609-09-6

Basic information

• Product Name: Diethyl ketomalonate
• Synonyms: 2-Oxopropanedioic acid diethyl;2-Oxopropanedioic acid diethyl ester;Ketomalonic acid diethyl;Oxomalonic acid diethyl;Diethyl KETOMALONATE ester;Diethyl ketomalonate ,98%;Diethyl 2-oxomalonate 97%;Diethyl 2-oxopropane-1,3-dioate, Diethyl ketomalonate
• CAS NO: 609-09-6
• Molecular Formula: C₇H₁₀O₅
• Molecular Weight: 174.15
• EINECS: 210-176-2
• Product Categories: Pharmaceutical Intermediates
• Mol File: 609-09-6.mol
• Article Data: 20

Chemical Properties

• Melting Point: -70°C
• Boiling Point: 95-98 °C12 mm Hg(lit.)
• Flash Point: >230 °F
• Appearance: green-yellow/liquid
• Density: 1.142 g/mL at 25 °C(lit.)
• Vapor Pressure: 0.208mmHg at 25°C
• Refractive Index: n20/D 1.415
• Storage Temp.: Inert atmosphere,Room Temperature
• Solubility: Chloroform (Slightly), Methanol
• Water Solubility: Fully miscible with water.
• Sensitive: Moisture Sensitive
• Merck: 14,5913
• BRN: 971873
• CAS DataBase Reference: Diethyl ketomalonate(CAS DataBase Reference)
• NIST Chemistry Reference: Diethyl ketomalonate(609-09-6)
• EPA Substance Registry System: Diethyl ketomalonate(609-09-6)

Safety Data

• Hazard Codes: Xi
• Safety Statements: 24/25
• WGK Germany: 3
• F: 21
• TSCA: T
• HazardClass: IRRITANT, MOISTURE SENSITIVE
• Hazardous Substances Data: 609-09-6(Hazardous Substances Data)

Usage

Chemical Properties

Clear yellow liquid

Uses

Diethyl ketomalonate, reagent employed in Wittig and Aza-Wittig reactions for synthesis of triazoles, and 2-azadienes, respectively.

Synthesis Reference(s)

Synthetic Communications, 24, p. 695, 1994 DOI: 10.1080/00397919408012648The Journal of Organic Chemistry, 46, p. 2598, 1981 DOI: 10.1021/jo00325a039

InChI:InChI=1/C7H10O5/c1-3-11-6(9)5(8)7(10)12-4-2/h3-4H2,1-2H3

Synthetic route

1,3-diethyl 2-diazopropanedioate (5256-74-6) → Diethyl ketomalonate (609-09-6)

Conditions	Yield
With 3,3-dimethyldioxirane In acetone for 29h; Ambient temperature;	100%
With tert-butylhypochlorite In formic acid
With chloro(1,5-cyclooctadiene)rhodium(I) dimer; 1,1'-sulfinylbisbenzene; lanthanum(lll) triflate In 1,4-dioxane at 120℃; for 16h; Glovebox; Sealed tube;	50 %Spectr.

diethyl N,N-dimethylaminomethylenemalonate (18856-68-3) → Diethyl ketomalonate (609-09-6)

Conditions	Yield
With ozone	94%

diethyl malonate (105-53-3) → Diethyl ketomalonate (609-09-6)

Conditions	Yield
With hydrogenchloride; sodium chlorate; dihydrogen peroxide; sodium hydroxide In water at 10 - 35℃; pH=5 - 10;	89%
With chlorine dioxide; sodium hydroxide In water at 10 - 18℃; for 5h; pH=10;	89%
Stage #1: diethyl malonate With acetic acid In water at 70 - 80℃; for 0.5h; Stage #2: With sodium chlorite In water at 0 - 80℃;	56%

diethyl 2-cyanomalonate (4513-67-1) → Diethyl ketomalonate (609-09-6)

Conditions	Yield
With aluminum oxide; tetrabutylammomium bromide; oxygen; cyclohexene In acetonitrile Hg cathode, Pt anode, -1.0 V vs SCE;	83%

diethyl methylenemalonate (3377-20-6) → Diethyl ketomalonate (609-09-6)

Conditions	Yield
With formaldehyd; ozone; Pd-on-C In methanol	82%
Yield given. Multistep reaction;

Diethyl 2-bromomalonate (685-87-0) → Diethyl ketomalonate (609-09-6)

Conditions	Yield
With silver nitrate In ethanol; acetonitrile for 22h; Heating;	77%
With Amberlyst A-26; nitrate form In benzene for 7h; Heating;	70%
With pyridine N-oxide In acetone; acetonitrile; Petroleum ether
Multi-step reaction with 2 steps 1: alcohol / 40 - 50 °C 2: bromine / 110 °C / Destillation des Reaktionsprodukts unter verminderten Druck View Scheme

diethyl malonate (105-53-3) → diethyl dichloromalonate (20165-81-5) + Diethyl ketomalonate (609-09-6)

Conditions	Yield
With hydrogenchloride; sodium chlorate; dihydrogen peroxide; sodium hydroxide In water at 10 - 35℃; pH=5 - 10;	A n/a B 76%
With chlorine dioxide; sodium hydroxide In water at 10 - 18℃; for 5h;	A n/a B 76%

5--4,5-dihydro-2,5-dimethyl-4-phenyl-3-furancarbonsaeure-ethylester (91473-89-1) → 2,5-Dimethyl-4-phenyl-3-pyrrolcarbonsaeure-ethylester (16206-31-8) + Diethyl ketomalonate (609-09-6)

Conditions	Yield
With hydrogenchloride In methanol; water Heating;	A 51% B n/a

5-Methoxy-[1,2,4]trioxolane-3,3-dicarboxylic acid diethyl ester (82255-47-8) → Diethyl ketomalonate (609-09-6)

Conditions	Yield
With phosphorus trichloride for 8h; Ambient temperature;	44%
With phosphorus trichloride for 8h; Ambient temperature;	44%

2-ethoxy-2-oxoacetic anhydride (119174-42-4) → Diethyl ketomalonate (609-09-6)

Conditions	Yield
at 240℃;

ethanol (64-17-5) + diethyl dibromomalonate (631-22-1) + potassium acetate (127-08-2) → Diethyl ketomalonate (609-09-6)

dihydroxymalonic acid diethyl ester (631-23-2) → Diethyl ketomalonate (609-09-6)

Conditions	Yield
With phosphorus pentoxide Destillieren;

diethyl 2,3-dioxosuccinate (59743-08-7) → Diethyl ketomalonate (609-09-6)

diethyl 2-acetoxymalonate (5468-23-5) → Diethyl ketomalonate (609-09-6)

Conditions	Yield
With bromine at 110℃; Destillation des Reaktionsprodukts unter verminderten Druck;

bromo-nitro-malonic acid diethyl ester (42065-95-2) → Diethyl ketomalonate (609-09-6)

diethyl malonate (105-53-3) → dihydroxymalonic acid diethyl ester (631-23-2) + Diethyl ketomalonate (609-09-6)

Conditions	Yield
With nitrogen oxides
With ammonium cerium (IV) nitrate In acetonitrile at 0 - 20℃; for 4h; Overall yield = 69 %;

2-hydroxy-malonic acid diethyl ester (13937-08-1) → Diethyl ketomalonate (609-09-6)

Conditions	Yield
With bromine

diethyl dibromomalonate (631-22-1) → Diethyl ketomalonate (609-09-6)

Conditions	Yield
With 2-morpholin-4-yldisulfanyl-benzothiazole
Multi-step reaction with 2 steps 1: ethanol / 1.) 50 deg C, 2 h, 2.) reflux, overnight 2: tetrabutylammonium bromide View Scheme

diethyl ethylidenemalonate (1462-12-0) → Diethyl ketomalonate (609-09-6)

Conditions	Yield
With ozone; triphenylphosphine 1.) CH2Cl2, -78 deg C, 2 h; Yield given. Multistep reaction;

chloroformic acid ethyl ester (541-41-3) + ethyl 2-cyanoacetate (105-56-6) + Azobenzene (1227476-15-4) → diphenyl hydrazine (122-66-7) + Diethyl ketomalonate (609-09-6)

Conditions	Yield
With tetrabutylammomium bromide; oxygen; cyclohexene 1.) acetonitrile, -1.3 V vs. SCE 2.) acetonitrile, -1.0 V vs. SCE; Yield given. Multistep reaction;

diethyl α-acetoxy-α-bromomalonate (60308-73-8) → Diethyl ketomalonate (609-09-6)

Conditions	Yield
With tetrabutylammomium bromide Yield given;

selenium(IV) oxide (7446-08-4) + diethyl malonate (105-53-3) → Diethyl ketomalonate (609-09-6)

Conditions	Yield
at 120 - 130℃;

selenium(IV) oxide (7446-08-4) + diethyl malonate (105-53-3) → carbon dioxide (124-38-9) + ethyl acetate (141-78-6) + Diethyl ketomalonate (609-09-6) + CO

Conditions	Yield
bei Siedetemperatur;

tetrachloromethane (56-23-5) + selenium(IV) oxide (7446-08-4) + diethyl malonate (105-53-3) → oxomalonic acid monoethyl ester (27728-17-2) + oxalic acid diethyl ester (95-92-1) + Diethyl ketomalonate (609-09-6) + CO

Conditions	Yield
Produkt 5: CO2;

isonitrosomalonic acid diethyl ester → Diethyl ketomalonate (609-09-6)

Conditions	Yield
With dinitrogen pentoxide at 0℃;

ethanol (64-17-5) + mesoxalacidic barium → Diethyl ketomalonate (609-09-6)

Conditions	Yield
With hydrogenchloride

ethyl iodide (75-03-6) + silver salt of/the/ dioxymalonic acid → Diethyl ketomalonate (609-09-6)

hydrogenchloride (7647-01-0) + (1-ethoxy-ethylidenamino)-malonic acid diethyl ester + potassium ethoxide (917-58-8) → Diethyl ketomalonate (609-09-6)

diethyl 2-acetoxymalonate (5468-23-5) + bromine (7726-95-6) → Diethyl ketomalonate (609-09-6)

1,2,5-trimethyl-1H-pyrrole (930-87-0) + Diethyl ketomalonate (609-09-6) → 2-Hydroxy-2-(1,2,5-trimethyl-1H-pyrrol-3-yl)-malonic acid diethyl ester (95679-85-9)

Conditions	Yield
In dichloromethane at 20℃; under 750.06 Torr; for 24h;	100%

1,4-dimethoxybezene (150-78-7) + Diethyl ketomalonate (609-09-6) → diethyl (2,5-dimethoxyphenyl)tartronate (83026-20-4)

Conditions	Yield
With tin(IV) chloride In dichloromethane 1.) 0 deg C, 10 min, 2.) 20 deg C, 19 h;	100%

1-methoxy-3-trimethylsilyl-1,3-butadiene (940926-96-5) + Diethyl ketomalonate (609-09-6) → 6-Methoxy-4-trimethylsilanyl-3,6-dihydro-pyran-2,2-dicarboxylic acid diethyl ester (103560-11-8)

Conditions	Yield
In benzene at 50℃; for 10h;	100%

(3R,5R,7R)-1-(buta-1,3-dien-2-yl)adamantane (92406-83-2) + Diethyl ketomalonate (609-09-6) → 4-Adamantan-1-yl-3,6-dihydro-pyran-2,2-dicarboxylic acid diethyl ester (92406-95-6)

Conditions	Yield
In toluene for 39h; Heating;	100%

2-(2,2,2-trifluoroethoxy)-4-oxo-5,6-benzo-1,3,2-dioxaphosphorinane (137073-22-4) + Diethyl ketomalonate (609-09-6) → 5-(2,2,2-trifluoroethoxy)-2,2,3,3-tetrakis(ethoxycarbonyl)-7-oxo-8,9-benzo-1,4,6,10-tetraoxa-5λ5-phosphaspiro<4,5>decane

Conditions	Yield
In dichloromethane	100%

2-(2,2,3,3-tetrafluoropropoxy)benzo[e][1,3,2]dioxaphosphinin-4-one (137073-23-5) + Diethyl ketomalonate (609-09-6) → 5-(2,2,3,3-tetrafluoropropoxy)-2,2,3,3-tetrakis(ethoxycarbonyl)-7-oxo-8,9-benzo-1,4,6,10-tetraoxa-5λ5-phosphaspiro<4,5>decane

Conditions	Yield
In dichloromethane	100%

Methyl-5-hydroxy-2,2-diphenyl-4H-1,3-dithiin-6-carboxylat (139101-75-0) + Diethyl ketomalonate (609-09-6) → Diethyl-2-hydroxy-2-(6-methoxycarbonyl-5-oxo-2,2-diphenyl-1,3-dithian-4-yl)malonat (139101-79-4)

Conditions	Yield
With 4-methyl-morpholine In benzene for 12h;	100%

triphenyl(t-butoxycarbonylimino)phosphorane (68014-21-1) + Diethyl ketomalonate (609-09-6) → 2-(N-tert-butoxycarbonylimino)malonic acid diethyl ester (408346-61-2)

Conditions	Yield
In tetrahydrofuran for 24h; aza-Wittig reaction; Heating;	100%
In tetrahydrofuran at 80℃; for 12h;	89%
In tetrahydrofuran for 18h; Heating;
In tetrahydrofuran for 18h; Reflux;

4,4-difluoro-3,5,8-trimethyl-4-bora-3a,4a-diaza-s-indacene (1449105-33-2) + Diethyl ketomalonate (609-09-6) → C19H23BF2N2O5

Conditions	Yield
With piperidine; acetic acid In toluene at 60℃;	100%

4,4-difluoro-1,3,5,7,8-pentamethyl-4-bora-3a,4a-diaza-s-indecene (121207-31-6) + Diethyl ketomalonate (609-09-6) → C21H27BF2N2O5

Conditions	Yield
With piperidine; acetic acid In toluene at 60℃;	100%

toluene (108-88-3) + Diethyl ketomalonate (609-09-6) → diethyl 2-hydroxy-2-(4-methylphenyl)propane-1,3-dioate (412014-15-4)

Conditions	Yield
With tin(IV) chloride at 20℃; for 2h;	99%
With tin(IV) chloride

3,7-dimethyl-6-octenylamine (53339-59-6) + Diethyl ketomalonate (609-09-6) → Diethyl (3',7'-Dimethyl-6-octenylimino)malonate (119392-65-3)

Conditions	Yield
In benzene Heating;	99%

2-(n-pentyl)-1-ethoxy-1,3-butadiene (100507-81-1) + Diethyl ketomalonate (609-09-6) → 3-n-Pentyl-2-ethoxy-5,6-dihydro-2H-pyran-6,6-dicarbonsaeure-diethylester

Conditions	Yield
at 50℃; for 6h;	99%

1-methoxy-1,3-butadiene (10034-09-0) + Diethyl ketomalonate (609-09-6) → 6-Methoxy-3,6-dihydro-pyran-2,2-dicarboxylic acid diethyl ester (23012-61-5)

Conditions	Yield
	99%

(S)-3-acetoxy-1-triphenylphosphoranylidene-2-butanone (95832-86-3) + Diethyl ketomalonate (609-09-6) → 2-((S)-3-Acetoxy-2-oxo-butylidene)-malonic acid diethyl ester

Conditions	Yield
In chloroform for 48h; Ambient temperature;	99%

2-phenyl-1-(1-phenylcyclopropyl)-ethan-1-one + Diethyl ketomalonate (609-09-6) → C22H20O5

Conditions	Yield
With trimethylsilyl trifluoromethanesulfonate In 1,2-dichloro-ethane at 60℃; for 12h; stereoselective reaction;	99%

2-(4-bromophenyl)-1-cyclopropylethan-1-one + Diethyl ketomalonate (609-09-6) → C16H15BrO5 (1198272-06-8)

Conditions	Yield
With trimethylsilyl trifluoromethanesulfonate In 1,2-dichloro-ethane at 60℃; for 12h;	99%

2-(3-methylphenyl)-1-cyclopropylethan-1-one (56594-98-0) + Diethyl ketomalonate (609-09-6) → C17H18O5 (1198272-10-4)

Conditions	Yield
With trimethylsilyl trifluoromethanesulfonate In 1,2-dichloro-ethane at 60℃; for 12h;	99%

1-benzyl-3-(1-cyanovinyl)-2-oxoindolin-3-yl tert-butyl carbonate + Diethyl ketomalonate (609-09-6) → diethyl 1'-benzyl-4-cyano-2'-oxo-2H-spiro[furan-3,3'-indoline]-2,2-dicarboxylate

Conditions	Yield
Stage #1: 1-benzyl-3-(1-cyanovinyl)-2-oxoindolin-3-yl tert-butyl carbonate; Diethyl ketomalonate In ethyl acetate at -40℃; for 0.0833333h; Stage #2: With C29H28N2O In ethyl acetate at -40℃; enantioselective reaction;	99%

acetamide (60-35-5) + Diethyl ketomalonate (609-09-6) → diethyl α-hydroxy(acetylamino)malonate (84636-50-0)

Conditions	Yield
In acetonitrile at 60℃; for 18h;	99%

1-methylindole (603-76-9) + Diethyl ketomalonate (609-09-6) → diethyl α-hydroxy-α-(1-methylindol-3-yl)-malonate (127744-44-9)

Conditions	Yield
In toluene for 3h; Heating;	98%
In toluene at 100℃; for 3h; Heating;	95%

1-ethoxy-2-methyl-1,3-butadien (17015-31-5) + Diethyl ketomalonate (609-09-6) → 3-Methyl-2-ethoxy-5,6-dihydro-2H-pyran-6,6-dicarbonsaeure-diethylester

Conditions	Yield
at 50℃; for 6h;	98%

Acetic acid (3E,5Z)-6-methoxy-hexa-3,5-dienyl ester (81420-09-9) + Diethyl ketomalonate (609-09-6) → (3S,6R)-3-(2-Acetoxy-ethyl)-6-methoxy-3,6-dihydro-pyran-2,2-dicarboxylic acid diethyl ester (81420-13-5)

Conditions	Yield
In benzene at 60℃; under 6375510 Torr; for 48h;	98%

8-oxo-7-azabicyclo<4.2.0>oct-2-ene (20205-48-5, 77003-43-1, 77131-40-9, 98856-65-6) + Diethyl ketomalonate (609-09-6) → 2-Hydroxy-2-((1S,6R)-8-oxo-7-aza-bicyclo[4.2.0]oct-3-en-7-yl)-malonic acid diethyl ester (77131-41-0)

Conditions	Yield
for 24h; Ambient temperature;	98%

(3-methoxycarbonylpropionyl)methylenetriphenylphosphorane (84028-77-3) + Diethyl ketomalonate (609-09-6) → 2-Ethoxycarbonyl-4-oxo-hept-2-enedioic acid 1-ethyl ester 7-methyl ester (206999-00-0)

Conditions	Yield
In chloroform for 48h; Ambient temperature;	98%

levodopa (59-92-7) + Diethyl ketomalonate (609-09-6) → 6,7-dihydroxy-3,4-dihydro-2H-isoquinoline-1,1,3-tricarboxylic acid diethyl ester

Conditions	Yield
With trifluoroacetic acid In toluene at 85℃; for 2h; Pictet-Spegler condensation;	98%

L-DOPA methyl ester (7101-51-1) + Diethyl ketomalonate (609-09-6) → 6,7-dihydroxy-3,4-dihydro-2H-isoquinoline-1,1,3-tricarboxylic acid diethyl ester methyl ester

Conditions	Yield
With trifluoroacetic acid In toluene at 85℃; for 2h; Pictet-Spegler condensation;	98%

2-(3,5-diisopropoxy-4-methoxy-phenyl)-ethylamine + Diethyl ketomalonate (609-09-6) → 6,8-diisopropoxy-7-methoxy-3,4-dihydro-2H-isoquinoline-1,1-dicarboxylic acid diethyl ester

Conditions	Yield
With trifluoroacetic acid In toluene at 85℃; for 4h; Pictet-Spegler condensation;	98%

α-tert-butoxycarbonyl-α-phenyl-γ-methylidene-δ-valerolactone (1086018-36-1, 1086018-32-7, 1086018-34-9) + Diethyl ketomalonate (609-09-6) → 3-tert-butyl 2,2-diethyl 5-methylene-3-phenyl-3,4-dihydro-2H-pyran-2,2,3(3H,4H)-tricarboxylatecarboxylate (1181692-87-4)

Conditions	Yield
With allyl(cyclopentadiene)palladium(II); C38H30NO2P In tetrahydrofuran at 40℃; for 3h; diastereoselective reaction;	98%

Upstream product

• 105-53-3 diethyl malonate 
• 13937-08-1 2-hydroxy-malonic acid diethyl ester 
• 3377-20-6 diethyl methylenemalonate 
• 1462-12-0 diethyl ethylidenemalonate 
• 7446-08-4 selenium(IV) oxide 
• 56-23-5 tetrachloromethane 
• 64-17-5 ethanol 
• 75-03-6 ethyl iodide 
• 7647-01-0 hydrogenchloride 
• 917-58-8 potassium ethoxide 
• 5468-23-5 diethyl 2-acetoxymalonate 
• 7726-95-6 bromine 
• 6829-41-0 diethyl oximinomalonate 
• 119174-42-4 2-ethoxy-2-oxoacetic anhydride 

Downstream Products

• 114983-15-2 2-oxo-1,2-dihydro-pyrido[2,3-b]pyrazine-3-carboxylic acid ethyl ester 
• 114097-17-5 3-oxo-3,4-dihydro-pyrido[2,3-b]pyrazine-2-carboxylic acid ethyl ester 
• 1471-86-9 2-carbethoxy-4-methylpyrido<2,3-b>pyrazin-3(4H)-one 
• 57346-40-4 diethyl 2-hydroxy-2-(2-oxocyclohexyl)propanedioate 
• 6174-95-4 1,1,2,2-tetracarboethoxy-ethylene 
• 109496-98-2 5‐phenylindoline‐2,3‐dione 
• 860755-05-1 hydroxy-p-toluidino-malonic acid diethyl ester 
• 94309-68-9 diethyl di(phenylamino)malonate 
• 76-84-6 triphenylmethyl alcohol 
• 83026-11-3 (4-dimethylamino-phenyl)-hydroxy-malonic acid diethyl ester 
• 1219-05-2 3,4-Dihydro-6,7-dimethyl-3-oxo-chinoxalin-2-carbonsaeure-ethylester 
• 24588-58-7 diethyl 3,6-dihydro-2H-pyran-2,2-dicarboxylate 
• 24588-60-1 4,5-dimethyl-3,6-dihydro-pyran-2,2-dicarboxylic acid diethyl ester 
• 5588-87-4 1H-benzo[e]indole-1,2(3H)-dione 

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