2136-75-6

Basic information

• Product Name: (FORMYLMETHYLENE)TRIPHENYLPHOSPHORANE
• Synonyms: FORMYLMETHYLENETRIPHENYLPHOSPORANE;Formylmethylenetriphenylphosphorane, 98 %;(Formylmethylene)triphenylphosphorane, 97%, may cont. up to ca 3% water;2-(Triphenylphosphoranylidene)acetaldehyde;2-Oxoethylidenetriphenylphosphorane;Triphenyl(2-oxoethylidene)phosphorane;(Triphenylphosphoranylidene)acetaldehyde,97%;(Triphenylphosphoranylidene)acetaldehydeDISC 10/19/00
• CAS NO: 2136-75-6
• Molecular Formula: C₂₀H₁₇OP
• Molecular Weight: 304.32
• EINECS: 218-375-6
• Product Categories: Wittig Reagents;Synthetic Organic Chemistry;Wittig & Horner-Emmons Reaction;Wittig Reaction
• Mol File: 2136-75-6.mol
• Article Data: 18

Chemical Properties

• Melting Point: 185-188 °C(lit.)
• Boiling Point: 472.618 °C at 760 mmHg
• Flash Point: 239.631 °C
• Appearance: Pink to brown/Fine Crystalline Powder
• Density: 1.162 g/cm³
• Vapor Pressure: 1.2E-08mmHg at 25°C
• Refractive Index: 1.62
• Storage Temp.: Keep Cold
• Solubility: Soluble in Chloroform, Methanol.
• Sensitive: Air Sensitive
• Stability: Stable. Combustible. Incompatible with strong oxidizing agents.
• BRN: 523797
• CAS DataBase Reference: (FORMYLMETHYLENE)TRIPHENYLPHOSPHORANE(CAS DataBase Reference)
• NIST Chemistry Reference: (FORMYLMETHYLENE)TRIPHENYLPHOSPHORANE(2136-75-6)
• EPA Substance Registry System: (FORMYLMETHYLENE)TRIPHENYLPHOSPHORANE(2136-75-6)

Safety Data

• Hazard Codes: Xi
• Statements: 36/37/38
• Safety Statements: 26-36
• WGK Germany: 3
• Hazardous Substances Data: 2136-75-6(Hazardous Substances Data)

Usage

Description

(Formylmethylene)triphenylphosphorane, also known as Wittig reagent, is an organophosphorus compound with the chemical formula (C6H5)3P=CHCOH. It is a pink to brown crystalline powder that plays a crucial role in organic synthesis due to its unique reactivity and versatility.

Uses

1. Used in Pharmaceutical Industry:
(Formylmethylene)triphenylphosphorane is used as a pharmaceutical intermediate for the synthesis of various drugs. Its ability to act as a Wittig reagent allows for the creation of complex molecular structures, which are essential in the development of new medications.
2. Used in Organic Synthesis:
In the field of organic chemistry, (formylmethylene)triphenylphosphorane is used as a Wittig reagent for the conversion of aldehydes and ketones to two-carbon homologated, α,β-unsaturated carbonyl compounds. This reaction is widely employed in the synthesis of various organic compounds, including natural products and complex molecules.
3. Used in Agrochemicals:
(Formylmethylene)triphenylphosphorane is also utilized as a raw material in the synthesis of agrochemicals, such as pesticides and herbicides. Its role in creating specific molecular structures contributes to the development of effective and targeted chemical solutions for agricultural applications.
4. Used in Wittig Reactions:
(Formylmethylene)triphenylphosphorane is used as a Wittig reagent for the conversion of aldehydes and ketones to α,β-unsaturated carbonyl compounds. This reaction is a valuable tool in organic synthesis, allowing for the formation of new carbon-carbon double bonds and the creation of a wide range of chemical products.

Purification Methods

Recrystallise it from Me2CO, or dissolve it in *C6H6, wash with N NaOH, dry (MgSO4), evaporate, and crystallise the residue from Me2CO. It can be prepared from its precursor, formylmethyltriphenylphosphonium chloride (which crystallises from CHCl3/EtOAc), by treatment with Et3N and extraction with *C6H6. [Tripett & Walker J Chem Soc 1266 1961.]

InChI:InChI=1/C20H17OP/c21-16-17-22(18-10-4-1-5-11-18,19-12-6-2-7-13-19)20-14-8-3-9-15-20/h1-17H

Synthetic route

formylmethyltriphenylphosphonium chloride (62942-43-2) → (triphenylphosphoranylidene)acetaldehyde (2136-75-6)

Conditions	Yield
With sodium hydroxide In water at 20 - 30℃; for 0.5h;	97%
With water; sodium hydroxide at 20 - 60℃; for 3h; pH=> 9; Time;	96%
With triethylamine In ethanol for 1h;	1.24 g
With sodium hydroxide In dichloromethane; water at 0 - 10℃;
With sodium hydroxide In water pH=7-8;	4.1 g

Methylenetriphenylphosphorane (19493-09-5) + formic acid ethyl ester (109-94-4) → (triphenylphosphoranylidene)acetaldehyde (2136-75-6)

Conditions	Yield
In benzene	81%

Methyltriphenylphosphonium bromide (1779-49-3) + formic acid ethyl ester (109-94-4) → (triphenylphosphoranylidene)acetaldehyde (2136-75-6)

Conditions	Yield
Stage #1: Methyltriphenylphosphonium bromide With potassium tert-butylate In diethyl ether at 20℃; for 1.5h; Stage #2: formic acid ethyl ester In diethyl ether at 20℃;	76%
With n-butyllithium In diethyl ether
With n-butyllithium

2-chloroethanal (107-20-0) + triphenylphosphine (603-35-0) → (triphenylphosphoranylidene)acetaldehyde (2136-75-6)

Conditions	Yield
In chloroform; water for 24h; Reflux;	53%
In chloroform; water for 5h; Heating;	51%
With pyrographite 1.) reflux, 5 h, CHCl3, 2.) 30 min, room temp., water; Yield given. Multistep reaction;

triphenylphosphine (603-35-0) + Bromoacetaldehyde diethyl acetal (2032-35-1) → (triphenylphosphoranylidene)acetaldehyde (2136-75-6)

Conditions	Yield
In nitromethane Heating;

triphenylphosphonium bromide acetaldehyde (19753-63-0) → (triphenylphosphoranylidene)acetaldehyde (2136-75-6)

Conditions	Yield
With n-butyllithium In 1,2-dimethoxyethane; hexane for 1h; Ambient temperature;
With sodium hydroxide In toluene at 5℃; for 3h; Temperature; Inert atmosphere;

<2-(dimethylamino)vinyl>triphenylphosphonium chloride (90601-11-9) → (triphenylphosphoranylidene)acetaldehyde (2136-75-6)

Conditions	Yield
With sodium hydroxide; sulfuric acid 1) H2O, benzene, CH2Cl2, 5 min, 2) H2O, benzene, CH2Cl2; Yield given. Multistep reaction;

P-(formylmethyl)triphenylphosphonium cation (47181-98-6) → (triphenylphosphoranylidene)acetaldehyde (2136-75-6)

Conditions	Yield
With base In water; dimethyl sulfoxide at 25℃; Kinetics; deprotonation;

triphenylphosphine (603-35-0) → (triphenylphosphoranylidene)acetaldehyde (2136-75-6)

Conditions	Yield
Multi-step reaction with 3 steps 1: 10 h / 80 °C 2: sulfuric acid; water / 2 h / 40 °C 3: sodium hydroxide / water / 0.5 h / 20 - 30 °C View Scheme

2-cyano-3,3-bis(4-fluorophenyl)-2-propenal (128995-63-1) + (triphenylphosphoranylidene)acetaldehyde (2136-75-6) → 4-cyano-5,5-bis(4-fluorophenyl)-2,4-pentadienal (130200-45-2)

Conditions	Yield
In benzene for 1h; Heating;	100%
In ethyl acetate; benzene	1.43 g (100%)

(triphenylphosphoranylidene)acetaldehyde (2136-75-6) + methyl-4-(3-formyl-4-hydroxyphenylaminocarbonyl)butanoate (134578-05-5) → methyl-4-[3-(2-formyl-(E)-ethenyl)-4-hydroxyphenylaminocarbonyl]butanoate (197707-54-3)

Conditions	Yield
In dichloromethane at 25℃; for 2h;	100%

tert-butyl 3-oxoazetidine-1-carboxylate (398489-26-4) + (triphenylphosphoranylidene)acetaldehyde (2136-75-6) → tert-butyl 3-(2-oxomethylene)azetidine-1-carboxylic acid (1223573-23-6)

Conditions	Yield
In dichloromethane at 40℃; for 6h;	100%
In dichloromethane at 40℃; for 6h;	100%
In dichloromethane at 40℃;	99%

(S,Z)-2-(benzyloxy)dec-4-enal (1394257-23-8) + (triphenylphosphoranylidene)acetaldehyde (2136-75-6) → (S,2E,6Z)-4-(benzyloxy)dodeca-2,6-dienal (1394257-22-7)

Conditions	Yield
In benzene at 60℃; for 4h; Wittig reaction; Inert atmosphere;	99%

dimethyl cis-but-2-ene-1,4-dioate (624-48-6) + (triphenylphosphoranylidene)acetaldehyde (2136-75-6) → dimethyl 2-(2-(triphenyl phosphaneylidene)acetyl)succinate

Conditions	Yield
With [Ir(dF(CF3)ppy)2(dtbbpy)]Cl In benzene for 16h; Sealed tube; Irradiation; Heating; Inert atmosphere;	99%

2-nitro-4-cyano-benzaldehyde (90178-78-2) + (triphenylphosphoranylidene)acetaldehyde (2136-75-6) → 4-(4-Formyl-1,3-butadienyl)-3-nitrobenzonitril (104291-55-6)

Conditions	Yield
In benzene for 4h; Heating;	96%

benzyl 2,3-O-isopropylidene-α-D-lyxo-pentodialdo-1,4-furanoside (102919-04-0, 102854-75-1) + (triphenylphosphoranylidene)acetaldehyde (2136-75-6) → benzyl (E)-5,6-dideoxy-2,3-O-isopropylidene-α-D-lyxo-hept-5-enodialdo-1,4-furanoside (108182-76-9)

Conditions	Yield
In benzene for 2.5h; Heating;	95%

(triphenylphosphoranylidene)acetaldehyde (2136-75-6) + (+)-(2R,3S)-2,3-epoxydodecanal (246545-41-5) → (+)-(E)-(4R,5R)-4,5-epoxytetradec-2-enal

Conditions	Yield
In toluene for 12h; Condensation; Heating;	95%

(triphenylphosphoranylidene)acetaldehyde (2136-75-6) + (2RS,3RS)-3-(tert-butyldimethylsilyl)-2,3-epoxypropanal → 5-(tert-butyldimethylsilyl)-4,5-epoxy-(E)-2-pentenal

Conditions	Yield
In acetonitrile for 0.416667h; Heating;	95%

(triphenylphosphoranylidene)acetaldehyde (2136-75-6) + 3,3-diphenyloxirane carboxaldehyde → C17H14O2

Conditions	Yield
Inert atmosphere;	95%
In chloroform at 25℃; for 5h; Inert atmosphere;	1.6 g

2',4',4"-tri-O-acetyldesmycosin (112389-48-7) + (triphenylphosphoranylidene)acetaldehyde (2136-75-6) → C47H73NO17 (658684-19-6)

Conditions	Yield
In benzene at 80℃; for 2h; Wittig reaction;	94%

(triphenylphosphoranylidene)acetaldehyde (2136-75-6) + 4-(trifluoromethyl)-2-nitrobenzaldehyde (109466-87-7) → (E)-3-(2-nitro-4-(trifluoromethyl)phenyl)acrylaldehyde

Conditions	Yield
In acetonitrile at 20℃;	94%

perfluorobenzaldehyde (653-37-2) + (triphenylphosphoranylidene)acetaldehyde (2136-75-6) → (E)-3-(perfluorophenyl)acrylaldehyde (849796-05-0)

Conditions	Yield
In toluene at 80℃; for 1h; Wittig-Horner olefination;	93%

5-nitrofurane-2-carboxaldehyde (698-63-5) + (triphenylphosphoranylidene)acetaldehyde (2136-75-6) → 3-(5-nitrofuran-2-yl)-2-propenal (1874-22-2)

Conditions	Yield
In toluene for 6h; Reflux; Inert atmosphere;	93%
In dichloromethane at 20℃; Wittig Olefination;	30%

(4S,5R)-4-benzyloxymethyl-2,2-dimethyl-1,3-dioxolane-5-carboxaldehyde (81028-12-8) + (triphenylphosphoranylidene)acetaldehyde (2136-75-6) → (E)-3-((4S,5S)-5-Benzyloxymethyl-2,2-dimethyl-[1,3]dioxolan-4-yl)-propenal

Conditions	Yield
In benzene for 1h; Heating;	92%

methyl 2β-formyl-3β<(benzyloxycarbonyl)amino>-4-cyclohexene-α-carboxylate (77823-89-3) + (triphenylphosphoranylidene)acetaldehyde (2136-75-6) → methyl 2β-<3-oxo-2(E)-propenyl>-3β<(benzyloxycarbonyl)amino>-4-cyclohexene-α-carboxylate (77823-90-6, 98819-46-6, 98819-47-7)

Conditions	Yield
In toluene for 2h; Heating;	92%

(triphenylphosphoranylidene)acetaldehyde (2136-75-6) + ((2S,3R,4S,5R,6R)-3,4,5-Tris-benzyloxy-6-benzyloxymethyl-2-hydroxy-tetrahydro-pyran-2-yl)-acetaldehyde (389121-76-0) → (E)-4-((2S,3R,4S,5R,6R)-3,4,5-Tris-benzyloxy-6-benzyloxymethyl-2-hydroxy-tetrahydro-pyran-2-yl)-but-2-enal (389121-79-3)

Conditions	Yield
	92%

(triphenylphosphoranylidene)acetaldehyde (2136-75-6) + methyl (2S)-2-[(tert-butoxy)carbonylamino]-4-oxobutanoate (87884-14-8) → C12H19NO5 (116613-74-2)

Conditions	Yield
In tetrahydrofuran at 35℃; for 48h; Wittig reaction;	92%

C13H26O4Si (1224702-13-9) + (triphenylphosphoranylidene)acetaldehyde (2136-75-6) → C15H28O4Si

Conditions	Yield
In phenol for 17h; Wittig reaction; Reflux;	92%

C64H110O17Si3 + (triphenylphosphoranylidene)acetaldehyde (2136-75-6) → C66H112O17Si3

Conditions	Yield
In toluene at 100℃; for 1h; Wittig Olefination; Inert atmosphere;	92%

2-((3-hydroxy-1,4-dioxo-1,4-dihydronaphthalen-2-yl)methyl)benzaldehyde + (triphenylphosphoranylidene)acetaldehyde (2136-75-6) → (4bS*,5R*,6R*,11aR*)-6-hydroxy-11,13-dioxo-4b,6,11,12-tetrahydro-5H-6,11a-methanodibenzo[a,f]azulene-5-carbaldehyde

Conditions	Yield
In dichloromethane at 50℃; for 7h;	92%

(4R,5S)-5-Benzhydryloxymethyl-2,2-dimethyl-[1,3]dioxolane-4-carbaldehyde (86363-76-0) + (triphenylphosphoranylidene)acetaldehyde (2136-75-6) → (E)-3-((4S,5S)-5-Benzhydryloxymethyl-2,2-dimethyl-[1,3]dioxolan-4-yl)-propenal (86348-32-5)

Conditions	Yield
In benzene Ambient temperature;	91%

(triphenylphosphoranylidene)acetaldehyde (2136-75-6) + 1,2:3,4:6,7-tri-O-isopropylidene-α-D-threo-D-galacto-octodialdo-1,5-pyranose (99202-72-9, 99265-85-7, 106293-95-2, 106293-96-3) → (E)-8,9-dideoxy-1,2:3,4:6,7-tri-O-isopropylidene-α-D-threo-D-galacto-dec-8-enodialdo-1,5-pyranose (99202-73-0, 106400-53-7)

Conditions	Yield
In benzene for 1.16667h; Heating;	91%
In benzene Heating;	91%

(triphenylphosphoranylidene)acetaldehyde (2136-75-6) + N-phenyl-acetimidoyl iodide → [(E)-2-(Acetyl-phenyl-amino)-vinyl]-triphenyl-phosphonium; iodide

Conditions	Yield
In acetonitrile at 20℃; for 24h;	91%

N-phenylacetimidoyl chloride (874-69-1) + (triphenylphosphoranylidene)acetaldehyde (2136-75-6) → [(E)-2-(Acetyl-phenyl-amino)-vinyl]-triphenyl-phosphonium; iodide

Conditions	Yield
With sodium iodide In acetonitrile at 20℃; for 24h;	91%

4-(n-butyl)benzaldehyde (1200-14-2) + (triphenylphosphoranylidene)acetaldehyde (2136-75-6) → (E)-3-(4-butylphenyl)acrylaldehyde (20850-09-3)

Conditions	Yield
In benzene for 30h; Heating;	90.6%

3,3-bis(4-fluorophenyl)-2-(2-methyl-2H-tetrazol-5-yl)-2-propenal (118875-10-8) + (triphenylphosphoranylidene)acetaldehyde (2136-75-6) → 5,5-bis(4-fluorophenyl)-4-(2-methyl-2H-tetrazol-5-yl)-2,4-pentadienal (130200-54-3)

Conditions	Yield
In benzene for 0.5h; Heating;	90.5%
	0.66 g (90.5%)

(3aR,5S,5aR,8aS,8bR)-2,2,7,7-Tetramethyl-tetrahydro-bis[1,3]dioxolo[4,5-b;4',5'-d]pyran-5-carbaldehyde (4933-77-1) + (triphenylphosphoranylidene)acetaldehyde (2136-75-6) → (E)-6,7-didehydro-6,7-dideoxy-1,2:3,4-di-O-isopropylidene-α-D-galacto-octodialo-1,5-pyranose (100759-67-9, 50256-79-6)

Conditions	Yield
In benzene for 12h; Heating;	90%
In benzene for 4.5h; Heating;	90%
In benzene Heating;	90%
In dichloromethane for 12h; Ambient temperature;	88%

Methyl 5S-benzoyloxy-5-formylvalerate (76745-20-5) + (triphenylphosphoranylidene)acetaldehyde (2136-75-6) → Benzoic acid (E)-(S)-1-(3-methoxycarbonyl-propyl)-4-oxo-but-2-enyl ester (80335-91-7)

Conditions	Yield
In benzene for 2h; Heating;	90%
In acetone for 5h; Heating;	54%

Upstream product

• 90601-11-9 <2-(dimethylamino)vinyl>triphenylphosphonium chloride 
• 107-20-0 2-chloroethanal 
• 603-35-0 triphenylphosphine 
• 47181-98-6 P-(formylmethyl)triphenylphosphonium cation 
• 62942-43-2 formylmethyltriphenylphosphonium chloride 
• 19493-09-5 Methylenetriphenylphosphorane 
• 109-94-4 formic acid ethyl ester 
• 19753-63-0 triphenylphosphonium bromide acetaldehyde 
• 1779-49-3 Methyltriphenylphosphonium bromide 
• 2032-35-1 Bromoacetaldehyde diethyl acetal 

Downstream Products

• 28447-15-6 trans-3-(3-pyridyl)acrolein 
• 130273-24-4 ethyl 9,9-bis(4-fluorophenyl)-5-hydroxy-8-(1-methyl-1H-tetrazol-5-yl)-3-oxo-6,8-nonadienoate 
• 130200-53-2 ethyl 11,11-bis(4-fluorophenyl)-5-hydroxy-10-(1-methyl-1H-tetrazol-5-yl)-3-oxo-6,8,10-undecatrienoate 
• 108182-76-9 benzyl (E)-5,6-dideoxy-2,3-O-isopropylidene-α-D-lyxo-hept-5-enodialdo-1,4-furanoside 
• 104291-55-6 4-(4-Formyl-1,3-butadienyl)-3-nitrobenzonitril 
• 111043-66-4 2,6-dioxabicyclo<3.2.1>octane 
• 120595-01-9 Acetic acid (2S,3R,4S,5R)-4-benzyloxy-5-ethyl-2,4-dimethyl-2-[(2S,3R)-3-((E)-3-oxo-propenyl)-oxiranyl]-tetrahydro-furan-3-yl ester 
• 77823-90-6 methyl 2β-<3-oxo-2(E)-propenyl>-3β<(benzyloxycarbonyl)amino>-4-cyclohexene-α-carboxylate 
• 114894-84-7 benzyl 4-benzyloxycarbonylamino-4,6,7-trideoxy-6-ene-2,3-O-isopropylidene-α-D-manno-octadialdopyranoside 
• 104291-54-5 3-(2-Formylvinyl)-4-nitrobenzonitril 
• 73213-61-3 methyl boninenalate 
• 110920-99-5 (E)-(R)-4-Benzyloxy-4-((3aR,5R,5aS,8aS,8bR)-2,2,7,7-tetramethyl-tetrahydro-bis[1,3]dioxolo[4,5-b;4',5'-d]pyran-5-yl)-but-2-enal 
• 141277-53-4 [(E)-(R)-1-(tert-Butyl-dimethyl-silanyloxymethyl)-4-oxo-but-2-enyl]-(3-methyl-but-2-enyl)-carbamic acid phenyl ester 
• 140230-86-0 4-(2-Chloro-phenyl)-2-methyl-6-((E)-3-oxo-propenyl)-1,4-dihydro-pyridine-3,5-dicarboxylic acid 3-isopropyl ester 5-methyl ester 

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