5413-05-8

Basic information

• Product Name: ETHYL 2-PHENYLACETOACETATE
• Synonyms: ETHYL 3-OXO-2-PHENYLBUTANOATE;ETHYL 2-PHENYLACETOACETATE;2-Phenylacetoacetic acid ethyl ester;Benzeneacetic acid, .alpha.-acetyl-, ethyl ester;2-Phenyl-3-oxobutanoic acid ethyl ester;2-Phenyl-3-oxobutyric acid ethyl ester;Benzeneacetic acid, a-acetyl-, ethyl ester;Ethyl a-acetylbenzeneacetate
• CAS NO: 5413-05-8
• Molecular Formula: C₁₂H₁₄O₃
• Molecular Weight: 206.24
• EINECS: 226-500-0
• Product Categories: Aromatics Compounds
• Mol File: 5413-05-8.mol
• Article Data: 26

Chemical Properties

• Melting Point: 140-144°C/10mm
• Boiling Point: 140-144°C 10mm
• Flash Point: 140-144°C/10mm
• Appearance: /
• Density: 1,085 g/cm3
• Vapor Pressure: 0.00354mmHg at 25°C
• Refractive Index: 1.5130
• Solubility: Chloroform (Slightly), Methanol (Slightly)
• PKA: 10.69±0.46(Predicted)
• BRN: 1912655
• CAS DataBase Reference: ETHYL 2-PHENYLACETOACETATE(CAS DataBase Reference)
• NIST Chemistry Reference: ETHYL 2-PHENYLACETOACETATE(5413-05-8)
• EPA Substance Registry System: ETHYL 2-PHENYLACETOACETATE(5413-05-8)

Safety Data

• Safety Statements: 24/25
• Hazardous Substances Data: 5413-05-8(Hazardous Substances Data)

Usage

Uses

Ethyl 2-Phenylacetoacetate is used in preparation of iridium polysubstituted quinoline diketonate complex and application as OLED.

InChI:InChI=1/C12H14O3/c1-3-15-12(14)11(9(2)13)10-7-5-4-6-8-10/h4-8,11H,3H2,1-2H3/t11-/m1/s1

Synthetic route

3-Oxo-2-phenyl-butyrimidic acid ethyl ester (687981-26-6) → ethyl 2-phenylacetoacetate (5413-05-8)

Conditions	Yield
With hydrogenchloride In ethanol at 40℃; for 1.5h;	97%
With sulfuric acid; water In ethyl acetate at 20 - 50℃; for 4.5h;

iodobenzene (591-50-4) + ethyl acetoacetate (141-97-9) → ethyl 2-phenylacetoacetate (5413-05-8) + Ethyl 2-phenylethanoate (101-97-3)

Conditions	Yield
With potassium carbonate; copper(l) iodide In dimethyl sulfoxide at 80℃; for 20h;	A 9% B 89%
With potassium phosphate; copper(l) iodide In dimethyl sulfoxide at 80℃; for 20h;	A 26% B 20%

iodobenzene (591-50-4) + ethyl acetoacetate (141-97-9) → ethyl 2-phenylacetoacetate (5413-05-8)

Conditions	Yield
With copper(l) iodide; caesium carbonate In 1,4-dioxane at 70℃; for 25h;	78%

ethyl 2-diazo-3-hydroxy-3-phenylbutanoate (27262-63-1) → ethyl 2-phenylacetoacetate (5413-05-8)

Conditions	Yield
dirhodium tetraacetate In dichloromethane for 1h; Ambient temperature;	75%
With tris-(dibenzylideneacetone)dipalladium(0); para-iodoanisole; diisopropylamine; XPhos In toluene at 100℃; for 48h; Inert atmosphere;	57%

acetic anhydride (108-24-7) + Ethyl 2-phenylethanoate (101-97-3) → ethyl 2-phenylacetoacetate (5413-05-8)

Conditions	Yield
Stage #1: Ethyl 2-phenylethanoate With sodium hydride In tetrahydrofuran at 60℃; for 0.5h; Cooling with ice; Stage #2: acetic anhydride In tetrahydrofuran at 0 - 20℃; for 1h;	61%
Stage #1: Ethyl 2-phenylethanoate With sodium hydride In tetrahydrofuran at 60℃; for 0.5h; Stage #2: acetic anhydride In tetrahydrofuran at 20℃; for 1h;	51%
Stage #1: Ethyl 2-phenylethanoate With sodium hydride In tetrahydrofuran at 60℃; for 0.5h; Stage #2: acetic anhydride In tetrahydrofuran at 20℃; for 1h; Further stages.;	51%
Stage #1: Ethyl 2-phenylethanoate With sodium hydride In tetrahydrofuran at 60℃; for 0.5h; Inert atmosphere; Stage #2: acetic anhydride In tetrahydrofuran at 0℃;

ethyl acetoacetate (141-97-9) + diphenyliodonium hexafluorophosphate (58109-40-3) → ethyl 2-phenylacetoacetate (5413-05-8)

Conditions	Yield
With potassium tert-butylate In N,N-dimethyl-formamide at 20℃; for 24h; Inert atmosphere;	60%

ethyl acetoacetate (141-97-9) + triphenylbismuth carbonate (47252-14-2) → ethyl 2-phenylacetoacetate (5413-05-8)

Conditions	Yield
In dichloromethane at 40℃; for 20h;	59%
	59%

diphenyliodonium tetrafluoroborate + ethyl acetoacetate (141-97-9) → ethyl 2-phenylacetoacetate (5413-05-8)

Conditions	Yield
Stage #1: ethyl acetoacetate With potassium tert-butylate In N,N-dimethyl-formamide at 0℃; for 0.5h; Inert atmosphere; Stage #2: diphenyliodonium tetrafluoroborate In N,N-dimethyl-formamide at 0 - 20℃; for 18h; Reagent/catalyst; Inert atmosphere;	53%

(6-chloropyridin-3-yl)(phenyl)iodonium trifluoromethanesulfonate + ethyl acetoacetate (141-97-9) → ethyl 2-phenylacetoacetate (5413-05-8) + ethyl 2-(6-chloropyridin-3-yl)-3-oxobutanoate

Conditions	Yield
Stage #1: ethyl acetoacetate With potassium tert-butylate In N,N-dimethyl-formamide at 0℃; for 0.5h; Inert atmosphere; Stage #2: (6-chloropyridin-3-yl)(phenyl)iodonium trifluoromethanesulfonate In N,N-dimethyl-formamide at 0 - 20℃; Inert atmosphere; chemoselective reaction;	A 12% B 50%

Diphenyliodonium triflate (66003-76-7) + ethyl acetoacetate (141-97-9) → ethyl 2-phenylacetoacetate (5413-05-8)

Conditions	Yield
With potassium tert-butylate In N,N-dimethyl-formamide at 20℃; for 24h; Inert atmosphere;	45%

bromobenzene (108-86-1) + ethyl acetoacetate (141-97-9) → ethyl 2-phenylacetoacetate (5413-05-8)

Conditions	Yield
With potassium phosphate; palladium diacetate; di-tert-butyl (2'-methyl-[1,1'-biphenyl]-2-yl)phosphine In toluene Reflux;	25%
With potassium phosphate; palladium diacetate; di-tert-butyl (2'-methyl-[1,1'-biphenyl]-2-yl)phosphine In toluene at 90℃; for 16h;

ethyl acetoacetate (141-97-9) + diphenyliodonium bromide (1483-73-4) → ethyl 2-phenylacetoacetate (5413-05-8)

Conditions	Yield
With potassium tert-butylate In N,N-dimethyl-formamide at 20℃; for 24h; Inert atmosphere;	10%

2-phenylmalonic acid monoethyl ester (17097-90-4) + isopropylmagnesium bromide (920-39-8) → ethyl 2-phenylacetoacetate (5413-05-8)

Conditions	Yield
With tetrahydrofuran anschliessend mit Acetylchlorid Umsetzen;

ethyl acetate (141-78-6) + Ethyl 2-phenylethanoate (101-97-3) → ethyl 2-phenylacetoacetate (5413-05-8)

Conditions	Yield
With diethyl ether; sodium

Ethyl 2-phenylethanoate (101-97-3) → ethyl 2-phenylacetoacetate (5413-05-8)

Conditions	Yield
With diethyl ether; ammonia; sodium amide Erwaermen des Reaktionsprodukts mit Phenylacetat in Aether;
With lithium diisopropyl amide In tetrahydrofuran; heptane-tetrahydrofuranethylbenzene; water; ethyl acetate

ethanol (64-17-5) + 1-phenyl-1-cyanopropan-2-one (4468-48-8) → ethyl 2-phenylacetoacetate (5413-05-8)

Conditions	Yield
With hydrogenchloride Loesen des salzsauren Iminoaethers in Alkohol und anschl. Verduennen mit Wasser;

1-phenyl-1-cyanopropan-2-one (4468-48-8) → ethyl 2-phenylacetoacetate (5413-05-8)

Conditions	Yield
ueber den Iminoaether;

diazoacetic acid ethyl ester (623-73-4) + acetophenone (98-86-2) → ethyl 2-phenylacetoacetate (5413-05-8)

Conditions	Yield
(i) nBuLi, (ii) HCl; Multistep reaction;

ethyl 2-diazo-3-hydroxy-3-phenylbutanoate (27262-63-1) → ethyl 2-phenylacetoacetate (5413-05-8) + acetophenone (98-86-2) + ethyl 2-benzoylpropionate (10488-87-6)

Conditions	Yield
palladium dichloride In benzene Product distribution; Heating; other temp., other times, other solv., other matal salts as catalysts;

ethyl 2-diazo-3-hydroxy-3-phenylbutanoate (27262-63-1) → ethyl 2-phenylacetoacetate (5413-05-8) + ethyl 2-benzoylpropionate (10488-87-6)

Conditions	Yield
palladium dichloride In benzene Heating; Yield given. Yields of byproduct given. Title compound not separated from byproducts;

ethyl 4-bromo-3-oxo-2-phenylbutanoate (408320-75-2) → ethyl 2-phenylacetoacetate (5413-05-8)

Conditions	Yield
With acetic acid; zinc In diethyl ether

ethanol (64-17-5) + 2-diazo-1-phenylbutane-1,3-dione (2009-96-3) → ethyl 2-phenylacetoacetate (5413-05-8)

Conditions	Yield
In 1,4-dioxane Heating;

diethyl ether (60-29-7) + Phenyl acetate (122-79-2) + sodium phenylacetic acid ethyl ester → ethyl 2-phenylacetoacetate (5413-05-8)

acetyl chloride (75-36-5) + bromomercurio-phenyl-acetic acid ethyl ester → ethyl 2-phenylacetoacetate (5413-05-8)

Conditions	Yield
With toluene

acetyl chloride (75-36-5) + potassium phenylacetic acid ester → ethyl 2-phenylacetoacetate (5413-05-8)

Conditions	Yield
at 20℃;

bromobenzene (108-86-1) + ethyl acetoacetate (141-97-9) → ethyl 2-phenylacetoacetate (5413-05-8) + Ethyl 2-phenylethanoate (101-97-3)

Conditions	Yield
With potassium phosphate; di-tert-butyl (2'-methyl-[1,1'-biphenyl]-2-yl)phosphine; palladium diacetate In toluene at 90℃; for 16h; Product distribution; Further Variations:; Catalysts; Reaction partners; Reagents;	A n/a B 93 % Chromat.

acetophenone (98-86-2) → ethyl 2-phenylacetoacetate (5413-05-8)

Conditions	Yield
Multi-step reaction with 2 steps 1: 47 percent / diispropylamine, n-butyllithium / tetrahydrofuran; hexane / 0.5 h / -78 °C 2: PdCl2 / benzene / Heating View Scheme

phenylacetonitrile (140-29-4) → ethyl 2-phenylacetoacetate (5413-05-8)

Conditions	Yield
Multi-step reaction with 2 steps 1: sodium ethylate 2: hydrogen chloride / Loesen des salzsauren Iminoaethers in Alkohol und anschl. Verduennen mit Wasser View Scheme

trifluoromethylsulfonic anhydride (358-23-6) + ethyl 2-phenylacetoacetate (5413-05-8) → ethyl (Z)-2-phenyl-3-(trifluoromethylsulfonyloxy)but-2-enoate (1037590-38-7)

Conditions	Yield
Stage #1: ethyl 2-phenylacetoacetate With lithium hydroxide In water; toluene at 5 - 10℃; for 0.0833333h; Stage #2: trifluoromethylsulfonic anhydride In water; toluene at 5 - 15℃; Schotten-Baumann type reaction; optical yield given as %de; stereoselective reaction;	98%

2-aminopyridine (504-29-0) + ethyl 2-phenylacetoacetate (5413-05-8) → 2-methyl-3-phenyl-4H-pyrido[1,2-a]pyrimidin-4-one

Conditions	Yield
With bismuth(III) chloride at 100℃; for 3h; Green chemistry;	96%

ethyl 2-phenylacetoacetate (5413-05-8) → 3-methyl-4-phenyl-1H-pyrazol-5-ol (64754-67-2)

Conditions	Yield
With acetic acid; hydrazine for 1h; Heating / reflux;	92%

ethyl 2-phenylacetoacetate (5413-05-8) + N,N-dimethyl-formamide (68-12-2, 33513-42-7) → C15H19NO4

Conditions	Yield
With tert.-butylhydroperoxide at 70℃; for 0.5h;	90%

ethyl 2-phenylacetoacetate (5413-05-8) + 3-amino-5-methoxyphenol (162155-27-3) → 5-hydroxy-7-methoxy-4-methyl-3-phenylquinolin-2(1H)-one (1392191-15-9)

Conditions	Yield
In chlorobenzene at 160℃; for 0.5h; Microwave irradiation;	89%
In chlorobenzene at 160℃; Microwave irradiation;	89%

1H-benzimidazol-2-acetonitrile (4414-88-4) + ethyl 2-phenylacetoacetate (5413-05-8) → 3-methyl-1-oxo-2-phenyl-1H,5H-pyrido[1,2-a]benzimidazole-4-carbonitrile (577775-45-2)

Conditions	Yield
With ammonium acetate at 140 - 150℃; for 0.666667h;	85%
With ammonium acetate at 140 - 150℃;	85%
With ammonium acetate at 150℃; neat (no solvent);	81%

ethyl 2-phenylacetoacetate (5413-05-8) → (Z)-ethyl 3-amino-2-phenylbut-2-enoate (1160169-26-5)

Conditions	Yield
With ammonium formate In ethanol Molecular sieve; Reflux;	85%

N-formyldiethylamine (617-84-5) + ethyl 2-phenylacetoacetate (5413-05-8) → C17H23NO4

Conditions	Yield
With tert.-butylhydroperoxide at 70℃; for 0.5h;	83%

Isopropenyl acetate (108-22-5) + ethyl 2-phenylacetoacetate (5413-05-8) → (Z)-ethyl 3-acetoxy-2-phenylbut-2-enoate

Conditions	Yield
With toluene-4-sulfonic acid at 130℃; for 18h; Inert atmosphere;	81%

[7-methyl-2-(3H-imidazo[4,5-b]pyridine)-2-yl]acetonitrile (577777-13-0) + ethyl 2-phenylacetoacetate (5413-05-8) → 4,7-dimethyl-9-oxo-8-phenyldipyrido[1,2-a;3',2'-d]imidazole-6-carbonitrile (577777-14-1)

Conditions	Yield
With ammonium acetate at 140 - 150℃; for 1h;	80%

ethyl 2-phenylacetoacetate (5413-05-8) + recorcinol (108-46-3) → 7-hydroxy-4-methyl-3-phenyl-chromen-2-one (2555-23-9)

Conditions	Yield
With sulfuric acid at 0 - 20℃; Pechmann Condensation;	78%
With sulfuric acid
With ethanol; phosphorus pentoxide
With sulfuric acid at 100℃;

pyrid-2-ylhydrazine (4930-98-7) + ethyl 2-phenylacetoacetate (5413-05-8) → 5-methyl-4-phenyl-2-(pyridin-2-yl)-1H-pyrazol-3(2H)-one (101800-02-6)

Conditions	Yield
With acetic acid for 1h; Heating / reflux;	78%

ethyl 2-phenylacetoacetate (5413-05-8) → ethyl 4-bromo-3-oxo-2-phenylbutanoate (408320-75-2)

Conditions	Yield
With bromine In chloroform at 25℃; for 1h;	78%

ethyl 2-phenylacetoacetate (5413-05-8) + urethane (51-79-6) → 4-methyl-5-(phenyl)-2H-1,3-oxazine-2,6(3H)-dione (106013-88-1)

Conditions	Yield
With trichlorophosphate at 95℃; for 1.75h;	76%
With trichlorophosphate at 90℃; for 2.5h;	70%
With trichlorophosphate at 90℃;

ethyl 2-cyanomethyl-1H-benzimidazole-4-carboxylate (577776-85-3) + ethyl 2-phenylacetoacetate (5413-05-8) → ethyl 4-cyano-3-methyl-1-oxo-2-phenyl-1H,5H-pyrido[1,2-a]benzimidazole-6-carboxylate (577776-86-4)

Conditions	Yield
With ammonium acetate at 140 - 150℃; for 0.5h;	75%

ethyl 2-phenylacetoacetate (5413-05-8) → ethyl 2-phenyl-2-bromoacetate (2882-19-1)

Conditions	Yield
With aluminum oxide; sodium carbonate; copper(ll) bromide In benzene at 50℃; for 1h;	74%

ethyl 2-phenylacetoacetate (5413-05-8) + 2-hydroxyresorcinol (87-66-1) → 7,8-dihydroxy-4-methyl-3-phenyl-coumarin (859740-03-7)

Conditions	Yield
With sulfuric acid at 0 - 20℃; Pechmann Condensation;	72%
With sulfuric acid
With phosphoric acid

(4-tert-butyl-1H-imidazol-2-yl)acetonitrile (863399-52-4) + ethyl 2-phenylacetoacetate (5413-05-8) → 2-tert-butyl-7-methyl-5-oxo-6-phenyl-1,5-dihydroimidazo[1,2-a]pyridine-8-carbonitrile

Conditions	Yield
With ammonium acetate at 140℃; for 6h;	71%
With ammonium acetate at 150℃; for 3.5h;	33%

[5-(pyridin-4-yl)-2H-[1,2,4]triazol-3-yl]-acetonitrile (59282-73-4) + ethyl 2-phenylacetoacetate (5413-05-8) → 7-methyl-5-oxo-6-phenyl-2-(pyridin-4-yl)-1,5-dihydro-[1,2,4]triazolo[1,5-a]pyridine-8-carbonitrile

Conditions	Yield
With ammonium acetate at 150℃; for 3h;	69%

pyrid-2-ylhydrazine (4930-98-7) + ethyl 2-phenylacetoacetate (5413-05-8) → 3-methyl-4-phenyl-1-(pyridin-2-yl)-1H-pyrazol-5-ol (140398-47-6)

Conditions	Yield
With acetic acid at 130℃; for 0.0833333h; Microwave irradiation; regioselective reaction;	69%
With acetic acid Reflux;

ethyl 2-phenylacetoacetate (5413-05-8) + aniline (62-53-3) → 2-methyl-3-phenylhydroquinolin-4-one

Conditions	Yield
Stage #1: ethyl 2-phenylacetoacetate; aniline With acetic acid In benzene at 100℃; Conrad-Limpach reaction; Stage #2: In diphenylether; benzene for 0.25h; Conrad-Limpach reaction; Reflux;	63%

(4-methyl-1H-imidazol-2-yl)acetonitrile (863399-39-7) + ethyl 2-phenylacetoacetate (5413-05-8) → 2,7-dimethyl-5-oxo-6-phenyl-1,5-dihydroimidazo[1,2-a]pyridine-8-carbonitrile

Conditions	Yield
With ammonium acetate at 150℃; for 3.5h;	61%
at 140℃; for 3h;	61%

ethyl 2-phenylacetoacetate (5413-05-8) + aniline (62-53-3) → (Z)-2-phenyl-3-(phenylamino)but-2-enoic acid ethyl ester

Conditions	Yield
With acetic acid In toluene Heating;	60%

ethyl 2-phenylacetoacetate (5413-05-8) + 4-chloro-m-anisidine (13726-14-2) → 6-chloro-7-methoxy-2-methyl-3-phenylquinolin-4(1H)-one (1248347-00-3)

Conditions	Yield
Stage #1: ethyl 2-phenylacetoacetate; 4-chloro-m-anisidine With acetic acid In benzene Conrad-Limpach Synthesis; Inert atmosphere; Reflux; Dean-Stark; Stage #2: In toluene at 260℃; for 0.05h; Conrad-Limpach Synthesis; Inert atmosphere; Microwave irradiation;	60%
Stage #1: ethyl 2-phenylacetoacetate; 4-chloro-m-anisidine With acetic acid In benzene for 18h; Conrad-Limpach Synthesis; Reflux; Stage #2: In diphenylether; benzene for 0.2h; Conrad-Limpach Synthesis; Reflux;

Upstream product

• 60-29-7 diethyl ether 
• 122-79-2 Phenyl acetate 
• 591-50-4 iodobenzene 
• 141-97-9 ethyl acetoacetate 
• 623-73-4 diazoacetic acid ethyl ester 
• 98-86-2 acetophenone 
• 101-97-3 Ethyl 2-phenylethanoate 
• 75-36-5 acetyl chloride 
• 140-29-4 phenylacetonitrile 
• 108-24-7 acetic anhydride 
• 108-86-1 bromobenzene 
• 64-17-5 ethanol 
• 2009-96-3 2-diazo-1-phenylbutane-1,3-dione 
• 408320-75-2 ethyl 4-bromo-3-oxo-2-phenylbutanoate 

Downstream Products

• 6623-45-6 2-ethyl-2-phenyl-acetoacetic acid ethyl ester 
• 856847-84-2 2,5-dimethyl-4-phenyl-1,2-dihydro-pyrazol-3-one 
• 4433-88-9 2-phenylacetoacetic acid 
• 64-17-5 ethanol 
• 124-38-9 carbon dioxide 
• 103-79-7 1-phenyl-acetone 
• 1248346-87-3 6,8-dichloro-2-methyl-3-phenylquinolin-4(1H)-one 
• 1248346-86-2 7,8-dichloro-2-methyl-3-phenylquinolin-4(1H)-one 
• 1248346-88-4 5,7-dichloro-2-methyl-3-phenylquinolin-4(1H)-one 
• 1248346-89-5 6,7-dichloro-2-methyl-3-phenylquinolin-4(1H)-one 
• 1248346-94-2 5,6-dichloro-2-methyl-3-phenylquinolin-4(1H)-one 
• 1068515-49-0 3-methyl-4-phenyl-1-(pyrimidin-2-yl)-1H-pyrazol-5-ol 
• 1068515-53-6 1-(1H-benzo[d]imidazol-2-yl)-3-methyl-4-phenyl-1H-pyrazol-5-ol 
• 1354790-67-2 C₁₄H₁₂N₄O₂ 

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