4411-89-6

Basic information

• Product Name: 2-PHENYL-2-BUTENAL
• Synonyms: (2Z)-2-Phenyl-2-butenal;.alpha.-ethylidenebenzeneacetaldehyde;2-Phenylcronaldehyde;2-Phenyl-2-butenal, mixture of cis and trans ;.alpha.-ethylidene-Benzeneacetaldehyde;2-Butenal, 2-phenyl;2-Phenylacetaldehyde, alpha-ethylidene;2-phenylbut-2-enal
• CAS NO: 4411-89-6
• Molecular Formula: C₁₀H₁₀O
• Molecular Weight: 146.19
• EINECS: 224-567-0
• Product Categories: Alphabetical Listings;Flavors and Fragrances;O-P
• Mol File: 4411-89-6.mol
• Article Data: 26

Chemical Properties

• Boiling Point: 177 °C15 mm Hg(lit.)
• Flash Point: 222 °F
• Appearance: /
• Density: 1.034 g/mL at 25 °C(lit.)
• Vapor Pressure: 0.00639mmHg at 25°C
• Refractive Index: n20/D 1.561(lit.)
• Water Solubility: Soluble in oil and ethanol. Insoluble in water.
• Sensitive: Air Sensitive
• CAS DataBase Reference: 2-PHENYL-2-BUTENAL(CAS DataBase Reference)
• NIST Chemistry Reference: 2-PHENYL-2-BUTENAL(4411-89-6)
• EPA Substance Registry System: 2-PHENYL-2-BUTENAL(4411-89-6)

Safety Data

• Hazard Codes: Xi
• Statements: 36/37/38
• Safety Statements: 26-36
• WGK Germany: 3
• TSCA: Yes
• Hazardous Substances Data: 4411-89-6(Hazardous Substances Data)

Usage

Chemical Properties

2-Phenyl-2-butenal has a green, floral, woody aroma

Occurrence

Reported as the odorous component in black tea and Phallus impudicus. Also reported found in cocoa, roasted hazelnut, asparagus, coffee, cocoa, microbial fermented tea, roasted filbert, American potato chips, soybean, rice bran, malt, katsuobishi (dried bonito), okra, roasted macadamia nut and roasted sesame seeds.

Uses

2-Phenyl-2-butenal can be used to compare acrylamide and furan concentrations, antioxidant activities, and volatility profiles in cold or hot coffees.

Preparation

From acetaldehyde and phenyl acetaldehyde.

Taste threshold values

Taste characteristics at 10 ppm: green, vegetative, floral, cocoa and nutty.

InChI:InChI=1/C10H10O/c1-2-9(8-11)10-6-4-3-5-7-10/h2-8H,1H3/b9-2-

Synthetic route

α-naphthol (90-15-3) + 4-phenyl-4-vinyl-1,3-dioxolan -2-one (1459246-62-8) → (E/Z)-2-phenylcrotonaldehyde (4411-89-6)

Conditions	Yield
With bis(η3-allyl-μ-chloropalladium(II)) In toluene at 90℃; for 12h; Inert atmosphere; Schlenk technique; regioselective reaction;	95%

1-Phenylprop-1-yne (673-32-5) + carbon monoxide (201230-82-2) → (E/Z)-2-phenylcrotonaldehyde (4411-89-6) + α-methyl-trans-cinnamaldehyde (15174-47-7)

Conditions	Yield
With hydrogen; palladium diacetate; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene; palladium(II) iodide In toluene at 70℃; under 75007.5 Torr; for 18h; Catalytic behavior; Reagent/catalyst; Autoclave;	A n/a B 83%

1-methoxy-1,3-diethoxy-2-phenylbutane (113446-25-6) → (E/Z)-2-phenylcrotonaldehyde (4411-89-6)

Conditions	Yield
With hydrogenchloride at 70 - 90℃; for 1h;	77.8%

4-phenyl-4-vinyl-1,3-dioxolan -2-one (1459246-62-8) → (E/Z)-2-phenylcrotonaldehyde (4411-89-6) + (Z)-6-hydroxy-2,5-diphenyl-2-vinylhex-4-enal

Conditions	Yield
With [1,2-bis-(phenylsulfinyl)ethane]palladium(II) acetate; bis[2-(diphenylphosphino)phenyl] ether In N,N-dimethyl-formamide at 20℃; for 12h; Catalytic behavior; Reagent/catalyst; Solvent; Inert atmosphere; Schlenk technique;	A n/a B 75%

2-phenyl-2-vinyloxirane (97699-36-0) → (E/Z)-2-phenylcrotonaldehyde (4411-89-6) + 4-chloro-2-phenylbut-2-enal

Conditions	Yield
With copper(II) choride dihydrate; lithium chloride In ethyl acetate for 1.5h;	A 8% B 59%

2-phenyl-2-vinyloxirane (97699-36-0) → (E)-4-chloro-2-phenylbut-2-enal + (E/Z)-2-phenylcrotonaldehyde (4411-89-6)

Conditions	Yield
With copper(II) choride dihydrate; lithium chloride In ethyl acetate for 1.5h; Reflux; Inert atmosphere;	A 59% B 8%

formic acid (64-18-6) + 1-phenyl-3-butene-1,2-diol (19261-14-4) → (E/Z)-2-phenylcrotonaldehyde (4411-89-6)

Conditions	Yield
optically inactive 1-phenyl-butene-(3)-diol-(1.2) of mp: 43 degree;

buta-1,3-dien-1-ylbenzene (1515-78-2) → (E/Z)-2-phenylcrotonaldehyde (4411-89-6)

Conditions	Yield
With diethyl ether; iodine; mercury(II) oxide anschliessend Behandeln mit AgNO3-Loesung;

2-amino-1-phenyl-but-3-en-1-ol (174309-35-4) → (E/Z)-2-phenylcrotonaldehyde (4411-89-6)

Conditions	Yield
With acetic acid; sodium nitrite at 0℃;

phenylacetaldehyde (122-78-1) + acetaldehyde (75-07-0) → (E/Z)-2-phenylcrotonaldehyde (4411-89-6)

Conditions	Yield
With ethanol; sodium acetate at 110℃;

2-phenyl-2-vinyloxirane (97699-36-0) + phenol (108-95-2) → (E/Z)-2-phenylcrotonaldehyde (4411-89-6) + 1-Phenoxy-2-phenyl-but-3-en-2-ol (99321-81-0) + 4-phenoxy-2-phenylbut-2-en-1-ol (99321-88-7) + 4-phenoxy-2-phenylbut-2-en-1-ol (99321-88-7, 99321-89-8) + 2-((E)-4-Hydroxy-3-phenyl-but-2-enyl)-phenol (99321-94-5) + 2-((E)-4-Hydroxy-3-phenyl-but-2-enyl)-phenol (99321-94-5, 99321-95-6)

Conditions	Yield
With sodium In 1,4-dioxane at 120℃; Product distribution;

2-phenyl-3-vinyloxirane (20248-57-1) + kieselguhr → (E/Z)-2-phenylcrotonaldehyde (4411-89-6)

Conditions	Yield
at 250℃; under 16 Torr;

2-phenyl-3-vinyloxirane (20248-57-1) + magnesium bromide ether adduct → (E/Z)-2-phenylcrotonaldehyde (4411-89-6)

Conditions	Yield
at 110℃;

1.2-epoxy-1-phenyl-butene-(3) → (E/Z)-2-phenylcrotonaldehyde (4411-89-6)

Conditions	Yield
With magnesium bromide ethyl etherate at 110 - 115℃;
With kieselguhr at 250℃; under 16 Torr;

1-phenyl-butene-(3)-diol-(1.2) → (E/Z)-2-phenylcrotonaldehyde (4411-89-6)

Conditions	Yield
With formic acid
With sulfuric acid

sulfuric acid (7664-93-9) + 1-phenyl-3-butene-1,2-diol (19261-14-4) → (E/Z)-2-phenylcrotonaldehyde (4411-89-6) + compound C20H20O2

Conditions	Yield
optically inactive 1-phenyl-butene-(3)-diol-(1.2) of mp: 43 degree;

2-amino-1-phenyl-but-3-en-1-ol (174309-35-4) + acetic acid (64-19-7) + sodium nitrite → (E/Z)-2-phenylcrotonaldehyde (4411-89-6)

Conditions	Yield
at 0℃;

1-(2-methoxyvinyl)benzene (4747-15-3) → (E/Z)-2-phenylcrotonaldehyde (4411-89-6)

Conditions	Yield
Multi-step reaction with 2 steps 1: 78 percent / zinc chloride / ethyl acetate 2: 77.8 percent / 18percent aq. HCl / 1 h / 70 - 90 °C View Scheme

4-phenyl-4-vinyl-1,3-dioxolan -2-one (1459246-62-8) → (E/Z)-2-phenylcrotonaldehyde (4411-89-6)

Conditions	Yield
With titanium(IV) isopropylate; tris(dibenzylideneacetone)dipalladium(0) chloroform complex; o-phenylenebis(diphenylphosphine) In toluene at 24℃; for 18h; Glovebox; Inert atmosphere;	> 95 %Spectr.
With dichloro(1,5-cyclooctadiene)palladium(II); silver trifluoromethanesulfonate; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene In dichloromethane at 80℃; for 2h;

Allyl acetate (591-87-7) + 4-phenyl-4-vinyl-1,3-dioxolan -2-one (1459246-62-8) → (E/Z)-2-phenylcrotonaldehyde (4411-89-6) + C13H14O

Conditions	Yield
With bis(tri-t-butylphosphine)palladium(0); bis[2-(diphenylphosphino)phenyl] ether In tetrahydrofuran at 100℃; for 4h; Reagent/catalyst; Temperature; Sealed tube; chemoselective reaction;	A n/a B 76 %Spectr.

Allyl acetate (591-87-7) + 4-phenyl-4-vinyl-1,3-dioxolan -2-one (1459246-62-8) → (E/Z)-2-phenylcrotonaldehyde (4411-89-6) + C13H14O + C20H20O2

Conditions	Yield
With [1,2-bis-(phenylsulfinyl)ethane]palladium(II) acetate; bis[2-(diphenylphosphino)phenyl] ether In tetrahydrofuran at 50℃; for 12h; Sealed tube; chemoselective reaction;	A n/a B 43 %Spectr. C n/a

Allyl acetate (591-87-7) + 4-phenyl-4-vinyl-1,3-dioxolan -2-one (1459246-62-8) → (E/Z)-2-phenylcrotonaldehyde (4411-89-6) + 3-phenyl-4-hydroxy-2-butenyl acetate + C13H14O + C20H20O2

Conditions	Yield
With [1,2-bis-(phenylsulfinyl)ethane]palladium(II) acetate; bis[2-(diphenylphosphino)phenyl] ether In tetrahydrofuran at 20℃; for 12h; Reagent/catalyst; Sealed tube; chemoselective reaction;	A n/a B n/a C 34 %Spectr. D n/a

Allyl acetate (591-87-7) + 4-phenyl-4-vinyl-1,3-dioxolan -2-one (1459246-62-8) → (E/Z)-2-phenylcrotonaldehyde (4411-89-6) + 3-phenyl-4-hydroxy-2-butenyl acetate + C13H14O

Conditions	Yield
With [1,2-bis-(phenylsulfinyl)ethane]palladium(II) acetate; bis[2-(diphenylphosphino)phenyl] ether In tetrahydrofuran at 0℃; for 12h; Sealed tube; chemoselective reaction;	A n/a B n/a C 20 %Spectr.

acetophenone (98-86-2) → (E/Z)-2-phenylcrotonaldehyde (4411-89-6)

Conditions	Yield
Multi-step reaction with 4 steps 1: N-Bromosuccinimide; trimethylsilyl trifluoromethanesulfonate / acetonitrile / 72 h / 20 °C 2: tetrahydrofuran / 2.5 h / -78 °C 3: sodium hydroxide / tetrahydrofuran; water / 3 h / 20 °C 4: copper(II) choride dihydrate; lithium chloride / ethyl acetate / 1.5 h View Scheme
Multi-step reaction with 5 steps 1: bromine / diethyl ether / 0 - 20 °C 2: sodium formate; methanol / Reflux 3: tetrahydrofuran / 0 - 20 °C / Inert atmosphere 4: pyridine / dichloromethane / 0 - 20 °C / Inert atmosphere 5: 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene; dichloro(1,5-cyclooctadiene)palladium(II); silver trifluoromethanesulfonate / dichloromethane / 2 h / 80 °C View Scheme

α-bromoacetophenone (70-11-1) → (E/Z)-2-phenylcrotonaldehyde (4411-89-6)

Conditions	Yield
Multi-step reaction with 3 steps 1: tetrahydrofuran / 2.5 h / -78 °C 2: sodium hydroxide / tetrahydrofuran; water / 3 h / 20 °C 3: copper(II) choride dihydrate; lithium chloride / ethyl acetate / 1.5 h View Scheme
Multi-step reaction with 4 steps 1: sodium formate; methanol / Reflux 2: tetrahydrofuran / 0 - 20 °C / Inert atmosphere 3: pyridine / dichloromethane / 0 - 20 °C / Inert atmosphere 4: 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene; dichloro(1,5-cyclooctadiene)palladium(II); silver trifluoromethanesulfonate / dichloromethane / 2 h / 80 °C View Scheme

1-phenyl-2-hydroxyethanone (582-24-1) → (E/Z)-2-phenylcrotonaldehyde (4411-89-6)

Conditions	Yield
Multi-step reaction with 3 steps 1: tetrahydrofuran / 0 - 20 °C / Inert atmosphere 2: pyridine / dichloromethane / 0 - 20 °C / Inert atmosphere 3: 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene; dichloro(1,5-cyclooctadiene)palladium(II); silver trifluoromethanesulfonate / dichloromethane / 2 h / 80 °C View Scheme

1,2-dihydroxy-2-phenyl-3-butene (1159837-56-5) → (E/Z)-2-phenylcrotonaldehyde (4411-89-6)

Conditions	Yield
Multi-step reaction with 2 steps 1: pyridine / dichloromethane / 0 - 20 °C / Inert atmosphere 2: 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene; dichloro(1,5-cyclooctadiene)palladium(II); silver trifluoromethanesulfonate / dichloromethane / 2 h / 80 °C View Scheme

α-bromoacetophenone (70-11-1) → (E)-4-chloro-2-phenylbut-2-enal + (E/Z)-2-phenylcrotonaldehyde (4411-89-6)

Conditions	Yield
Multi-step reaction with 3 steps 1: tetrahydrofuran / 2.5 h / -78 °C / Inert atmosphere 2: sodium hydroxide / tetrahydrofuran; water / 3 h / 20 °C / Inert atmosphere 3: lithium chloride; copper(II) choride dihydrate / ethyl acetate / 1.5 h / Reflux; Inert atmosphere View Scheme

1-Bromo-2-phenyl-3-buten-2-ol (120609-13-4) → (E)-4-chloro-2-phenylbut-2-enal + (E/Z)-2-phenylcrotonaldehyde (4411-89-6)

Conditions	Yield
Multi-step reaction with 2 steps 1: sodium hydroxide / tetrahydrofuran; water / 3 h / 20 °C / Inert atmosphere 2: lithium chloride; copper(II) choride dihydrate / ethyl acetate / 1.5 h / Reflux; Inert atmosphere View Scheme

N-methylmaleimide (930-88-1) + (E/Z)-2-phenylcrotonaldehyde (4411-89-6) + O-benzyl carbamate (621-84-1) → N-(2-methyl-5-phenyl-1,3-dioxo-2,3,3a,4,7,7a-hexahydro-1H-isoindol-4-yl)-benzyloxycarbonylamine

Conditions	Yield
With toluene-4-sulfonic acid In toluene at 110℃;	98%

(E/Z)-2-phenylcrotonaldehyde (4411-89-6) + acetylenedicarboxylic acid diethyl ester (762-21-0) → biphenyl-3,4-dicarboxylic acid diethyl ester

Conditions	Yield
With acetamide; toluene-4-sulfonic acid In 1-methyl-pyrrolidin-2-one at 120℃; for 24h;	91%

(E/Z)-2-phenylcrotonaldehyde (4411-89-6) + (1-bromovinyl)triisopropylsilane (1352211-40-5) → C21H34OSi

Conditions	Yield
Stage #1: (1-bromovinyl)triisopropylsilane With n-butyllithium In tetrahydrofuran at -78℃; for 1h; Stage #2: (E/Z)-2-phenylcrotonaldehyde In tetrahydrofuran at -78℃; for 1h;	90%

(E/Z)-2-phenylcrotonaldehyde (4411-89-6) + lithium dimethylcuprate → 3-methyl-2-phenylbutanal (2439-44-3)

Conditions	Yield
In diethyl ether at -23℃; for 0.25h;	78%

chloro-trimethyl-silane (75-77-4) + (E/Z)-2-phenylcrotonaldehyde (4411-89-6) → 1-trimethylsilyloxy-2-phenyl-1,3-butadiene (107905-17-9)

Conditions	Yield
With triethylamine; zinc(II) chloride at 50℃;	61%

(E/Z)-2-phenylcrotonaldehyde (4411-89-6) + (E)-3,4-dihydronaphthalen-1(2H)-one O-acetyl oxime (28353-74-4) → 4-methyl-3-phenyl-5,6-dihydrobenzo[h]quinoline (1426022-60-7) + 2-methyl-3-phenyl-5,6-dihydrobenzo[h]quinoline (1426022-62-9)

Conditions	Yield
With copper(l) iodide; diisopropylamine In dimethyl sulfoxide at 60℃; for 16h; Inert atmosphere; Schlenk technique; Sealed tube;	A 41% B 13%

(E/Z)-2-phenylcrotonaldehyde (4411-89-6) + (E)-3,4-dihydronaphthalen-1(2H)-one O-acetyl oxime (28353-74-4) → 4-methyl-3-phenyl-5,6-dihydrobenzo[h]quinoline (1426022-60-7)

Conditions	Yield
With copper(l) iodide; pyrrolidinium perchlorate In dimethyl sulfoxide at 60℃; for 16h; Inert atmosphere; Schlenk technique; Sealed tube; regioselective reaction;	36%

4-hydroxy-6-phenyl-2H-pyran-2-one (5526-38-5) + (E/Z)-2-phenylcrotonaldehyde (4411-89-6) → (2RS)-2-methyl-3,7-diphenyl-2H,5H-pyrano[4,3-b]pyran-5-one (1206159-77-4)

Conditions	Yield
With calcium sulfate; 3-amino propanoic acid In isopropyl alcohol at 82℃; for 1h; domino Knoevenagel condensation/electrocyclization; Inert atmosphere;	34%

(E/Z)-2-phenylcrotonaldehyde (4411-89-6) + aniline (62-53-3) → 1,3-diphenyl-1H-pyrrole (53646-85-8)

Conditions	Yield
With iodine In toluene at 20℃; for 8h;	32%

(E/Z)-2-phenylcrotonaldehyde (4411-89-6) + methylmagnesium bromide (75-16-1) → 3-phenyl-4-methyl-3-buten-2-ol (4743-68-4)

Conditions	Yield
With diethyl ether

(E/Z)-2-phenylcrotonaldehyde (4411-89-6) → 2-phenyl-crotonaldehyde-semicarbazone

2-bromoprop-1-ene (557-93-7) + (E/Z)-2-phenylcrotonaldehyde (4411-89-6) → 2-methyl-4-phenyl-hexa-1,4-dien-3-ol (38552-66-8) + 3,4-dimethyl-pent-4-enal (58654-03-8)

Conditions	Yield
(i) Mg, THF, (ii) /BRN= 1856381/, Et2O; Multistep reaction;

(E/Z)-2-phenylcrotonaldehyde (4411-89-6) → <1-Hydroxy-propen-(1)-yl>-benzol-formiat (5551-18-8)

Conditions	Yield
With peracetic acid; diacetyl peroxide; acetic anhydride In acetic acid for 10.5h;

(E/Z)-2-phenylcrotonaldehyde (4411-89-6) + benzyl chloride (100-44-7) → 3,5-Diphenyl-4-hydroxy-penten-(2) (13881-18-0)

Conditions	Yield
(i) Mg, Et2O, (ii) /BRN= 1856381/; Multistep reaction;

ethyl 2-butyl-3-oxooctanoate (96610-59-2) + (E/Z)-2-phenylcrotonaldehyde (4411-89-6) → (E)-2,4-Dibutyl-5-hydroxy-3-oxo-6-phenyl-oct-6-enoic acid ethyl ester

Conditions	Yield
With n-butyllithium; sodium hydride Yield given. Multistep reaction;

propylidenetriphenylphosphorane (16666-78-7) + (E/Z)-2-phenylcrotonaldehyde (4411-89-6) → 3-Phenyl-2,4-heptadien

(E/Z)-2-phenylcrotonaldehyde (4411-89-6) + trimethyl phosphonoacetate (5927-18-4) → Methyl-4-phenyl-2,4-hexadienoat

Conditions	Yield
(i) NaH, (ii) /BRN= 1856381/; Multistep reaction;

(E/Z)-2-phenylcrotonaldehyde (4411-89-6) + 3-phenyl-propenal (104-55-2) → (1,1':4',1''-terphenyl)-2'-carbaldehyde (2928-27-0)

Conditions	Yield
With magnesium oxide at 280℃; under 20 Torr;

(E/Z)-2-phenylcrotonaldehyde (4411-89-6) + 3-(4-methylphenyl)acrylaldehyde (1504-75-2) → 2'-Formyl-4-methyl-p-terphenyl (21235-95-0)

Conditions	Yield
With magnesium oxide at 280℃; under 20 Torr;

Upstream product

• 7664-93-9 sulfuric acid 
• 19261-14-4 1-phenylbut-3-ene-1,2-diol 
• 64-18-6 formic acid 
• 97699-36-0 2-phenyl-2-vinyloxirane 
• 673-32-5 1-Phenylprop-1-yne 
• 201230-82-2 carbon monoxide 
• 591-50-4 iodobenzene 
• 1085339-80-5 2-(buta-1,2-dienyloxy)tetrahydro-2H-pyran 
• 108-86-1 bromobenzene 
• 56895-69-3 3-methyl-2-phenyl-1,1-dichlorocyclopropane 
• 123-73-9 trans-Crotonaldehyde 
• 507233-69-4 triphenyl bismuth ⁽²⁺⁾; dichloride 
• 13141-45-2 (Z)-1,4-diphenylbut-1-ene-3-yne 
• 81505-22-8 (1-Dimethoxymethyl-allyl)-benzene 

Downstream Products

• 4743-68-4 3-phenyl-4-methyl-3-buten-2-ol 
• 188299-19-6 (S,S)-1,3-dimethyl-4,5-diphenylimidazolidin-2-one 
• 107905-17-9 1-trimethylsilyloxy-2-phenyl-1,3-butadiene 
• 13881-18-0 3,5-Diphenyl-4-hydroxy-penten-⁽²⁾ 
• 53783-59-8 (E)-2-phenyl-but-2-en-1-ol 
• 60991-13-1 E,Z,Z-1,5-Diphenyl-1,3,5-heptatrien 
• 60991-15-3 E,E,Z-1,5-Diphenyl-1,3,5-heptatrien 

Relevant articles and documents

Pd-Catalyzed Umpolung of π-Allylpalladium Intermediates: Assembly of All-Carbon α-Vinyl Quaternary Aldehydes through C(sp3)-C(sp3) Coupling

Construction of sterically congested all-carbon quaternary centers represents a formidable challenge in synthetic chemistry. The method described herein provides direct and facile access to a series of structurally diverse and synthetically useful aliphatic aldehydes, bearing an all-carbon α-vinyl quaternary center and a 1,5-diene functionality, through Pd-catalyzed umpolung of vinylethylene carbonates (VECs). The reaction features electrophilic-to-nucleophilic reactivity reversal of the VEC-derived π-allyl-palladium intermediate via an unusual β-hydride elimination process, and the resultant enolate is chemoselectively coupled with allylic acetate to form an α-vinyl aldehyde embedded with an all-carbon quaternary center.

Rhodium-Catalyzed Regioselective Hydroformylation of Alkynes to α,β-Unsaturated Aldehydes Using Formic Acid

A rhodium-catalyzed hydroformylation of alkynes with formic acid was developed. The method provides α,β-unsaturated aldehydes in high yield and E-selectivity without the need to handle toxic CO gas.

Synthetic Strategy for Tetraphenyl-Substituted All-E-Carotenoids with Improved Molecular Properties

The synthetic method of tetraphenyl-substituted all-E-carotenes 1 with improved properties of antioxidant and molecular electronic conductance was developed through the formation of tetraphenyl-substituted all-E-apocarotenedial 4. The synthesis highlighted the preparation of novel subunits containing phenyl substituent(s) with E-configuration starting from the key (E)-4-chloro-2-phenylbut-2-enal (10), utilizing conjugation effect with formyl group or easy recrystallization of sulfone compounds. Sulfone-mediated coupling methods of Julia and modified Julia–Kocienski olefinations utilizing the subunits were demonstrated to produce tetraphenyl-substituted apocarotenedials 4. The major all-E-forms (73–85 % selectivity) were easily purified by SiO2 chromatography and trituration with Et2O due to the presence of the polar formyl groups. The olefination of all-E-apocarotenedials 4 and Wittig salt 5 provided all-E-9,9',13,13'-tetraphenylcarotenes 1.