101372-99-0

Synthetic route

(4E,6E,10Z)-hexadeca-4,6,10-trien-1-ol (101373-01-7) + acetic anhydride (108-24-7) → (4E,6E,10Z)-4,6,10-hexadecatrienyl acetate (101372-99-0)

Conditions	Yield
With pyridine at 20℃; Concentration; Inert atmosphere;	97%

acetic anhydride (108-24-7) + (E,Z)-4,6,10-hexadecatrienyl alcohol (101373-00-6, 101373-01-7, 142143-85-9) → (4E,6E,10Z)-4,6,10-hexadecatrienyl acetate (101372-99-0) + (4E,6Z,10Z)-4,6,10-hexadecatrienyl acetate (139650-81-0)

Conditions	Yield
With pyridine Ambient temperature; Yield given. Yields of byproduct given;

(Z)-4-decenal (30390-50-2, 65405-70-1, 21662-09-9) → (4E,6E,10Z)-4,6,10-hexadecatrienyl acetate (101372-99-0)

Conditions	Yield
Multi-step reaction with 3 steps 1: 1.) n-BuLi / 1.) THF, hexane, 0 deg C, 1 h, 2.) THF, hexane, RT, 30 min 2: PPTs / methanol / 24 h / Ambient temperature 3: pyridine / Ambient temperature View Scheme

1-<(tetrahydropyranyl)oxy>-(4E,10Z)-hexadecatriene (142143-84-8, 142143-87-1) → (4E,6E,10Z)-4,6,10-hexadecatrienyl acetate (101372-99-0)

Conditions	Yield
Multi-step reaction with 2 steps 1: PPTs / methanol / 24 h / Ambient temperature 2: pyridine / Ambient temperature View Scheme

(Z)-4-decenyltriphenylphosphonium bromide (144054-75-1) → (4E,6E,10Z)-4,6,10-hexadecatrienyl acetate (101372-99-0)

Conditions	Yield
Multi-step reaction with 3 steps 1: 1.) t-BuOK / 1.) THF, -30 deg C, 30 min, 2.) THF, 2 h 2: PPTs / methanol / 24 h / Ambient temperature 3: pyridine / Ambient temperature View Scheme

6-<(tetrahydropyranyl)oxy>-2E-hexanetriphenylphosphonium bromide (144054-76-2) → (4E,6E,10Z)-4,6,10-hexadecatrienyl acetate (101372-99-0)

Conditions	Yield
Multi-step reaction with 3 steps 1: 1.) n-BuLi / 1.) THF, hexane, 0 deg C, 1 h, 2.) THF, hexane, RT, 30 min 2: PPTs / methanol / 24 h / Ambient temperature 3: pyridine / Ambient temperature View Scheme

(6E,10Z)-1-tetrahydropyran-2-yloxy-hexadecadiene-4-yne → (4E,6E,10Z)-4,6,10-hexadecatrienyl acetate (101372-99-0)

Conditions	Yield
Multi-step reaction with 3 steps 1: toluene-4-sulfonic acid / methanol / 20 °C 2: lithium; ammonium hydroxide 3: pyridine / 20 °C / Inert atmosphere View Scheme

(6E,10Z)-hexadecadiene-4-yn-1-ol → (4E,6E,10Z)-4,6,10-hexadecatrienyl acetate (101372-99-0)

Conditions	Yield
Multi-step reaction with 2 steps 1: lithium; ammonium hydroxide 2: pyridine / 20 °C / Inert atmosphere View Scheme

pent-1-yn-5-ol (5390-04-5) → (4E,6E,10Z)-4,6,10-hexadecatrienyl acetate (101372-99-0)

Conditions

Yield

Multi-step reaction with 6 steps 1.1: toluene-4-sulfonic acid / dichloromethane / 0 °C / Inert atmosphere 2.1: tetrakis(triphenylphosphine) palladium(0); copper(l) iodide; diisopropylamine / tetrahydrofuran / 8 h / 20 °C / Inert atmosphere 3.1: iron(III)-acetylacetonate; 1-methyl-pyrrolidin-2-one / tetrahydrofuran / -20 - -15 °C / Inert atmosphere 3.2: 8 h / -15 - 20 °C / Inert atmosphere 4.1: toluene-4-sulfonic acid / methanol / 20 °C 5.1: lithium; ammonium hydroxide 6.1: pyridine / 20 °C / Inert atmosphere View Scheme

1-(tetrahydropyranyloxy)-4-pentyn (62992-46-5) → (4E,6E,10Z)-4,6,10-hexadecatrienyl acetate (101372-99-0)

Conditions

Yield

Multi-step reaction with 5 steps 1.1: tetrakis(triphenylphosphine) palladium(0); copper(l) iodide; diisopropylamine / tetrahydrofuran / 8 h / 20 °C / Inert atmosphere 2.1: iron(III)-acetylacetonate; 1-methyl-pyrrolidin-2-one / tetrahydrofuran / -20 - -15 °C / Inert atmosphere 2.2: 8 h / -15 - 20 °C / Inert atmosphere 3.1: toluene-4-sulfonic acid / methanol / 20 °C 4.1: lithium; ammonium hydroxide 5.1: pyridine / 20 °C / Inert atmosphere View Scheme

trans-7-chloro-1-tetrahydropyran-2-yloxy-6-hepten-4-yne → (4E,6E,10Z)-4,6,10-hexadecatrienyl acetate (101372-99-0)

Conditions	Yield
Multi-step reaction with 4 steps 1.1: iron(III)-acetylacetonate; 1-methyl-pyrrolidin-2-one / tetrahydrofuran / -20 - -15 °C / Inert atmosphere 1.2: 8 h / -15 - 20 °C / Inert atmosphere 2.1: toluene-4-sulfonic acid / methanol / 20 °C 3.1: lithium; ammonium hydroxide 4.1: pyridine / 20 °C / Inert atmosphere View Scheme

(Z)-4-decenal (30390-50-2, 65405-70-1, 21662-09-9) → (4E,6E,10Z)-4,6,10-hexadecatrienyl acetate (101372-99-0) + (4E,6Z,10Z)-4,6,10-hexadecatrienyl acetate (139650-81-0)

Conditions	Yield
Multi-step reaction with 3 steps 1: n-butyllithium / 1.) THF, hexane, 0 deg C, 1 h, 2.) THF, hexane, RT, 30 min 2: pyridinium p-toluenesulfonate / methanol / 24 h / Ambient temperature 3: pyridine / Ambient temperature View Scheme

(Z)-4-decenyltriphenylphosphonium bromide (144054-75-1) → (4E,6E,10Z)-4,6,10-hexadecatrienyl acetate (101372-99-0) + (4E,6Z,10Z)-4,6,10-hexadecatrienyl acetate (139650-81-0)

Conditions	Yield
Multi-step reaction with 3 steps 1: potassium tert-butylate / 1.) THF, -30 deg C, 30 min, 2.) THF, 2 h 2: pyridinium p-toluenesulfonate / methanol / 24 h / Ambient temperature 3: pyridine / Ambient temperature View Scheme

6-<(tetrahydropyranyl)oxy>-2E-hexanetriphenylphosphonium bromide (144054-76-2) → (4E,6E,10Z)-4,6,10-hexadecatrienyl acetate (101372-99-0) + (4E,6Z,10Z)-4,6,10-hexadecatrienyl acetate (139650-81-0)

Conditions	Yield
Multi-step reaction with 3 steps 1: n-butyllithium / 1.) THF, hexane, 0 deg C, 1 h, 2.) THF, hexane, RT, 30 min 2: pyridinium p-toluenesulfonate / methanol / 24 h / Ambient temperature 3: pyridine / Ambient temperature View Scheme

(4E,6E,10Z)-4,6,10-hexadecatrienyl acetate (101372-99-0) + ethenetetracarbonitrile (670-54-2) → Acetic acid 3-[5,5,6,6-tetracyano-4-((Z)-non-3-enyl)-cyclohex-2-enyl]-propyl ester

Upstream product

• 144054-76-2 6-<(tetrahydropyranyl)oxy>-2E-hexanetriphenylphosphonium bromide 
• 144054-75-1 (Z)-4-decenyltriphenylphosphonium bromide 
• 30390-50-2 (Z)-4-decenal 
• 62992-46-5 1-(tetrahydropyranyloxy)-4-pentyn 
• 5390-04-5 pent-1-yn-5-ol 
• 101373-01-7 (4E,6E,10Z)-hexadeca-4,6,10-trien-1-ol 
• 108-24-7 acetic anhydride 
• 142143-84-8 1-<(tetrahydropyranyl)oxy>-(4E,10Z)-hexadecatriene 
• 101373-00-6 (E,Z)-4,6,10-hexadecatrienyl alcohol 

Relevant academic research and scientific papers

Synthesis method for conopomorpha sinensis bradley sex pheromone compound

The invention discloses a synthesis method for a conopomorpha sinensis bradley sex pheromone compound. The synthesis method comprises the following steps: taking 4-pentyne-1-alcohol as a starting rawmaterial, protecting hydroxyl with 3,4-dihydropyran to obtain a compound 5 protected by THP on the hydroxyl, enabling the compound 5 to generate coupled reaction with trans-dichloroethylene under co-catalysis of a metal palladium compound and cuprous iodide to obtain a compound 6; under catalysis of a metal iron compound, enabling the compound 6 to generate further coupled reaction with bromo cis-3-nonene Grignard reagent to obtain a compound 7; removing a THP protective group of the compound 7 under catalysis of toluenesulfonic acid monohydrate to form a compound 8; reducing the compound 8 toprepare (4E,6E,10Z)-hexadecatriene alcohol, and enabling the (4E,6E,10Z)-hexadecatriene alcohol to generate esterification reaction to obtain (4E,6E,10Z)-hexadecatriene acetate. The synthesis raw materials are simple and easily available, are low in cost, and the synthesis steps are short; and meanwhile, stereoselectivity is high, the yield is obviously increased, and the post-treatment is simpleand convenient.

Synthesis of the sex pheromone of cocoa pod borer moth, Conopomorpha Cramerella

Two new unambiguous synthesis routes for the components of the sex pheromone of the cocoa pod borer, Conopomorpha Cramerella (Snellen), are successfully developed.