33956-49-9

Basic information

• Product Name: 8,10-DODECADIEN-1-OL
• Synonyms: codlelure;codlingmothpheromone;ent34872;pheroconcm;trans-8,trans-10-dodecadien-1-ol;CODLEMONE;E,E-8,10-DODECADIEN-1-OL;8,10-DODECADIEN-1-OL
• CAS NO: 33956-49-9
• Molecular Formula: C₁₂H₂₂O
• Molecular Weight: 182.3
• EINECS: 251-761-2
• Product Categories: insect pheromone
• Mol File: 33956-49-9.mol
• Article Data: 28

Chemical Properties

• Melting Point: 30-32 °C
• Boiling Point: 270.7±9.0℃ (760 Torr)
• Flash Point: 62 °C
• Appearance: /
• Density: 0.862±0.06 g/cm3 (20 ºC 760 Torr)
• Vapor Pressure: 0.000886mmHg at 25°C
• Refractive Index: 1.5050 (estimate)
• Storage Temp.: 2-8°C
• PKA: 15.19±0.10(Predicted)
• BRN: 2325636
• CAS DataBase Reference: 8,10-DODECADIEN-1-OL(CAS DataBase Reference)
• NIST Chemistry Reference: 8,10-DODECADIEN-1-OL(33956-49-9)
• EPA Substance Registry System: 8,10-DODECADIEN-1-OL(33956-49-9)

Safety Data

• Hazard Codes: Xi
• Statements: 36/37/38-43-38
• Safety Statements: 26-36/37
• RIDADR: UN 3082 9 / PGIII
• WGK Germany: 3
• RTECS: JR1775000
• Hazardous Substances Data: 33956-49-9(Hazardous Substances Data)

Usage

Description

(8E,10E)-Dodecadien-1-ol is a sex pheromone of Laspeyresia pomonella.

Uses

8,10-DODECADIEN-1-OL is used as organic synthesis intermediates and pharmaceutical intermediates, mainly used in laboratory research and development processes and chemical production processes.

Synthesis

To a mixed so lution of Methyl5-oxo-(E,E)-8,10-dodecadienoate (15.7g, 0.07 mol) and p-toluene sulfonylhydrazine (16.3g, 0.0875 mol) in DMF - sulfolane (350ml, 1 : 1) was added p-toluenesulfonic acid (1.75g) and sodium cyanoborohydride (17.6g, 0.28mol) at room temperature, and the solution was heated at 100 ℃ for 4 hr. After cooling to room temperature, the reaction mixture was diluted with water (1000ml) and extracted with cyclohexane. The cyclohexane solution was washed with water, dried over Na2SO4 and concentrated in vacuo. Column chromatography of the oily residue over silica gel (Merck Kieselgel 60) with petroleum ether-ether (10:1) gave 4 (5.6g, 38%) as a pale yellow liquid.A solution of Methyl (E,E)-8,10-dodecadienoate (4.2g, 0.02mol) in absolute ether (40ml) was added dropwise to a slurry of lithium aluminum hydride (0.38g, 0.01mol) in absolute ether (60 ml) with stirring at room temperature. Stirring was continued for 1 hr at room temperature. After the mixture was refluxed for I hr, the reaction was quen ched with 2NH2SO4 (30ml) and the mixture was worked up by the usual procedure to give the alcohol 5, with a nearly quantitative yield, which solidified during storage in a refrigerator, (recrystallized from pe troleum ether). The purity was 97% on GLC analysis.

InChI:InChI=1/C12H22O/c1-2-3-4-5-6-7-8-9-10-11-12-13/h2-5,13H,6-12H2,1H3/b3-2+,5-4+

Synthetic route

trans-2-methyl-5-(7-hydroxyheptyl)-3-sulfolene (87241-02-9) → (8E,10E)-dodeca-8,10-dienol (33956-49-9)

Conditions	Yield
With potassium carbonate In ethanol at 125℃; for 0.5h;	100%
With potassium carbonate In ethanol at 125℃;	98%

(E,E)-sorbyl acetate (57006-69-6) + trimethylsilyl 6-chloro-1-hexyl ether (34714-00-6) → (8E,10E)-dodeca-8,10-dienol (33956-49-9)

Conditions	Yield
Stage #1: (E,E)-sorbyl acetate; trimethylsilyl 6-chloro-1-hexyl ether With sodium In toluene at 0 - 80℃; for 12h; Inert atmosphere; Green chemistry; Stage #2: With sulfuric acid In water; toluene at 0 - 20℃; for 1h; Temperature; Green chemistry;	77.47%

(E)-9-(phenylsulfinyl)-10-dodecen-1-ol (83248-82-2) → (8E,10E)-dodeca-8,10-dienol (33956-49-9)

Conditions	Yield
With triethylamine In toluene at 80℃; for 18h;	60%

(8E,10Z)-dodeca-8,10-dien-1-ol (33956-50-2) → (8E,10E)-dodeca-8,10-dienol (33956-49-9)

Conditions	Yield
With thiophenol at 100℃; for 2h;	30%

dodec-8-en-10-yn-1-ol (39616-28-9, 113982-52-8) → (8E,10E)-dodeca-8,10-dienol (33956-49-9)

Conditions	Yield
With lithium aluminium tetrahydride In tetrahydrofuran; diethylene glycol dimethyl ether at 140℃; for 2h;	10%

1,6-hexanediol (629-11-8) + (E,E)-sorbyl acetate (57006-69-6) → (8E,10E)-dodeca-8,10-dienol (33956-49-9)

Conditions	Yield
Multistep reaction;

trans-Crotonaldehyde (123-73-9) + 8-hydroxy-octyl-triphenyl-phosphonium bromide (65734-62-5) → (8E,10E)-dodeca-8,10-dienol (33956-49-9)

Conditions	Yield
With phenyllithium 1.) THF/diethyl ether, 20 min, 2.) -75 deg C, 15 min, -30 deg C, 30 min, 25 deg C; Yield given. Multistep reaction. Yields of byproduct given;

(8E,10E)-8,10-Dodecadienyl-(tetrahydro-2-pyranyl)ether (37935-49-2) → (8E,10E)-dodeca-8,10-dienol (33956-49-9)

Conditions	Yield
With toluene-4-sulfonic acid In methanol; water at 60℃; for 2h; Yield given;
With toluene-4-sulfonic acid In methanol at 50℃; for 2h; Yield given;
With methanesulfonic acid; water In methanol at 60℃; for 3h; Hydrolysis;	0.74 g
With toluene-4-sulfonic acid In methanol at 70℃; for 0.5h;

(E,E)-sorbyl acetate (57006-69-6) + (6-((tetrahydro-2H-pyran-2-yl)oxy)hexyl)magnesium chloride (69049-76-9) → (8E,10E)-dodeca-8,10-dienol (33956-49-9)

Conditions	Yield
With hydrogen cation; copper(l) iodide Yield given. Multistep reaction;

1-bromo-3E,5E-heptadiene (37935-45-8) + C8H19ClMgOSi → (8E,10E)-dodeca-8,10-dienol (33956-49-9)

Conditions	Yield
With dilithium tetrachlorocuprate; water 1) -5 - 0 deg C, 3 h; 2) 20 deg C, 12 h, THF, ether; 2) aq. EtOH, 2 h, boiling; Yield given. Multistep reaction;

7-((1R,2S,3R,5S,6R,7S)-5-Methyl-4,4-dioxo-4λ6-thia-tricyclo[5.2.1.02,6]dec-8-en-3-yl)-heptan-1-ol (86593-91-1) → (8E,10E)-dodeca-8,10-dienol (33956-49-9)

Conditions	Yield
at 600℃;

12-THPO-dodeca-2E,4-diene (37935-49-2, 74502-07-1, 75787-30-3, 96754-38-0, 96754-39-1) → (8Z,10E)-8,10-Dodecadien-1-ol (33956-50-2) + (8E,10E)-dodeca-8,10-dienol (33956-49-9)

Conditions	Yield
With methanol; toluene-4-sulfonic acid In water at 60℃;
With methanol; toluene-4-sulfonic acid In diethyl ether; water for 2h; Heating; Yield given. Yields of byproduct given;

(E)-8-Benzenesulfonyl-dodec-10-en-1-ol (107735-59-1) → (8E,10Z)-dodeca-8,10-dien-1-ol (33956-50-2) + (8E,10E)-dodeca-8,10-dienol (33956-49-9)

Conditions	Yield
With potassium tert-butylate In tetrahydrofuran at 60℃; for 1h; Yield given. Yields of byproduct given. Title compound not separated from byproducts;

8-Acetoxy-9-phenylsulphinyl-1-tetrahydropyranyloxydodec-10(E)-ene (96249-88-6) → (8E,10E)-dodeca-8,10-dienol (33956-49-9)

Conditions	Yield
With sodium amalgam; pyridinium p-toluenesulfonate 1) MeOH, EtOAc, -35 deg C, 5 h, 2) MeOH, reflux, 3 h; Yield given. Multistep reaction;

(8E,10E)-1,8,10-Dodecatrien (69775-54-8) → (8E,10E)-dodeca-8,10-dienol (33956-49-9)

Conditions	Yield
With sodium hydroxide; 9-borabicyclo[3.3.1]nonane dimer; dihydrogen peroxide 1) THF; 2) water.; Yield given. Multistep reaction;

(8E,10E)-8,10-Dodecadiensaeure-methylester (60099-82-3) → (8E,10E)-dodeca-8,10-dienol (33956-49-9)

Conditions	Yield
With lithium aluminium tetrahydride In diethyl ether 1.) r.t., 1 h, 2.) reflux, 1 h; Yield given;

2-[((8E,10E)-Dodeca-8,10-dienyl)oxy]-tetrahydro-pyran → (8E,10Z)-dodeca-8,10-dien-1-ol (33956-50-2) + (8E,10E)-dodeca-8,10-dienol (33956-49-9)

(8E,10E)-8,10-dodecadien-1-oxytrimethylsilane (38568-98-8) → (8E,10E)-dodeca-8,10-dienol (33956-49-9)

Conditions	Yield
With water In ethanol for 2h; Heating;
With toluene-4-sulfonic acid In methanol; water at 60℃; for 3h; Temperature;	117 g

ethyl 6-(chloroformyl)hexanoate (14794-32-2) + tricarbonyl(1,3-pentadiene)iron → (8E,10E)-dodeca-8,10-dienol (33956-49-9) + (8E,10E)-dodeca-8,10-dienal (69775-58-2) + (E,E)-8,10-dodecadienoic acid

Conditions	Yield
Multistep reaction;

methyl 2Z,5E-heptadienoate (40415-88-1) → (8E,10E)-dodeca-8,10-dienol (33956-49-9)

Conditions	Yield
Multi-step reaction with 4 steps 1: 98 percent / triethylamine / 12 h / 20 °C 2: 88 percent / LiAlH4 / diethyl ether / 3 h / 20 °C 3: 70 percent / PBr3, pyridine / hexane / 1) 0 deg C, 3h; 2) 20 deg C, 12 h 4: 1) Li2CuCl4; 2) water / 1) -5 - 0 deg C, 3 h; 2) 20 deg C, 12 h, THF, ether; 2) aq. EtOH, 2 h, boiling View Scheme

(3E, 5E)-hepta-3,5-dien-1-ol (37944-01-7) → (8E,10E)-dodeca-8,10-dienol (33956-49-9)

Conditions	Yield
Multi-step reaction with 2 steps 1: 70 percent / PBr3, pyridine / hexane / 1) 0 deg C, 3h; 2) 20 deg C, 12 h 2: 1) Li2CuCl4; 2) water / 1) -5 - 0 deg C, 3 h; 2) 20 deg C, 12 h, THF, ether; 2) aq. EtOH, 2 h, boiling View Scheme

methyl (3E,5Z)-3,5-heptadienoate (32793-94-5) → (8E,10E)-dodeca-8,10-dienol (33956-49-9)

Conditions	Yield
Multi-step reaction with 4 steps 1: 81 percent / LiAlH4 / diethyl ether / 3 h / 20 °C 2: 70 percent / PBr3, pyridine / hexane / 1) 0 deg C, 2 h; 2) 20 deg C, 12 h 3: 1) Li2CuCl4; 2) p-toluenesulfonic acid / 1) THF, 0 deg C, 3 h, then 20 deg C, 12 h; 2) methanol, water, 60 deg C, 3 h 4: 30 percent / C6H5SH / 2 h / 100 °C View Scheme

methyl (3E,5E)-3,5-heptadienoate (32775-96-5) → (8E,10E)-dodeca-8,10-dienol (33956-49-9)

Conditions	Yield
Multi-step reaction with 3 steps 1: 88 percent / LiAlH4 / diethyl ether / 3 h / 20 °C 2: 70 percent / PBr3, pyridine / hexane / 1) 0 deg C, 3h; 2) 20 deg C, 12 h 3: 1) Li2CuCl4; 2) water / 1) -5 - 0 deg C, 3 h; 2) 20 deg C, 12 h, THF, ether; 2) aq. EtOH, 2 h, boiling View Scheme

(3E, 5Z)-hepta-3,5-dien-1-ol (85110-94-7) → (8E,10E)-dodeca-8,10-dienol (33956-49-9)

Conditions	Yield
Multi-step reaction with 3 steps 1: 70 percent / PBr3, pyridine / hexane / 1) 0 deg C, 2 h; 2) 20 deg C, 12 h 2: 1) Li2CuCl4; 2) p-toluenesulfonic acid / 1) THF, 0 deg C, 3 h, then 20 deg C, 12 h; 2) methanol, water, 60 deg C, 3 h 3: 30 percent / C6H5SH / 2 h / 100 °C View Scheme

1-bromo-3E,5Z-heptadiene (85134-50-5) → (8E,10E)-dodeca-8,10-dienol (33956-49-9)

Conditions	Yield
Multi-step reaction with 2 steps 1: 1) Li2CuCl4; 2) p-toluenesulfonic acid / 1) THF, 0 deg C, 3 h, then 20 deg C, 12 h; 2) methanol, water, 60 deg C, 3 h 2: 30 percent / C6H5SH / 2 h / 100 °C View Scheme

methyl 2,5Z-heptadienoate (18261-30-8, 32793-92-3, 32793-93-4, 40415-88-1, 41792-07-8) → (8E,10E)-dodeca-8,10-dienol (33956-49-9)

Conditions	Yield
Multi-step reaction with 5 steps 1: triethylamine / heptane / 12 h / Heating 2: 81 percent / LiAlH4 / diethyl ether / 3 h / 20 °C 3: 70 percent / PBr3, pyridine / hexane / 1) 0 deg C, 2 h; 2) 20 deg C, 12 h 4: 1) Li2CuCl4; 2) p-toluenesulfonic acid / 1) THF, 0 deg C, 3 h, then 20 deg C, 12 h; 2) methanol, water, 60 deg C, 3 h 5: 30 percent / C6H5SH / 2 h / 100 °C View Scheme

4-propenyl-1,3-dioxane, E-isomer (114988-54-4) → (8E,10E)-dodeca-8,10-dienol (33956-49-9)

Conditions	Yield
Multi-step reaction with 4 steps 1: 76 percent / H2SO4 / 15 h / 20 - 60 °C 2: 33 percent / H2SO4 / 160 °C / 40 Torr 3: Li2CuCl4 / tetrahydrofuran / 3 h / -10 °C 4: 0.74 g / water; MsOH / methanol / 3 h / 60 °C View Scheme

(E,E)-sorbyl acetate (57006-69-6) + Br-Mg-CH2-CH2-CH(OR)2 → (8E,10E)-dodeca-8,10-dienol (33956-49-9)

Conditions	Yield
Multi-step reaction with 2 steps 1: Li2CuCl4 / tetrahydrofuran / 3 h / -10 °C 2: 0.74 g / water; MsOH / methanol / 3 h / 60 °C View Scheme

(6-((tetrahydro-2H-pyran-2-yl)oxy)hexyl)magnesium chloride (69049-76-9) → (8E,10E)-dodeca-8,10-dienol (33956-49-9)

Conditions	Yield
Multi-step reaction with 2 steps 1: Li2CuCl4 / tetrahydrofuran / 3 h / -10 °C 2: 0.74 g / water; MsOH / methanol / 3 h / 60 °C View Scheme

(8E,10E)-dodeca-8,10-dienol (33956-49-9) + methanesulfonyl chloride (124-63-0) → Methanesulfonic acid (8E,10E)-dodeca-8,10-dienyl ester (88076-03-3)

Conditions	Yield
With triethylamine In dichloromethane	99%

(8E,10E)-dodeca-8,10-dienol (33956-49-9) → (8E,10E)-dodeca-8,10-dienal (69775-58-2)

Conditions	Yield
With pyridinium chlorochromate In dichloromethane	65%
With pyridinium chlorochromate In dichloromethane at 20℃; for 2h;	64%
With pyridinium chlorochromate In dichloromethane	60%

(8E,10E)-dodeca-8,10-dienol (33956-49-9) + acetic anhydride (108-24-7) → (E,E)-8,10-dodecadienyl acetate (53880-51-6)

(8E,10E)-dodeca-8,10-dienol (33956-49-9) + acetobromomaltose (61651-22-7, 76843-44-2, 141243-53-0) → 8(E),10(E)-Dodecadienyl β-D-Maltopyranoside (86217-86-9)

Conditions	Yield
Yield given. Multistep reaction;

(8E,10E)-dodeca-8,10-dienol (33956-49-9) → Sodium 8(E),10(E)-Dodecadienyl Sulfate (86217-85-8)

Conditions	Yield
With sodium hydroxide; sulfur trioxide pyridine complex 1.) pyridine, 10 min.; Yield given. Multistep reaction;

(8E,10E)-dodeca-8,10-dienol (33956-49-9) + acetic anhydride (108-24-7) → (8Z,10E)-8,10-dodecadienyl acetate (67992-59-0) + (8E,10Z)-dodeca-8,10-dien-1-yl acetate (67992-60-3) + (E,E)-8,10-dodecadienyl acetate (53880-51-6)

Conditions	Yield
With pyridine Title compound not separated from byproducts;	A 1.0 % Chromat. B 4.0 % Chromat. C 95.0 % Chromat.

(8E,10E)-dodeca-8,10-dienol (33956-49-9) + 2-hydroxy-2-methylpropanenitrile (75-86-5) → (E,E)-trideca-9,11-dienenitrile

Conditions	Yield
With triphenylphosphine; diethylazodicarboxylate 1.) ether, -20 deg C, 20 min, 2.) ether, -20 deg C, 20 h; Yield given. Multistep reaction;

Upstream product

• 629-11-8 1,6-hexanediol 
• 57006-69-6 (E,E)-sorbyl acetate 
• 37935-49-2 (8E,10E)-8,10-Dodecadienyl-(tetrahydro-2-pyranyl)ether 
• 37935-45-8 1-bromo-3E,5E-heptadiene 
• 37944-01-7 (3E, 5E)-hepta-3,5-dien-1-ol 
• 37935-49-2 12-THPO-dodeca-2E,4-diene 
• 39616-28-9 dodec-8-en-10-yn-1-ol 
• 69049-76-9 (6-((tetrahydro-2H-pyran-2-yl)oxy)hexyl)magnesium chloride 
• 123-73-9 trans-Crotonaldehyde 
• 65734-62-5 8-hydroxy-octyl-triphenyl-phosphonium bromide 
• 103980-84-3 (1E,3E)-1-bromopenta-1,3-diene 
• 34714-00-6 trimethylsilyl 6-chloro-1-hexyl ether 
• 13038-22-7 non-8-en-1-yl acetate 
• 53880-51-6 (E,E)-8,10-dodecadienyl acetate 

Downstream Products

• 53880-51-6 (E,E)-8,10-dodecadienyl acetate 
• 67992-59-0 (8Z,10E)-8,10-dodecadienyl acetate 
• 67992-60-3 (8E,10Z)-dodeca-8,10-dien-1-yl acetate 
• 86217-90-5 3a,4,7,7a-Tetrahydro-2-(4-sodium sulfophenyl)-4β-(7-sodium sulfatoheptyl)-7β-methyl-1H-isoindole-1,3(2H)-dione 
• 86217-88-1 2-(3-Sodium sulfo-2,6-diisopropylphenyl)-5,8-dihydro-5β-(7-sodium sulfatoheptyl)-8β-methyl-1H-<1,2,4>triazolo<1,2-a>pyridazine-1,3(2H)-dione 
• 86217-91-6 3a,4,7,7a-Tetrahydro-2-(4-sodium sulfophenyl)-4β-<7-(β-D-maltopyranosyloxy)heptyl>-7β-methyl-1H-isoindole-1,3(2H)-dione 
• 86217-89-2 2-(3-Sodium sulfo-2,6-diisopropylphenyl)-5,8-dihydro-5β-<7-(β-D-maltopyranosyloxy)heptyl>-8β-methyl-1H-<1,2,4>triazolo<1,2-a>pyridazine-1,3(2H)-dione 

Relevant articles and documents

Insect pheromones and their analogs I. Synthesis of the sex attractant of the codling moth

The synthesis of the sex attractant of the codling moth Laspeyresia pomonella has been performed using as the initial compounds linear dimers of butadiene with methyl acrylate.

Synthesis of dodeca-8E,10E-dien-1-ol - The sex pheromone of Laspeyresia pomonella via the acetolysis of 4-propenyl-1,3-dioxane

A new scheme has been developed for the synthesis of dodeca-8E,10E-dien-1-ol (the sex pheromone of the codling moth) from sorbyl acetate, available from 4-propenyl-1,3-dioxane through the intermediate diacetate of 3-propenyl-2-oxapentane-1,5-diol.

Stereoselective Cross-Coupling of Grignard Reagents and Conjugated Dienylbromides using Iron Salts with Magnesium Alkoxides

A convenient procedure allowing iron-catalyzed cross-coupling of alkyl or aryl Grignard reagents and conjugated dienyl bromides is reported, relying on the use of cheap and non-toxic magnesium alkoxides as sole additives. An excellent stereoselectivity is observed in the alkyl-dienyl series. This sequence has been applied to the synthesis of the sex pheromone of codling moth, illustrating its applicability for obtaining targets of industrial interest. Preliminary mechanistic studies carried out on the aryl-dienyl cross-coupling suggest that in situ generated ate homoleptic organoiron(II) species act as catalytically relevant intermediates. A modified preparative method for the realization of THF solutions of dienyl bromides as “ready-to-use” coupling partners is also discussed, circumventing the thermal instability of those derivatives.

SYNTHESIS OF PHEROMONES AND RELATED MATERIALS VIA OLEFIN METATHESIS

Methods for preparation of olefins, including 8- and 11-unsaturated monoenes and polyenes, via transition metathesis-based synthetic routes are described. Metathesis reactions in the methods are catalyzed by transition metal catalysts including tungsten-, molybdenum-, and ruthenium-based catalysts. The olefins include insect pheromones useful in a number of agricultural applications.

SYNTHESIS OF OLEFINIC ALCOHOLS VIA ENZYMATIC TERMINAL HYDROXYLATION

In certain aspects, the present invention provides methods for producing terminally hydroxylated alkenes and alkynes by contacting an unsaturated or saturated hydrocarbon substrate with a hydroxylase enzyme. Exemplary terminal hydroxylases useful for carrying out the methods of the invention exhibit strong selectivity towards one terminal carbon of a hydrocarbon substrate and include, but are not limited to, non-heme diiron alkane monooxygenases, cytochromes P450 (e.g., cytochromes P450 of the CYP52 and CYP153 family), as well as long chain alkane hydroxylases. In some embodiments, the terminally hydroxylated alkene or alkyne is further converted to a terminal alkenal. In certain embodiments, terminally hydroxylated alkenes and alkynes are useful as insect pheromones which modify insect behavior. In other embodiments, terminally hydroxylated alkenes and alkynes are useful intermediates for producing pheromones via acetylation or oxidation of the alcohol moiety.