6728-31-0

Basic information

• Product Name: CIS-4-HEPTENAL
• Synonyms: FEMA 3289;CIS-4-HEPTEN-1-AL;CIS-4-HEPTENAL;C4 HEPTENAL;TIMTEC-BB SBB006608;(4Z)-4-Heptenal;(Z)-4-Hepten-1-al;(z)-4-heptena
• CAS NO: 6728-31-0
• Molecular Formula: C₇H₁₂O
• Molecular Weight: 112.17
• EINECS: 229-779-7
• Product Categories: Alphabetical Listings;Flavors and Fragrances;G-H;Alpha Sort;E-L;Volatiles/ Semivolatiles
• Mol File: 6728-31-0.mol
• Article Data: 8

Chemical Properties

• Melting Point: -53.35°C (estimate)
• Boiling Point: 60 °C25 mm Hg(lit.)
• Flash Point: 105 °F
• Appearance: Clear colorless to light yellow/Liquid
• Density: 0.850 g/mL at 20 °C(lit.)
• Vapor Pressure: 3.64mmHg at 25°C
• Refractive Index: n20/D 1.434
• Storage Temp.: 0-6°C
• BRN: 1902614
• CAS DataBase Reference: CIS-4-HEPTENAL(CAS DataBase Reference)
• NIST Chemistry Reference: CIS-4-HEPTENAL(6728-31-0)
• EPA Substance Registry System: CIS-4-HEPTENAL(6728-31-0)

Safety Data

• Statements: 10
• Safety Statements: 16-24/25
• RIDADR: UN 1989 3/PG 3
• WGK Germany: 3
• F: 10-23
• HazardClass: 3
• PackingGroup: III
• Hazardous Substances Data: 6728-31-0(Hazardous Substances Data)

Usage

Description

cis-4-Heptenal has an odor reminiscent of heptaldehyde. It is suggestive of fried fats on dilution. It is used to impart a fried, buttery flavor. It is prepared from Hemiptera insects (trans-form); from pen-ten-l-en-3-ol converted to the corresponding vinyl ether which undergoes a Claisen rearrangement to 4-heptenal (transform).

Chemical Properties

Different sources of media describe the Chemical Properties of 6728-31-0 differently. You can refer to the following data:
1. cis-4-Heptenal has an odor reminiscent of heptaldehyde The odor is suggestive of fried fats on dilution It is used to impart a fried, buttery favor.
2. clear colorless to light yellow liquid
3. (Z)-4-Heptenal is a widespread volatile trace constituent of food flavors. It is a colorless, oily liquidwith a powerful, fatty, somewhat fishy, and, in high dilution, creamy odor. It can be prepared by several ways, for example, by starting from (Z)-3-hexenol. (Z)-4-Heptenal is used in cream, butter, and fat flavors.

Occurrence

Reported found as a constitutent in butterfat, microbial fermented tea and black Hemiptera bugs

Preparation

From Hemiptera bugs (trans-form); from penten-1-en-3-ol converted to the corresponding vinyl ether, which undergoes a Claisen rearrangement to 4-heptenal (trans-form).

Aroma threshold values

Detection: 0.4 ppb.

InChI:InChI=1/C7H12O/c1-2-3-4-5-6-7-8/h3-4,7H,2,5-6H2,1H3/b4-3-

Synthetic route

(Z)-4-hepten-1-ol (6191-71-5) → (Z)-4-heptenal (6728-31-0)

7,7-diethoxy-hept-3c-ene (18492-65-4) → (Z)-4-heptenal (6728-31-0)

Conditions	Yield
With formic acid

2-hex-3-enyl-4,4,6-trimethyl-[1,3]oxazinane (36872-14-7) → (Z)-4-heptenal (6728-31-0)

Conditions	Yield
With oxalic acid

(Z)-3-Hexen-1-ol (928-96-1) → (Z)-4-heptenal (6728-31-0)

Conditions	Yield
Multistep reaction;
Multi-step reaction with 3 steps 1: PBr3, Py 2: (i) Mg, (ii) /BRN= 1719716/ 3: HCO2H View Scheme

(Z)-1-Bromo-3-hexene (5009-31-4) + carbon monoxide (201230-82-2) → (Z)-4-heptenal (6728-31-0)

Conditions	Yield
With 2,2'-azobis(isobutyronitrile); tri-n-butyl-tin hydride In benzene at 80℃; under 49400 Torr; for 3h;	80 % Chromat.

(Z)-2-(hept-4-en-1-yloxy)tetrahydro-2H-pyran (530086-82-9) → (Z)-4-heptenal (6728-31-0)

Conditions	Yield
Multi-step reaction with 2 steps 1: 74 percent / conc. H2SO4 / acetone; H2O / 20 °C 2: 65 percent / NACAA / CH2Cl2; pyridine / 0.33 h / 20 °C View Scheme
Multi-step reaction with 2 steps 1: toluene-4-sulfonic acid / methanol / 15 h / 20 °C 2: 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; [bis(acetoxy)iodo]benzene / dichloromethane / 1 h / 20 °C View Scheme

1-bromo-pent-2-yne (16400-32-1) → (Z)-4-heptenal (6728-31-0)

Conditions	Yield
Multi-step reaction with 5 steps 1: 60 percent / benzene / 12 h / Heating 2: 65 percent / NaCl, H2O / dimethylsulfoxide / 8 h / 160 °C 3: 76 percent / LAH, EtOH / diethyl ether 4: 80 percent / H2, quinoline / Lindlar's catalyst / hexane 5: 58 percent / pyridinium chlorochromate, NaOAc / CH2Cl2 / 4 h View Scheme

hept-4-yn-1-ol (42397-24-0) → (Z)-4-heptenal (6728-31-0)

Conditions	Yield
Multi-step reaction with 2 steps 1: 80 percent / H2, quinoline / Lindlar's catalyst / hexane 2: 58 percent / pyridinium chlorochromate, NaOAc / CH2Cl2 / 4 h View Scheme

pent-2-yn-1-ol (6261-22-9) → (Z)-4-heptenal (6728-31-0)

Conditions	Yield
Multi-step reaction with 6 steps 1: 77 percent / PBr3, pyridine / diethyl ether / Ambient temperature 2: 60 percent / benzene / 12 h / Heating 3: 65 percent / NaCl, H2O / dimethylsulfoxide / 8 h / 160 °C 4: 76 percent / LAH, EtOH / diethyl ether 5: 80 percent / H2, quinoline / Lindlar's catalyst / hexane 6: 58 percent / pyridinium chlorochromate, NaOAc / CH2Cl2 / 4 h View Scheme

ethyl 2-carbethoxy-hept-4-yn-1-oate (98442-18-3) → (Z)-4-heptenal (6728-31-0)

Conditions	Yield
Multi-step reaction with 4 steps 1: 65 percent / NaCl, H2O / dimethylsulfoxide / 8 h / 160 °C 2: 76 percent / LAH, EtOH / diethyl ether 3: 80 percent / H2, quinoline / Lindlar's catalyst / hexane 4: 58 percent / pyridinium chlorochromate, NaOAc / CH2Cl2 / 4 h View Scheme

ethyl hept-4-yn-1-oate (98442-19-4) → (Z)-4-heptenal (6728-31-0)

Conditions	Yield
Multi-step reaction with 3 steps 1: 76 percent / LAH, EtOH / diethyl ether 2: 80 percent / H2, quinoline / Lindlar's catalyst / hexane 3: 58 percent / pyridinium chlorochromate, NaOAc / CH2Cl2 / 4 h View Scheme

(Z)-4-Heptensaeure-ethylester (39924-27-1) → (Z)-4-heptenal (6728-31-0)

Conditions	Yield
Multi-step reaction with 2 steps 1: 82 percent / LiAlH4 / diethyl ether 2: 76 percent / pyridinium chlorochromate / CH2Cl2 / 2 h View Scheme

(Z)-1-Bromo-3-hexene (5009-31-4) → (Z)-4-heptenal (6728-31-0)

Conditions	Yield
Multi-step reaction with 2 steps 1: (i) Mg, (ii) /BRN= 1719716/ 2: HCO2H View Scheme

hept-4-ynal → (Z)-4-heptenal (6728-31-0)

Conditions	Yield
With hydrogen In ethanol	10.5 g (94%)

(Z)-4-heptenal (6728-31-0) + ethyl acetate (141-78-6) → ethyl (+/-)-(Z)-3-hydroxy-non-6-enoate (1202014-45-6)

Conditions	Yield
Stage #1: ethyl acetate With lithium diisopropyl amide In tetrahydrofuran; hexane at -78℃; for 0.333333h; Stage #2: (Z)-4-heptenal In tetrahydrofuran; hexane at -78℃; for 2h;	100%

(Z)-4-heptenal (6728-31-0) + benzoic acid (65-85-0) + Tert-butyl isocyanate (1609-86-5) → (Z)-1-(tert-butylcarbamoyl)hept-4-enyl benzoate

Conditions	Yield
In tetrahydrofuran at 20℃;	99%

p-toluene sulfinic acid (536-57-2) + (Z)-4-heptenal (6728-31-0) + benzamide (55-21-0) → (Z)-N-(1-tosylhept-4-enyl)benzamide (1000681-66-2)

Conditions	Yield
With magnesium sulfate In dichloromethane at 20℃;	99%

methanol (67-56-1) + (Z)-4-heptenal (6728-31-0) + dibenzyl azodicarboxylate (2449-05-0) → benzyl (S,Z)-(2-oxo-4-(pent-2-en-1-yl)oxazolidin-3-yl)carbamate + benzyl (R,Z)-(2-oxo-4-(pent-2-en-1-yl)oxazolidin-3-yl)carbamate

Conditions	Yield
Stage #1: (Z)-4-heptenal; dibenzyl azodicarboxylate With D-Prolin In acetonitrile at 0℃; for 0.5h; Stage #2: methanol With sodium tetrahydroborate In acetonitrile at 0℃; for 2.63333h; Stage #3: With sodium hydroxide In acetonitrile at 20℃; for 3h; enantioselective reaction;	A 99% B n/a

nitromethane (75-52-5) + (Z)-4-heptenal (6728-31-0) → (+/-)-(Z)-1-nitrooct-5-en-2-ol (925210-18-0)

Conditions	Yield
With potassium tert-butylate In tetrahydrofuran; nitromethane; tert-butyl alcohol at 20℃; for 1h; Henry reaction;	98%
With potassium tert-butylate In tetrahydrofuran; tert-butyl alcohol Henry reaction;

(Z)-4-heptenal (6728-31-0) + bis-(2,2,2-trifluoroethyl)(methoxycarbonylmethyl)phosphonate (88738-78-7) → C10H16O2 (1170320-52-1)

Conditions	Yield
With 18-crown-6 ether; potassium hexamethylsilazane In tetrahydrofuran at -78℃; Still-Gennari reaction;	98%

(Z)-4-heptenal (6728-31-0) + phenylmagnesium bromide → (Z)-1-phenylhept-4-en-1-ol (151322-33-7)

Conditions	Yield
In diethyl ether for 0.333333h; Heating;	97%

(Z)-4-heptenal (6728-31-0) + (R)-2-methylpropane-2-sulfinamide (196929-78-9) → (R)-N-[(Z)-hept-4-en-(E)-ylidene]-(2-tert-butane)sulfinamide (949886-14-0)

Conditions	Yield
With copper(II) sulfate In dichloromethane at 20℃;	97%

(Z)-4-heptenal (6728-31-0) + benzylmagnesium chloride (6921-34-2) → (Z)-1-phenyl-5-octen-2-ol (151322-34-8)

Conditions	Yield
In diethyl ether for 0.333333h; Heating;	96%
In tetrahydrofuran Heating;

1-nitrohexane (646-14-0) + (Z)-4-heptenal (6728-31-0) → (Z)-8-nitrotridec-3-en-7-ol

Conditions	Yield
With sodium hydroxide; cetyltrimethylammonium chloride for 3h; Ambient temperature;	95%

(Z)-4-heptenal (6728-31-0) + allylmagnesium bromide (1730-25-2) → (7Z)-1,7-decadien-4-ol (670227-73-3)

Conditions	Yield
In diethyl ether at 0 - 20℃; for 0.583333h;	95%

(Z)-4-heptenal (6728-31-0) + allyltributylstanane (24850-33-7) → (7Z)-1,7-decadien-4-ol (670227-73-3)

Conditions	Yield
With cerium(III) chloride; sodium iodide In acetonitrile at 20℃; for 25.5h;	93%

(Z)-4-heptenal (6728-31-0) + methyl (triphenylphosphoranylidene)acetate (21204-67-1) → Methyl-6Z,2E-nonadienoat (41654-18-6)

Conditions	Yield
In dichloromethane at 40℃;	93%

(Z)-4-heptenal (6728-31-0) + vinyl magnesium bromide (1826-67-1) + methyl chloroformate (79-22-1) → (Z)-methyl nona-1,6-dien-3-yl carbonate

Conditions	Yield
Stage #1: (Z)-4-heptenal; vinyl magnesium bromide In tetrahydrofuran; diethyl ether at 0℃; for 0.5h; Inert atmosphere; Stage #2: methyl chloroformate In tetrahydrofuran; diethyl ether at 20℃; for 2h; Inert atmosphere;	92%

(Z)-4-heptenal (6728-31-0) + allyldimethylphenylsilane (18001-18-8) → 3-dimethylphenylsilyl-deca-1,7-dien-4-ol

Conditions	Yield
Stage #1: allyldimethylphenylsilane With n-butyllithium In tetrahydrofuran; hexane at 20℃; for 0.25h; Stage #2: With triisopropoxytitanium(IV) chloride In tetrahydrofuran; hexane at -78℃; for 0.333333h; Stage #3: (Z)-4-heptenal In tetrahydrofuran; hexane at -78℃; for 1.5h; Further stages.;	88%

Nitroethane (79-24-3) + (Z)-4-heptenal (6728-31-0) → (Z)-2-Nitro-non-6-en-3-ol (138668-11-8, 138668-22-1)

Conditions	Yield
With Amberlyst A-21 for 6h;	87%

trimethylsilyl cyanide (7677-24-9) + (Z)-4-heptenal (6728-31-0) → (Z)-1-aminooct-5-en-2-ol

Conditions	Yield
Stage #1: trimethylsilyl cyanide; (Z)-4-heptenal With potassium cyanide; 18-crown-6 ether In dichloromethane at 25℃; for 3h; Stage #2: With lithium aluminium tetrahydride In diethyl ether at 25℃; for 7h;	86%

(Z)-4-heptenal (6728-31-0) + (2R,3R)-3-Hydroxy-4-(4-methoxy-phenoxy)-2-methyl-butyric acid (779356-69-3) → (5R,6R)-2-((Z)-Hex-3-enyl)-6-(4-methoxy-phenoxymethyl)-5-methyl-[1,3]dioxan-4-one

Conditions	Yield
Stage #1: (2R,3R)-3-Hydroxy-4-(4-methoxy-phenoxy)-2-methyl-butyric acid With 1,1,1,3,3,3-hexamethyl-disilazane In dichloromethane at 35℃; for 18h; Stage #2: (Z)-4-heptenal With 2,6-di-tert-butyl-4-methylpyridine; trimethylsilyl trifluoromethanesulfonate In dichloromethane at -78℃; for 0.5h; Stage #3: With trifluorormethanesulfonic acid In dichloromethane	86%

(Z)-4-heptenal (6728-31-0) + (2R,3R)-3-Hydroxy-4-(4-methoxy-phenoxy)-2-methyl-butyric acid (779356-69-3) → C19H26O5 (779356-70-6) + C19H26O5

Conditions	Yield
Stage #1: (2R,3R)-3-Hydroxy-4-(4-methoxy-phenoxy)-2-methyl-butyric acid With 1,1,1,3,3,3-hexamethyl-disilazane In dichloromethane at 20 - 35℃; for 18h; Inert atmosphere; Stage #2: (Z)-4-heptenal With 2,6-di-tert-butyl-4-methylpyridine; trimethylsilyl trifluoromethanesulfonate In dichloromethane at -78℃; for 0.5h; Inert atmosphere; optical yield given as %de;	A 86% B n/a

(Z)-4-heptenal (6728-31-0) + methyl 2-cyanoacetate (105-34-0) → methyl (Z)-2-amino-5-(pent-2-en-1-yl)thiophene-3-carboxylate

Conditions	Yield
With sulfur; triethylamine for 12h; Gewald Aminoheterocycles Synthesis; Reflux; Inert atmosphere;	86%

(Z)-4-heptenal (6728-31-0) + acetylenemagnesium bromide (4301-14-8) → (Z)-non-6-en-1-yn-3-ol

Conditions	Yield
In tetrahydrofuran at 0℃; for 5h;	86%

(Z)-4-heptenal (6728-31-0) + 1-phenylsulfonyl-2-propanone (5000-44-2) → (7Z)-4-hydroxy-1-phenylsulfonyl-7-decen-2-one (797752-54-6)

Conditions	Yield
Stage #1: 1-phenylsulfonyl-2-propanone With N,N,N,N,N,N-hexamethylphosphoric triamide; lithium diisopropyl amide In tetrahydrofuran; hexane at 0℃; for 4h; Stage #2: (Z)-4-heptenal In tetrahydrofuran; hexane at 0 - 20℃; Further stages.;	85%

(Z)-4-heptenal (6728-31-0) → (R,Z)-hept-4-ene-1,2-diol (1214888-17-1)

Conditions	Yield
Stage #1: (Z)-4-heptenal With Nitrosobenzene; L-proline In chloroform at 0℃; for 2h; Stage #2: With sodium tetrahydroborate In ethanol; chloroform at 0℃; for 2h; Stage #3: With acetic acid; zinc In ethanol at 20℃; for 16h;	84%

(Z)-4-heptenal (6728-31-0) → (Z)-4-hepten-1-ol (6191-71-5)

Conditions	Yield
With sodium tetrahydroborate In methanol at 0℃; for 0.5h;	84%

1-benzofurane (271-89-6) + (Z)-4-heptenal (6728-31-0) → (Z)-1-(benzofuran-2-yl)hept-4-en-1-ol

Conditions	Yield
Stage #1: 1-benzofurane With n-butyllithium In diethyl ether; hexane at -78 - 20℃; for 3.75h; Inert atmosphere; Stage #2: (Z)-4-heptenal In diethyl ether; hexane at -78℃; for 1.5h; Inert atmosphere;	84%

(Z)-4-heptenal (6728-31-0) + 2-(but-3-en-2-yl)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-ol → (S,8Z)-undeca-2,8-dien-5-ol

Conditions	Yield
With (R)-10-camphorsulfonic acid In dichloromethane at 25℃; for 96h;	83%

(Z)-4-heptenal (6728-31-0) + methylmagnesium bromide (75-16-1)

Conditions	Yield
Stage #1: (Z)-4-heptenal; methylmagnesium bromide In tetrahydrofuran; toluene at -78 - 20℃; Stage #2: With water; ammonium chloride In tetrahydrofuran; toluene	83%

(Z)-4-heptenal (6728-31-0) + 4-flourophenylmagnesium bromide (352-13-6) → (Z)-1-(4-fluorophenyl)hept-4-en-1-ol

Conditions	Yield
In tetrahydrofuran; diethyl ether at 0 - 20℃; for 1h;	83%

cyclohexenone (930-68-7) + (Z)-4-heptenal (6728-31-0) → 2-((R,Z)-1-hydroxyhept-4-enyl)cyclohex-2-enone

Conditions	Yield
Stage #1: cyclohexenone; (R)-1-(3,5-bis(trifluoromethyl)phenyl)-3-(1-(2-(dimethylamino)naphthalen-1-yl)naphthalen-2-yl)thiourea In acetonitrile at 0℃; for 0.166667h; Baylis-Hillman Reaction; Stage #2: (Z)-4-heptenal In acetonitrile for 72h; Product distribution / selectivity;	82%

(Z)-4-heptenal (6728-31-0) + eschenmoser's salt (33797-51-2) → (Z)-2-methylenehept-4-enal

Conditions	Yield
With triethylamine In dichloromethane at 20℃; for 15h;	80%

Upstream product

• 21891-36-1 hept-4-ynal 
• 5009-31-4 (Z)-1-Bromohex-3-ene 
• 39924-27-1 (Z)-4-Heptensaeure-ethylester 
• 98442-19-4 ethyl hept-4-yn-1-oate 
• 98442-18-3 ethyl 2-carbethoxy-hept-4-yn-1-oate 
• 6261-22-9 pent-2-yn-1-ol 
• 42397-24-0 hept-4-yn-1-ol 
• 16400-32-1 1-bromo-pent-2-yne 
• 530086-82-9 (Z)-2-(hept-4-en-1-yloxy)tetrahydro-2H-pyran 
• 6191-71-5 (Z)-4-hepten-1-ol 
• 201230-82-2 carbon monoxide 
• 928-96-1 (Z)-3-Hexen-1-ol 
• 36872-14-7 2-hex-3-enyl-4,4,6-trimethyl-[1,3]oxazinane 
• 18492-65-4 7,7-diethoxy-hept-3c-ene 

Downstream Products

• 138668-12-9 (2E,6Z)-2-nitro-2,6-nonadiene 
• 151322-33-7 1-phenyl-cis-4-hepten-1-ol 
• 557-48-2 2E,6Z-nonadienal 
• 67019-89-0 2,6-nonadiene nitrile 
• 1208882-46-5 N-((2R,3R)-2-hydroxy-3-((Z)-pent-2-enyl)-2,3-dihydrobenzofuran-5-yl)-4-methylbenzenesulfonamide 
• 925210-21-5 (+/-)-(Z)-benzyl 2-(tetrahydro-2H-pyran-2-yloxy)oct-5-enylcarbamate 
• 925210-20-4 (+/-)-(Z)-4-methyl-N-(2-(tetrahydro-2H-pyran-2-yloxy)oct-5-enyl)benzenesulfonamide 

Relevant articles and documents

Synthesis method of aggregation pheromone (E)-cis-6, 7-epoxy-2-nonenal of Aromia bungii

The invention relates to a synthesis method of aggregation pheromone (E)-cis-6, 7-epoxy-2-nonenal of Aromia bungii, which belongs to the field of pharmaceutical synthesis. The synthesis method comprises the following steps: taking 1, 4-butanediol as a raw material, singly protecting diol with DHP (dihexylphthalate) and then oxidizing TEMPO (tetramethylpiperidine oxide) into 4-((tetrahydro-2H-pyran-2-base) oxy) butyraldehyde; performing a Wittig reaction, so as to obtain (Z)-2-(hepta-4- alkene-1-base-oxy) tetrahydro-2H-pyran; removing the protection of the DHP and oxidizing TEMPO, so as to obtain (Z)-4-heptenal; performing a Wittig reaction, so as to obtain (2E, 6Z)-nona-2, 6-heptadienal; finally, performing epoxidation, so as to obtain the aggregation pheromone (E)-cis-6, 7-epoxy-2-nonenalof the Aromia bungii. The total yield is 6.5%. In the synthesis method, the 1, 4-butanediol with low cost is taken as the starting raw material; the synthesis method has the advantages of being simple in operation and mild in conditions, therefore, the synthesis method is suitable for large-scale preparation.

A study of 1,5-hydrogen shift and cyclization reactions of an alkali isomerized methyl linolenoate

Heating a mixture formed by alkali isomerization of methyl linolenoate (1) produces a complex mixture with the bicyclic hexahydroindenoic esters 4β-(7-methoxycarbonylheptyl)-5α-methyl-2,3,3aα,4,5, 7aαhexahydroindene (CL5) and 4β-ethyl-5α-(6-methoxycarbonylhexyl)-2,3,3aα,4,5, 7aα-hexahydroindene (CL6) as main components. Similar isomerization reactions of three synthetic model compounds, methyl 9Z,13E,15Z-octadecatrienoate (2), 9Z,14E,16E-octadecatrienoate (4) and 9Z,11E,15Z-octadecatrienoate (5) corroborated the results obtained with alkali isomerized methyl linolenoate.

A New Synthesis of Nona-2E,6Z-dienal

Monosodio ethyl malonate on alkylation with 1-bromo-pent-2-yne (III) furnishes the diester (IV) which on decarbethoxylation with NaCl/DMSO, followed by LAH/EtOH reduction of the resultant ester (V), yields the carbinol (VI).Hydrogenation of VI in the presence of Lindlar's catalyst produces hept-4Z-en-1-ol (VII), which on pyridinium chlorochromate oxidation gives the aldehyde (VIII).Wittig-Horner reaction on VIII using ethyl diethylphosphonoacetate produces the dienoate (IX), which on LAH/EtOH reduction followed by oxidation with Corey's reagent, affords the title compound(I).