689-89-4

Basic information

• Product Name: Methyl sorbate
• Synonyms: Methyl (2E,4E)-hexa-2,4-dienoate;(2E,4E)-2,4-Hexadienoic acid methyl ester;METHYL 2,4-HEXADIENOATE;METHYL T2 T4 HEXADIENOATE;METHYL SORBATE;FEMA 3714;2,4-HEXADIENOIC ACID METHYL ESTER;SORBIC ACID METHYL ESTER
• CAS NO: 689-89-4
• Molecular Formula: C₇H₁₀O₂
• Molecular Weight: 126.15
• EINECS: 211-712-8
• Mol File: 689-89-4.mol
• Article Data: 43

Chemical Properties

• Melting Point: 15°C
• Boiling Point: 180 °C(lit.)
• Flash Point: 158 °F
• Appearance: yellowish liquid
• Density: 0.968 g/mL at 25 °C(lit.)
• Vapor Pressure: 0.915mmHg at 25°C
• Refractive Index: n20/D 1.503(lit.)
• CAS DataBase Reference: Methyl sorbate(CAS DataBase Reference)
• NIST Chemistry Reference: Methyl sorbate(689-89-4)
• EPA Substance Registry System: Methyl sorbate(689-89-4)

Safety Data

• Hazard Codes: Xi
• Statements: 36/38
• Safety Statements: 26-36
• WGK Germany: 3
• Hazardous Substances Data: 689-89-4(Hazardous Substances Data)

Usage

Description

Methyl sorbate has a fruity, sweet, anise odor.

Chemical Properties

Methyl sorbate has a fruity, sweet, anise odor

Occurrence

Reported found in guanabana, starfruit and pineapple

Taste threshold values

Taste characteristics at 20 ppm: fruity, sweet, brown, vanilla and nutty

Synthesis Reference(s)

Chemistry Letters, 15, p. 1553, 1986Tetrahedron Letters, 30, p. 843, 1989 DOI: 10.1016/S0040-4039(01)80631-6

InChI:InChI=1/C7H10O2/c1-3-4-5-6-7(8)9-2/h3-6H,1-2H3/b4-3-,6-5+

Synthetic route

methanol (67-56-1) + sorbic Acid (110-44-1) → (2E,4E)-methylhexa-2,4-dienoate (689-89-4)

Conditions	Yield
With thionyl chloride at -10℃; for 2h; Reflux; Inert atmosphere;	99%
With chloro-trimethyl-silane In dichloromethane for 16h;	99%
Stage #1: sorbic Acid With oxalyl dichloride In dichloromethane; N,N-dimethyl-formamide at 0℃; for 1h; Inert atmosphere; Stage #2: methanol In dichloromethane; N,N-dimethyl-formamide at 0 - 20℃;	95%

sorbic Acid (110-44-1) + tert-butyl methyl ether (1634-04-4) → (2E,4E)-methylhexa-2,4-dienoate (689-89-4)

Conditions	Yield
With iron(III) trifluoromethanesulfonate at 90℃; Schlenk technique;	86%

methyl 2-hexynoate (18937-79-6) → (2E,4E)-methylhexa-2,4-dienoate (689-89-4)

Conditions	Yield
With tributylphosphine; IrH5(P-(i-Pr)3)2 In toluene at 110℃; for 24h;	85%

methanol (67-56-1) + sorbinyl chloride (2614-88-2) → (2E,4E)-methylhexa-2,4-dienoate (689-89-4)

Conditions	Yield
	85%
at 0℃;	81%

methyl (E)-4-oxo-2-butenoate (5837-72-9) + (triphenylphosphoranylidene)acetaldehyde (2136-75-6) → (2E,4E)-methylhexa-2,4-dienoate (689-89-4)

Conditions	Yield
In dichloromethane for 4h; Heating;	82%

(E)-3-((4S,5S)-5-Methyl-2-oxo-[1,3]dioxolan-4-yl)-acrylic acid methyl ester → (2E,4E)-methylhexa-2,4-dienoate (689-89-4)

Conditions	Yield
With copper(l) iodide; boron trifluoride diethyl etherate; methylmagnesium bromide In tetrahydrofuran at -78℃; for 0.333333h;	82%

(1Z,3E)-1-(t-butyldimethylsilyloxy)-1-methoxyhexa-1,3-diene (287193-97-9) → (2E,4E)-methylhexa-2,4-dienoate (689-89-4)

Conditions	Yield
With chloranil In dichloromethane for 0.00277778h; Elimination;	72%

acrylic acid methyl ester (292638-85-8) + 4,4,5,5-tetramethyl-2-[(1E)-prop-1-en-1-yl]-1,3,2-dioxaborolane (83947-58-4) → (2E,4E)-methylhexa-2,4-dienoate (689-89-4)

Conditions	Yield
With silver hexafluoroantimonate; [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2; copper(II) acetate monohydrate In 1,2-dichloro-ethane at 80℃; for 12h; Inert atmosphere; Sealed tube; stereoselective reaction;	70%

Epoxy-4,5 hexene-2 (E) oate de methyle (51830-12-7) → (2E,4E)-methylhexa-2,4-dienoate (689-89-4) + (+/-)-methyl-E-5-hydroxyhex-3-enoate (113351-26-1)

Conditions	Yield
With maleic anhydride; carbon monoxide; N-ethyl-N,N-diisopropylamine; sodium bromide; Pd2(C4H7)2Cl2 In methanol under 22800 Torr; Ambient temperature;	A 7% B 67%

sorbic Acid (110-44-1) + dimethyl sulfoxide (67-68-5) → (2E,4E)-methylhexa-2,4-dienoate (689-89-4)

Conditions	Yield
With copper(II) chloride monohydrate; dihydrogen peroxide; oxygen; potassium carbonate; calcium chloride at 80℃; for 15h; Sealed tube; Green chemistry;	32%

tributyl-amine (102-82-9) + acrylic acid methyl ester (292638-85-8) + triphenylphosphine (603-35-0) → (2E,4E)-methylhexa-2,4-dienoate (689-89-4)

Conditions	Yield
palladium diacetate	4%

diazomethane (186581-53-3, 908094-01-9) + sorbic Acid (110-44-1) → (2E,4E)-methylhexa-2,4-dienoate (689-89-4)

diazomethane (186581-53-3, 908094-01-9) + hexa-2,4-dienoic acid (110-44-1) → (2E,4E)-methylhexa-2,4-dienoate (689-89-4) + (2Z,4Z)-hexadienoic acid methyl ester (53892-48-1) + (2Z,4E)-hexadienoic acid methyl ester (6932-46-3) + (2E,4Z)-hexadienoic acid methyl ester (30361-31-0)

Conditions	Yield
1.) benzene, irradiation; 2.) MeOH; Yield given. Multistep reaction. Yields of byproduct given;

methanol (67-56-1) + (E)-4-Benzenesulfonyl-2-diethylamino-hepta-2,6-dienenitrile (344890-72-8) → (2E,4E)-methylhexa-2,4-dienoate (689-89-4)

Conditions	Yield
With sulfuric acid; 1,8-diazabicyclo[5.4.0]undec-7-ene 2.) CH2Cl2; Multistep reaction;

2-methylthiophene-5-carboxylic acid (1918-79-2) → (2E,4E)-methylhexa-2,4-dienoate (689-89-4) + Methyl 2,5-Dihydro-5-methyl-2-thiophenecarboxylate (71624-92-5) + methyl (E)-hex-3-enoate (13894-61-6) + methyl (E)-hex-4-enoate (14017-81-3) + methyl (Z)-hex-3-enoate (13894-62-7) + Methyl (Z)-5-Mercapto-3-hexenoate (86610-45-9)

Conditions	Yield
With methanol; sulfuric acid; ammonia; lithium Product distribution; Mechanism; 1) -78 degC, 60 min, 2) room temp., 24 h; other amount of Li: 10 eq.;	A 2 % Spectr. B 71 % Spectr. C 8.5 % Spectr. D n/a E n/a F 18 % Spectr.

trans-Crotonaldehyde (123-73-9) + Malonic acid monomethyl ester (16695-14-0) → (2E,4E)-methylhexa-2,4-dienoate (689-89-4) + (2Z,4E)-hexadienoic acid methyl ester (6932-46-3) + methyl (E)-3,5-hexadienoate (32775-94-3)

Conditions	Yield
dmap In pyridine at 60℃; for 24h; Yields of byproduct given. Title compound not separated from byproducts;

trans-Crotonaldehyde (123-73-9) + trimethyl phosphonoacetate (5927-18-4) → (2E,4E)-methylhexa-2,4-dienoate (689-89-4) + (2Z,4E)-hexadienoic acid methyl ester (6932-46-3) + (E)-3-(6-Methyl-cyclohexa-1,3-dienyl)-acrylic acid methyl ester (95636-75-2) + (E)-3-(2,6-Dimethyl-5,6-dihydro-2H-pyran-3-yl)-acrylic acid methyl ester (95636-76-3)

Conditions	Yield
With potassium tert-butylate DMF, rt; Yield given. Multistep reaction. Yields of byproduct given;

(2E)-5-Hydroxy-2-hexensaeuremethylester (19870-59-8) → (2E,4E)-methylhexa-2,4-dienoate (689-89-4)

Conditions	Yield
With sulfuric acid In methanol Heating;

Methyl (cis,E)-3-(2-Methyl-5,8-dioxaspiro<3.4>oct-1-yl)-2-propenoate (127379-38-8) → (2E,4E)-methylhexa-2,4-dienoate (689-89-4) + (2Z,4E)-hexadienoic acid methyl ester (6932-46-3) + (2E,4Z)-hexadienoic acid methyl ester (30361-31-0)

Conditions	Yield
In benzene-d6 at 189.6℃; Rate constant;
In acetonitrile at 144.4℃; Rate constant;

Methyl (cis,E)-3-(2-Methyl-5,8-dioxaspiro<3.4>oct-1-yl)-2-propenoate (127379-38-8) → (2E,4E)-methylhexa-2,4-dienoate (689-89-4) + (2E,4Z)-hexadienoic acid methyl ester (30361-31-0) + Methyl cis-9-Methyl-1,4-dioxaspiro<4.5>dec-7-ene-6-carboxylate (127281-00-9, 110434-36-1, 110434-37-2, 127281-01-0) + Methyl trans-9-Methyl-1,4-dioxaspiro<4.5>dec-7-ene-6-carboxylate (127281-01-0, 110434-36-1, 110434-37-2, 127281-00-9)

Conditions	Yield
In benzene-d6 at 190℃; Yield given. Further byproducts given. Yields of byproduct given;

Methyl (trans,Z)-3-(2-Methyl-5,8-dioxaspiro<3.4>oct-1-yl)-2-propenoate (127379-37-7) → (2E,4E)-methylhexa-2,4-dienoate (689-89-4) + (2Z,4Z)-hexadienoic acid methyl ester (53892-48-1) + (2Z,4E)-hexadienoic acid methyl ester (6932-46-3) + (2E,4Z)-hexadienoic acid methyl ester (30361-31-0) + Methyl cis-9-Methyl-1,4-dioxaspiro<4.5>dec-7-ene-6-carboxylate (127281-00-9, 110434-36-1, 110434-37-2, 127281-01-0) + Methyl trans-9-Methyl-1,4-dioxaspiro<4.5>dec-7-ene-6-carboxylate (127281-01-0, 110434-36-1, 110434-37-2, 127281-00-9)

Conditions	Yield
In benzene-d6 at 195℃; Thermodynamic data; Mechanism; Kinetics; product yield/distribution, ΔH(excit.)R, ΔS(excit.)R, ΔH(excit.)C, ΔS(excit.)C; other temperature, stereospecificity, stereoselectivity;

Methyl (trans,Z)-3-(2-Methyl-5,8-dioxaspiro<3.4>oct-1-yl)-2-propenoate (127379-37-7) → (2E,4E)-methylhexa-2,4-dienoate (689-89-4) + (2Z,4E)-hexadienoic acid methyl ester (6932-46-3) + (2E,4Z)-hexadienoic acid methyl ester (30361-31-0) + Methyl cis-9-Methyl-1,4-dioxaspiro<4.5>dec-7-ene-6-carboxylate (127281-00-9, 110434-36-1, 110434-37-2, 127281-01-0) + Methyl trans-9-Methyl-1,4-dioxaspiro<4.5>dec-7-ene-6-carboxylate (127281-01-0, 110434-36-1, 110434-37-2, 127281-00-9)

Conditions	Yield
In benzene-d6 at 170.2℃; Thermodynamic data; Mechanism; Kinetics; product yield/distribution, ΔH(excit.)R, ΔS(excit.)R, ΔH(excit.)C, ΔS(excit.)C; stereospecificity, stereoselectivity; other vinylcyclobutanes;

Methyl (trans,Z)-3-(2-Methyl-5,8-dioxaspiro<3.4>oct-1-yl)-2-propenoate (127379-37-7) → (2E,4E)-methylhexa-2,4-dienoate (689-89-4) + (2Z,4E)-hexadienoic acid methyl ester (6932-46-3) + Methyl cis-9-Methyl-1,4-dioxaspiro<4.5>dec-7-ene-6-carboxylate (127281-00-9, 110434-36-1, 110434-37-2, 127281-01-0) + Methyl trans-9-Methyl-1,4-dioxaspiro<4.5>dec-7-ene-6-carboxylate (127281-01-0, 110434-36-1, 110434-37-2, 127281-00-9)

Conditions	Yield
In benzene-d6 at 170℃; other temperatures; Yield given. Further byproducts given. Yields of byproduct given;

Methyl (trans,E)-3-(2-Methyl-5,8-dioxaspiro<3.4>oct-1-yl)-2-propenoate (127280-96-0) → (2E,4E)-methylhexa-2,4-dienoate (689-89-4) + (2Z,4E)-hexadienoic acid methyl ester (6932-46-3) + (2E,4Z)-hexadienoic acid methyl ester (30361-31-0) + Methyl cis-9-Methyl-1,4-dioxaspiro<4.5>dec-7-ene-6-carboxylate (127281-00-9, 110434-36-1, 110434-37-2, 127281-01-0)

Conditions	Yield
In benzene-d6 at 190℃; other temperatures; Yield given;	A n/a B n/a C n/a D 61 % Spectr.
In benzene-d6 at 179.8℃; Thermodynamic data; Kinetics; Mechanism; product yield/distribution; ΔH(excit.)R, ΔS(excit.)R, ΔH(excit.)C, ΔS(excit.)C; stereospecificity, stereoselectivity; other temperature;	A n/a B n/a C n/a D 65 % Spectr.

Methyl (trans,E)-3-(2-Methyl-5,8-dioxaspiro<3.4>oct-1-yl)-2-propenoate (127280-96-0) → (2E,4E)-methylhexa-2,4-dienoate (689-89-4) + (2E,4Z)-hexadienoic acid methyl ester (30361-31-0) + Methyl cis-9-Methyl-1,4-dioxaspiro<4.5>dec-7-ene-6-carboxylate (127281-00-9, 110434-36-1, 110434-37-2, 127281-01-0)

Conditions	Yield
In benzene-d6 at 170.8℃; Thermodynamic data; Kinetics; Mechanism; product yield/distribution; ΔH(excit.)R, ΔS(excit.)R, ΔH(excit.)C, ΔS(excit.)C; stereospecificity, stereoselectivity;	A n/a B n/a C 70 % Spectr.

Methyl (trans,E)-3-(2-Methyl-5,8-dioxaspiro<3.4>oct-1-yl)-2-propenoate (127280-96-0) → (2E,4E)-methylhexa-2,4-dienoate (689-89-4) + Methyl cis-9-Methyl-1,4-dioxaspiro<4.5>dec-7-ene-6-carboxylate (127281-00-9, 110434-36-1, 110434-37-2, 127281-01-0)

Conditions	Yield
In benzene-d6 at 160.2℃; Thermodynamic data; Kinetics; Mechanism; product yield/distribution; ΔG(excit.), ΔH(excit.)R, ΔS(excit.)R, ΔH(excit.)C, ΔS(excit.)C; stereospecificity, stereoselectivity;	A 25 % Spectr. B 75 % Spectr.

(E)-4-(4-Chloro-benzenesulfinyl)-hex-2-enoic acid methyl ester → (2E,4E)-methylhexa-2,4-dienoate (689-89-4) + (2E,4Z)-hexadienoic acid methyl ester (30361-31-0)

Conditions	Yield
In xylene for 2h; Heating; Yield given. Yields of byproduct given. Title compound not separated from byproducts;

(E)-(2S,3S)-2-Hydroxy-3-trimethylsilanyl-hex-4-enoic acid methyl ester (108965-77-1, 108965-78-2) → (2E,4E)-methylhexa-2,4-dienoate (689-89-4) + (2Z,4Z)-hexadienoic acid methyl ester (53892-48-1) + (2Z,4E)-hexadienoic acid methyl ester (6932-46-3)

Conditions	Yield
With boron trifluoride diethyl etherate In dichloromethane at -20℃; Yield given. Yields of byproduct given;

(E)-(2S,3S)-2-Hydroxy-3-trimethylsilanyl-hex-4-enoic acid methyl ester (108965-77-1, 108965-78-2) → (2E,4E)-methylhexa-2,4-dienoate (689-89-4) + (2E,4Z)-hexadienoic acid methyl ester (30361-31-0)

Conditions	Yield
With potassium hydride In tetrahydrofuran at -78 - -40℃; Yield given. Yields of byproduct given;

5-methyl-2-carbomethoxy-2,5-dihydrothiophene-1,1-dioxide (88418-76-2) → (2E,4E)-methylhexa-2,4-dienoate (689-89-4) + (2E,4Z)-hexadienoic acid methyl ester (30361-31-0)

Conditions	Yield
In toluene for 3h; Heating; Yield given. Yields of byproduct given. Title compound not separated from byproducts;

(2E,4E)-methylhexa-2,4-dienoate (689-89-4) → methyl 3,4-hexadienoate (81981-05-7)

Conditions	Yield
With trifluoroacetic acid In dichloromethane for 36h; Irradiation;	100%

(2E,4E)-methylhexa-2,4-dienoate (689-89-4) → methyl (Z)-hex-3-enoate (13894-62-7)

Conditions	Yield
With hydrogen; tricarbonyl(η(6)-1,2,3-trimethoxybenzene)chromium In tetrahydrofuran at 80℃; under 45600 Torr; for 5h; different catalysts, different temperatures;	100%
With hydrogen; tricarbonyl(η(6)-1,2,3-trimethoxybenzene)chromium In tetrahydrofuran at 100℃; under 45600 Torr; for 5h; various catalysts, other temperatures;	100%
With hydrogen; methyl benzoate*Cr(CO)3 In acetone at 100℃; under 53200 Torr; for 16h;	94%
With hydrogen; (η(6)-benzene)(η(2)-methylacrylate)dicarbonylchromium In tetrahydrofuran at 23℃; under 750.06 Torr; for 54h;	87%
With hydrogen; chromium(0) hexacarbonyl

(2E,4E)-methylhexa-2,4-dienoate (689-89-4) → methyl (E)-3,5-hexadienoate (32775-94-3)

Conditions	Yield
With N,N,N,N,N,N-hexamethylphosphoric triamide; lithium diisopropyl amide In tetrahydrofuran; hexane at -78℃; for 1h;	99%
With n-butyllithium; diisopropylamine In tetrahydrofuran; N,N,N,N,N,N-hexamethylphosphoric triamide; hexane at -78℃; for 1.5h;	76.6%
With 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone; n-butyllithium; lithium diisopropyl amide In tetrahydrofuran; hexane at -78℃; for 1.25h; Inert atmosphere;	70%
With lithium diisopropyl amide In tetrahydrofuran; N,N,N,N,N,N-hexamethylphosphoric triamide
With n-butyllithium; diisopropylamine; Hexamethylphosphorous triamide In tetrahydrofuran; hexane at -78 - 0℃; for 1h; Schlenk technique;

(2E,4E)-methylhexa-2,4-dienoate (689-89-4) → 1,4-trans-threo-disyndiotactic poly((E,E)-methyl sorbate), Mn = 5.4E4 Da, Mw/Mn = 1.4; monomer(s): methyl 2,4-hexadienoate

Conditions	Yield
With tert.-butyl lithium; bis(2,6-di-tert-butyl-4-methylphenoxide)methylaluminum In toluene; pentane at -20℃; for 72h;	98%

(2E,4E)-methylhexa-2,4-dienoate (689-89-4) → methyl (E)-hex-2-enoate (13894-63-8)

Conditions	Yield
With hydrogen; montmorillonit-bipyridinpalladium(II)-acetate In tetrahydrofuran Ambient temperature;	97%

(2E,4E)-methylhexa-2,4-dienoate (689-89-4) + (η6-7β-methyl-1,3,5-cycloheptatriene)tricarbonylchromium(0) → 10α,11β-dimethyl-7α-(methoxycarbonyl)-(1Hβ,6Hβ)-bicyclo[4.4.1]undeca-2,4,8-triene (129000-89-1)

Conditions	Yield
In hexane for 3h; Irradiation;	97%

(2E,4E)-methylhexa-2,4-dienoate (689-89-4) + benzaldehyde (100-52-7) → (2E,4E)-7-Hydroxy-7-phenyl-hepta-2,4-dienoic acid methyl ester

Conditions	Yield
Stage #1: (2E,4E)-methylhexa-2,4-dienoate; benzaldehyde With aluminium tris(2,6-diphenylphenoxide) In toluene at -78℃; for 0.333333h; Complexation; Stage #2: With 2,2,6,6-tetramethylpiperidinyl-lithium In tetrahydrofuran; hexane; toluene at -78℃; for 0.5h; Crossed aldol condensation;	97%

(2E,4E)-methylhexa-2,4-dienoate (689-89-4) + (E)-(1-methoxyprop-1-enyloxy)trimethylsilane (72658-09-4) → methyl 5-methoxy-2-methyl-3-(1-propenyl)-5-trimethylsiloxy-4-pentenoate

Conditions	Yield
aluminum ion-exchanged montmorillonite In dichloromethane at -50℃; for 0.5h;	96%

(2E,4E)-methylhexa-2,4-dienoate (689-89-4) + (η6-1,3,5-cycloheptatriene)tricarbonylchromium(0) → 7α-(methoxycarbonyl)-10α-methyl-(1Hβ,6Hβ)-bicyclo[4.4.1]undeca-2,4,8-triene (86067-63-2, 143428-66-4)

Conditions	Yield
In hexane for 0.5h; Irradiation;	96%

(2E,4E)-methylhexa-2,4-dienoate (689-89-4) → 1,4-trans-threo-disyndiotactic poly((E,E)-methyl sorbate), Mn = 3.1E4 Da, Mw/Mn = 1.2; monomer(s): methyl 2,4-hexadienoate

Conditions	Yield
With tert.-butyl lithium; bis(2,6-di-tert-butyl-4-methylphenoxide)methylaluminum; (-)-sparteine In toluene; pentane at -20℃; for 72h;	96%

(2E,4E)-methylhexa-2,4-dienoate (689-89-4) → Sorbyl alcohol (17102-64-6)

Conditions	Yield
With 5%-palladium/activated carbon; hydrogen In methanol at 50℃; under 45004.5 Torr; for 12h; Temperature; Pressure; Autoclave; Green chemistry;	94.95%
With strain of the zygomycete fungus S. racemosum MUT 770 In dimethyl sulfoxide for 72h; Enzymatic reaction;	23%
With lithium aluminium tetrahydride
With diisobutylaluminium hydride In toluene at -40℃; for 2h; Inert atmosphere;

(2E,4E)-methylhexa-2,4-dienoate (689-89-4) → methyl (E)-4-oxo-2-butenoate (5837-72-9)

Conditions	Yield
With ozone In methanol; dichloromethane at -30℃;	90%
With dimethylsulfide; ozone In dichloromethane	90%
With sodium perchlorate In water; acetonitrile (electrolysis);

(2E,4E)-methylhexa-2,4-dienoate (689-89-4) → (3E,7E)-5,6-Dimethyl-deca-3,7-dienedioic acid dimethyl ester (29653-35-8, 138823-73-1, 138823-74-2)

Conditions	Yield
With methanol; samarium diiodide In tetrahydrofuran; N,N,N,N,N,N-hexamethylphosphoric triamide Ambient temperature;	90%

(2E,4E)-methylhexa-2,4-dienoate (689-89-4) + lithium (R)-N-3,4-dimethoxybenzyl-N-(α-methylbenzyl)amide → (E)-(S)-3-[(3,4-Dimethoxy-benzyl)-((R)-1-phenyl-ethyl)-amino]-hex-4-enoic acid methyl ester (213467-20-0)

Conditions	Yield
	90%

(2E,4E)-methylhexa-2,4-dienoate (689-89-4) + benzaldehyde (100-52-7) → (Z)-methyl 2-[hydroxy(phenyl)methyl]hex-3-enoate

Conditions	Yield
With [Rh(OH)(cod)]2; triethyl borane In tetrahydrofuran at 20 - 50℃; Inert atmosphere; stereoselective reaction;	90%

(2E,4E)-methylhexa-2,4-dienoate (689-89-4) + N-p-Anisylmonothiomaleimide (167258-61-9) → rel-(5S,7R,10S)-Methyl 7-methyl-1-p-methoxyphenyl-2-oxo-6-thia-1-azaspiro<4.5>deca-3,8-diene-10-carboxylate

Conditions	Yield
In benzene for 15h; Ambient temperature;	89%

(2E,4E)-methylhexa-2,4-dienoate (689-89-4) → (E)-(4S,5S)-4,5-Dihydroxy-hex-2-enoic acid methyl ester (143289-07-0)

Conditions	Yield
With AD-mix-α Sharpless reaction;	88%

(2E,4E)-methylhexa-2,4-dienoate (689-89-4) → 1,4-trans-threo-disyndiotactic poly((E,E)-methyl sorbate), Mn = 4.2E4 Da, Mw/Mn = 1.6; monomer(s): methyl 2,4-hexadienoate

Conditions	Yield
With tert.-butyl lithium; bis(2,6-di-tert-butyl-4-methylphenoxide)methylaluminum; (-)-sparteine In toluene; pentane at -50℃; for 72h;	88%

(2E,4E)-methylhexa-2,4-dienoate (689-89-4) → 1,4-trans-threo-disyndiotactic poly((E,E)-methyl sorbate), Mn = 4.4E4 Da, Mw/Mn = 1.6; monomer(s): methyl 2,4-hexadienoate

Conditions	Yield
With menthyl ethyl ether; tert.-butyl lithium; bis(2,6-di-tert-butyl-4-methylphenoxide)methylaluminum In toluene; pentane at -50℃; for 72h;	88%

(2E,4E)-methylhexa-2,4-dienoate (689-89-4) → 1,4-trans-threo-disyndiotactic poly((E,E)-methyl sorbate), Mn = 3.3E4 Da, Mw/Mn = 1.4; monomer(s): methyl 2,4-hexadienoate

Conditions	Yield
With tert.-butyl lithium; bis(2,6-di-tert-butyl-4-methylphenoxide)methylaluminum; (-)-sparteine In toluene; pentane at -60℃; for 168h;	87%

(2E,4E)-methylhexa-2,4-dienoate (689-89-4) + 2-diazopropane (2684-60-8) → 5,5-Dimethyl-4-((E)-propenyl)-4,5-dihydro-1H-pyrazole-3-carboxylic acid methyl ester (96685-07-3)

Conditions	Yield
In diethyl ether; ethylbenzene at -5℃;	85%

(2E,4E)-methylhexa-2,4-dienoate (689-89-4) → (+/-) methyl (4,5)-trans-epoxy-(2E)-hexenoate (14202-27-8, 51830-12-7, 67315-16-6, 70095-87-3, 70494-79-0, 139686-29-6, 139686-31-0, 139686-32-1)

Conditions	Yield
With 3-chloro-benzenecarboperoxoic acid In dichloromethane for 24h; Ambient temperature;	85%
With 3-chloro-benzenecarboperoxoic acid In dichloromethane Yield given;

(2E,4E)-methylhexa-2,4-dienoate (689-89-4) → <1-2H2>2,4-hexadien-1-ol

Conditions	Yield
With lithium aluminium deuteride In diethyl ether at -78 - 20℃;	85%

(2E,4E)-methylhexa-2,4-dienoate (689-89-4) + 7-exo-nethylcyclopentatriene complex → 10α,11β-dimethyl-7α-(methoxycarbonyl)-(1Hβ,6Hβ)-bicyclo[4.4.1]undeca-2,4,8-triene (129000-89-1)

Conditions	Yield
Irradiation;	83%

(2E,4E)-methylhexa-2,4-dienoate (689-89-4) → Epoxy-4,5 hexene-2 (E) oate de methyle (51830-12-7) + methyl (E)-4-oxo-2-butenoate (5837-72-9) + methyl (E,E)-5-formyl-2,4-pentadienoate (40188-21-4)

Conditions	Yield
With tert.-butylhydroperoxide; chloroperoxidase In phosphate buffer pH=6; Enzymatic reaction;	A 4% B 13% C 83%

(2E,4E)-methylhexa-2,4-dienoate (689-89-4) + (R)-N-allyl (1-phenylethyl)amine (126275-19-2) → methyl (3S,4E,αR)-3-[N-allyl-N-(α-methylbenzyl)amino]hex-4-enoate (1202039-13-1)

Conditions	Yield
Stage #1: (R)-N-allyl (1-phenylethyl)amine With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.5h; Inert atmosphere; Stage #2: (2E,4E)-methylhexa-2,4-dienoate In tetrahydrofuran; hexane at -78℃; for 2h; Stage #3: With ammonium chloride In tetrahydrofuran; hexane; water at -78 - 20℃; for 0.25h; optical yield given as %de; diastereoselective reaction;	83%

Upstream product

• 186581-53-3 diazomethane 
• 110-44-1 hexa-2,4-dienoic acid 
• 1918-79-2 2-methylthiophene-5-carboxylic acid 
• 18937-79-6 methyl 2-hexynoate 
• 108965-77-1 (E)-(2S,3S)-2-Hydroxy-3-trimethylsilanyl-hex-4-enoic acid methyl ester 
• 123-73-9 trans-Crotonaldehyde 
• 191018-96-9 methyl 2-[bis(2,4-difluorophenoxy)phosphoryl]acetate 
• 84477-32-7 (E)-4-(4-Chloro-phenylsulfanyl)-hex-2-enoic acid methyl ester 
• 102-82-9 tributyl-amine 
• 292638-85-8 acrylic acid methyl ester 
• 603-35-0 triphenylphosphine 
• 71-91-0 tetraethylammonium bromide 
• 110-44-1 sorbic Acid 
• 1634-04-4 tert-butyl methyl ether 

Downstream Products

• 74312-60-0 methyl (2Z,4E)-3-phenyl-2,4-hexadienoate 
• 74312-59-7 methyl (2E,4Z)-5-phenylhexa-2,4-dienoate 
• 110317-86-7 cis-2-Hydroxy-3,4-dimethyl-1,5-cyclohexadien-1-carbonsaeure-methylester 
• 110317-87-8 trans-2-Hydroxy-3,4-dimethyl-1,5-cyclohexadien-1-carbonsaeure-methylester 
• 110317-84-5 cis-4,5-Dimethyl-6-oxo-1-cyclohexen-1-carbonsaeure-methylester 
• 110317-85-6 trans-4,5-Dimethyl-6-oxo-1-cyclohexen-1-carbonsaeure-methylester 
• 110486-03-8 cis-2-Hydroxy-3-ethyl-4-methyl-1,5-cyclohexadien-1-carbonsaeure-methylester 
• 110317-89-0 trans-2-Hydroxy-3-ethyl-4-methyl-1,5-cyclohexadien-1-carbonsaeure-methylester 
• 110318-28-0 cis-5-Ethyl-4-methyl-6-oxo-1-cyclohexen-1-carbonsaeure-methylester 
• 110317-88-9 trans-5-Ethyl-4-methyl-6-oxo-1-cyclohexen-1-carbonsaeure-methylester 
• 110318-07-5 (2E,4E)-7-Cyclohexyl-7-oxo-2,4-heptadiensaeure-methylester 
• 110318-08-6 (3E,5E)-7-Cyclohexyl-7-oxo-3,5-heptadiensaeure-methylester 
• 2527-96-0 methyl 5-methyl-2-furancarboxylate 
• 106369-42-0 methyl 5-methyl-2-selenophenecarboxylate 

Relevant articles and documents

Ruthenium-Catalyzed Oxidative Cross-Coupling Reaction of Activated Olefins with Vinyl Boronates for the Synthesis of (E, E)-1,3-Dienes

An oxidative cross-coupling reaction between activated olefins and vinyl boronate derivatives has been developed for the highly stereoselective construction of synthetically useful (E,E)-1,3-dienes. The highlight of this reaction is that exclusive stereoselectivity (only E,E-isomer) was achieved from a base-free, ligand-free, and mild catalytic condition with a less expensive [RuCl2(p-cymene)]2 catalyst.

Efficient flow fischer esterification of carboxylic acids with alcohols using sulfonic acid-functionalized silica as supported catalyst

Flow Fischer esterification of carboxylic acids using hydroxy-substituted sulfonic acid-functionalized silica (HOSAS) packed into a stainless steel column reactor was investigated. HO-SAS well catalyzed flow esterification of long chain carboxylic acids with methanol within 3min of residence time at 110°C, and the methyl esters were quantitatively obtained. The flow esterification protocol was applied to the synthesis of a variety of esters (19 examples) and scalable synthesis was also successful.