406-87-1

Basic information

• Product Name: 4,4,4-TRIFLUOROBUTYRALDEHYDE
• Synonyms: 4,4,4-TRIFLUOROBUTANAL;4,4,4-TRIFLUOROBUTYRALDEHYDE;4,4,4-Trifluorobutyraldehyde 95%;4,4,4-Trifluorobutyraldehyde95%;4,4,4-Trifluorobutyraldehyde, tech.;4,4,4-Trifluorobutanal 95%;5,5,5-trifluoropentanal;4,4,4-Trifluorobutyraldehyde, 4,4,4-Trifluorobutaldehyde
• CAS NO: 406-87-1
• Molecular Formula: C₄H₅F₃O
• Molecular Weight: 126.08
• Mol File: 406-87-1.mol
• Article Data: 22

Chemical Properties

• Boiling Point: 94-97°C
• Flash Point: -3.606 °C
• Appearance: /
• Density: 1,2 g/cm3
• Vapor Pressure: 2.25mmHg at 25°C
• Refractive Index: 1.3387 (589.3 nm 25℃)
• CAS DataBase Reference: 4,4,4-TRIFLUOROBUTYRALDEHYDE(CAS DataBase Reference)
• NIST Chemistry Reference: 4,4,4-TRIFLUOROBUTYRALDEHYDE(406-87-1)
• EPA Substance Registry System: 4,4,4-TRIFLUOROBUTYRALDEHYDE(406-87-1)

Safety Data

• Hazard Codes: F,Xi,Xn
• Statements: 36/37/38-51-36-22
• Safety Statements: 26-36
• HazardClass: IRRITANT, FLAMMABLE
• Hazardous Substances Data: 406-87-1(Hazardous Substances Data)

Usage

Synthesis Reference(s)

The Journal of Organic Chemistry, 49, p. 336, 1984 DOI: 10.1021/jo00176a023

InChI:InChI=1/C4H5F3O2/c5-4(6,7)2-1-3(8)9/h1-2H2,(H,8,9)

Synthetic route

1,1,1-trifluoropropylene (677-21-4) + carbon monoxide (201230-82-2) → 4,4,4-trifluorobutanal (406-87-1) + 3,3,3-trifluoro-2-methylpropionaldehyde (58928-28-2)

Conditions	Yield
With hydrogen; carbonylhydridetris(triphenylphosphine)rhodium(I) In toluene at 80℃; for 15h; in an autoclave;	A 2.6% B 90%
Stage #1: carbon monoxide With hydroxo(1,5-cyclooctadiene)rhodium (I) dimer; hydrogen; 4,5-bis(diphenylphos4,5-bis(diphenylphosphino)-9,9-dimethylxanthenephino)-9,9-dimethylxanthene In N,N-dimethyl-formamide at 80℃; under 190.013 - 570.038 Torr; for 1h; Stage #2: 1,1,1-trifluoropropylene In N,N-dimethyl-formamide at 80℃; for 15h; Solvent; Reagent/catalyst; Pressure; Temperature;	A 89% B 1.2%
With hydrogen; dicobalt octacarbonyl 1.) toluene, room temperature, 130 atm, 2.) 100 deg C, 20 h; Yield given. Multistep reaction. Yields of byproduct given;

1,1,1-trifluoropropylene (677-21-4) + carbon monoxide (201230-82-2) → 4,4,4-trifluorobutanal (406-87-1)

Conditions	Yield
Stage #1: carbon monoxide With hydroxo(1,5-cyclooctadiene)rhodium (I) dimer; hydrogen; 4,5-bis(diphenylphos4,5-bis(diphenylphosphino)-9,9-dimethylxanthenephino)-9,9-dimethylxanthene In N,N-dimethyl-formamide at 100℃; under 380.026 Torr; for 1h; Stage #2: 1,1,1-trifluoropropylene In N,N-dimethyl-formamide at 100℃; under 190.013 - 570.038 Torr; for 18h;	92%
With dichloro( 1,5-cyclooctadiene)platinum(ll); hydrogen; 4,5-bis(diphenylphos4,5-bis(diphenylphosphino)-9,9-dimethylxanthenephino)-9,9-dimethylxanthene; tin(ll) chloride In toluene at 80℃; under 72007.2 Torr; for 48h; Inert atmosphere; Autoclave; Schlenk technique; regioselective reaction;

3-bromo-1,1,1-trifluoropropane (460-32-2) + N,N-dimethyl-formamide (68-12-2, 33513-42-7) → 4,4,4-trifluorobutanal (406-87-1)

Conditions	Yield
With lithium In 2-methyltetrahydrofuran at -15 - -10℃; for 1h; Inert atmosphere;	84.8%
Stage #1: 3-bromo-1,1,1-trifluoropropane With iodine; magnesium In 2-methyltetrahydrofuran at 45 - 68℃; for 3h; Inert atmosphere; Stage #2: N,N-dimethyl-formamide In 2-methyltetrahydrofuran at -25 - -20℃; for 1h; Temperature; Solvent; Inert atmosphere;	71.4%

4,4,4-trifluorobutanol (461-18-7) → 4,4,4-trifluorobutanal (406-87-1)

Conditions	Yield
With pyridinium chlorochromate In dichloromethane for 2h; Ambient temperature;	15%
With potassium dichromate; sulfuric acid
With sodium hypochlorite; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; sodium hydrogencarbonate; potassium bromide In dichloromethane; water at -8 - 0℃; pH=8.5;

1,1,1-trifluoro-3-iodopropane (460-37-7) + N,N-dimethyl-formamide (68-12-2, 33513-42-7) → 4,4,4-trifluorobutanal (406-87-1)

Conditions	Yield
Stage #1: 1,1,1-trifluoro-3-iodopropane With magnesium In tetrahydrofuran at 35 - 65℃; for 2h; Inert atmosphere; Stage #2: N,N-dimethyl-formamide In 2-methyltetrahydrofuran at -25 - -20℃; for 1h; Inert atmosphere;	78%

3-chloro-1,1,1-trifluoropropane (460-35-5) + N,N-dimethyl-formamide (68-12-2, 33513-42-7) → 4,4,4-trifluorobutanal (406-87-1)

Conditions	Yield
Stage #1: 3-chloro-1,1,1-trifluoropropane With magnesium In tetrahydrofuran; ethylene dibromide at 50 - 65℃; for 3h; Inert atmosphere; Stage #2: N,N-dimethyl-formamide In tetrahydrofuran at -20 - -15℃; for 1h; Inert atmosphere;	70.8%

1,1,1-trifluoropropylene (677-21-4) + carbon monoxide (201230-82-2) → 4,4,4-trifluorobutanal (406-87-1) + 1,1,1-trifluoropropane (421-07-8) + 3,3,3-trifluoro-2-methylpropionaldehyde (58928-28-2)

Conditions	Yield
With hydrogen; hexarhodium hexadecacarbonyl; triphenylphosphine In toluene at 110℃; under 83600.1 Torr; for 22h; Product distribution; other platinum, cobalt, ruthenium catalyst;
With hydrogen; hexarhodium hexadecacarbonyl; triphenylphosphine 1.) toluene, room temperature, 110 atm, 2.) 80 deg C, 22 h; Yield given. Multistep reaction. Yields of byproduct given;
With hydrogen; dodecacarbonyl-triangulo-triruthenium In toluene at 100℃; for 16h; Product distribution; Mechanism; in an autoclave; hydrofomylation with other ruthenium, rhodium, cobalt, and platinum catalysts; effect of reaction temperature and CO pressure; investigation of various (perfluoroalkyl)ethenes;	A n/a B 38 % Chromat. C n/a
Stage #1: carbon monoxide With [Rh(OH)(cod)]2; hydrogen; 4,5-bis(diphenylphos4,5-bis(diphenylphosphino)-9,9-dimethylxanthenephino)-9,9-dimethylxanthene In N,N-dimethyl-formamide at 80℃; under 760.051 Torr; for 1h; Stage #2: 1,1,1-trifluoropropylene In N,N-dimethyl-formamide at 80℃; for 15h; Solvent; Temperature; Time; Concentration;

ethyl 4,4,4-trifluorobutanoate (371-26-6) → 4,4,4-trifluorobutanal (406-87-1)

Conditions	Yield
With hydrogenchloride In dichloromethane

1,1,1-trifluoropropylene (677-21-4) + carbon monoxide (201230-82-2) → 4,4,4-trifluorobutanal (406-87-1) + (R)-trifluoromethylpropanal + (S)-2-trifluoromethylpropanal

Conditions	Yield
With acetylacetonatodicarbonylrhodium(l); hydrogen; (R,S)-binaphos In benzene at 35℃; under 76000 Torr; for 42h; Yield given. Yields of byproduct given. Title compound not separated from byproducts;
With acetylacetonatodicarbonylrhodium(l); hydrogen; (R,S)-binaphos In benzene at 35℃; under 76000 Torr; for 46h; Yield given. Yields of byproduct given. Title compound not separated from byproducts;
With polymer-supported (R,S)-BINAPHOS-Rh(acac); hydrogen In benzene at 60℃; under 7600 Torr; Product distribution; Further Variations:; Reagents; Hydroformylation;
With hydrogen In benzene at 40℃; under 60800 Torr; for 18h; Hydroformylation;
With hydrogen; Rh(I)-(R,S)-BINAPHOS under 38000 Torr; for 0.5h; Title compound not separated from byproducts;

oxalyl dichloride (79-37-8) + 4,4,4-trifluorobutanol (461-18-7) → 4,4,4-trifluorobutanal (406-87-1)

Conditions	Yield
With triethylamine In dichloromethane; dimethyl sulfoxide

2-(2,2,2-Trifluoro-ethylazo)-prop-2-yl-hydroperoxide (87841-75-6) + ethyl vinyl ether → 4,4,4-trifluorobutanal (406-87-1)

Conditions	Yield
at 50℃;	70%

3,3,3-trifluoropropyl magnesium chloride (461-21-2) + orthoformic acid triethyl ester (122-51-0) → 4,4,4-trifluorobutanal (406-87-1)

Conditions	Yield
With diethyl ether beim Behandeln der Reaktionsloesung mit wss.Salzsaeure;

4,4,4-trifluorobutene (1524-26-1) → 4,4,4-trifluorobutanal (406-87-1) + 4,4,4-trifluorobutan-2-one (2366-70-3)

Conditions	Yield
With tetrafluoroboric acid; palladium diacetate; p-benzoquinone In water; acetonitrile at 40℃; for 16h; Wacker Oxidation; regioselective reaction;

allyl alcohol (107-18-6) + trifluoroacetic acid (76-05-1) → 4,4,4-trifluorobutanal (406-87-1)

Conditions	Yield
With sulfuric acid; sodium acetate 1.) MeOH, electrolyis, 2.) H2O, reflux; Yield given. Multistep reaction;

Upstream product

• 461-18-7 4,4,4-trifluorobutanol 
• 677-21-4 1,1,1-trifluoropropylene 
• 201230-82-2 carbon monoxide 
• 107-18-6 allyl alcohol 
• 76-05-1 trifluoroacetic acid 
• 79-37-8 oxalyl dichloride 
• 371-26-6 ethyl 4,4,4-trifluorobutanoate 
• 460-37-7 1,1,1-trifluoro-3-iodopropane 
• 68-12-2 N,N-dimethyl-formamide 
• 460-32-2 3-bromo-1,1,1-trifluoropropane 
• 460-35-5 3-chloro-1,1,1-trifluoropropane 
• 1524-26-1 4,4,4-trifluorobutene 
• 87841-75-6 2-(2,2,2-Trifluoro-ethylazo)-prop-2-yl-hydroperoxide 
• 109-92-2 ethyl vinyl ether 

Downstream Products

• 2365-80-2 2-amino-5,5,5-trifluoropentanoic acid 
• 1160360-44-0 5-((3,4-dichlorobenzyl)(4,4,4-trifluorobutyl)amino)-1-methyl-3-propyl-1H-pyrazolo[4,3-d]pyrimidin-7(6H)-one 
• 64-18-6 formic acid 
• 2240-88-2 3,3,3-Trifluoropropanol 
• 460-40-2 3,3,3-trifluoropropanal 
• 122489-79-6 2-phenyl-4-(4,4,4-trifluorobutylidene)-5-oxazolone 
• 122519-46-4 2-phenyl-4-(4,4,4-trifluorobutylidene)-5-oxazolone 
• 1292321-31-3 C₃₀H₃₉F₅N₂O₂ 
• 1146699-59-3 5,5,5-trifluoro-2-(R-1-phenylethylamino)pentanenitrile 
• 1239671-53-4 1-(4'-methoxylphenyl)-4,4,4-trifluorobutan-1-one 
• 1038996-15-4 C₂₄H₃₁F₆NO₂Si 
• 1011481-34-7 methyl {(2S,4R)-1-[(1S)-4,4-dimethyl-1-(3,3,3-trifluoropropyl)pent-2-yn-1-yl]-2-[4-(trifluoromethyl)phenyl]piperidin-4-yl}acetate 
• 1036705-67-5 4-[4-(4-fluoro-3-methylphenylamino)pyrimidin-2-ylamino]-N-methyl-N-[1-(4,4,4-trifluorobutyl)piperidin-3-yl]benzamide 
• 690-95-9 4,4,4-trifluorobutanenitrile 

Relevant articles and documents

Electrochemical Synthesis of 4,4,4-Trifluorobutanal

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Highly selective hydroformylation of 3,3,3-trifluoropropene to 4,4,4-trifluorobutanal using Rh/Xantphos catalyst

Synthesis of 4,4,4-trifluorobutanal by Rh-catalyzed hydroformylation of 3,3,3-trifluoropropene with bis(4,5-diphenylphosphino)xanthene as a ligand was investigated. The uses of [Rh(OH)(cod)]2 (cod = 1,5-cyclooctadinene) and dimethylformamide in CO/H2 = 75/25 mixed gas under atmospheric pressure at 80 C for 15 h provided the highest aldehyde yield 90%. The molar ratio of linear aldehyde (4,4,4-trifluorobutanal) to branched aldehyde (3,3,3-trifluoro-2-methylpropanal) was 99/1. The successive addition of dimethylformamide solution of 3,3,3-trifluoropropene under atmospheric pressure revealed that 4,4,4-trifluorobutanal formation increased linearly with the reaction time and the total turnover number reached 500 after 10 h retaining 99% selectivity of 4,4,4-trifluorobutanal at 80 C.

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