13894-63-8

Basic information

• Product Name: METHYL TRANS-2-HEXENOATE, 98
• Synonyms: METHYL TRANS-2-HEXENOATE, 98;(E)-Hex-2-enoicacidmethylester;2-Hexenoicacid,methylester,(2E)-;2-Hexenoicacid,methylester,(E)-;Methyl (2E)-2-hexenoate;Methyl (E)-2-hexenoate;methyl(E)-hex-2-enoate;methylester,(e)-2-hexenoicaci
• CAS NO: 13894-63-8
• Molecular Formula: C7H11O2-
• Molecular Weight: 127.16104
• EINECS: 237-663-2
• Mol File: 13894-63-8.mol
• Article Data: 18

Chemical Properties

• Boiling Point: 57-58°C 13mm
• Flash Point: 45°C
• Appearance: /
• Density: 0,915 g/cm3
• Vapor Pressure: 4.06mmHg at 25°C
• Refractive Index: 1.4330
• Storage Temp.: 2-8°C
• BRN: 1700768
• CAS DataBase Reference: METHYL TRANS-2-HEXENOATE, 98(CAS DataBase Reference)
• NIST Chemistry Reference: METHYL TRANS-2-HEXENOATE, 98(13894-63-8)
• EPA Substance Registry System: METHYL TRANS-2-HEXENOATE, 98(13894-63-8)

Safety Data

• Statements: 10-36/37/38
• Safety Statements: 26-36
• RIDADR: 3272
• TSCA: Yes
• HazardClass: 3
• PackingGroup: III
• Hazardous Substances Data: 13894-63-8(Hazardous Substances Data)

Usage

Synthesis Reference(s)

Journal of the American Chemical Society, 69, p. 300, 1947 DOI: 10.1021/ja01194a042

InChI:InChI=1/C7H12O2/c1-3-4-5-6-7(8)9-2/h5-6H,3-4H2,1-2H3/b6-5+

Synthetic route

methanol (67-56-1) + (E)-2-Hexenoic acid (13419-69-7) → methyl (E)-hex-2-enoate (13894-63-8)

Conditions	Yield
Stage #1: (E)-2-Hexenoic acid With oxalyl dichloride In tetrahydrofuran; N,N-dimethyl-formamide for 0.5h; Cooling with ice; Stage #2: methanol In tetrahydrofuran; N,N-dimethyl-formamide at 10 - 35℃; for 2h;	100%
With ethenetetracarbonitrile at 60℃; for 48h;	43%
With sulfuric acid Ambient temperature;
With sulfuric acid Reflux;

(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%

(E)-2-Hexenoic acid (13419-69-7) + methyl iodide (74-88-4) → methyl (E)-hex-2-enoate (13894-63-8)

Conditions	Yield
With cesium fluoride In N,N-dimethyl-formamide at 10 - 15℃; for 24h;	80%

3-Benzenesulfonyl-hexanoic acid methyl ester (93101-95-2) → methyl (E)-hex-2-enoate (13894-63-8)

Conditions	Yield
With 1,8-diazabicyclo[5.4.0]undec-7-ene In dichloromethane	76%

methyl (triphenylphosphoranylidene)acetate (21204-67-1) + butan-1-ol (71-36-3) → methyl (E)-hex-2-enoate (13894-63-8) + methyl (Z)-hex-2-enoate (13894-64-9)

Conditions	Yield
Stage #1: butan-1-ol With Celite; pyridinium chlorochromate In dichloromethane at 20℃; Stage #2: methyl (triphenylphosphoranylidene)acetate In dichloromethane at 20℃; for 24h; Wittig olefination;	A 73% B n/a

butyraldehyde (123-72-8) + methyl (triphenylphosphoranylidene)acetate (21204-67-1) → methyl (E)-hex-2-enoate (13894-63-8)

Conditions	Yield
In tetrahydrofuran for 4h; Reflux;	70%

butyraldehyde (123-72-8) + methyl (triphenylphosphoranylidene)acetate (21204-67-1) → methyl (E)-hex-2-enoate (13894-63-8) + methyl (Z)-hex-2-enoate (13894-64-9)

Conditions	Yield
for 3h; Heating;	A 51% B n/a
In hexane at 25℃; for 42h; Yield given. Yields of byproduct given;
With silica gel In hexane at 25℃; for 2h; Yield given. Yields of byproduct given;

diazomethane (186581-53-3, 908094-01-9) + (E)-2-Hexenoic acid (13419-69-7) → methyl (E)-hex-2-enoate (13894-63-8)

methanol (67-56-1) + 2-hydroxy-3-heptenenitrile (148811-03-4) → methyl (E)-hex-2-enoate (13894-63-8)

Conditions	Yield
With tert.-butylhydroperoxide; triethylamine; tris(triphenylphosphine)ruthenium(II) chloride 1.) benzene, 15 to 20 deg C, 8 h; Yield given. Multistep reaction;
With tert.-butylhydroperoxide; triethylamine; tris(triphenylphosphine)ruthenium(II) chloride 1) CH2Cl2, benzene, r.t., overnight, 2) 3 h; Yield given. Multistep reaction;

methyl (trimethylsilyl)acetate (2916-76-9) + butyraldehyde (123-72-8) → methyl (E)-hex-2-enoate (13894-63-8) + methyl (Z)-hex-2-enoate (13894-64-9)

Conditions	Yield
With lithium diisopropyl amide In tetrahydrofuran

Methyl diethylphosphonoacetate (1067-74-9) + butyraldehyde (123-72-8) → methyl (E)-hex-2-enoate (13894-63-8)

Conditions	Yield
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: butyraldehyde In 1,2-dimethoxyethane at 0 - 20℃; for 3h; Inert atmosphere;

trimethyl phosphonoacetate (5927-18-4) + butyraldehyde (123-72-8) → methyl (E)-hex-2-enoate (13894-63-8) + methyl (Z)-hex-2-enoate (13894-64-9)

Conditions	Yield
With sodium methylate In N,N-dimethyl-formamide for 6h; Ambient temperature; Yield given. Yields of byproduct given. Title compound not separated from byproducts;

diazomethane (186581-53-3, 908094-01-9) + hex-2t(?)-enoic acid → methyl (E)-hex-2-enoate (13894-63-8)

Conditions	Yield
With diethyl ether

(E)-4-Benzenesulfonyl-2-diethylamino-hept-2-enenitrile (344890-71-7) → methyl (E)-hex-2-enoate (13894-63-8)

Conditions	Yield
Multi-step reaction with 2 steps 1: 76 percent / HCl (3N) / 20 °C 2: 76 percent / DBU / CH2Cl2 View Scheme

(E)-2-Hexenal (6728-26-3) → methyl (E)-hex-2-enoate (13894-63-8)

Conditions	Yield
Multi-step reaction with 2 steps 1: ZnI2, 2N HCl 2: 1.) t-BuOOH 2.) Et3N / 1.) RuCl2(PPh3)3 / 1.) benzene, 15 to 20 deg C, 8 h View Scheme

oxalyl dichloride (79-37-8) + (E)-2-Hexenoic acid (13419-69-7) + sodium hydrogencarbonate (144-55-8) → methyl (E)-hex-2-enoate (13894-63-8)

Conditions	Yield
In tetrahydrofuran; methanol; N,N-dimethyl-formamide

trimethyl phosphonoacetate (5927-18-4) + butyraldehyde (123-72-8) → methyl (E)-hex-2-enoate (13894-63-8)

Conditions	Yield
Horner-Wadsworth-Emmons Olefination;

methyl (E)-hex-2-enoate (13894-63-8) + o-lithiomethylphenyl isocyanide (63212-31-7) → 3-(2-Isocyano-benzyl)-2-methyl-hexanoic acid ethyl ester

Conditions	Yield
	100%

methyl (E)-hex-2-enoate (13894-63-8) + o-lithiomethylphenyl isocyanide → methyl 4-(o-isocyanophenyl)-3-propylbutyrate

Conditions	Yield
	100%

nitromethane (75-52-5) + methyl (E)-hex-2-enoate (13894-63-8) → methyl 3-(nitromethyl)hexanoate

Conditions	Yield
With 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3, 2-diazaphosphorine supported on polystyrene at 30℃; for 22h; Michael condensation;	95%
With 1,8-diazabicyclo[5.4.0]undec-7-ene In methanol Michael addition;

methyl (E)-hex-2-enoate (13894-63-8) + tert-butyl (1S,4R)-2-(1-(N,N-diisopropylaminocarbonyl)-7,7-dimethyl-bicyclo[2.2.1]hept-2-ylideneamino)ethanoate → 1-tert-butyl methyl (2R,3S)-N-2-(((1S,4R)-1-(N,N-diisopropylaminocarbonyl)-7,7-dimethyl-bicyclo[2.2.1]heptan-2-ylidene)amino)-3-propyl-glutamate

Conditions

Yield

Stage #1: tert-butyl (1S,4R)-2-(1-(N,N-diisopropylaminocarbonyl)-7,7-dimethyl-bicyclo[2.2.1]hept-2-ylideneamino)ethanoate With n-butyllithium; diisopropylamine; lithium diisopropyl amide In tetrahydrofuran; hexane at -78℃; for 0.5h; Inert atmosphere; Cooling with acetone-dry ice; Stage #2: methyl (E)-hex-2-enoate In tetrahydrofuran at -78℃; for 3h; Inert atmosphere; Stage #3: With oxalic acid In tetrahydrofuran; water at 0℃; Inert atmosphere; diastereoselective reaction;

90%

methyl (E)-hex-2-enoate (13894-63-8) + (1S,2S,5'S)-N,N-diisopropyl [2-spiro-2'-(5'-methyl-1',3'-dioxolane-4'-one)-7,7-dimethylbicyclo[2.2.1]hept-1-yl]methanesulfonamide (256393-10-9) → (1S,2S,5'R,1''S)-N,N-diisopropyl-{7,7-dimethyl-2-spiro-2'-[5',5'-(2'-carbomethoxy-1''-propyl)ethylmethyl-1',3'-dioxolane-4'-one]}bicyclo[2.2.1]hept-1-ylmethanesulfonamide

Conditions	Yield
Stage #1: (1S,2S,5'S)-N,N-diisopropyl [2-spiro-2'-(5'-methyl-1',3'-dioxolane-4'-one)-7,7-dimethylbicyclo[2.2.1]hept-1-yl]methanesulfonamide With lithium diisopropyl amide In tetrahydrofuran; hexane at -100℃; for 0.5h; Stage #2: methyl (E)-hex-2-enoate In tetrahydrofuran; hexane at -78℃; for 3h; Michael addition; Further stages.;	88%

methyl (E)-hex-2-enoate (13894-63-8) → 3-propylepoxyethane-2-carboxylic acid methyl ester

Conditions	Yield
With 3-chloro-benzenecarboperoxoic acid In 1,2-dichloro-ethane at 50℃; for 3h;	88%

methyl (E)-hex-2-enoate (13894-63-8) → γ-bromo methyl-2-hexenoate (91664-06-1)

Conditions	Yield
With N-Bromosuccinimide In tetrachloromethane	87%

methyl (E)-hex-2-enoate (13894-63-8) + [2-(4-Benzyloxy-phenyl)-ethyl]-((S)-1-phenyl-ethyl)-amine (267888-94-8) → (S)-3-[[2-(4-Benzyloxy-phenyl)-ethyl]-((S)-1-phenyl-ethyl)-amino]-hexanoic acid methyl ester (267888-95-9)

Conditions	Yield
With n-butyllithium Addition;	82%

methyl (E)-hex-2-enoate (13894-63-8) + 1-amino-2-propene (107-11-9) → methyl 3-(N-allylamino)hexanoate

Conditions	Yield
In methanol for 8h; Heating;	80%

methyl (E)-hex-2-enoate (13894-63-8) + methylmagnesium bromide (75-16-1) → (S)-(-)-methyl 3-methylhexanoate (116169-10-9)

Conditions	Yield
With copper(l) iodide; 1,1′-binaphthalene-2,2′-diylbis[bis(4-methylphenyl)phosphine] In diethyl ether; tert-butyl methyl ether at -20℃; for 2.5h; Inert atmosphere; optical yield given as %ee; enantioselective reaction;	79%

methyl (E)-hex-2-enoate (13894-63-8) + (R)-N-benzyl-1-phenylethylamine (38235-77-7) → methyl (+)-(3R,αR)-3-(N-benzyl-N-α-methylbenzylamino)hexanoate (210294-87-4)

Conditions	Yield
Stage #1: (R)-N-benzyl-1-phenylethylamine With n-butyllithium In tetrahydrofuran; hexane at 0℃; for 0.25h; Stage #2: methyl (E)-hex-2-enoate In tetrahydrofuran; hexane at -78℃;	77%

methyl (E)-hex-2-enoate (13894-63-8) + ethylmagnesium bromide (925-90-6) + 4-bromo-aniline (106-40-1) → (R)-N-(4-bromophenyl)-3-ethylhexanamide

Conditions

Yield

Stage #1: ethylmagnesium bromide With copper(I) bromide dimethylsulfide complex In diethyl ether; tert-butyl methyl ether at -75℃; for 0.0833333h; Schlenk technique; Inert atmosphere; Stage #2: methyl (E)-hex-2-enoate In diethyl ether; tert-butyl methyl ether at -75℃; for 3h; Schlenk technique; Inert atmosphere; Stage #3: 4-bromo-aniline In diethyl ether; tert-butyl methyl ether at -75 - 20℃; Schlenk technique; Inert atmosphere; enantioselective reaction;

77%

methyl (E)-hex-2-enoate (13894-63-8) + cyclopenta-1,3-diene (542-92-7) → methyl (1R,2S,3S,4S)-3-propylbicyclo[2.2.1]hept-5-ene-2-carboxylate

Conditions	Yield
With triethyl((1-methoxy-2-methylprop-1-en-1-yl)oxy)silane; C74H33F30N3O8P2S2 In toluene at -80℃; for 30h; Diels-Alder Cycloaddition; Inert atmosphere; stereoselective reaction;	76%

methyl (E)-hex-2-enoate (13894-63-8) + (S)-2'-(1-Ethyl-1-methoxy-propyl)-[1,1']bipyrrolidinyl-2-one (181293-31-2) → (2'S,R,R)-(-)-3-[2'-(1-ethyl-1-methoxypropyl)-2-oxobipyrrolidinyl-3-yl]-hexanoic acid methyl ester (263748-72-7)

Conditions	Yield
Stage #1: (S)-2'-(1-Ethyl-1-methoxy-propyl)-[1,1']bipyrrolidinyl-2-one With lithium diisopropyl amide In tetrahydrofuran at -78℃; for 3h; Metallation; Stage #2: methyl (E)-hex-2-enoate In tetrahydrofuran at -100 - -78℃; Addition;	70%

methyl (E)-hex-2-enoate (13894-63-8) + ethylmagnesium bromide (925-90-6) + aniline (62-53-3) → (R)-3-ethyl-N-phenylhexanamide

Conditions

Yield

Stage #1: ethylmagnesium bromide With copper(I) bromide dimethylsulfide complex In diethyl ether; tert-butyl methyl ether at -75℃; for 0.0833333h; Schlenk technique; Inert atmosphere; Stage #2: methyl (E)-hex-2-enoate In diethyl ether; tert-butyl methyl ether at -75℃; for 3h; Schlenk technique; Inert atmosphere; Stage #3: aniline In diethyl ether; tert-butyl methyl ether at -75 - 20℃; Schlenk technique; Inert atmosphere; enantioselective reaction;

65%

methyl (E)-hex-2-enoate (13894-63-8) + 4-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)-N,N-diisobutyl-2-nitroaniline → (+/-)-methyl 3-(4-(diisobutylamino)-3-nitrophenyl)hexanoate

Conditions	Yield
With chloro(1,5-cyclooctadiene)rhodium(I) dimer; sodium hydroxide In 1,4-dioxane at 50℃; Inert atmosphere;	64.2%

methyl (E)-hex-2-enoate (13894-63-8) + tert-butyldimethylsilyl chloride (18162-48-6) → (1Z,3Z)-[1-methyloxy-1,3-hexadienyloxy]tert-butyldimethylsilane (287193-98-0)

Conditions	Yield
With N,N,N,N,N,N-hexamethylphosphoric triamide; n-butyllithium; diisopropylamine In tetrahydrofuran; hexane at -78 - 20℃; for 0.666667h; silylation;	61%
Stage #1: methyl (E)-hex-2-enoate With potassium hexamethylsilazane In tetrahydrofuran at -78℃; for 1.33333h; Inert atmosphere; Stage #2: tert-butyldimethylsilyl chloride In tetrahydrofuran at -78 - 20℃; Inert atmosphere;

methyl (E)-hex-2-enoate (13894-63-8) + acetoacetic acid methyl ester (105-45-3) → dimethyl 2-acetyl-3-propylglutarate

Conditions	Yield
With sodium methylate In methanol for 72h; Heating;	60%

Phenylselenyl chloride (5707-04-0) + methyl (E)-hex-2-enoate (13894-63-8) + benzylamine (100-46-9) → 3-benzylamino-2-phenylselanyl-hexanoic acid methyl ester

Conditions	Yield
Stage #1: Phenylselenyl chloride; methyl (E)-hex-2-enoate With zinc(II) chloride In dichloromethane at 20℃; for 0.5h; Addition; Stage #2: benzylamine at 20℃; for 14h; Alkylation;	59%

methyl (E)-hex-2-enoate (13894-63-8) → C7H11BrO2 (931382-07-9) + C7H11BrO2 (931382-06-8)

Conditions	Yield
Stage #1: methyl (E)-hex-2-enoate With bromine In n-heptane at 20℃; for 1h; Inert atmosphere; Stage #2: With potassium carbonate In n-heptane; acetonitrile at 60℃; for 2h; Inert atmosphere;	A 57% B 18%

methyl (E)-hex-2-enoate (13894-63-8) + benzylamine (100-46-9) → rac-methyl 3-(benzylamino)hexanoate

Conditions	Yield
Stage #1: methyl (E)-hex-2-enoate With bismuth (III) nitrate pentahydrate at 0℃; for 0.0833333h; Stage #2: benzylamine	57%

methyl (E)-hex-2-enoate (13894-63-8) + ethylmagnesium bromide (925-90-6) + benzyl-methyl-amine (103-67-3) → (R)-N-benzyl-3-ethyl-N-methylhexanamide

Conditions

Yield

Stage #1: ethylmagnesium bromide With copper(I) bromide dimethylsulfide complex In diethyl ether; tert-butyl methyl ether at -75℃; for 0.0833333h; Schlenk technique; Inert atmosphere; Stage #2: methyl (E)-hex-2-enoate In diethyl ether; tert-butyl methyl ether at -75℃; for 3h; Schlenk technique; Inert atmosphere; Stage #3: benzyl-methyl-amine In diethyl ether; tert-butyl methyl ether at -75 - 20℃; Schlenk technique; Inert atmosphere; enantioselective reaction;

54%

methyl (cis-(3S,4R)-3,4-isopropylidenedioxypyrrolidin-2-ylidene)acetate + methyl (E)-hex-2-enoate (13894-63-8) → methyl (1S,2R,7R)-1,2-isopropylidenedioxy-7-propyl-1,2,3,5,6,7-hexahydro-5-indolizinone-8-carboxylate (933776-59-1) + methyl (1S,2R,7S)-1,2-isopropylidenedioxy-7-propyl-1,2,3,5,6,7-hexahydro-5-indolizinone-8-carboxylate (933776-43-3)

Conditions	Yield
With sodium hydride In tetrahydrofuran at 25℃; for 4h;	A 33% B 52%

Upstream product

• 186581-53-3 diazomethane 
• 13419-69-7 (E)-2-Hexenoic acid 
• 67-56-1 methanol 
• 74-88-4 methyl iodide 
• 123-72-8 butyraldehyde 
• 21204-67-1 methyl (triphenylphosphoranylidene)acetate 
• 5927-18-4 trimethyl phosphonoacetate 
• 79-37-8 oxalyl dichloride 
• 144-55-8 sodium hydrogencarbonate 
• 6728-26-3 (E)-2-Hexenal 
• 344890-71-7 (E)-4-Benzenesulfonyl-2-diethylamino-hept-2-enenitrile 
• 71-36-3 butan-1-ol 
• 1067-74-9 Methyl diethylphosphonoacetate 
• 2916-76-9 methyl (trimethylsilyl)acetate 

Downstream Products

• 96530-28-8 (E)-1-Benzenesulfonyl-hept-3-en-2-one 
• 112545-21-8 (R)-2-((R)-1-Phenyl-ethyl)-3-propyl-isoxazolidin-5-one 
• 112545-26-3 (S)-2-((R)-1-Phenyl-ethyl)-3-propyl-isoxazolidin-5-one 
• 928-95-0 (E)-2-Hexen-1-ol 
• 91298-66-7 (S)-2-aminopentanonic acid 
• 267888-95-9 (S)-3-[[2-(4-Benzyloxy-phenyl)-ethyl]-((S)-1-phenyl-ethyl)-amino]-hexanoic acid methyl ester 
• 93620-38-3 rac-3-(N-benzylamino)hexanoic acid 
• 117709-02-1 3-propylepoxyethane-2-carboxylic acid methyl ester 
• 160801-75-2 (-)-(2S,3S)-3-amino-2-hydroxyhexanoic acid 

Relevant articles and documents

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The use of mechanochemistry to carry out enantioselective reactions has been explored in the last ten years with excellent results. Several chiral organocatalysts and even enzymes have proved to be resistant to milling conditions, which allows for rather efficient enantioselective transformations under ball-milling conditions. The present article reports the first example of a liquid-assisted grinding (LAG) mechanochemical enzymatic resolution of racemic β3-amino esters employing Candida antarctica lipase B (CALB) to afford highly valuable enantioenriched N-benzylated-β3-amino acids in good yields. Furthermore the present protocol is readily scalable.

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A proton pump inhibitor containing a compound represented by the formula (I) wherein X and Y are the same or different and each is a bond or a spacer having 1 to 20 carbon atoms in the main chain, R 1 is an optionally substituted hydrocarbon group or an optionally substituted heterocyclic group, R 2 , R 3 and R 4 are the same or different and each is a hydrogen atom, an optionally substituted hydrocarbon group, an optionally substituted thienyl group, an optionally substituted benzo[b]thienyl group, an optionally substituted furyl group, an optionally substituted pyridyl group, an optionally substituted pyrazolyl group, an optionally substituted pyrimidinyl group, an acyl group, a halogen atom, a cyano group or a nitro group, R 5 and R 6 are the same or different and each is a hydrogen atom or an optionally substituted hydrocarbon group, which has a superior proton pump action and shows an antiulcer activity and the like after conversion to a proton pump inhibitor in the body, or a salt thereof. or a prodrug thereof is provided.

PROTON PUMP INHIBITORS

A proton pump inhibitor containing a compound represented by the formula (I) wherein X and Y are the same or different and each is a bond or a spacer having 1 to 20 carbon atoms in the main chain, R1 is an optionally substituted hydrocarbon group or an optionally substituted heterocyclic group, R2, R3 and R4 are the same or different and each is a hydrogen atom, an optionally substituted hydrocarbon group, an optionally substituted thienyl group, an optionally substituted benzo[b]thienyl group, an optionally substituted furyl group, an optionally substituted pyridyl group, an optionally substituted pyrazolyl group, an optionally substituted pyrimidinyl group, an acyl group, a halogen atom, a cyano group or a nitro group, R5 and R6 are the same or different and each is a hydrogen atom or an optionally substituted hydrocarbon group, which has a superior proton pump action and shows an antiulcer activity and the like after conversion to a proton pump inhibitor in the body, or a salt thereof. or a prodrug thereof is provided.