7367-81-9

Basic information

• Product Name: METHYL TRANS-2-OCTENOATE
• Synonyms: METHYL TRANS-2-OCTENOATE;METHYL T2 OCTENOATE;METHYL OCT-2-ENOATE;METHYL 2-OCTENOATE;FEMA 3712;Methyltransoctenoate;methyl (E)-oct-2-enoate;METHYL TRANS-2-OCTENOATE 96+%
• CAS NO: 7367-81-9
• Molecular Formula: C₉H₁₆O₂
• Molecular Weight: 156.22
• EINECS: 230-912-6
• Product Categories: Alphabetical Listings;Flavors and Fragrances;M-N
• Mol File: 7367-81-9.mol
• Article Data: 39

Chemical Properties

• Boiling Point: 89-91 °C9 mm Hg(lit.)
• Flash Point: 181 °F
• Appearance: /
• Density: 0.898 g/mL at 25 °C(lit.)
• Refractive Index: n20/D 1.442(lit.)
• CAS DataBase Reference: METHYL TRANS-2-OCTENOATE(CAS DataBase Reference)
• NIST Chemistry Reference: METHYL TRANS-2-OCTENOATE(7367-81-9)
• EPA Substance Registry System: METHYL TRANS-2-OCTENOATE(7367-81-9)

Safety Data

• Statements: 36/37/38
• Safety Statements: 26-36/37/39
• WGK Germany: 3
• Hazardous Substances Data: 7367-81-9(Hazardous Substances Data)

Usage

Description

Methyl trans-2-octenoate has a fruity green odor.

Synthetic route

methyl 2-octynoate (111-12-6) → methyl (E)-oct-2-enoate (7367-81-9)

Conditions	Yield
Stage #1: methyl 2-octynoate With tris-(dibenzylideneacetone)dipalladium(0); 1,4-di(diphenylphosphino)-butane In 1,4-dioxane; water at 20℃; for 0.25h; Inert atmosphere; Stage #2: With formic acid In 1,4-dioxane at 80℃; for 10h; Inert atmosphere; optical yield given as %ee; stereoselective reaction;	93%
Stage #1: methyl 2-octynoate With Triethoxysilane; tris(acetonitrile)pentamethylcyclopentadienylruthenium(II) hexafluorophosphate In dichloromethane at 20℃; for 0.5h; Stage #2: With copper(l) iodide; tetrabutyl ammonium fluoride In tetrahydrofuran at 20℃; for 20h; Further stages.;	83%

methyl (2Z)-3-iodooct-2-enoate (160729-74-8) → methyl (E)-oct-2-enoate (7367-81-9)

Conditions	Yield
Stage #1: methyl (2Z)-3-iodooct-2-enoate In tetrahydrofuran; 1-methyl-pyrrolidin-2-one; diethyl ether at -78℃; for 0.5h; Stage #2: With water In tetrahydrofuran; 1-methyl-pyrrolidin-2-one; diethyl ether at 20℃; for 0.5h; Further stages.;	92%

((1R,2S)-1-Methoxy-2-pentyl-cyclopropoxy)-trimethyl-silane → methyl (E)-oct-2-enoate (7367-81-9) + (E)-methyl oct-3-enoate (35234-16-3) + 2,3-dichloro-5,6-dicyanohydroquinone (4640-41-9) + methyl (Z)-oct-3-enoate (69668-85-5)

Conditions	Yield
With 2,3-dicyano-5,6-dichloro-p-benzoquinone In acetonitrile at 60℃; for 20h; Yields of byproduct given;	A 76% B n/a C 86% D n/a
With 2,3-dicyano-5,6-dichloro-p-benzoquinone In acetonitrile at 60℃; for 20h; Yield given;	A 76% B n/a C 86% D n/a

(E)-allyl methyl hept-1-en-1-ylphosphonate + (E)-diallyl hept-1-en-1-ylphosphonate + acrylic acid methyl ester (292638-85-8) → methyl (E)-oct-2-enoate (7367-81-9) + 2-methoxy-2,5-dihydro-1,2-oxaphosphole 2-oxide + (E)-methyl 4-((2-oxido-1,2-oxaphosphol-2(5H)-yl)oxy)but-2-enoate

Conditions	Yield
With tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride; copper(l) iodide In dichloromethane for 16h; Inert atmosphere; Reflux;	A 86% B n/a C n/a

hexanal (66-25-1) + methyl (triphenylphosphoranylidene)acetate (21204-67-1) → methyl (E)-oct-2-enoate (7367-81-9)

Conditions	Yield
In dichloromethane at 20℃; for 17h; Wittig Olefination; Inert atmosphere;	85%
In benzene for 48h; Heating;	83%
In tetrahydrofuran for 4h; Reflux;	80%
In dichloromethane at 23℃; for 17h; Inert atmosphere;	70%

methanol (67-56-1) + 1-Heptyne (628-71-7) + carbon monoxide (201230-82-2) → methyl (E)-oct-2-enoate (7367-81-9) + methyl α-pentyl acrylate (69565-06-6)

Conditions	Yield
With palladium diacetate; toluene-4-sulfonic acid; 1,4-di(diphenylphosphino)-butane In acetonitrile at 110℃; under 5171.62 Torr; for 1h; Autoclave; regioselective reaction;	A 85% B 15%

methyl (triphenylphosphoranylidene)acetate (21204-67-1) + hexan-1-ol (111-27-3) → methyl (E)-oct-2-enoate (7367-81-9) + 2-cis octenoic acid methyl ester (68854-59-1)

Conditions	Yield
Stage #1: hexan-1-ol With Celite; pyridinium chlorochromate In dichloromethane at 20℃; Stage #2: methyl (triphenylphosphoranylidene)acetate In dichloromethane at 20℃; for 24h; Wittig olefination;	A 82% B n/a

hexanal (66-25-1) + methyl (triphenylphosphoranylidene)acetate (21204-67-1) → methyl (E)-oct-2-enoate (7367-81-9) + 2-cis octenoic acid methyl ester (68854-59-1)

Conditions	Yield
for 3h; Heating;	A 80% B n/a
In water at 20℃; for 1h; Wittig reaction; Title compound not separated from byproducts.;

(E)-allyl methyl hept-1-en-1-ylphosphonate + acrylic acid methyl ester (292638-85-8) → methyl (E)-oct-2-enoate (7367-81-9) + 2-methoxy-2,5-dihydro-1,2-oxaphosphole 2-oxide

Conditions	Yield
With tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride; copper(l) iodide In dichloromethane for 16h; Inert atmosphere; Reflux;	A 78% B n/a

(+/-)-trimethyl(1-methoxy-2-pentylcyclopropoxy)silane (344332-97-4) → methyl (E)-oct-2-enoate (7367-81-9) + methyl (Z)-non-3-enoate (41654-16-4) + methyl (trans-3-nonenoate) (36781-67-6)

Conditions	Yield
With 2,3-dicyano-5,6-dichloro-p-benzoquinone In acetonitrile at 60℃; for 20h; Yields of byproduct given;	A 76% B n/a C n/a
With 2,3-dicyano-5,6-dichloro-p-benzoquinone In acetonitrile at 60℃; for 20h; Yield given. Yields of byproduct given. Title compound not separated from byproducts;

methyl (2S,3S)-2-iodo-3-hydroxyoctanoate (171016-45-8) + C5H3F3O4S → methyl (E)-oct-2-enoate (7367-81-9) + methyl (2S,3S)-2-iodo-3-(butynoyloxy)octanoate (171231-65-5)

Conditions	Yield
In dichloromethane 1.) from -20 deg C to r.t.; 2.) r.t., 10 h;	A 25% B 75%

methyl (2R,3S)-3-pentyloxiranecarboxylate (107797-02-4) → methyl (E)-oct-2-enoate (7367-81-9) + methyl (2S,3S)-2-iodo-3-hydroxyoctanoate (171016-45-8) + methyl (2S,3R)-2-hydroxy-3-iodooctanoate

Conditions	Yield
With chloro-trimethyl-silane; sodium iodide In acetonitrile at -20℃; for 1h;	A 7 % Spectr. B 72% C 6 % Spectr.

methyl (2S,3S)-2-iodo-3-hydroxyoctanoate (171016-45-8) + TMS-propynoyl triflate (1026856-11-0) → methyl (E)-oct-2-enoate (7367-81-9) + methyl (2S,3S)-2-iodo-3-(trimethylsilylpropynoyloxy)octanoate (171231-64-4)

Conditions	Yield
In dichloromethane 1.) from -20 deg C to r.t.; 2.) r.t., 10 h;	A 25% B 71%

(E)-8-bromooct-2-enoic acid methyl ester (68750-34-5) → methyl (E)-oct-2-enoate (7367-81-9) + methyl cyclohexylacetate (14352-61-5)

Conditions	Yield
With 2,2'-azobis(isobutyronitrile); tri-n-butyl-tin hydride In benzene for 10h; Heating;	A n/a B 66%

Malonic acid monomethyl ester (16695-14-0) + hexanal (66-25-1) → methyl (E)-oct-2-enoate (7367-81-9)

Conditions	Yield
With pyrrolidine; pyridine at 20℃; for 24h;	66%

hexanal (66-25-1) + bromoacetic acid methyl ester (96-32-2) → methyl (E)-oct-2-enoate (7367-81-9)

Conditions	Yield
With triphenyl phosphite; tri-n-butylarsine; potassium carbonate In tetrahydrofuran; acetonitrile for 31h; Ambient temperature;	64%

methyl 2-diazooctanoate → methyl (E)-oct-2-enoate (7367-81-9) + 2-cis octenoic acid methyl ester (68854-59-1) + C9H16O2

Conditions	Yield
With Li[Al(perfluoro-tertbutoxide)4]; [Fe(N,N’-bis(pentafluorophenyl)-o-phenylenediamide)(tetrahydrofuran)]2 In dichloromethane at 25℃; for 24h; Schlenk technique; Inert atmosphere;	A n/a B n/a C 64%

Methyl diethylphosphonoacetate (1067-74-9) + hexanal (66-25-1) → methyl (E)-oct-2-enoate (7367-81-9)

Conditions	Yield
With triethylamine In acetonitrile at 20℃; under 6000480 Torr; for 24h; Horner-Wadsworth-Emmons reaction;	54%
With sodium hydride In diethylene glycol dimethyl ether
Stage #1: Methyl diethylphosphonoacetate With sodium hydride In 1,2-dimethoxyethane at 0℃; for 0.5h; Inert atmosphere; Stage #2: hexanal In 1,2-dimethoxyethane at 0 - 20℃; for 3h; Inert atmosphere;

2-methylpropen-1-ylmagnesium bromide (38614-36-7) + methyl (E)-2-iodo-2-octenoate (144079-78-7) → methyl (E)-oct-2-enoate (7367-81-9) + 7,8-di(carbomethoxy)-6,8-tetradecadiene (144079-84-5) + methyl (Z)-2-(2-methyl-1-propenyl)-2-octenoate (145099-83-8) + methyl (E)-2-(2-methyl-1-propenyl)-2-octenoate (145099-84-9)

Conditions	Yield
With zinc(II) chloride; tetrakis(triphenylphosphine) palladium(0) In tetrahydrofuran 1) -25 deg C, 3.5 h, 2) room temperature, 16 h, 3) reflux, 4 h; Further byproducts given. Yields of byproduct given;	A n/a B 16% C n/a D n/a
With zinc(II) chloride; tetrakis(triphenylphosphine) palladium(0) In tetrahydrofuran 1) -25 deg C, 3.5 h, 2) room temperature, 16 h, 3) reflux, 4 h; Yield given. Further byproducts given. Title compound not separated from byproducts;	A n/a B 16% C n/a D n/a

3-hydroxyoctanoic acid methyl ester (7367-87-5) → methyl (E)-oct-2-enoate (7367-81-9) + methyl 3-fluorooctanoate + methyl 3-fluorooctanoate

Conditions	Yield
With diethylamino-sulfur trifluoride In dichloromethane at -70℃; for 0.333333h; Inert atmosphere; Overall yield = 40 %; Overall yield = 17 mg;	A 15% B n/a C n/a

methyl 2-octynoate (111-12-6) → methyl (E)-oct-2-enoate (7367-81-9) + 2-cis octenoic acid methyl ester (68854-59-1)

Conditions	Yield
With N,N,N,N,N,N-hexamethylphosphoric triamide; copper(l) iodide; methyllithium; diisobutylaluminium hydride In tetrahydrofuran; hexane at -50℃; for 1h;	A 12% B 7%
With quinoline; hydrogen; Lindlar's catalyst In ethyl acetate under 760 Torr; Yield given. Yields of byproduct given;

diazomethane (186581-53-3, 908094-01-9) + (E)-oct-2-enoic acid (1871-67-6) → methyl (E)-oct-2-enoate (7367-81-9)

Conditions	Yield
With diethyl ether durch Veresterung;
In diethyl ether

1,1-dimethoxyethylene (922-69-0) + hexanal (66-25-1) → methyl (E)-oct-2-enoate (7367-81-9)

Conditions	Yield
at 200℃;

methanol (67-56-1) + 1-Heptyne (628-71-7) + carbon monoxide (201230-82-2) → methyl (E)-oct-2-enoate (7367-81-9)

Conditions	Yield
With bis-triphenylphosphine-palladium(II) chloride; tin(ll) chloride

trans-Methyl-N-phenyl-2-octenoimidat (56830-01-4) → methyl (E)-oct-2-enoate (7367-81-9)

Conditions	Yield
With hydrogenchloride

dichloromethane (75-09-2) + Z-dimethyltertiobutylsilyloxy-1 methoxy-1 heptene-1 (100340-44-1) → methyl (E)-oct-2-enoate (7367-81-9) + 2-cis octenoic acid methyl ester (68854-59-1) + tert-Butyl-((1S,2R,3R)-2-chloro-1-methoxy-3-pentyl-cyclopropoxy)-dimethyl-silane + tert-Butyl-((1S,2S,3R)-2-chloro-1-methoxy-3-pentyl-cyclopropoxy)-dimethyl-silane

Conditions	Yield
With sodium hexamethyldisilazane Product distribution; Mechanism; multistep reaction: 1.) pentane -15 deg C; 2.) methanol-triethylamine, reflux; studied: the stereochemistry (E or Z) in the addition reaction of ketene alkylsilyl acetals with chloro-, chloromethyl- and chlorophenyl carbenes;

methyl hexanoate (106-70-7) + trimethyl phosphonoacetate (5927-18-4) → methyl (E)-oct-2-enoate (7367-81-9) + 2-cis octenoic acid methyl ester (68854-59-1)

Conditions	Yield
With n-butyllithium; diisobutylaluminium hydride In tetrahydrofuran at -78℃; Yield given. Yields of byproduct given;

methyl α-iodocaprylate (73635-61-7) → methyl (E)-oct-2-enoate (7367-81-9) + (E)-methyl oct-3-enoate (35234-16-3)

Conditions	Yield
With 1,8-diazabicyclo[5.4.0]undec-7-ene In N,N-dimethyl-formamide at 80℃; for 3h; Yield given;

methyl 2-phenylsulfinylacetate (14090-83-6) + 1-Iodohexane (638-45-9) → methyl (E)-oct-2-enoate (7367-81-9) + (E)-2-Hexyl-oct-2-enoic acid methyl ester (111036-55-6, 135987-03-0)

Conditions	Yield
With sodium hydride 1) DMF, 20 deg C, 0.2 h, 2) toluene, 110 deg C, 15 min; Yield given. Multistep reaction. Yields of byproduct given;

methyl (E)-oct-2-enoate (7367-81-9) → methyl (2R,3S)-2,3-dihydroxyoctanoate (1593758-37-2)

Conditions	Yield
With methanesulfonamide; AD-mix-α In water; tert-butyl alcohol at 0 - 20℃; for 96h;	98%
With methanesulfonamide; AD-mix-α; water In tert-butyl alcohol at 0℃; for 96h; Sharpless Dihydroxylation; Inert atmosphere; stereoselective reaction;	75%

methyl (E)-oct-2-enoate (7367-81-9) → 2-hydroxyoctanoic acid methyl ester (73634-76-1)

Conditions	Yield
With phenylsilane; oxygen; bis(dipivaloylmethanato)manganese(II) In isopropyl alcohol at 0℃; under 760 Torr; for 5h;	94%

nitromethane (75-52-5) + methyl (E)-oct-2-enoate (7367-81-9) → 3-nitrooctanoic acid methyl ester (664304-85-2)

Conditions	Yield
With 1,8-diazabicyclo[5.4.0]undec-7-ene at 20℃;	94%

tert-butyl acetoacetate (1694-31-1) + methyl (E)-oct-2-enoate (7367-81-9) → C16H26O4

Conditions	Yield
With sodium methylate In methanol for 2.5h; Inert atmosphere; Reflux;	91%

methyl (E)-oct-2-enoate (7367-81-9) + lithium benzyl-(R)-1-phenylethylamide → (R)-3-[Benzyl-((R)-1-phenyl-ethyl)-amino]-octanoic acid methyl ester (486449-97-2)

Conditions	Yield
	90%

2,2-dimethyl-3-butyne (917-92-0) + methyl (E)-oct-2-enoate (7367-81-9) → methyl 3-[(E)-3,3-dimethyl-1-butene-1-yl]octanoate

Conditions	Yield
Stage #1: 3,3-Dimethylbut-1-yne With CpZrHCl In dichloromethane at 20℃; for 0.25h; Stage #2: methyl (E)-oct-2-enoate; chloro(1,5-cyclooctadiene)rhodium(I) dimer In 1,4-dioxane at 20℃; for 1h; Further stages.;	90%

methyl (E)-oct-2-enoate (7367-81-9) → (E)-oct-2-enoic acid (1871-67-6)

Conditions	Yield
With potassium fluoride; tetrabutyl ammonium fluoride In tetrahydrofuran; water at 70℃; for 7h;	90%
With lithium hydroxide In tetrahydrofuran; water for 2.5h; Reflux;

methyl (E)-oct-2-enoate (7367-81-9) + 2,2,2-trifluoroethyl 2-(4-bromophenyl)-2-diazoacetate → 1-methyl 9-(2,2,2-trifluoroethyl) (7R,8S,E)-8-(4-bromophenyl)-7-methylnon-2-enedioate

Conditions	Yield
Stage #1: methyl (E)-oct-2-enoate With dirhodium tetrakis((S)-1-(5-trifluoromethyl-2-chlorophenyl)-2,2-diphenylcyclopropanecarboxylate) In dichloromethane at 23℃; for 0.166667h; Inert atmosphere; Stage #2: 2,2,2-trifluoroethyl 2-(4-bromophenyl)-2-diazoacetate In dichloromethane at 23℃; for 2h; Reagent/catalyst; Inert atmosphere; stereoselective reaction;	90%

methyl (E)-oct-2-enoate (7367-81-9) → (2S,3R)-(+)-methyl 2,3-dihydroxyoctanoate (132486-46-5)

Conditions	Yield
With methanesulfonamide; AD-mix-β In water; tert-butyl alcohol at 0 - 20℃; for 96h;	88%

methyl (E)-oct-2-enoate (7367-81-9) → (2S*,3R*)-methyl 2,3-epoxyoctanoate (100939-32-0)

Conditions	Yield
With [2,2]bipyridinyl; silver(I) acetate; lithium perchlorate In water; acetonitrile electrochemical oxidation;	80%

methyl (E)-oct-2-enoate (7367-81-9) + bis(pinacol)diborane (73183-34-3) → (S)-Methyl 3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)octanoate (1198171-98-0)

Conditions	Yield
With [CN2(C6H3-2-Mes-5-iPr)(Mes)C2H2Ph2]BF4; 1,8-diazabicyclo[5.4.0]undec-7-ene; MeOH In tetrahydrofuran (N2), 22°C, 14 h;	80%
With methanol; BF4(1-)*C42H45N2(1+); 1,8-diazabicyclo[5.4.0]undec-7-ene In tetrahydrofuran at 22℃; for 14h; Inert atmosphere; enantioselective reaction;	80%

methyl (E)-oct-2-enoate (7367-81-9) → methyl 3-oxooctanoate (22348-95-4)

Conditions	Yield
With methanol; water; oxygen; toluene-4-sulfonic acid; palladium dichloride In N,N-dimethyl acetamide at 80℃; under 4560.31 Torr; for 3h; Reagent/catalyst; Solvent; Time; Pressure; Concentration; Autoclave; regioselective reaction;	79%

methyl (E)-oct-2-enoate (7367-81-9) + (1Z,4Z)-1,5-diiodopenta-1,4-diene (63382-68-3) → (E)-1-heptenylbenzene (10201-58-8)

Conditions	Yield
Stage #1: (1Z,4Z)-1,5-diiodopenta-1,4-diene With n-butyllithium; isopropylmagnesium chloride In tetrahydrofuran; hexane at -20℃; for 2h; Inert atmosphere; Stage #2: methyl (E)-oct-2-enoate In tetrahydrofuran; hexane at -20℃; for 2h; Inert atmosphere;	60%

Upstream product

• 111-12-6 methyl 2-octynoate 
• 106-70-7 methyl hexanoate 
• 5927-18-4 trimethyl phosphonoacetate 
• 75-09-2 dichloromethane 
• 100340-44-1 Z-dimethyltertiobutylsilyloxy-1 methoxy-1 heptene-1 
• 67-56-1 methanol 
• 628-71-7 1-Heptyne 
• 201230-82-2 carbon monoxide 
• 922-69-0 1,1-dimethoxyethylene 
• 66-25-1 hexanal 
• 186581-53-3 diazomethane 
• 1871-67-6 (E)-oct-2-enoic acid 
• 638-45-9 1-Iodohexane 
• 111-27-3 hexan-1-ol 

Downstream Products

• 111-11-5 methyl octanate 
• 86654-32-2 α-formylcaprylate 
• 592-76-7 1-Heptene 
• 1871-67-6 (E)-oct-2-enoic acid 
• 22348-95-4 methyl 3-oxooctanoate 
• 116429-06-2 methyl 3-methoxy-2-octenoate 
• 28540-79-6 E-7-tetradecen-1-yl acetate 
• 37011-95-3 (7E)-tetradec-7-en-1-ol 
• 56318-83-3 (E)-1-bromo-oct-2-ene 
• 104883-49-0 3-Amino octanoic acid 
• 486449-97-2 (R)-3-[Benzyl-((R)-1-phenyl-ethyl)-amino]-octanoic acid methyl ester 
• 73634-76-1 2-hydroxyoctanoic acid methyl ester 
• 18409-17-1 (E)-oct-2-en-1-ol 
• 141627-79-4 Methyl 3-phthalimidooctanoate 

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