3738-00-9

Basic information

• Product Name: AMBROX DL
• Synonyms: 1-b]furan,dodecahydro-3a,6,6,9a-tetramethyl-Naphtho[2;Dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1-b]furan;AMBROX DL;DODECAHYDRO-3A,6,6,9A-TETRAMETHYLNAPHTO-(2,1-B)-FURAN;Dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1-b]fur;Ambermor;Tetramethyl perhydronaphthofuran;Naphtho2,1-bfuran, dodecahydro-3a,6,6,9a-tetramethyl-
• CAS NO: 3738-00-9
• Molecular Formula: C₁₆H₂₈O
• Molecular Weight: 236.39
• EINECS: 223-118-6
• Mol File: 3738-00-9.mol
• Article Data: 19

Chemical Properties

• Melting Point: 75-76 °C
• Boiling Point: 273.9 ºC at 760 mmHg
• Flash Point: 104.8 ºC
• Appearance: White crystalline solid
• Density: 0.939 g/cm³
• CAS DataBase Reference: AMBROX DL(CAS DataBase Reference)
• NIST Chemistry Reference: AMBROX DL(3738-00-9)
• EPA Substance Registry System: AMBROX DL(3738-00-9)

Safety Data

• Hazardous Substances Data: 3738-00-9(Hazardous Substances Data)

Usage

Chemical Properties

3a,6,6,9a-Tetramethyldodecahydronaphtho[2,1-b]furan is a crystalline autoxidation product of ambrein with a typical ambergris odor. It is prepared from (?)-sclareol, a diterpene alcohol obtained from extraction of clary sage plants. Oxidative degradation to a lactone (“sclareolide”), hydrogenation of the latter to the corresponding diol, and dehydration yield the title compound.

Occurrence

Reported found in clary sage oil.

Preparation

Racemic sclareolide can be prepared by cyclization of homofarnesic acid in the presence of SnCl4 as a catalyst . Pure diastereomers are obtained by acid cyclization of (E)- and (Z)-4-methyl-6-(2,6,6-trimethylcyclohex-l(2)-enyl)-3- hexen-1-ol, prepared from 2-methyl-4-(2,6,6-trimethylcyclohex-l(2)-enyl)-2- butenal [394]. If the racemic sclareolide mixture is resolved into its enantiomers, the (–)-oxide may also be obtained by a totally synthetic route

Synthesis Reference(s)

Synthesis, p. 216, 1983 DOI: 10.1055/s-1983-30287

Trade name

Compound starting from natural sclareol: Ambermore, Ambermore-DL, Ambermore-EX (Aromor), Ambrox? Super (Firmenich), Ambroxan? (Kao), Ambroxide (Symrise); compound starting from homofarnesic acid derivatives: Ambrox? DL (Firmenich); compound starting from 2-methyl- 4-(2,6,6-trimethylcyclohex-l(2)enyl)-2-butenal: Cetalox? (Firmenich), Cetalor (Aromor).

InChI:InChI=1/C16H28O/c1-14(2)8-5-9-15(3)12(14)6-10-16(4)13(15)7-11-17-16/h12-13H,5-11H2,1-4H3

Synthetic route

2-((4aSR,8aSR)-2,5,5,8a-tetramethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalen-1-yl)ethan-1-ol → (3aRS,5aSR,9aSR,9bRS)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan (3738-00-9)

Conditions	Yield
iron(III) chloride; silica gel In dichloromethane; 1,2-dichloro-ethane at 24℃; for 0.333333h; Product distribution / selectivity;	79%
iron(III) chloride; silica gel In dichloromethane; 1,2-dichloro-ethane at 24℃; for 0.333333h; Product distribution / selectivity;	79%
iron(III) chloride In dichloromethane; 1,2-dichloro-ethane at 10℃; for 3h; Product distribution / selectivity;
scandium tris(trifluoromethanesulfonate) In dichloromethane at 20℃; for 6h; Product distribution / selectivity;
iron(III) chloride In dichloromethane; 1,2-dichloro-ethane at 10℃; for 3h; Product distribution / selectivity;

2-((4aSR,8aSR)-2,5,5,8a-tetramethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalen-1-yl)ethan-1-ol → (3aRS,5aSR,9aSR,9bRS)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan (3738-00-9) + (3aSR,5aSR,9aSR,9bRS)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan (3738-00-9)

Conditions	Yield
scandium tris(trifluoromethanesulfonate) In dichloromethane at 20℃; for 6h; Product distribution / selectivity;
methanesulfonic acid In dichloromethane at 0℃; for 0.333333h; Product distribution / selectivity;
iron(III) chloride; silica gel In dichloromethane; 1,2-dichloro-ethane at 20℃; for 0.333333h; Product distribution / selectivity;

Upstream product

• 110202-08-9 (Z)-4-Methyl-6-(2',6',6'-trimethyl-1'-cyclohexenyl)hex-3-en-1-ol 
• 110202-07-8 (E)-4-Methyl-6-(2',6',6'-trimethyl-1'-cyclohexenyl)hex-3-en-1-ol 
• 105014-28-6 (4aR,8aS)-1-Allyl-2,5,5,8a-tetramethyl-decahydro-naphthalen-2-ol 
• 118672-99-4 3-oxo-5-(2,6,6-trimethyl-cyclohex-2-enyl)-pentanoic acid methyl ester 
• 10207-83-7 (1S,2R,8aS)-1-(2-Hydroxy-ethyl)-2,5,5,8a-tetramethyl-decahydro-naphthalen-2-ol 
• 320756-17-0 biscyclohomofarnesane-8α,12-diol 
• 10207-83-7 (8α-Methyl)-iresan-8β,11-diol 
• 10207-83-7 (+/-)-(1α,2β,4aβ,8aα)-decahydro-2-hydroxyl-2,5,5,8a-tetramethyl-1-naphthaleneethanol 
• 95575-96-5 (2E,6E)-3-methyl-7-((tetrahydro-2H-pyran-2-yloxy)methyl)octa-2,6-dienyl acetate 
• 211687-98-8 2-((2E,6E)-2,6-Dimethyl-nona-2,6,8-trienyloxy)-tetrahydro-pyran 
• 95575-97-6 (2E,6E)-3,7-Dimethyl-8-(tetrahydro-pyran-2-yloxy)-octa-2,6-dienal 
• 99733-97-8 3-methyl-5-(2',6',6'-trimethylcyclohex-1'-enyl)-1-penten-3-ol 
• 459-89-2 (3E,7E)-homofarnesol 
• 133859-01-5 (E)-4-Methyl-6-(2',2'-dimethyl-6'-methylidenecyclohexyl)hex-3-en-1-ol 

Downstream Products

• 3738-00-9 (3aRS,5aSR,9aRS,9bSR)-dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1-b]furan 
• 3738-00-9 (-)-norlabdane 
• 122566-19-2 <3aR-(3aα,4α,6aα,10aS^*)> dodecahydro-3a,4,7,7-tetramethyl-2H-naphtho<8a,1-b>furan 

Relevant articles and documents

Synthesis and Applications of Cyclohexenyl Halides Obtained by a Cationic Carbocyclisation Reaction

The synthesis of cyclic alkenyl halides (mainly fluorides, chlorides and bromides) from alkynol or enyne derivatives by an acid-mediated cationic cyclisation reaction is disclosed. This high-yielding, scalable and technically simple method complements and challenges conventional methodologies. This study includes the development of biomimetic cationic cyclisation reactions of polyenyne derivatives to give interesting halogen-containing polycyclic compounds. The application of this reaction in the key step of the synthesis of two terpenes, namely austrodoral and pallescensin A, and the potent odorant 9-epi-Ambrox demonstrates the potential of the reaction for natural product synthesis.

Scalable Synthesis of the Amber Odorant 9-epi-Ambrox through a Biomimetic Cationic Cyclization/Nucleophilic Bromination Reaction

A novel biomimetic nucleophilic bromocyclization reaction is used in the key step of a new and straightforward synthesis of 9-epi-Ambrox, an organic compound of high interest and value in the context of fragrances. This strategic reaction allows access to 9-epi-Ambrox on a gram scale from a dienyne derivative, easily available from geraniol, following a sequence of seven steps (35% global yield) with just one purification process. Both enantiomers of the molecule were obtained by a challenging enzymatic resolution.

Trans-tetrahydrofurans by OH-assisted Ru-catalyzed isomerization of 2-butene-1,4-diols

We herein report a general method for the synthesis of 1,2-annulated trans-tetrahydrofurans by the OH-assisted Ru-catalyzed isomerization of (Z)-2-butene-1,4-diols (using Chaudret's catalyst), followed by reduction of the incipient lactol (using Et3SiH and Amberlyst 15). Alternatively, the lactol can be oxidized to the corresponding lactone (using Ikariya's catalyst). It was shown by labeling experiments that an addition/elimination pathway is (at least to some extent) operative for the isomerization reaction. Only 0.5 mol-% of Chaudret's Ru catalyst is sufficient for the rapid and stereoselective isomerization of enediols of the type shown. This allows ready access to trans-tetrahydrofurans.