20-7)

Conditions	Yield
sodium iodide In dimethyl sulfoxide at 90℃; for 24h;	A 69% B 21%

(+)-isolongiborneol (465-24-7, 16846-28-9, 18374-92-0, 27551-75-3, 51897-51-9) → longifolene (475-20-7)

Conditions	Yield
With dmap; methanesulfonyl chloride In pyridine at 105℃; for 16h;	66%

(-)-(1R)(2R)(7S)(8R)(9S)-3,3,7-Trimethyl-8-(acetoxymethyl)tricyclo<5.4.01,7.02,9>undecane (18367-70-9) → longifolene (475-20-7)

Conditions	Yield
In benzene at 525℃;	56%

10-keto-longifolene (99481-28-4) → longifolene (475-20-7)

Conditions	Yield
With potassium hydroxide; hydrazine hydrate In diethylene glycol for 4h; Heating;	55%

Trimethyl-((1S,3aR,4S,8aS,9S)-4,8,8-trimethyl-decahydro-1,4-methano-azulen-9-ylmethyl)-ammonium; iodide (82053-87-0) → longifolene (475-20-7) + N,N-Dimethylisolongifolamine (82053-85-8)

Conditions	Yield
With silver(l) oxide 1.) aq. MeOH, 30 deg C, 3 h; 2.) pyrolyse (oil-bath(250 deg C), 40 mm); Yield given. Multistep reaction;	A n/a B 54%
With silver(l) oxide 1.) aq. MeOH, 30 deg C, 3 h; 2.) pyrolyse (oil-bath(250 deg C), 40 mm); Yield given. Multistep reaction;	A 10% B n/a

[(1R,2S,7S,8S,9S)-3,3,7-trimethyltricyclo[5.4.0.02,9]undec-8-yl]methyl 4-methylbenzenesulfonate (4678-06-2, 4678-07-3) → longifolene (475-20-7) + (-)-isolongifolene (1135-66-6)

Conditions	Yield
With aluminum oxide In Petroleum ether for 12h;	A 2 g B 9%

(+)-α-Longipinene (5989-08-2) → β-himachalene (1461-03-6) + α-himachalene (3853-83-6) + longifolene (475-20-7) + (-)-isolongifolene (1135-66-6)

Conditions	Yield
With boron trifluoride diethyl etherate In diethyl ether at 18 - 29℃; for 7h;	A 10 % Chromat. B 46 % Chromat. C 32 % Chromat. D 2 % Chromat.
With boron trifluoride diethyl etherate In diethyl ether at 28 - 29℃; for 7h; Product distribution; other acid, other solvent, other temperature, other time;	A 10 % Chromat. B 46 % Chromat. C 32 % Chromat. D 2 % Chromat.

(+)-α-Longipinene (5989-08-2) → β-himachalene (1461-03-6) + longifolene (475-20-7) + (-)-isolongifolene (1135-66-6)

Conditions	Yield
With sulfuric acid In acetic acid at 50 - 51℃; for 1h;	A 52 % Chromat. B 4 % Chromat. C 32 % Chromat.

(1S,3aR,4S,8aR)-4,8,8,9-Tetramethyl-decahydro-1,4-methano-azulen-9-ol → longifolene (475-20-7)

Conditions	Yield
With thionyl chloride In pyridine at 0℃; for 0.166667h; Yield given;

3α-Brom-7βH-longifolan → longifolene (475-20-7)

Conditions	Yield
With ethanol at 40 - 60℃; Kinetics;

(-)-Isolongifolol (1139-17-9) → longifolene (475-20-7)

Conditions	Yield
Multi-step reaction with 2 steps 1: 81.5 percent / Et3N / DMAP / CH2Cl2 / 0 - 23 °C 2: 21 percent / NaI / dimethylsulfoxide / 24 h / 90 °C View Scheme
Multi-step reaction with 2 steps 1: 4.8 g / pyridine / 1.) 5 deg C, 1 h, 2.) 25 deg C, 12 h 2: 2 g / alumina / petroleum ether / 12 h View Scheme

(-)-longicamphenylone (116403-51-1) → longifolene (475-20-7)

Conditions	Yield
Multi-step reaction with 2 steps 1: diethyl ether; tetrahydrofuran / 3 h / 50 °C 2: SOCl2 / pyridine / 0.17 h / 0 °C View Scheme

(-)-(1R,2R,7S,9S)-3,3-dimethyltricyclo<5.4.0.02,9>undecan-8-one → longifolene (475-20-7)

Conditions	Yield
Multi-step reaction with 3 steps 1: 1.) lithium cyclohexylisopropylamide / 1.) hexane-THF, -78 deg C, +60 deg C, 1.5 h; 2.) THF, reflux, 16 h 2: diethyl ether; tetrahydrofuran / 3 h / 50 °C 3: SOCl2 / pyridine / 0.17 h / 0 °C View Scheme

(1R)(2R)(4R)(5R)(7S)(8R)(9S)-3,3,7-Trimethyl-4-methoxy-5-hydroxy-8-(hydroxymethyl)tricyclo<5.4.01,7.02,9>undecane → longifolene (475-20-7)

Conditions	Yield
Multi-step reaction with 7 steps 1: 74 percent / pyridine / diethyl ether / 6 h / 0 °C 2: 0.240 g / pyridine / CH2Cl2 / 21 °C 3: Bu3SnH, AIBN / toluene / 4 h / Heating 4: NaI, Me3SiCl, NEt3 / CH2Cl2 / 1 h / 21 °C 5: pyridine / CH2Cl2 / 3 h / 21 °C 6: Bu3SnH, AIBN / toluene / 5 h / 110 °C 7: 56 percent / benzene / 525 °C View Scheme

(1R)(2R)(4R)(5R)(7S)(8R)(9S)-3,3,7-Trimethyl-4-methoxy-5-hydroxy-8-(hydroxymethyl)tricyclo<5.4.01,7.02,9>-10-undecene → longifolene (475-20-7)

Conditions

Yield

Multi-step reaction with 8 steps 1: pyridine / diethyl ether / 14 h / 0 °C 2: 67 percent / pyridine / CH2Cl2 / 3 h / 21 °C 3: 89 percent / Bu3SnH, AIBN / toluene / 3 h / Heating 4: 97 percent / H2 / 5percent Pd/C / ethyl acetate / 2 h / 1034.3 Torr 5: NaI, Me3SiCl, NEt3 / CH2Cl2 / 1 h / 21 °C 6: pyridine / CH2Cl2 / 3 h / 21 °C 7: Bu3SnH, AIBN / toluene / 5 h / 110 °C 8: 56 percent / benzene / 525 °C View Scheme

(1R)(2R)(7S)(8R)(9S)-3,3,7-Trimethyl-4-hydroxy-8-(acetoxymethyl)tricyclo<5.4.01,7.02,9>undecane → longifolene (475-20-7)

Conditions	Yield
Multi-step reaction with 3 steps 1: pyridine / CH2Cl2 / 3 h / 21 °C 2: Bu3SnH, AIBN / toluene / 5 h / 110 °C 3: 56 percent / benzene / 525 °C View Scheme

(1R)(2R)(4R)(7S)(8R)(9S)-3,3,7-Trimethyl-4-methoxy-8-(acetoxymethyl)tricyclo<5.4.01,7.02,9>undecane → longifolene (475-20-7)

Conditions	Yield
Multi-step reaction with 4 steps 1: NaI, Me3SiCl, NEt3 / CH2Cl2 / 1 h / 21 °C 2: pyridine / CH2Cl2 / 3 h / 21 °C 3: Bu3SnH, AIBN / toluene / 5 h / 110 °C 4: 56 percent / benzene / 525 °C View Scheme

(1S)(2R)(5R)(6R)(8R)(9S)(12R)-1,7,7-Trimethyl-6-methoxy-4-oxatetracyclo<7.3.1.02,9>-10-tridecen-3-one → longifolene (475-20-7)

Conditions	Yield
Multi-step reaction with 8 steps 1: 92 percent / H2 / 5percent Pd/C / ethyl acetate / 4 h / 1551.4 Torr / Ambient temperature 2: 74 percent / pyridine / diethyl ether / 6 h / 0 °C 3: 0.240 g / pyridine / CH2Cl2 / 21 °C 4: Bu3SnH, AIBN / toluene / 4 h / Heating 5: NaI, Me3SiCl, NEt3 / CH2Cl2 / 1 h / 21 °C 6: pyridine / CH2Cl2 / 3 h / 21 °C 7: Bu3SnH, AIBN / toluene / 5 h / 110 °C 8: 56 percent / benzene / 525 °C View Scheme
Multi-step reaction with 9 steps 1: LiAlH4 / diethyl ether / 0 deg C to r.t. 2: pyridine / diethyl ether / 14 h / 0 °C 3: 67 percent / pyridine / CH2Cl2 / 3 h / 21 °C 4: 89 percent / Bu3SnH, AIBN / toluene / 3 h / Heating 5: 97 percent / H2 / 5percent Pd/C / ethyl acetate / 2 h / 1034.3 Torr 6: NaI, Me3SiCl, NEt3 / CH2Cl2 / 1 h / 21 °C 7: pyridine / CH2Cl2 / 3 h / 21 °C 8: Bu3SnH, AIBN / toluene / 5 h / 110 °C 9: 56 percent / benzene / 525 °C View Scheme

(1R)(2R)(4R)(5R)(7S)(8R)(9S)-3,3,7-Trimethyl-4-methoxy-5-hydroxy-8-(acetoxymethyl)tricyclo<5.4.01,7.02,9>undecane → longifolene (475-20-7)

Conditions	Yield
Multi-step reaction with 6 steps 1: 0.240 g / pyridine / CH2Cl2 / 21 °C 2: Bu3SnH, AIBN / toluene / 4 h / Heating 3: NaI, Me3SiCl, NEt3 / CH2Cl2 / 1 h / 21 °C 4: pyridine / CH2Cl2 / 3 h / 21 °C 5: Bu3SnH, AIBN / toluene / 5 h / 110 °C 6: 56 percent / benzene / 525 °C View Scheme

(1R)(2R)(4R)(7S)(8R)(9S)-3,3,7-Trimethyl-4-methoxy-8-(acetoxymethyl)tricyclo<5.4.01,7.02,9>-10-undecene → longifolene (475-20-7)

Conditions	Yield
Multi-step reaction with 5 steps 1: 97 percent / H2 / 5percent Pd/C / ethyl acetate / 2 h / 1034.3 Torr 2: NaI, Me3SiCl, NEt3 / CH2Cl2 / 1 h / 21 °C 3: pyridine / CH2Cl2 / 3 h / 21 °C 4: Bu3SnH, AIBN / toluene / 5 h / 110 °C 5: 56 percent / benzene / 525 °C View Scheme

(1R)(2R)(4R)(5R)(7S)(8R)(9S)-3,3,7-Trimethyl-4-methoxy-5-hydroxy-8-(acetoxymethyl)tricyclo<5.4.01,7.02,9>-10-undecene → longifolene (475-20-7)

Conditions	Yield
Multi-step reaction with 7 steps 1: 67 percent / pyridine / CH2Cl2 / 3 h / 21 °C 2: 89 percent / Bu3SnH, AIBN / toluene / 3 h / Heating 3: 97 percent / H2 / 5percent Pd/C / ethyl acetate / 2 h / 1034.3 Torr 4: NaI, Me3SiCl, NEt3 / CH2Cl2 / 1 h / 21 °C 5: pyridine / CH2Cl2 / 3 h / 21 °C 6: Bu3SnH, AIBN / toluene / 5 h / 110 °C 7: 56 percent / benzene / 525 °C View Scheme

Acetic acid (1S,3aR,4S,7S,8aS,9R)-4,8,8-trimethyl-7-phenoxythiocarbonyloxy-decahydro-1,4-methano-azulen-9-ylmethyl ester → longifolene (475-20-7)

Conditions	Yield
Multi-step reaction with 2 steps 1: Bu3SnH, AIBN / toluene / 5 h / 110 °C 2: 56 percent / benzene / 525 °C View Scheme

Acetic acid (1S,3aR,4S,6R,7R,8aS,9R)-7-methoxy-4,8,8-trimethyl-6-phenoxythiocarbonyloxy-decahydro-1,4-methano-azulen-9-ylmethyl ester → longifolene (475-20-7)

Conditions	Yield
Multi-step reaction with 5 steps 1: Bu3SnH, AIBN / toluene / 4 h / Heating 2: NaI, Me3SiCl, NEt3 / CH2Cl2 / 1 h / 21 °C 3: pyridine / CH2Cl2 / 3 h / 21 °C 4: Bu3SnH, AIBN / toluene / 5 h / 110 °C 5: 56 percent / benzene / 525 °C View Scheme

Acetic acid (1S,3aR,4S,6R,7R,8aS,9R)-7-methoxy-4,8,8-trimethyl-6-phenoxythiocarbonyloxy-1,3a,4,5,6,7,8,8a-octahydro-1,4-methano-azulen-9-ylmethyl ester → longifolene (475-20-7)

Conditions	Yield
Multi-step reaction with 6 steps 1: 89 percent / Bu3SnH, AIBN / toluene / 3 h / Heating 2: 97 percent / H2 / 5percent Pd/C / ethyl acetate / 2 h / 1034.3 Torr 3: NaI, Me3SiCl, NEt3 / CH2Cl2 / 1 h / 21 °C 4: pyridine / CH2Cl2 / 3 h / 21 °C 5: Bu3SnH, AIBN / toluene / 5 h / 110 °C 6: 56 percent / benzene / 525 °C View Scheme

1,4-methanoazulen-9-ol, decahydro-1,5,5,8α-tetramethyl-(1R,3αR,4S,8αS,9S)- (465-24-7) → longifolene (475-20-7)

Conditions	Yield
Multi-step reaction with 3 steps 1: 85 percent / PCC, / CH2Cl2 / 3 h / Ambient temperature 2: 92 percent / LiAlH4, / tetrahydrofuran / 3 h / 0 °C 3: 66 percent / MeSO2Cl, DMAP, / pyridine / 16 h / 105 °C View Scheme

8-oxolongibornane (465-26-9) → longifolene (475-20-7)

Conditions	Yield
Multi-step reaction with 2 steps 1: 92 percent / LiAlH4, / tetrahydrofuran / 3 h / 0 °C 2: 66 percent / MeSO2Cl, DMAP, / pyridine / 16 h / 105 °C View Scheme

11-hydroxylongicyclene (51830-69-4, 72496-29-8, 107537-54-2) → longifolene (475-20-7)

Conditions	Yield
Multi-step reaction with 4 steps 1: 80 percent / 32percent HBr, acetic acid / 18 h / Ambient temperature 2: silver perchlorate / acetone; H2O / 18 h / Ambient temperature 3: Jones' reagent 4: 55 percent / 85percent hydrazine hydrate, KOH / bis-(2-hydroxy-ethyl) ether / 4 h / Heating View Scheme

8,11-dibromolongibornane (91482-03-0, 99529-80-3) → longifolene (475-20-7)

Conditions	Yield
Multi-step reaction with 3 steps 1: silver perchlorate / acetone; H2O / 18 h / Ambient temperature 2: Jones' reagent 3: 55 percent / 85percent hydrazine hydrate, KOH / bis-(2-hydroxy-ethyl) ether / 4 h / Heating View Scheme

(1S,3aR,4S,8aS)-4,8,8-Trimethyl-9-methylene-decahydro-1,4-methano-azulen-3-ol (99481-27-3) → longifolene (475-20-7)

Conditions	Yield
Multi-step reaction with 2 steps 1: Jones' reagent 2: 55 percent / 85percent hydrazine hydrate, KOH / bis-(2-hydroxy-ethyl) ether / 4 h / Heating View Scheme

longifolene (475-20-7) → (-)-isolongifolene (1135-66-6)

Conditions	Yield
With boron trifluoride diethyl etherate In dichloromethane at 35℃; for 8h; Rearrangement;	91%
With β-Zeolite In benzene	74%
With sulfuric acid; acetic acid
With sodium thiosulfate at 100℃; for 0.75h; Reagent/catalyst; Temperature; Sonication;

longifolene (475-20-7) → (1S,3aR,4S,8aR,9S)-1,2,3,3a,4,5,6,7,8,8a-decahydro-4,8,8-trimethylspiro[1,4-methanoazulene-9,2'-oxirane]

Conditions	Yield
With ozone In acetone at -80℃;	91%

longifolene (475-20-7) → (-)-isolongifolene (1135-66-6) + (-)-alloisolongifolene (87064-18-4)

Conditions	Yield
chloroacetic acid for 24h; Heating;	A 90% B 10%
bromoacetic acid for 24h; Heating; or ICH2COOH;	A 15% B 85%
bromoacetic acid for 24h; Heating; also with ICH2COOH or ClCH2COOH;	A 25% B 85%
With aluminum oxide; sodium at 180℃;	A 62% B 28%

longifolene (475-20-7) → 3,3,7-trimethyl tricyclo<5.4.0.0> undecan-8-carboxylic acid

Conditions	Yield
With cobalt; oxygen; isobutyraldehyde In acetonitrile for 37h;	65%

longifolene (475-20-7) + N-(tert-butyl)-N-((ethoxycarbonothioyl)thio)-3,5-bis(trifluoromethyl)benzamide → O-ethyl S-[(1S,3aR,4S,6S,8aS)-4,8,8-trimethyl-9-methylenedecahydro-1,4-methanoazulen-6-yl]carbonodithioate

Conditions	Yield
In neat (no solvent) at 20℃; Irradiation; Inert atmosphere; diastereoselective reaction;	54%

longifolene (475-20-7) → 8-epoxy-3,3,7-trimethyltricyclo<5.4.0.0>undecane

Conditions	Yield
With oxygen; isobutyraldehyde; cobalt dichloride In acetonitrile at 25℃;	52%
With cobalt dichloride; oxygen; isobutyraldehyde In acetonitrile for 15h;	51%

longifolene (475-20-7) → (1S,3aR,4S,8aS,9S)-decahydro-4,8,8-trimethyl-1,4-methanoazulen-9-carboxylic acid (487-74-1)

Conditions	Yield
With oxygen; isobutyraldehyde; (MeO2CCH(Bn)N=CH(C6H4O)-o)2Co In acetonitrile at 25℃;	51%
Multi-step reaction with 2 steps 1: (i) CrO3, (ii) /BRN= 102415/ 2: KOH / methanol View Scheme
Multi-step reaction with 4 steps 1: Heating; Irradiation 2: (i) KOCH2tBu, (ii) aq. KMnO4 3: LiAlH4 / diethyl ether / Heating 4: (i) Al2O3, benzene, (ii) O2, Et2O View Scheme

longifolene (475-20-7) → (1R,2S,7S,8S,9S)-3,3,7-trimethyltricyclo[5.4.0.02,9]undecane-8-carbaldehyde (25491-00-3)

Conditions	Yield
With ozone In dichloromethane at -80 - 20℃; for 840000h;	51%
Multi-step reaction with 4 steps 1: Heating; Irradiation 2: (i) KOCH2tBu, (ii) aq. KMnO4 3: LiAlH4 / diethyl ether / Heating 4: Al2O3 / benzene View Scheme

longifolene (475-20-7) + acetic anhydride (108-24-7) → Longibornan-9-ol-acetat (61262-69-9) + (-)-isolongifolene (1135-66-6) + ω-acetyllongifolene (3338-56-5)

Conditions	Yield
With boron trifluoride diethyl etherate for 0.5h; Product distribution; Mechanism; other terpenes and reagents;	A 2% B 50% C 24%
With boron trifluoride diethyl etherate for 0.5h; ice bath;	A 2% B 50% C 24%

longifolene (475-20-7) → (-)-longicamphenylone (116403-51-1)

Conditions	Yield
With potassium permanganate; adogen 464 In dichloromethane; acetic acid for 48h; Ambient temperature;	45%
With Perbenzoic acid; chloroform
With chromium(VI) oxide; acetic acid
With chromium(VI) oxide In acetic acid
Multi-step reaction with 2 steps 1: PhCO3H / CHCl3; ethanol 2: PhCO3H / CHCl3; ethanol View Scheme

longifolene (475-20-7) → (-)-longicamphenylone (116403-51-1) + 3,3,7-trimethyl tricyclo<5.4.0.0> undecan-8-carboxylic acid

Conditions	Yield
With potassium permanganate; N-benzyl-N,N,N-triethylammonium chloride In dichloromethane; acetic acid for 48h; Ambient temperature;	A 42% B 22%
With potassium permanganate In dichloromethane; acetic acid Ambient temperature;	A 10% B 26%

longifolene (475-20-7) → (1S,3aR,4S,8aS,9R)-decahydro-4,8,8-trimethyl-1,4-methanoazulen-9-carboxylic acid (487-73-0) + (1S,3aR,4S,8aS,9S)-decahydro-4,8,8-trimethyl-1,4-methanoazulen-9-carboxylic acid (487-74-1) + longidione (474-96-4, 4439-95-6, 140223-97-8) + (-)-longicamphenylone (116403-51-1)

Conditions	Yield
With ruthenium(II) chloride; sodium periodate In chloroform; water; acetonitrile for 8h; Ambient temperature; Yield given. Title compound not separated from byproducts;	A n/a B n/a C 5.5% D 36%
With ruthenium(II) chloride; sodium periodate In chloroform; water; acetonitrile for 8h; Ambient temperature;	A n/a B n/a C 5.5% D 36%

longifolene (475-20-7) → (+)-Longicyclen (1137-12-8, 41437-68-7)

Conditions	Yield
With aluminum oxide; sodium at 110℃;	28%

longifolene (475-20-7) + acetic anhydride (108-24-7) → 7-endo-N-acetyl-13-longifolanamide (124024-34-6) + 7-endo-13,13-diacetoxylongifolane (124024-33-5) + 13-acetoxy-7-exo-acetamidolongifolane (124024-35-7)

Conditions	Yield
With hexaaquairon(II) perchlorate; dihydrogen peroxide In acetonitrile at 30℃; for 0.0833333h;	A 3.6% B 27.1% C 21.2%
With hexaaquairon(II) perchlorate; dihydrogen peroxide In acetonitrile at 30℃; for 0.0833333h;	A 3.6% B 27.1% C 21.2%

longifolene (475-20-7) → (1S,3aR,4S,8aS,9R)-decahydro-4,8,8-trimethyl-1,4-methanoazulen-9-carboxylic acid (487-73-0) + (-)-longicamphenylone (116403-51-1) + (1S,3aR,4S,8aR,9S)-1,2,3,3a,4,5,6,7,8,8a-decahydro-4,8,8-trimethylspiro[1,4-methanoazulene-9,2'-oxirane] + (E)-[(1S,3aR,4S,8aR)-decahydro-4,8,8-trimethyl-1,4-methanoazulen-9-ylidene]methanol

Conditions	Yield
With potassium permanganate; Aliquat 336 In dichloromethane Further byproducts given;	A n/a B 22% C n/a D n/a

longifolene (475-20-7) + acetic anhydride (108-24-7) → Longibornan-9-ol-acetat (61262-69-9) + (-)-isolongifolene (1135-66-6) + 1-(octahydro-7,7,8,8-tetramethyl-2,3b-methano-3bH-cyclopenta[1,3]cyclopropa[1,2]benzen-4-yl)ethanone (59056-72-3) + ω-acetyllongifolene (3338-56-5)

Conditions	Yield
With tin(IV) chloride for 0.5h; ice bath; Yields of byproduct given;	A n/a B 1.77 g C 11% D n/a

tetrachloromethane (56-23-5) + diacetyl peroxide (110-22-5) + longifolene (475-20-7) → (3S,7S)-3-chloro-15-trichloromethyl-longifolane (2615-47-6, 94669-77-9)

longifolene (475-20-7) → (7Ξ)-longifolane-7,15-diol

Conditions	Yield
With osmium(VIII) oxide; diethyl ether

longifolene (475-20-7) → (1R)-2,2,5a-trimethyl-(5at,10at)-decahydro-1r,8-cyclo-heptalen-7-one (1139-53-3, 140223-99-0)

Conditions	Yield
With lead(IV) acetate; acetic acid anschl. mit aethanol. NaOH;

diazomethane (186581-53-3, 908094-01-9) + longifolene (475-20-7) → (7R)-longifolanoic acid-(15)-methyl ester (13928-57-9, 99032-59-4) + (7S)-longifolanoic acid-(15)-methyl ester (13928-57-9, 99032-59-4)

Conditions	Yield
(i) CrO3, (ii) /BRN= 102415/; Multistep reaction;

diazoacetic acid ethyl ester (623-73-4) + longifolene (475-20-7) → C19H30O2

Conditions	Yield
With copper

methanol (67-56-1) + longifolene (475-20-7) → (7S)-longifolanoic acid-(15)-methyl ester (13928-57-9, 99032-59-4)

Conditions	Yield
(i) CrO3, aq. H2SO4, AcOH, (ii) /BRN= 1098229/, benzene; Multistep reaction;

tetrachloromethane (56-23-5) + longifolene (475-20-7) → (3S,7S)-3-chloro-15-trichloromethyl-longifolane (2615-47-6, 94669-77-9)

Conditions	Yield
With diacetyl peroxide

isocyanate de chlorosulfonyle (1189-71-5) + longifolene (475-20-7) → C16H24ClNO3S

Conditions	Yield
In diethyl ether

Upstream product

• 82053-87-0 Trimethyl-((1S,3aR,4S,8aS,9S)-4,8,8-trimethyl-decahydro-1,4-methano-azulen-9-ylmethyl)-ammonium; iodide 
• 4678-06-2 [(1R,2S,7S,8S,9S)-3,3,7-trimethyltricyclo[5.4.0.0^2,9]undec-8-yl]methyl 4-methylbenzenesulfonate 
• 5989-08-2 (+)-α-Longipinene 
• 99481-28-4 10-keto-longifolene 
• 465-24-7 (+)-isolongiborneol 
• 18367-70-9 (-)-(1R)(2R)(7S)(8R)(9S)-3,3,7-Trimethyl-8-(acetoxymethyl)tricyclo<5.4.0^1,7.0^2,9>undecane 
• 143-33-9 sodium cyanide 
• 81572-03-4 <α-2H2>benzyl isolongifolyl thioether 
• 60909-27-5 (10S, 11S)-himachala-2,4-diene 
• 73301-70-9 (1S,3aR,4S,8aS,9S)-4,8,8-Trimethyl-decahydro-1,4-methano-azulene-9-carboxylic acid dimethylamide 
• 82053-85-8 N,N-Dimethylisolongifolamine 
• 99481-27-3 (1S,3aR,4S,8aS)-4,8,8-Trimethyl-9-methylene-decahydro-1,4-methano-azulen-3-ol 
• 91482-03-0 8,11-dibromolongibornane 
• 51830-69-4 11-hydroxylongicyclene 

Downstream Products

• 487-73-0 (1S,3aR,4S,8aS,9R)-decahydro-4,8,8-trimethyl-1,4-methanoazulen-9-carboxylic acid 
• 116403-51-1 (-)-longicamphenylone 
• 41530-82-9 (1S,3aR,4S,8aR,9S)-1,2,3,3a,4,5,6,7,8,8a-decahydro-4,8,8-trimethylspiro[1,4-methanoazulene-9,2'-oxirane] 
• 66537-42-6 (1S,3aR,4S,8aS,9R)-decahydro-4,8,8-trimethyl-1,4-methanoazulen-9-carboxaldehyde 
• 25491-00-3 (1R,2S,7S,8S,9S)-3,3,7-trimethyltricyclo[5.4.0.0^2,9]undecane-8-carbaldehyde 
• 475-23-0 Longicamphenilol 
• 71-43-2 benzene 
• 91-20-3 naphthalene 
• 129-00-0 pyrene 
• 86-73-7 9H-fluorene 
• 95-13-6 1-indene 
• 1135-66-6 (-)-isolongifolene 
• 1139-17-9 (-)-Isolongifolol 
• 115050-64-1 longifolan-15-oic acid anilide 

Relevant articles and documents

Cycloaddition Routes to Tricyclo1,7.02,9>undecanes: A Direct Total Synthesis of (+)-Longifolene via an Intramolecular Diels-Alder Strategy

The total synthesis of the sesquiterpene (+)-longifolene (1) by an intramolecular Diels-Alder cycloaddition strategy is described.Addition of methyllithium to the epoxyfulvene 13, derived from cyclopentadiene and 3,4-epoxy-2-butanone, led to an exo-tet cyclization of the resulting cyclopentadienyl anion to generate the spirohepta-4,6-diene alcohol 14.Resolution of this material was effected via its menthyl carbonate derivative 15.Oxidation of the (+)-R-alcohol with active MnO2 afforded the cyclopropyl aldehyde 16 which was condensed with the anion derived from methyl 3-methylcrotonate in the presence of cadmium chloride to gen erate the unsaturated lactone 20 or the unsaturated ester 18.Microwave heating of the silyl triene 19 effected cycloaddition to the adduct 21.Hydrogenolysis of the alcohol 22 afforded the "sinularene" skeleton 25.Cyclopropane ring cleavage of the derived ketones 23, 30, and the thiocarbonate 27 was examined but only in the Li/NH3 reduction of 30 was the longifolene skeleton 33 produced as a significant product which unfortunately could not be separated from its isomer 32.Consequently the successful route utilized regiospecific cleavage of the cyclopropane ring in the cyclopentadiene 20 in methanol catalyzed by BF3*Et2O to afford the substituted cyclopentadiene lactone(s) 34 (83percent).Cyclization proceeded smoothly, in a sealed tube, in toluene, in a microwave oven to afford the single tetracyclic adduct 39 in 97percent yield.Double bond hydrogenation and reduction of the lactone with LiAlH4 afforded the substituted longifolene skeleton, and the resulting primary alcohol was acetylated selectively to give 40.Free-radical-mediated replacement of the secondary oxygen functions was accomplished via the phenoxythiocarbonate derivative to afford the methoxy acetate 43.Alternatively the reaction sequence could b e modified to convert 39 to 41 to 42 and then to 43.Methoxy cleavage (Me3SiI) and a second free-radical reaction gave the acetate 44.Pyrolysis of this acetate (525 deg C) provided (+)-longifolene (1).

Enanthiospecific synthesis of longiborneol and longifolene

A trimethylsilyl enol ether (34) derived from camphor (1) undergoes intramolecular Mukaiyama reaction to provide a tricyclic ketone (36) that can serve as a key intermediate in a new enantiospecific synthesis of longiborneol (11) and longifolene (12).