685-88-1

Basic information

• Product Name: Diethyl fluoromalonate
• Synonyms: diethylfluoropropanedioate;Ethyl fluoromalonate;fluoro-malonicacidiethylester;fluoro-propanedioicacidiethylester;Malonic acid, fluoro-, diethyl ester;Monofluoromalonic acid diethyl ester;Propanedioic acid, fluoro-, diethyl ester;DIETHYL 2-FLUOROMALONATE
• CAS NO: 685-88-1
• Molecular Formula: C₇H₁₁FO₄
• Molecular Weight: 178.16
• EINECS: 211-684-7
• Product Categories: Small molecule;Fluorinated Building Blocks;Fluorinating Reagents & Building Blocks for Fluorinated Biochemical Compounds;Synthetic Organic Chemistry;C6 to C7;Carbonyl Compounds;Esters;Alkyl Fluorinated Building Blocks;Building Blocks;C6 to C7;Carbonyl Compounds;Chemical Synthesis;Organic Building Blocks;Organic Fluorinated Building Blocks;Other Fluorinated Organic Building Blocks
• Mol File: 685-88-1.mol
• Article Data: 35

Chemical Properties

• Boiling Point: 121-122 °C30 mm Hg(lit.)
• Flash Point: 144 °F
• Appearance: Clear colorless to pale yellow/Liquid
• Density: 1.129 g/mL at 25 °C(lit.)
• Vapor Pressure: 36.1mmHg at 25°C
• Refractive Index: n20/D 1.407(lit.)
• Storage Temp.: under inert gas (nitrogen or Argon) at 2-8°C
• PKA: 10.40±0.46(Predicted)
• BRN: 1775686
• CAS DataBase Reference: Diethyl fluoromalonate(CAS DataBase Reference)
• NIST Chemistry Reference: Diethyl fluoromalonate(685-88-1)
• EPA Substance Registry System: Diethyl fluoromalonate(685-88-1)

Safety Data

• Hazard Codes: C,T
• Statements: 34
• Safety Statements: 26-36/37/39-45-25-27
• RIDADR: UN 3265 8/PG 2
• WGK Germany: 3
• RTECS: OO1670000
• F: 19
• HazardClass: 8
• PackingGroup: III
• Hazardous Substances Data: 685-88-1(Hazardous Substances Data)

Usage

Chemical Properties

CLEAR COLOURLESS TO PALE YELLOW LIQUID

Uses

The kinetic parameters of diethyl fluoromalonate in hemolysates were used to study carboxylesterase activities in complex systems.

General Description

The reaction of diethyl fluoromalonate with electron-poor and electron-rich, sterically hindered and unhindered aryl bromides and chlorides were studied.

InChI:InChI=1/C3F6O4S/c4-2(5,6)1(10)13-14(11,12)3(7,8)9

Synthetic route

Diethyl fluoroxaloacetate (392-58-5) → fluoromalonic acid diethyl ester (685-88-1)

Conditions	Yield
at 500℃; under 18751.9 - 22502.3 Torr; Temperature; Pressure;	95.2%
at 220℃;
at 230 - 235℃;

diethyl 2-chloromalonate (14064-10-9) → fluoromalonic acid diethyl ester (685-88-1)

Conditions	Yield
With triethylamine tris(hydrogen fluoride); trimethylamine at 80 - 110℃; for 17h;	94%
With triethylamine tris(hydrogen fluoride); triethylamine at 80 - 110℃; for 17h; Heating / reflux;	84%
With potassium fluoride

diethyl malonate (105-53-3) → fluoromalonic acid diethyl ester (685-88-1)

Conditions	Yield
With copper nitrate hemi(pentahydrate); fluorine In acetonitrile at 0 - 5℃; for 2h; Time; Temperature; Concentration; Green chemistry;	94%
With triethylamine pentahydrogen fluoride salt; iodosylbenzene In 1,2-dichloro-ethane at 70℃; for 24h; Reagent/catalyst; Concentration;	85%
With fluorine; copper(II) nitrate In acetonitrile at 5 - 8℃; for 4h;	78%

2-(Diethoxy-phosphoryl)-2-fluoro-malonic acid diethyl ester (171916-50-0) → fluoromalonic acid diethyl ester (685-88-1)

Conditions	Yield
With water; silica gel In ethyl acetate at 20℃; for 16h; dephosphonylation;	89%
Stage #1: With magnesium chloride In toluene at 20℃; for 2h; Disproportionation; Stage #2: 2-(Diethoxy-phosphoryl)-2-fluoro-malonic acid diethyl ester With ammonium chloride In toluene at 20℃; for 6h; Disproportionation;	86%

1,3-diethyl 2-diazopropanedioate (5256-74-6) → fluoromalonic acid diethyl ester (685-88-1)

Conditions	Yield
With hydrogen fluoride In neat (no solvent) at 0℃; for 5h; Inert atmosphere;	84%

cupric nitrate 3H2O + α,α,α-trifluorotoluene (98-08-8) + diethyl malonate (105-53-3) → fluoromalonic acid diethyl ester (685-88-1)

Conditions	Yield
In acetonitrile	78%

sodium diethylmalonate (996-82-7) → fluoromalonic acid diethyl ester (685-88-1)

Conditions	Yield
With 1-fluoro-2,4,6-trimethylpyridinium trifluoromethanesulfonate In tetrahydrofuran at 0℃; for 0.1h;	73%
With xenon difluoride; dimethylsulfide; boron trifluoride diethyl etherate In dichloromethane at -78℃;	42%

sodium diethylmalonate (996-82-7) → fluoromalonic acid diethyl ester (685-88-1) + diethyl 2,2-difluoromalonate (680-65-9)

Conditions	Yield
With 1-fluoro-2,4,6-trimethylpyridinium trifluoromethanesulfonate In tetrahydrofuran at 0℃; for 0.1h;	A 73% B n/a
With perchloryl fluoride In tetrahydrofuran at 0℃; for 0.583333h;	A 84 % Spectr. B 16 % Spectr.

ethyl 2-fluoroacetate (459-72-3) + Diethyl carbonate (105-58-8) → fluoromalonic acid diethyl ester (685-88-1)

Conditions	Yield
With potassium ethoxide for 2h; Reflux;	65.5%

ethanol (64-17-5) + perfluoroacrylic acid (433-68-1) → fluoromalonic acid diethyl ester (685-88-1)

Conditions	Yield
With triethylamine Heating; var. reag.: LiOH, NaOEt;	65%

2,3,3,3-tetrafluoropropionic acid ethyl ester (399-92-8) + sodium ethanolate (141-52-6) → fluoromalonic acid diethyl ester (685-88-1)

Conditions	Yield
In methanol 1.) 0 deg C, 2.) room temperature, 30 min;	63%

3,3,3-Triethoxy-2-fluoro-propionic acid ethyl ester (77778-67-7) → fluoromalonic acid diethyl ester (685-88-1)

Conditions	Yield
With hydrogenchloride In ethanol for 1h; Ambient temperature;	63%
With ethanolate Yield given;

2,3,3,3-tetrafluoropropionic acid ethyl ester (399-92-8) → fluoromalonic acid diethyl ester (685-88-1)

Conditions	Yield
Stage #1: 2,3,3,3-tetrafluoropropionic acid ethyl ester With sodium ethanolate In ethanol at 20 - 30℃; for 0.5h; Stage #2: With hydrogenchloride In methanol at 20℃;	63%
Multi-step reaction with 2 steps 1: ethanol / 0.5 h / Ambient temperature 2: 63 percent / conc. HCl / ethanol / 1 h / Ambient temperature View Scheme
Multi-step reaction with 2 steps 1: EtO- 2: EtO- View Scheme
With sulfuric acid; sodium ethanolate In ethanol

ethoxycarbonylketene ethyltrimethylsilyl acetal (17906-37-5) → fluoromalonic acid diethyl ester (685-88-1) + diethyl 2,2-difluoromalonate (680-65-9)

Conditions	Yield
With fluorine In trichlorofluoromethane at -78℃;	A 59% B n/a

ethyl 2-fluoroacetate (459-72-3) + chloroformic acid ethyl ester (541-41-3) → fluoromalonic acid diethyl ester (685-88-1)

Conditions	Yield
In tetrahydrofuran	22%
(i) NaH, Et2O, (ii) /BRN= 385653/; Multistep reaction;
With sodium methylate In Petroleum ether for 1h; Heating;

diethyl acetylmalonate (570-08-1) → fluoromalonic acid diethyl ester (685-88-1)

Conditions	Yield
With perchloryl fluoride; ethanol; sodium ethanolate

Butyrylmalonsaeure-diethylester (21633-79-4) → fluoromalonic acid diethyl ester (685-88-1)

Conditions	Yield
With perchloryl fluoride; ethanol; sodium ethanolate

Diethyl 2-bromomalonate (685-87-0) → fluoromalonic acid diethyl ester (685-88-1)

Conditions	Yield
With potassium fluoride at 190℃;

ethanol (64-17-5) + 7-chloro-7-fluoro-2,5-dioxabicyclo<4.1.0>heptane (40623-35-6, 40623-36-7, 120201-74-3) → fluoromalonic acid diethyl ester (685-88-1)

Conditions	Yield
With Oxone; sulfuric acid 1.) reflux, 7 d, 2.) RT, 16 h; Yield given. Multistep reaction;

2,3,3,3-tetrafluoropropionitrile (431-32-3) + sodium ethanolate (141-52-6) → fluoromalonic acid diethyl ester (685-88-1)

Conditions	Yield
With hydrogenchloride 1.) EtOH, r.t., 30 min, 2.) EtOH, r.t., 30 min; Multistep reaction;

ethyl bromofluoroacetate (401-55-8) + chloroformic acid ethyl ester (541-41-3) → fluoromalonic acid diethyl ester (685-88-1)

Conditions	Yield
Yield given. Multistep reaction;

(Bis-ethoxycarbonyl-fluoro-methyl)-tributyl-phosphonium; chloride → fluoromalonic acid diethyl ester (685-88-1)

Conditions	Yield
With sodium hydrogencarbonate In tetrahydrofuran; water for 6h; Ambient temperature; Yield given;

diethyl malonate (105-53-3) → fluoromalonic acid diethyl ester (685-88-1) + diethyl 2,2-difluoromalonate (680-65-9)

Conditions	Yield
With sodium hydride; fluorine In acetonitrile 1.) r.t., 1 h, 2.) -15 deg C, 1 h; Title compound not separated from byproducts;	A 37 % Spectr. B 23 % Spectr.
With aluminium trichloride; 1-fluoro-2,4,6-trimethylpyridinium trifluoromethanesulfonate In 1,2-dichloro-ethane at 80℃; for 24h;	A 19 % Spectr. B 76 % Spectr.
With sodium hydride; fluorine In acetonitrile 1.) r.t., 1 h, 2.) -15 deg C, 1 h; Title compound not separated from byproducts;	A 14 % Spectr. B 37 % Spectr.

chloroformic acid ethyl ester (541-41-3) + fluoroacetic acid ethyl ester, sodium-compound → fluoromalonic acid diethyl ester (685-88-1) + fluoro-fluoroacetyl-malonic acid diethyl ester (664-38-0)

Conditions	Yield
With Petroleum ether

chloroformic acid ethyl ester (541-41-3) + sodium-compound of fluoroacetic acid ethyl ester → fluoromalonic acid diethyl ester (685-88-1) + 2-fluoro-2-fluoroacetyl-malonic acid diethyl ester

Conditions	Yield
With Petroleum ether
With diethyl ether

1,1,2,3,3,3-hexafluoropropyl ethyl ether (380-34-7) → fluoromalonic acid diethyl ester (685-88-1)

Conditions	Yield
Multi-step reaction with 3 steps 1: 82 percent / conc. sulfuric acid / 1 h / Ambient temperature 2: ethanol / 0.5 h / Ambient temperature 3: 63 percent / conc. HCl / ethanol / 1 h / Ambient temperature View Scheme
Multi-step reaction with 3 steps 1: H+ 2: EtO- 3: EtO- View Scheme
Multi-step reaction with 2 steps 1: conc. sulfuric acid / 1 h / Ambient temperature 2: 63 percent / methanol / 1.) 0 deg C, 2.) room temperature, 30 min View Scheme
Multi-step reaction with 2 steps 1.1: sulfuric acid / 20 - 30 °C 2.1: sodium ethanolate / ethanol / 0.5 h / 20 - 30 °C 2.2: 20 °C View Scheme

copper(II) nitrate + diethyl malonate (105-53-3) → fluoromalonic acid diethyl ester (685-88-1)

Conditions	Yield
With fluorine In acetonitrile

1,1'-carbonyldiimidazole (530-62-1) → fluoromalonic acid diethyl ester (685-88-1)

Conditions	Yield
In N-methyl-acetamide; dichloromethane

caro's acid (7722-86-3) + fluoromalonaldehyde bis(diethyl acetal) (120131-05-7) → fluoromalonic acid diethyl ester (685-88-1)

Conditions	Yield
With ammonium persulfate; sulfuric acid In ethanol; water

fluoromalonic acid diethyl ester (685-88-1) + 1-(2-fluorobenzyl)-5-(isoxazol-3-yl)-1H-pyrazole-3-carboximidamide (1354044-23-7) → 5-fluoro-2-(1-(2-fluorobenzyl)-5-(isoxazol-3-yl)-1H-pyrazol-3-yl)-6-hydroxypyrimidin-4(3H)-one (1446359-42-7)

Conditions	Yield
With 1,8-diazabicyclo[5.4.0]undec-7-ene In ethanol at 70℃; for 24h;	100%
With 1,8-diazabicyclo[5.4.0]undec-7-ene In ethanol at 70℃; for 24h;	100%

fluoromalonic acid diethyl ester (685-88-1) → sodium fluoromalonate

Conditions	Yield
With water; sodium hydroxide In ethanol at 60℃; for 0.75h;	100%

fluoromalonic acid diethyl ester (685-88-1) → potassium 3-ethoxy-2-fluoro-3-oxopropanoate

Conditions	Yield
With potassium hydroxide In ethanol at 20℃;	100%

fluoromalonic acid diethyl ester (685-88-1) → 2-fluoromalonic acid (473-87-0)

Conditions	Yield
With water; lithium hydroxide In methanol at 20℃; for 16h; air;	99%
With water; sodium hydroxide In ethanol at 60℃; for 2h;	98%
Stage #1: fluoromalonic acid diethyl ester With water; lithium hydroxide In ethanol at 25 - 50℃; for 16h; Stage #2: With hydrogenchloride In tert-butyl methyl ether; water pH=1;	88%

fluoromalonic acid diethyl ester (685-88-1) + (4R,4S)-4-(trifluoromethyl)-1,4,5,6-tetrahydropyrimidin-2-ylamine hydrochloride → (2R,2S)-7-fluoro-8-hydroxy-2-(trifluoromethyl)-1,2,3,4-tetrahydropyrimido[1,2-a]pyrimidin-6-one

Conditions	Yield
With sodium methylate In methanol for 3h;	99%

fluoromalonic acid diethyl ester (685-88-1) + 4,4,4-trifluoro-1-(4‘-nitrophenyl)but-2-en-1-one → (S)-diethyl 2-fluoro-2-(1,1,1-trifluoro-4-(4-nitrophenyl)-4-oxobutan-2-yl)malonate

Conditions	Yield
With potassium phosphate; N-((S)-1-(((S)-1-(diphenylphosphanyl)-3-ethylpentan-2-yl)amino)-3-methyl-1-oxobutan-2-yl)-3,5-bis(trifluoromethyl)benzamide; acrylic acid methyl ester In toluene at -20℃; for 24h; Michael Addition; enantioselective reaction;	99%

fluoromalonic acid diethyl ester (685-88-1) + N-butylammonium bromide (15567-09-6) → ethyl α-(N-butyl)carbamoylfluoroacetate

Conditions	Yield
With triethylamine In 1,4-dioxane at 20℃; for 12h;	99%

fluoromalonic acid diethyl ester (685-88-1) + (SS)-2-methyl-N-(2,2,2-trifluoroethylidene)-propane-2-sulfinamide → (S)-diethyl 2-[(S)-1-(tert-butanesulfinamido)-2,2,2-trifluoroethyl]-2-fluoromalonate (1372420-76-2)

Conditions	Yield
Stage #1: fluoromalonic acid diethyl ester With 1-ethyl-2,2,4,4,4-pentakis(dimethylamino)-2λ5,4λ5-catenadi(phosphazene) In toluene at -78℃; for 0.166667h; Mannich reaction; Inert atmosphere; Stage #2: (SS)-2-methyl-N-(2,2,2-trifluoroethylidene)-propane-2-sulfinamide In toluene at -78℃; for 24h; Mannich reaction; Inert atmosphere; optical yield given as %de; diastereoselective reaction;	98%
Stage #1: fluoromalonic acid diethyl ester With C13H36N6P2 In toluene at -78℃; for 0.166667h; Mannich Aminomethylation; Inert atmosphere; Stage #2: (SS)-2-methyl-N-(2,2,2-trifluoroethylidene)-propane-2-sulfinamide In toluene at -78℃; for 24h; Mannich Aminomethylation; Inert atmosphere; stereoselective reaction;	98%

N-isopropylurea (691-60-1) + fluoromalonic acid diethyl ester (685-88-1) → 5-fluoro-1-isopropylpyrimidine-2,4,6(1H,3H,5H)-trione

Conditions	Yield
With sodium methylate In methanol at 85℃; for 4h;	98%
With sodium methylate In methanol at 85℃; for 4h;	98%

fluoromalonic acid diethyl ester (685-88-1) + urea (57-13-6) → 5-fluorobarbituric acid (767-80-6)

Conditions	Yield
With sodium ethanolate In ethanol	97%
Stage #1: urea With sodium In ethanol Reflux; Stage #2: fluoromalonic acid diethyl ester In ethanol for 1.16667h; Reflux;	51%
With sodium methylate

fluoromalonic acid diethyl ester (685-88-1) → 2-fluoropropanediamide (815-59-8)

Conditions	Yield
With ammonia In methanol at 20℃; Inert atmosphere;	97%
With ammonia In methanol Ambient temperature;	94%
With ammonium hydroxide

fluoromalonic acid diethyl ester (685-88-1) + 3-(4-methoxyphenyl)-5-(bromomethyl)isoxazole (196877-76-6) → C18H20FNO6 (1204423-81-3)

Conditions	Yield
Stage #1: fluoromalonic acid diethyl ester With potassium tert-butylate In N,N-dimethyl-formamide at 20℃; for 0.166667h; Stage #2: 5-(bromomethyl)-3-(4-methoxyphenyl)isoxazole In N,N-dimethyl-formamide at 20℃; for 1h;	97%

fluoromalonic acid diethyl ester (685-88-1) + 1-(2-fluorobenzyl)-5-(isoxazol-3-yl)-1H-pyrazole-3-carboximidamide hydrochloride → 5-fluoro-2-(1-(2-fluorobenzyl)-5-(isoxazol-3-yl)-1H-pyrazol-3-yl)pyrimidine-4,6-diol

Conditions	Yield
With sodium methylate In methanol at 20 - 35℃; for 0.5h;	97%

2-chloro-N-(quinolin-8-yl)acetamide (32889-11-5) + fluoromalonic acid diethyl ester (685-88-1) + phenylacetylene (536-74-3) → C26H25FN2O5

Conditions	Yield
With copper(l) iodide; caesium carbonate In tetrahydrofuran at 80℃; for 1.5h; Sonogashira Cross-Coupling; Inert atmosphere; Sealed tube;	96%

2-chloro-N-(quinolin-8-yl)acetamide (32889-11-5) + fluoromalonic acid diethyl ester (685-88-1) + phenylacetylene (536-74-3) → (E)-diethyl 2-fluoro-2-(4-oxo-1-phenyl-4-(quinolin-8-ylamino)but-1-en-2-yl)malonate

Conditions	Yield
With copper(l) iodide; caesium carbonate In tetrahydrofuran at 80℃; for 1.5h; Inert atmosphere; stereoselective reaction;	96%

Benzyloxymethyl chloride (3587-60-8) + fluoromalonic acid diethyl ester (685-88-1) → 2-fluoro-2-benzyloxymethylmalonic acid diethyl ester (133384-77-7)

Conditions	Yield
Stage #1: fluoromalonic acid diethyl ester With sodium hydride In tetrahydrofuran at -10 - -5℃; Stage #2: Benzyloxymethyl chloride In tetrahydrofuran at -10 - -5℃;	95%
With sodium hydride In N,N-dimethyl-formamide for 1.5h; Ambient temperature;	75%
In tetrahydrofuran; mineral oil

fluoromalonic acid diethyl ester (685-88-1) + Cyclopropylamine (765-30-0) → ethyl α-(N-cyclopropyl)carbamoylfluoroacetate

Conditions	Yield
at 20℃; for 16h;	95%

fluoromalonic acid diethyl ester (685-88-1) + (1-furan-2-ylmethylidene)carbamic acid tert-butyl ester (479423-46-6) → diethyl 2-[(tert-butoxycarbonylamino)(furan-2-yl)methyl]-2-fluoromalonate (1236293-01-8)

Conditions	Yield
Stage #1: fluoromalonic acid diethyl ester With 1-{3,5-bis(trifluoromethyl)phenyl}-3-{(1R,2R)-2-(dimethylamino)cyclohexyl}thiourea In toluene at 20℃; for 0.0833333h; Mannich reaction; Stage #2: (1-furan-2-ylmethylidene)carbamic acid tert-butyl ester In toluene at -78℃; for 96h; Mannich reaction; optical yield given as %ee; enantioselective reaction;	94%

fluoromalonic acid diethyl ester (685-88-1) + morpholinylguanidine hydrogen sulphate (88497-68-1) → 5-fluoro-2-(morpholin-4-yl)pyrimidine-4,6-diol (944401-89-2)

Conditions	Yield
With sodium In ethanol for 12h; Reflux;	94%
Stage #1: fluoromalonic acid diethyl ester; morpholinylguanidine hydrogen sulphate With ethanol; sodium for 12.1667h; Reflux; Stage #2: With hydrogenchloride In water at 10℃; pH=4;	94%

fluoromalonic acid diethyl ester (685-88-1) + (2-nitroethenyl)benzene (102-96-5) → (S)-diethyl 2-fluoro-2-(2-nitro-1-phenylethyl)malonate

Conditions	Yield
With C37H31F6N3O In dichloromethane at 20℃; for 48h; Michael reaction; Inert atmosphere; optical yield given as %ee; enantioselective reaction;	93%
With C35H31F17N4OS In toluene at 25℃; for 24h; Michael Addition;

fluoromalonic acid diethyl ester (685-88-1) + urea (57-13-6) → 5-fluoropyrimidine-2,4,6-triol (767-80-6)

Conditions	Yield
Stage #1: fluoromalonic acid diethyl ester; urea With sodium ethanolate In ethanol for 60h; Reflux; Stage #2: With hydrogenchloride In water pH=2; Heating;	93%
Stage #1: fluoromalonic acid diethyl ester; urea With sodium acetate In ethanol for 60h; Reflux; Stage #2: With hydrogenchloride In water pH=2;	93%
With sodium ethanolate In ethanol at 90℃;	1.24 g

fluoromalonic acid diethyl ester (685-88-1) + benzhydrilium tetrafluoroborate → diethyl 2-(bis(2,3,6,7-tetrahydro-1H,5H-pyrido[3,2,1-ij]quinolin-9-yl)methyl)-2-fluoromalonate

Conditions	Yield
With potassium tert-butylate In dimethyl sulfoxide at 20℃; Inert atmosphere;	92%

fluoromalonic acid diethyl ester (685-88-1) + C10H15N3O2 → C13H14FN3O4

Conditions	Yield
In N,N-dimethyl-formamide at 70℃; for 7h; Temperature; Sealed tube; Inert atmosphere;	90.5%

fluoromalonic acid diethyl ester (685-88-1) + benzyl alcohol (100-51-6) → dibenzyl 2-fluoromalonate (133384-81-3)

Conditions	Yield
With toluene-4-sulfonic acid In toluene Heating;	90%

fluoromalonic acid diethyl ester (685-88-1) + benzaldehyde N-boc imine (150884-50-7) → (R)-diethyl 2-(((tert-butoxycarbonyl)amino)(phenyl)methyl)-2-fluoromalonate (1236292-94-6) + (S)-diethyl 2-(((tert-butoxycarbonyl)amino)(phenyl)methyl)-2-fluoromalonate (1236293-03-0)

Conditions	Yield
Stage #1: fluoromalonic acid diethyl ester With (S)-1-(1-(diphenylphosphino)-3-phenylpropan-2-yl)-3-(4-nitrophenyl)thiourea; acrylic acid methyl ester In dichloromethane at 20℃; for 0.166667h; Stage #2: benzaldehyde N-boc imine In diethyl ether at 20℃; for 3h; Mannich Aminomethylation;	A n/a B 90%
Stage #1: fluoromalonic acid diethyl ester With 1-{3,5-bis(trifluoromethyl)phenyl}-3-{(1R,2R)-2-(dimethylamino)cyclohexyl}thiourea In toluene at 20℃; for 0.0833333h; Mannich reaction; Stage #2: benzaldehyde N-boc imine In toluene at -78℃; for 24h; Mannich reaction; optical yield given as %ee; enantioselective reaction;

fluoromalonic acid diethyl ester (685-88-1) + 1-(4-chlorophenyl)-4,4,4-trifluorobut-2-en-1-one (1092546-75-2) → (S)-diethyl 2-(4-(4-chlorophenyl)-1,1,1-trifluoro-4-oxobutan-2-yl)-2-fluoromalonate

Conditions	Yield
With potassium phosphate; N-((S)-1-(((S)-1-(diphenylphosphanyl)-3-ethylpentan-2-yl)amino)-3-methyl-1-oxobutan-2-yl)-3,5-bis(trifluoromethyl)benzamide; acrylic acid methyl ester In toluene at -20℃; for 60h; Michael Addition; enantioselective reaction;	90%

Upstream product

• 14064-10-9 diethyl 2-chloromalonate 
• 392-58-5 Diethyl fluoroxaloacetate 
• 570-08-1 diethyl acetylmalonate 
• 21633-79-4 Butyrylmalonsaeure-diethylester 
• 459-72-3 ethyl 2-fluoroacetate 
• 541-41-3 chloroformic acid ethyl ester 
• 685-87-0 Diethyl 2-bromomalonate 
• 64-17-5 ethanol 
• 433-68-1 trifluoroacrylic acid 
• 399-92-8 2,3,3,3-tetrafluoropropionic acid ethyl ester 
• 141-52-6 sodium ethanolate 
• 105-53-3 diethyl malonate 
• 98-08-8 α,α,α-trifluorotoluene 
• 530-62-1 1,1'-carbonyldiimidazole 

Downstream Products

• 767-80-6 5-fluorobarbituric acid 
• 2708-77-2 D,L-erythro,threo-4-fluoroglutamic acid 
• 133384-81-3 dibenzyl 2-fluoromalonate 
• 16519-02-1 diethyl 2-methyl-2-fluoromalonate 
• 94721-39-8 2-Fluoro-malonic acid monoethyl ester 
• 100701-49-3 3-ethoxy-2-fluoro-3-oxopropionic acid 
• 23197-66-2 diethyl 2-fluoro-2-(4-methoxyphenyl)malonate 
• 617715-97-6 2-cyclopropyl-5-fluoro-4,6-pyrimidinediol 
• 945610-02-6 2-(4-tert-butoxycarbonyl-phenyl)-2-fluoro-malonic acid diethyl ester 
• 72959-94-5 (R)-(+)-ethyl 2-fluoropropionate 
• 102712-70-9 (R)-2-Fluoro-3-(toluene-4-sulfonyloxy)-propionic acid ethyl ester 
• 1023648-24-9 2-(2-{4-[3-(benzyloxy)phenylthio]-2-chlorophenyl}ethyl)-2-fluoromalonic acid diethyl ester 
• 1201676-74-5 C₁₆H₂₀FNO₆ 
• 1201676-70-1 C₁₅H₁₇F₂NO₆ 

Relevant articles and documents

Infrared and Raman spectra, vibrational assignment, and ab initio calculations of fluoromalononitrile

The infrared spectra (3500-80 cm-1) of gaseous and solid and the Raman spectra (3500-30 cm-1) of liquid with quantitative depolarization values and solid fluoromalononitrile, FHC(CN)2, have been recorded. These spectra have been interpreted in detail and a complete vibrational assignment is proposed based on infrared band contours, depolarization values, and relative infrared and Raman intensities. The assignment is supported by a normal coordinate calculation based upon force constants obtained from MP2/6-31G* ab initio calculations. Also, from these calculations the predicted infrared and Raman spectra have been obtained. The C-H bond distance is predicted to be 1.096 A from the isolated carbon-hydrogen stretching frequency. Optimized geometric parameters have been obtained from RHF/6-31G*, MP2/6-31G* and MP2/6-311 + + G** ab initio calculations. These results are discussed and compared with those obtained for some similar molecules.

Continuous synthesis method for 2-fluoroethyl malonate compound

The invention discloses a continuous synthesis method for a 2-fluoroethyl malonate compound. The continuous synthesis method comprises the following steps: taking a formula shown in the description asa raw material, and carrying out a continuous decarbonylation reaction in continuous reaction equipment, thereby obtaining the 2-fluoroethyl malonate compound represented by a formula shown in the description, wherein R and R' separately represent straight-chain or branched alkyl, substituted or unsubstituted aryl or substituted or unsubstituted heterocycle or cyclic alkyl and are the same or different. According to the method, the high-temperature decarbonylation reaction of 2-fluoro-3-oxo-disuccinate is achieved by adopting the continuous reaction equipment. Compared with the traditional pot type reaction, the amount of materials participating in reaction in unit time is reduced greatly, so that a high-temperature hazardous area is reduced, and the security risk is greatly lowered.

METHOD FOR PRODUCING FLUOROMALONIC ESTER DERIVATIVE

PROBLEM TO BE SOLVED: To provide a method for producing a fluoromalonic ester derivative, useful as a raw material of electronic materials and as a synthetic intermediate of an agrochemical, which does not use or waste an expensive fluorinating agent and also has a short process. SOLUTION: A fluoromalonic ester derivative represented by a formula (2) is produced by reacting a malonic ester derivative with the 2-position modified with R3 with N-fluoro-bis(methanesulfonyl)imide in the presence of a Lewis acid. (R1 and R2 are each independently a methyl group, an ethyl group, a C3-4 linear, branched or cyclic alkyl group, a phenyl group, or a benzyl group; and R3 is H, a methyl group or an ethyl group.) SELECTED DRAWING: None COPYRIGHT: (C)2016,JPO&INPIT