20320-59-6

Basic information

• Product Name: Diethyl(phenylacetyl)malonate
• Synonyms: Diethyl(phenylacetyl)malonate
• CAS NO: 20320-59-6
• Molecular Formula: C₁₅H₁₈O₅
• Molecular Weight: 278.30042
• Mol File: 20320-59-6.mol
• Article Data: 5

Chemical Properties

• Boiling Point: 120 °C(Press: 0.01 Torr)
• Appearance: /
• Density: 1.148±0.06 g/cm3(Predicted)
• PKA: 8.76±0.59(Predicted)
• CAS DataBase Reference: Diethyl(phenylacetyl)malonate(CAS DataBase Reference)
• NIST Chemistry Reference: Diethyl(phenylacetyl)malonate(20320-59-6)
• EPA Substance Registry System: Diethyl(phenylacetyl)malonate(20320-59-6)

Safety Data

• Hazardous Substances Data: 20320-59-6(Hazardous Substances Data)

Usage

Physical properties

Diethyl(phenylacetyl)malonate has a boiling point of 120 °C. Its density is predicted to be 1.148±0.06 g/cm3.

Uses

Organic synthesis intermediates.

Preparation

The anhydrous ethanol co-vaporized with diethyl phthalate and sodium metal is added dropwise to the mixture of diethyl malonate, carbon tetrachloride and magnesium, heated to start the reaction, and the temperature is controlled to smooth the reaction. Then add anhydrous diethyl ether, heat for 1h, add the diethyl ether solution of phenylacetyl chloride (add slowly, not to make the reaction too intense). After the reaction is completed, cool and add water, separate the oil layer, and evaporate the diethyl ether under reduced pressure to obtain diethyl(phenylacetyl)malonate.

Synthetic route

phenylacetyl chloride (103-80-0) + diethyl malonate (105-53-3) → diethyl 2-(2-phenylacetyl)malonate (20320-59-6)

Conditions	Yield
Stage #1: diethyl malonate With ethanol; magnesium In tetrachloromethane; toluene for 1h; Heating; Stage #2: phenylacetyl chloride In tetrachloromethane; toluene at 20℃; for 1h;	90%
With chloroform; magnesium
With magnesium

sodium diethylmalonate (996-82-7) + phenylacetyl chloride (103-80-0) → diethyl 2-(2-phenylacetyl)malonate (20320-59-6) + (α-phenylacetoxy-phenethylidene)-malonic acid diethyl ester

Conditions	Yield

diethyl ethoxymagnesium malonate + phenylacetyl chloride (103-80-0) → diethyl 2-(2-phenylacetyl)malonate (20320-59-6)

Conditions	Yield
With diethyl ether; ethanol

diethyl malonate (105-53-3) → diethyl 2-(2-phenylacetyl)malonate (20320-59-6)

Conditions	Yield
With sodium dann mit Phenylessigsaeurechlorid versetzen;

C7H11O4(1-)*C2H5O(1-)*Mg(2+) + phenylacetyl chloride (103-80-0) → diethyl 2-(2-phenylacetyl)malonate (20320-59-6)

Conditions	Yield

diethyl acetylmalonate (570-08-1) → diethyl 2-(2-phenylacetyl)malonate (20320-59-6)

Conditions	Yield
Multi-step reaction with 2 steps 1.1: 24 percent / NH2NH2 / ethanol / 3 h / Heating 2.1: Mg; EtOH / CCl4; toluene / 1 h / Heating 2.2: 90 percent / CCl4; toluene / 1 h / 20 °C View Scheme

ethyl 3-amino-2-ethoxycarbonyl-2-butenoate (137786-67-5) → diethyl 2-(2-phenylacetyl)malonate (20320-59-6)

Conditions	Yield
Multi-step reaction with 2 steps 1.1: 14 percent / 80 percent NH2NH2 / ethanol / 3 h / Heating 2.1: Mg; EtOH / CCl4; toluene / 1 h / Heating 2.2: 90 percent / CCl4; toluene / 1 h / 20 °C View Scheme

cycl-isopropylidene malonate (2033-24-1) → diethyl 2-(2-phenylacetyl)malonate (20320-59-6)

Conditions	Yield
Multi-step reaction with 2 steps 1: triethylamine / dichloromethane / 3.5 h / 20 °C / Cooling with ice 2: 3 h / Reflux View Scheme

phenylacetyl chloride (103-80-0) → diethyl 2-(2-phenylacetyl)malonate (20320-59-6)

Conditions	Yield
Multi-step reaction with 2 steps 1: triethylamine / dichloromethane / 3.5 h / 20 °C / Cooling with ice 2: 3 h / Reflux View Scheme

ethanol (64-17-5) + 2,2-dimethyl-5-(2-phenylacetyl)-1,3-dioxane-4,6-dione (74965-87-0) → diethyl 2-(2-phenylacetyl)malonate (20320-59-6)

Conditions	Yield
for 3h; Reflux;

phenylacetic acid (103-82-2) → diethyl 2-(2-phenylacetyl)malonate (20320-59-6)

Conditions	Yield
Multi-step reaction with 2 steps 1.1: thionyl chloride / dichloromethane / 1 h / 50 °C 2.1: sodium hydride / tetrahydrofuran / 1 h 2.2: 1 h / 0 - 20 °C View Scheme

diethyl 2-(2-phenylacetyl)malonate (20320-59-6) → ethyl 5-benzyl-3-oxo-2,3-dihydro-1H-pyrazole-4-carboxylate

Conditions	Yield
With hydrazine hydrate In acetic acid for 3h; Heating;	81%

diethyl 2-(2-phenylacetyl)malonate (20320-59-6) → ethyl 1,3-dihydroxy-2-naphthoate (6843-89-6)

Conditions	Yield
With methanesulfonic acid; phosphorus pentoxide at 20℃;	70%
With methanesulfonic acid at 30℃; for 48h;
With sulfuric acid at 25℃;

diethyl 2-(2-phenylacetyl)malonate (20320-59-6) + aniline (62-53-3) → 2,N-diphenylacetamide (621-06-7)

Conditions	Yield

diethyl 2-(2-phenylacetyl)malonate (20320-59-6) + recorcinol (108-46-3) → 4-benzyl-7-hydroxycoumarin (20280-94-8)

Conditions	Yield
With hydrogenchloride; acetic acid; zinc(II) chloride
With sulfuric acid

diethyl 2-(2-phenylacetyl)malonate (20320-59-6) + phenylmethanethiol (100-53-8) → 2-Benzylmercapto-3-phenyl-1-propen-1,1-dicarbonsaeure (20597-30-2)

Conditions	Yield
(i) ZnCl2, HCl, (ii) NaOH; Multistep reaction;

diethyl 2-(2-phenylacetyl)malonate (20320-59-6) + 2-Naphthalenesulfonyl chloride (93-11-8) → Naphthalin-2-sulfonsaeure-<1-benzyl-2,2-diaethoxycarbonyl-vinyl-ester> (101981-93-5)

Conditions	Yield
With ethanol; sodium ethanolate

diethyl 2-(2-phenylacetyl)malonate (20320-59-6) + 5-hydroxy-3-methylpyrazole (132712-71-1, 4344-87-0, 145091-87-8) → 2-benzyl-3-ethoxycarbonyl-7-methylpyrazolo<5,1-b><1,3>oxazin-5(5H)-one (91614-52-7) + 3-benzyl-2-ethoxycarbonyl-5-methylpyrazolo<1,2-a>pyrazole-1,7(1H,7H)-dione (91614-65-2) + 3-benzyl-2-ethoxycarbonyl-7-methylpyrazolo<1,2-a>pyrazole-1,5(1H,5H)-dione (91614-73-2)

Conditions	Yield
at 150 - 160℃; for 0.25h;	A 0.067 g B 0.073 g C 1.06 g

sulfuric acid (7664-93-9) + diethyl 2-(2-phenylacetyl)malonate (20320-59-6) → 1.3-dioxy-naphthoic acid-(2)-ethyl ester

Conditions	Yield

diethyl 2-(2-phenylacetyl)malonate (20320-59-6) + alcoholic potash → phenylacetic acid (103-82-2) + malonic acid (141-82-2)

Conditions	Yield

diethyl 2-(2-phenylacetyl)malonate (20320-59-6) + acetic acid (64-19-7) + phenylhydrazine (100-63-0) → 1-phenyl-3-benzyl-pyrazolone-(5)

Conditions	Yield

ethanol (64-17-5) + diethyl 2-(2-phenylacetyl)malonate (20320-59-6) + hydrochloride of hydroxylamine + natrium carbonate → 3-benzyl-isoxazolone-(5)-carboxylic acid-(4)-ethyl ester

Conditions	Yield

hydrogenchloride (7647-01-0) + diethyl 2-(2-phenylacetyl)malonate (20320-59-6) → 1-phenyl-acetone (103-79-7)

Conditions	Yield

diethyl ether (60-29-7) + diethyl 2-(2-phenylacetyl)malonate (20320-59-6) + phenylhydrazine (100-63-0) → diethyl malonate (105-53-3) + phenacetyl-phenylhydrazine + 1-phenyl-3-benzyl-pyrazolone-(5)-carboxylic acid-(4)-ethyl ester

Conditions	Yield

diethyl 2-(2-phenylacetyl)malonate (20320-59-6) → 2-benzyl-3-ethoxycarbonyl-7-methylpyrazolo<5,1-b><1,3>oxazin-5(5H)-one (91614-52-7)

Conditions	Yield
Multi-step reaction with 2 steps 1: 1.06 g / 0.25 h / 150 - 160 °C 2: 75 percent / acetonitrile / 2 h / Irradiation View Scheme

diethyl 2-(2-phenylacetyl)malonate (20320-59-6) → Naphthalin-2-sulfonsaeure-<1-benzyl-2,2-dicarboxy-vinyl-ester>

Conditions	Yield
Multi-step reaction with 2 steps 1: NaOEt, EtOH 2: aq. NaOH View Scheme

diethyl 2-(2-phenylacetyl)malonate (20320-59-6) → 2-Benzylsulfinyl-3-phenyl-1-propen-1,1-dicarbonsaeure (20597-37-9)

Conditions	Yield
Multi-step reaction with 2 steps 1: (i) ZnCl2, HCl, (ii) NaOH 2: AcOOH View Scheme

diethyl 2-(2-phenylacetyl)malonate (20320-59-6) → 2-Benzylsulfonyl-3-phenyl-1-propen-1,1-dicarbonsaeure (20597-44-8)

Conditions	Yield
Multi-step reaction with 2 steps 1: (i) ZnCl2, HCl, (ii) NaOH 2: AcOOH View Scheme

diethyl 2-(2-phenylacetyl)malonate (20320-59-6) → ethyl 3-ethoxy-5-benzyl-1H-pyrazole-4-carboxylate (1207432-20-9) + ethyl 5-benzyl-3-oxo-2,3-dihydro-1H-pyrazole-4-carboxylate

Conditions	Yield
With hydrazine hydrochloride In ethanol for 6h; Reflux;	A 2.3 g B n/a

Upstream product

• 105-53-3 diethyl malonate 
• 103-82-2 phenylacetic acid 
• 64-17-5 ethanol 
• 74965-87-0 2,2-dimethyl-5-(2-phenylacetyl)-1,3-dioxane-4,6-dione 
• 103-80-0 phenylacetyl chloride 
• 2033-24-1 cycl-isopropylidene malonate 
• 137786-67-5 ethyl 3-amino-2-ethoxycarbonyl-2-butenoate 
• 570-08-1 diethyl acetylmalonate 
• 996-82-7 sodium diethylmalonate 

Downstream Products

• 20597-30-2 2-Benzylmercapto-3-phenyl-1-propen-1,1-dicarbonsaeure 
• 1355011-60-7 4-oxo-5-phenyl-1,4-dihydropyridine-3-carboxylic acid 
• 1207432-20-9 ethyl 3-ethoxy-5-benzyl-1H-pyrazole-4-carboxylate 
• 6843-89-6 ethyl 1,3-dihydroxy-2-naphthoate 
• 20597-44-8 2-Benzylsulfonyl-3-phenyl-1-propen-1,1-dicarbonsaeure 
• 20597-37-9 2-Benzylsulfinyl-3-phenyl-1-propen-1,1-dicarbonsaeure 
• 91614-52-7 2-benzyl-3-ethoxycarbonyl-7-methylpyrazolo<5,1-b><1,3>oxazin-5(5H)-one 
• 105-53-3 diethyl malonate 
• 103-79-7 1-phenyl-acetone 
• 103-82-2 phenylacetic acid 
• 141-82-2 malonic acid 
• 91614-65-2 3-benzyl-2-ethoxycarbonyl-5-methylpyrazolo<1,2-a>pyrazole-1,7(1H,7H)-dione 
• 91614-73-2 3-benzyl-2-ethoxycarbonyl-7-methylpyrazolo<1,2-a>pyrazole-1,5(1H,5H)-dione 
• 101981-93-5 Naphthalin-2-sulfonsaeure-<1-benzyl-2,2-diaethoxycarbonyl-vinyl-ester> 

Relevant articles and documents

Comprehensive study on excited state intramolecular proton transfer in 2-(benzo[d]thiazol-2-yl)-3-methoxynaphthalen-1-ol and 2-(benzo[d]thiazol-2-yl)naphthalene-1,3-diol: Effect of solvent, aggregation, viscosity and TDDFT study

Three compounds DMT, MMT and DHT having dimehtoxy, mono-hydroxy and di-hydroxy groups respectively were prepared. Environmental interactions dependent photophysical properties especially excited state intramolecular proton transfer (ESIPT), solvatochromism, aggregation induced emission enhancement (AIEE) and viscosity dependent emission characteristics were studied. The effect of solvent polarity on ESIPT dynamics were studied using UV–vis and emission spectroscopy along with aggregation induced enhanced emission and viscosity effect. MMT and DHT showed unexpected and contrasting behavior in the solvents which are in good agreement with the density functional theory and time dependent density functional theory findings. Aggregation and viscosity study showed that cis-keto emission increased drastically in the aggregate state and highly viscous state due to restricted intramolecular rotation increasing the population of required cis enol rotamer (E). The study directs the potential applications of such molecules for advanced optoelectronics and viscosity based investigations.

INDOLIN-2-ONE DERIVATIVES AS PROTEIN KINASE INHIBITORS

A novel class of indoline-2-one derivatives are disclosed. These compounds are protein kinase inhibitors which are useful for treating hyperproliferative diseases such as cancer.

Efficient synthesis of 4-ethoxycarbonyl pyrazolin-5-one derivatives

Concise and efficient methods for the preparation of 3-substituted 4-ethoxycarbonylpyrazolin-5-ones are described. The synthetic strategies involve carbon-acylation in the presence of base, followed by ring cyclization with hydrazine or hydrazine monohydrochloride.