1559-02-0

Basic information

• Product Name: Diethyl 1,1-cyclopropanedicarboxylate
• Synonyms: CYCLOPROPANE-1,1-DICARBOXYLIC ACID DIETHYL ESTER;DIETHYL 1,1-CYCLOPROPANEDICARBOXYLATE;DIETHYL CYCLOPROPANE-1,1-DICARBOXYLATE;1,1-CYCLOPROPANEDICARBOXYLIC ACID DIETHYL ESTER;RARECHEM AL BO 0836;DIETHYL 1,1-CYCLOPROPANEDICARBOXYLATE, 9 7%;DiethyldifluoroMalonate96%;DIETHYL 1,1-CYCLOPROPANE-DICARBONYLATE
• CAS NO: 1559-02-0
• Molecular Formula: C₉H₁₄O₄
• Molecular Weight: 186.21
• EINECS: 209-917-2
• Product Categories: Cyclopropanes;Simple 3-Membered Ring Compounds;Cycloalkanes;C8 to C9;Carbonyl Compounds;Esters;Aliphatics;Building Blocks;C8 to C9;Carbonyl Compounds;Chemical Synthesis;Organic Building Blocks
• Mol File: 1559-02-0.mol
• Article Data: 41

Chemical Properties

• Melting Point: 134-136 °C(lit.)
• Boiling Point: 94-96 °C10 mm Hg(lit.)
• Flash Point: 188 °F
• Appearance: Clear colorless/Liquid
• Density: 1.055 g/mL at 25 °C(lit.)
• Vapor Pressure: 0.121mmHg at 25°C
• Refractive Index: n20/D 1.433(lit.)
• Storage Temp.: Sealed in dry,Room Temperature
• Solubility: Acetone (Slightly), Chlorform (Slightly), Methanol (Slightly)
• BRN: 2049509
• CAS DataBase Reference: Diethyl 1,1-cyclopropanedicarboxylate(CAS DataBase Reference)
• NIST Chemistry Reference: Diethyl 1,1-cyclopropanedicarboxylate(1559-02-0)
• EPA Substance Registry System: Diethyl 1,1-cyclopropanedicarboxylate(1559-02-0)

Safety Data

• Hazard Codes: Xi
• Statements: 36/37/38
• Safety Statements: 26-36-24/25-23
• RIDADR: UN 3261 8/PG 2
• WGK Germany: 3
• HazardClass: IRRITANT
• Hazardous Substances Data: 1559-02-0(Hazardous Substances Data)

Usage

Chemical Properties

clear colorless liquid

Uses

Diethyl 1,1-Cyclopropanedicarboxylate (cas# 1559-02-0) is a compound useful in organic synthesis.

Synthesis Reference(s)

Synthesis, p. 690, 1980 DOI: 10.1055/s-1980-29171

General Description

Diethyl cyclopropane-1,1-dicarboxylate participates in ring-opening addition reactions with various nucleophilic reagents.

Purification Methods

If it is free from OH bands in the IR, then fractionally distil the ester and redistil the middle fraction. Otherwise shake it with aqueous NaHCO3, dry it (MgSO4), filter and distil as before or re-esterify it. [As synthon see Danishefsky Acc Chem Res 12 66 1979, Beilstein 9 I 314, 9 II 512, 9 III 3595, 9 IV 2786.]

InChI:InChI=1/C9H14O4/c1-3-12-7(10)9(5-6-9)8(11)13-4-2/h3-6H2,1-2H3

Synthetic route

ethylene dibromide (106-93-4) + diethyl malonate (105-53-3) → diethyl cyclopropane-1,1-dicarboxylate (1559-02-0)

Conditions	Yield
With tetrabutylammomium bromide; potassium carbonate In N,N-dimethyl-formamide at 20℃; for 12h;	98%
With potassium carbonate; [bmim]Br In N,N-dimethyl-formamide at 20 - 70℃;	94%
With tetra(n-butyl)ammonium hydrogensulfate; potassium carbonate In dimethyl sulfoxide at 20℃; for 24h; Alkylation; Cyclization;	92%

diethyl malonate (105-53-3) + diphenyl(vinyl)sulfonium trifluoromethanesulfonate → diethyl cyclopropane-1,1-dicarboxylate (1559-02-0)

Conditions	Yield
With 1,8-diazabicyclo[5.4.0]undec-7-ene In dimethyl sulfoxide at 21℃; for 12h;	97%

1,2-dichloro-ethane (107-06-2) + diethyl malonate (105-53-3) → diethyl cyclopropane-1,1-dicarboxylate (1559-02-0)

Conditions	Yield
With potassium carbonate; sodium iodide In N,N-dimethyl-formamide Reflux;	93%
With water; potassium carbonate; tetrabutylammomium bromide In benzene at 80℃; for 12h;	85%
With tetrabutylammomium bromide; potassium carbonate at 120℃; Concentration; Temperature;	83.47%

potassium carbonate (584-08-7) + ethylene dibromide (106-93-4) + diethyl malonate (105-53-3) → diethyl cyclopropane-1,1-dicarboxylate (1559-02-0)

Conditions	Yield
tetra-(n-butyl)ammonium iodide In N,N-dimethyl-formamide	88.7%

1,2-Diiodoethane (624-73-7) + diethyl malonate (105-53-3) → diethyl cyclopropane-1,1-dicarboxylate (1559-02-0)

Conditions	Yield
With tetrabutylammomium bromide; potassium hydrogencarbonate Reflux;	80.77%

S-Ethenyl-S-(4-methylphenyl)-N-tolylsulfilimine (64648-13-1, 81115-85-7, 81115-90-4) + diethyl malonate (105-53-3) → diethyl cyclopropane-1,1-dicarboxylate (1559-02-0)

Conditions	Yield
With sodium hydride In tetrahydrofuran at 20℃; for 24h; Addition;	76%

S-ethenyl-S-phenyl-N-(toluene-4-sulfonyl)sulfilimine (56692-06-9) + diethyl malonate (105-53-3) → diethyl cyclopropane-1,1-dicarboxylate (1559-02-0)

Conditions	Yield
With sodium hydride In tetrahydrofuran at 20℃; for 24h; Addition;	35%

ethylene dibromide (106-93-4) + diethyl malonate (105-53-3) → oxirane (75-21-8) + diethyl cyclopropane-1,1-dicarboxylate (1559-02-0) + ethylene glycol (107-21-1)

Conditions	Yield
With tetraethylammonium perchlorate In N,N-dimethyl-formamide electrolysis;	A n/a B 13% C n/a

pyridine (110-86-1) + diethyl 2-(2-bromoethyl)-malonate (18721-64-7) + acetyl chloride (75-36-5) + toluene (108-88-3) → diethyl cyclopropane-1,1-dicarboxylate (1559-02-0)

diethyl 2-(2-bromoethyl)-malonate (18721-64-7) + sodium ethanolate (141-52-6) → diethyl cyclopropane-1,1-dicarboxylate (1559-02-0)

cyclopropane-1,1-dicarboxylic acid (598-10-7) → diethyl cyclopropane-1,1-dicarboxylate (1559-02-0)

Conditions	Yield
With sulfuric acid; benzene

1-carbethoxy-1-cyanocyclopropane (1558-81-2) → diethyl cyclopropane-1,1-dicarboxylate (1559-02-0)

Conditions	Yield
With hydrogenchloride; ethanol

sodium diethylmalonate (996-82-7) + 1,2-dichloro-ethane (107-06-2) → butane-1,1,4,4-tetracarboxylic acid (4435-38-5) + diethyl cyclopropane-1,1-dicarboxylate (1559-02-0)

Conditions	Yield
entsteht der Tetraaethylester; man isoliert den Ester durch fraktionierte Destillation im Vakuum;

sodium diethylmalonate (996-82-7) + 1,2-dichloro-ethane (107-06-2) → butane-1,1,4,4-tetracarboxylic acid tetraethyl ester (4450-43-5) + diethyl cyclopropane-1,1-dicarboxylate (1559-02-0)

Conditions	Yield
man isoliert durch fraktionierte Destillation im Vakuum;

diethyl acetylmalonate (570-08-1) + sodium ethanolate (141-52-6) + ethylene dibromide (106-93-4) → diethyl cyclopropane-1,1-dicarboxylate (1559-02-0)

diethyl acetylmalonate (570-08-1) + ethylene dibromide (106-93-4) → diethyl cyclopropane-1,1-dicarboxylate (1559-02-0)

Conditions	Yield
With sodium ethanolate

diethyl 2-chloroethylmalonate (18719-42-1) → diethyl cyclopropane-1,1-dicarboxylate (1559-02-0)

Conditions	Yield
With potassium tert-butylate In tert-butyl alcohol at 25℃; Rate constant; other reaction partners, other solvents;
With sodium ethanolate In ethanol
With potassium carbonate In ethanol Heating;

diethyl 2-(2-bromoethyl)-malonate (18721-64-7) → diethyl cyclopropane-1,1-dicarboxylate (1559-02-0)

Conditions	Yield
With potassium tert-butylate In tert-butyl alcohol at 25℃; Rate constant; other reaction partners, other solvents;
With sodium ethanolate In ethanol

(2-Dimethylsulfonio-ethyl)-malonsaeure-diethylester-Kation → diethyl cyclopropane-1,1-dicarboxylate (1559-02-0)

Conditions	Yield
With sodium ethanolate In ethanol

vinyl isocyanide (14668-82-7) + diethyl malonate (105-53-3) → diethyl cyclopropane-1,1-dicarboxylate (1559-02-0)

Conditions	Yield
With copper(I) oxide In benzene at 80℃; for 7h;

ethene (74-85-1) + diethyl malonate (105-53-3) → diethyl cyclopropane-1,1-dicarboxylate (1559-02-0)

Conditions	Yield
With sulfuryl dichloride; Dimethyldisulphide; sodium ethanolate; dimethyl sulfate Yield given. Multistep reaction;

diethyl ether (60-29-7) + diethyl 2-(2-bromoethyl)-malonate (18721-64-7) + acetyl chloride (75-36-5) + sodium → diethyl cyclopropane-1,1-dicarboxylate (1559-02-0)

diethyl ether (60-29-7) + diethyl 2-(2-bromoethyl)-malonate (18721-64-7) + ammonia (7664-41-7) → Cyclopropan-1-carbonsaeureethylester-1-carbonsaeureamid (6914-75-6) + diethyl cyclopropane-1,1-dicarboxylate (1559-02-0) + cyclopropane-1,1-dicarboxylic acid amide [4-(3-fluoro-benzyloxy)-phenyl]-amide (5813-85-4)

hydrogenchloride (7647-01-0) + ethanol (64-17-5) + 1-carbethoxy-1-cyanocyclopropane (1558-81-2) → diethyl cyclopropane-1,1-dicarboxylate (1559-02-0)

ethyl iodide (75-03-6) + silver salt of/the/ cyclopropane-1.1-dicarboxylic acid → diethyl cyclopropane-1,1-dicarboxylate (1559-02-0)

hydrogenchloride (7647-01-0) + ethanol (64-17-5) + 1-carbethoxy-1-cyanocyclopropane (1558-81-2) → diethyl 2-chloroethylmalonate (18719-42-1) + diethyl cyclopropane-1,1-dicarboxylate (1559-02-0)

sodium diethylmalonate (996-82-7) + ethylene dibromide (106-93-4) → diethyl cyclopropane-1,1-dicarboxylate (1559-02-0) + butane-α.α.δ.δ-tetracarboxylic acid tetraethyl ester

ethyl 2-cyanoacetate (105-56-6) → diethyl cyclopropane-1,1-dicarboxylate (1559-02-0)

Conditions	Yield
Multi-step reaction with 2 steps 1: alcoholic sodium ethylate 2: HCl; absolute alcohol View Scheme

polyethylene glycol monomethyl ether + 1,2-dichloro-ethane (107-06-2) + diethyl malonate (105-53-3) → diethyl cyclopropane-1,1-dicarboxylate (1559-02-0)

Conditions	Yield
With tetrabutylammomium bromide; potassium carbonate

diethyl methylenemalonate (3377-20-6) + dimethylsulfoxonium methylide (70775-39-2, 5367-24-8) → diethyl cyclopropane-1,1-dicarboxylate (1559-02-0)

Conditions	Yield
In tetrahydrofuran; mineral oil at 20 - 50℃; for 4.5h; Inert atmosphere;

diethyl cyclopropane-1,1-dicarboxylate (1559-02-0) → [1-(hydroxymethyl)cyclopropyl]methanol (39590-81-3)

Conditions	Yield
With lithium aluminium tetrahydride In tetrahydrofuran for 16h; Reduction; Heating;	99%
With lithium aluminium tetrahydride In tetrahydrofuran at 0℃;	88%
With lithium aluminium tetrahydride In tetrahydrofuran at 0℃; for 0.5h;	87%

diethyl cyclopropane-1,1-dicarboxylate (1559-02-0) + 2-methyl-6-iodobenzoic acid methyl ester (103440-55-7) → diethyl 2-(2-(methoxycarbonyl)-3-methylphenethyl)malonate

Conditions	Yield
Stage #1: 2-methyl-6-iodobenzoic acid methyl ester With TurboGrignard In tetrahydrofuran; 2-methyltetrahydrofuran at -78℃; for 0.5h; Inert atmosphere; Sealed tube; Stage #2: diethyl cyclopropane-1,1-dicarboxylate With 1,3-dimethyl-2-imidazolidinone; copper(I) iodide dimethyl sulfide complex In tetrahydrofuran; 2-methyltetrahydrofuran at -78 - 23℃; Inert atmosphere; Sealed tube;	99%

methyl 3-iodobiphenyl-2-carboxylate (960286-19-5) + diethyl cyclopropane-1,1-dicarboxylate (1559-02-0) → diethyl 2-(2-(2-(methoxycarbonyl)-[1,1'-biphenyl]-3-yl)ethyl)malonate

Conditions	Yield
Stage #1: methyl 3-iodobiphenyl-2-carboxylate With TurboGrignard In tetrahydrofuran; 2-methyltetrahydrofuran at -78℃; for 0.5h; Inert atmosphere; Sealed tube; Stage #2: diethyl cyclopropane-1,1-dicarboxylate With 1,3-dimethyl-2-imidazolidinone; copper(I) iodide dimethyl sulfide complex In tetrahydrofuran; 2-methyltetrahydrofuran at -78 - 23℃; Inert atmosphere; Sealed tube;	99%

diethyl cyclopropane-1,1-dicarboxylate (1559-02-0) + methyl 2-iodo-5-methoxybenzoate (857599-37-2) → diethyl 2-(4-methoxy-2-(methoxycarbonyl)phenethyl)malonate

Conditions	Yield
Stage #1: methyl 2-iodo-5-methoxybenzoate With TurboGrignard In tetrahydrofuran; 2-methyltetrahydrofuran at -78℃; for 0.5h; Inert atmosphere; Sealed tube; Stage #2: diethyl cyclopropane-1,1-dicarboxylate With 1,3-dimethyl-2-imidazolidinone; copper(I) iodide dimethyl sulfide complex In tetrahydrofuran; 2-methyltetrahydrofuran at -78 - 23℃; Inert atmosphere; Sealed tube;	99%

diethyl cyclopropane-1,1-dicarboxylate (1559-02-0) + methyl 2-iodo-4-methylbenzoate (103440-56-8) → diethyl 2-(2-(methoxycarbonyl)-5-methylphenethyl)malonate

Conditions	Yield
Stage #1: methyl 2-iodo-4-methylbenzoate With TurboGrignard In tetrahydrofuran; 2-methyltetrahydrofuran at -78℃; for 0.5h; Inert atmosphere; Sealed tube; Stage #2: diethyl cyclopropane-1,1-dicarboxylate With 1,3-dimethyl-2-imidazolidinone; copper(I) iodide dimethyl sulfide complex In tetrahydrofuran; 2-methyltetrahydrofuran at -78 - 23℃; Inert atmosphere; Sealed tube;	99%

diethyl cyclopropane-1,1-dicarboxylate (1559-02-0) + methylenecyclohexane (1192-37-6) → diethyl spiro<4.5>decane-1,1-dicarboxylate (104643-45-0)

Conditions	Yield
With ethylaluminum dichloride In hexane; 1,2-dichloro-ethane for 48h; Ambient temperature;	98%

diethyl cyclopropane-1,1-dicarboxylate (1559-02-0) + 5-bromo-2-iodo-benzoic acid methyl ester (181765-86-6) → diethyl 2-(4-bromo-2-(methoxycarbonyl)phenethyl)malonate

Conditions	Yield
Stage #1: 5-bromo-2-iodo-benzoic acid methyl ester With TurboGrignard In tetrahydrofuran; 2-methyltetrahydrofuran at -78℃; for 0.5h; Inert atmosphere; Sealed tube; Stage #2: diethyl cyclopropane-1,1-dicarboxylate With 1,3-dimethyl-2-imidazolidinone; copper(I) iodide dimethyl sulfide complex In tetrahydrofuran; 2-methyltetrahydrofuran at -78 - 23℃; Inert atmosphere; Sealed tube;	98%

diethyl cyclopropane-1,1-dicarboxylate (1559-02-0) + ethyl 2-iodo-5-methylbenzoate → diethyl 2-(2-(ethoxycarbonyl)-4-methylphenethyl)malonate

Conditions	Yield
Stage #1: ethyl 5-methyl-2-iodobenzoate With TurboGrignard In tetrahydrofuran; 2-methyltetrahydrofuran at -78℃; for 0.5h; Inert atmosphere; Sealed tube; Stage #2: diethyl cyclopropane-1,1-dicarboxylate With 1,3-dimethyl-2-imidazolidinone; copper(I) iodide dimethyl sulfide complex In tetrahydrofuran; 2-methyltetrahydrofuran at -78 - 23℃; Inert atmosphere; Sealed tube;	97%

diethyl cyclopropane-1,1-dicarboxylate (1559-02-0) → diethyl 2-(2-bromoethyl)-malonate (18721-64-7)

Conditions	Yield
With hydrogen bromide at 20℃;	95%
With hydrogen bromide at 0℃;

diphenyl diselenide (1666-13-3) + diethyl cyclopropane-1,1-dicarboxylate (1559-02-0) → diethyl 2-phenylselenoethylmalonate (90475-36-8)

Conditions	Yield
With sodium tetrahydroborate In ethanol at 0℃; for 18h;	95%
With sodium tetrahydroborate In ethanol at 20℃; for 24h; Inert atmosphere;	77%

diethyl cyclopropane-1,1-dicarboxylate (1559-02-0) + sodium phenylselenide (23974-72-3) → diethyl 2-phenylselenoethylmalonate (90475-36-8)

Conditions	Yield
In ethanol for 18h; Ambient temperature;	95%

diethyl cyclopropane-1,1-dicarboxylate (1559-02-0) + methyl 2-iodo 5-fluorobenzoate → diethyl 2-(4-fluoro-2-(methoxycarbonyl)phenethyl)malonate

Conditions	Yield
Stage #1: methyl 3-fluoro-6-iodobenzoate With TurboGrignard In tetrahydrofuran; 2-methyltetrahydrofuran at -78℃; for 0.5h; Inert atmosphere; Sealed tube; Stage #2: diethyl cyclopropane-1,1-dicarboxylate With 1,3-dimethyl-2-imidazolidinone; copper(I) iodide dimethyl sulfide complex In tetrahydrofuran; 2-methyltetrahydrofuran at -78 - 23℃; Inert atmosphere; Sealed tube;	95%

diethyl cyclopropane-1,1-dicarboxylate (1559-02-0) + dimethyl 2-iodoterephthalate (165534-79-2) → dimethyl 2-(4-ethoxy-3-(ethoxycarbonyl)-4-oxobutyl)terephthalate

Conditions	Yield
Stage #1: dimethyl 2-iodoterephthalate With TurboGrignard In tetrahydrofuran; 2-methyltetrahydrofuran at -78℃; for 0.5h; Inert atmosphere; Sealed tube; Stage #2: diethyl cyclopropane-1,1-dicarboxylate With 1,3-dimethyl-2-imidazolidinone; copper(I) iodide dimethyl sulfide complex In tetrahydrofuran; 2-methyltetrahydrofuran at -78 - 23℃; Inert atmosphere; Sealed tube;	95%

diethyl cyclopropane-1,1-dicarboxylate (1559-02-0) → 1,1-cyclopropanedicarboxylic acid monoethyl ester (3697-66-3)

Conditions	Yield
Stage #1: diethyl cyclopropane-1,1-dicarboxylate With sodium hydroxide; water In ethanol for 16h; Stage #2: With hydrogenchloride In water	94%
With ethanol; potassium hydrogencarbonate at 0 - 30℃; for 15h; Reagent/catalyst;	93%
Stage #1: diethyl cyclopropane-1,1-dicarboxylate With sodium hydroxide; water In ethanol at 20℃; Stage #2: With hydrogenchloride In water	91%

diethyl cyclopropane-1,1-dicarboxylate (1559-02-0) + methyl 2-iodo-5-methylbenzoate (103440-52-4) → diethyl 2-(2-(methoxycarbonyl)-4-methylphenethyl)malonate

Conditions	Yield
Stage #1: methyl 2-iodo-5-methylbenzoate With TurboGrignard In tetrahydrofuran; 2-methyltetrahydrofuran at -78℃; for 0.5h; Inert atmosphere; Sealed tube; Stage #2: diethyl cyclopropane-1,1-dicarboxylate With 1,3-dimethyl-2-imidazolidinone; copper(I) iodide dimethyl sulfide complex In tetrahydrofuran; 2-methyltetrahydrofuran at -78 - 23℃; Inert atmosphere; Sealed tube;	94%

diethyl cyclopropane-1,1-dicarboxylate (1559-02-0) + Tosyl isocyanate (4083-64-1) → diethyl 2-oxo-1-tosylpyrrolidine-3,3-dicarboxylate

Conditions	Yield
With C8H18BrI2Sn(2-)*BrMg(1+) In 1,2-dichloro-ethane at 25℃; for 24h; Catalytic behavior; Reagent/catalyst; Solvent; Inert atmosphere;	92%

diethyl cyclopropane-1,1-dicarboxylate (1559-02-0) → ethyl 1-(hydroxymethyl)cyclopropanecarboxylate (3697-68-5)

Conditions	Yield
With lithium tri(t-butoxy)aluminum hydride In tetrahydrofuran at 23 - 65℃; for 24h;	91%
With lithium tri-t-butoxyaluminum hydride In tetrahydrofuran at 65℃; for 24h;	91%
With lithium tri-t-butoxyaluminum hydride In tetrahydrofuran at 65℃; for 24h;	91%

diethyl cyclopropane-1,1-dicarboxylate (1559-02-0) + methyl 3-iodo-1-benzothiophene-2-carboxylate → diethyl 2-(2-(2-(methoxycarbonyl)benzo[b]thiophen-3-yl)ethyl)malonate

Conditions	Yield
Stage #1: methyl 3-iodo-1-benzothiophene-2-carboxylate With TurboGrignard In tetrahydrofuran; 2-methyltetrahydrofuran at -78℃; for 0.5h; Inert atmosphere; Sealed tube; Stage #2: diethyl cyclopropane-1,1-dicarboxylate With 1,3-dimethyl-2-imidazolidinone; copper(I) iodide dimethyl sulfide complex In tetrahydrofuran; 2-methyltetrahydrofuran at -78 - 23℃; Inert atmosphere; Sealed tube;	90%

diethyl cyclopropane-1,1-dicarboxylate (1559-02-0) → ethyl diethyl malonate (133-13-1)

Conditions	Yield
With samarium diiodide; tris(dibenzoylmethano)iron(III); tert-butyl alcohol In tetrahydrofuran for 0.5h; Ambient temperature;	89%
With hydrogen; palladium on activated charcoal In methanol Product distribution;
With (5,10,15,20-tetrakis-4-tolylporphyrinato)(methyl)rhodium(III); isopropyl alcohol In benzene-d6 at 200℃; for 48h; Darkness; Sealed tube; regioselective reaction;	14 %Spectr.

ethylidenecyclohexane (1003-64-1) + diethyl cyclopropane-1,1-dicarboxylate (1559-02-0) → diethyl 4-methylspiro<4.5>decane-1,1-dicarboxylate (104643-49-4)

Conditions	Yield
With ethylaluminum dichloride In hexane; 1,2-dichloro-ethane for 50h; Ambient temperature;	87%

diethyl cyclopropane-1,1-dicarboxylate (1559-02-0) + acetic anhydride (108-24-7) → diethyl (2-acetoxyethyl)malonate (110281-43-1)

Conditions	Yield
With boron trifluoride diethyl etherate In dichloromethane for 1.5h; Ambient temperature;	85%

diethyl cyclopropane-1,1-dicarboxylate (1559-02-0) → cyclopropane-1,1-dicarbonyl peroxide (34867-88-4)

Conditions	Yield
With methanesulfonic acid; urea hydrogen peroxide adduct for 24h;	85%

diethyl cyclopropane-1,1-dicarboxylate (1559-02-0) + methyl 2-iodo 4-chlorobenzoate (181765-85-5) → diethyl 2-(5-chloro-2-(methoxycarbonyl)phenethyl)malonate

Conditions	Yield
Stage #1: methyl 4-chloro-2-iodobenzoate With TurboGrignard In tetrahydrofuran; 2-methyltetrahydrofuran at -78℃; for 0.5h; Inert atmosphere; Sealed tube; Stage #2: diethyl cyclopropane-1,1-dicarboxylate With 1,3-dimethyl-2-imidazolidinone; copper(I) iodide dimethyl sulfide complex In tetrahydrofuran; 2-methyltetrahydrofuran at -78 - 23℃; Inert atmosphere; Sealed tube;	85%

diethyl cyclopropane-1,1-dicarboxylate (1559-02-0) + 2-ethoxycarbonyl-1-cyclopentanone (611-10-9) → 2-[2-(1-ethoxycarbonyl-2-oxo-cyclopentyl)-ethyl]-malonic acid diethyl ester

Conditions	Yield
With ytterbium(III) triflate In acetonitrile at 70℃; under 6000480 Torr; for 120h;	83%

diethyl cyclopropane-1,1-dicarboxylate (1559-02-0) + 4-Nitrophenyl isocyanate (100-28-7) → diethyl 1-(4-nitrophenyl)-2-oxopyrrolidine-3,3-dicarboxylate

Conditions	Yield
With C8H18BrI2Sn(2-)*BrMg(1+) In 1,2-dichloro-ethane at 40℃; for 24h; Inert atmosphere;	82%

diethyl cyclopropane-1,1-dicarboxylate (1559-02-0) + ethyl 2-oxocyclohexane carboxylate (1655-07-8) → 2-[2-(1-ethoxycarbonyl-2-oxo-cyclohexyl)-ethyl]-malonic acid diethyl ester

Conditions	Yield
With ytterbium(III) triflate In acetonitrile at 70℃; under 6000480 Torr; for 120h;	81%

Upstream product

• 110-86-1 pyridine 
• 18721-64-7 diethyl 2-(2-bromoethyl)-malonate 
• 75-36-5 acetyl chloride 
• 108-88-3 toluene 
• 141-52-6 sodium ethanolate 
• 598-10-7 cyclopropane-1,1-dicarboxylic acid 
• 1558-81-2 1-carbethoxy-1-cyanocyclopropane 
• 996-82-7 sodium diethylmalonate 
• 107-06-2 1,2-dichloro-ethane 
• 570-08-1 diethyl acetylmalonate 
• 106-93-4 ethylene dibromide 
• 105-53-3 diethyl malonate 
• 18719-42-1 diethyl 2-chloroethylmalonate 
• 14668-82-7 vinyl isocyanide 

Downstream Products

• 4435-38-5 butane-1,1,4,4-tetracarboxylic acid 
• 1558-97-0 (2-phenylsulfanyl-ethyl)-malonic acid diethyl ester 
• 10433-88-2 methyl(3-oxobutyl)propanedioic acid diethyl ester 
• 6914-74-5 1-aminocarbonylcyclopropanecarboxylic acid 
• 36821-26-8 2-oxopyrrolidine-3-carboxylic acid ethyl ester 
• 39590-81-3 [1-(hydroxymethyl)cyclopropyl]methanol 
• 33329-70-3 ethyl 1-formylcyclopropane-1-carboxylate 
• 1431299-95-4 1-(((5-(4-(benzo[d]thiazol-2-ylamino)phenyl)pyrimidin-2-yl)oxy)methyl)cyclopropanecarboxylic acid 
• 1431300-99-0 ethyl-1-(((5-(4-(benzo[d]thiazol-2-ylamino)phenyl)pyrimidin-2-yl)oxy)methyl)cyclopropanecarboxylate 
• 1407968-27-7 C₃₀H₃₀N₂O₆ 
• 1407968-26-6 C₂₄H₂₆N₂O₆ 
• 1407968-38-0 C₂₄H₂₆N₂O₆ 
• 1268842-79-0 1-(tert-butoxycarbonyl)cyclopropane-1-carboxylic acid 
• 1311265-18-5 1-((4-bromophenoxy)methyl)cyclopropanecarboxylic acid 

Relevant articles and documents

A convenient synthesis of cyclopropane malonyl peroxide

Cyclopropane-1,1-dicarbonyl peroxide was prepared in 85% yield by the reaction of diethyl cyclopropane-1,1-dicarboxylate with the urea hydrogen peroxide clathrate in the presence of methanesulfonic acid.

Polymers Containing Ring-Strain Energy. 1. New Monomers and Polymers Based on Cyclopropane, Norbornadiene, and Quadricyclane

The synthesis and polymerization chemistry of 1,1-bis(XCH2)cyclopropane was studied.Treatment of 1 with base in the presence of α,ω-dihalides did not produce a polyether.However, treatment of 4 with the bis(alkoxide) derived from hexanediol afforded a polyether of low molecular weight n=3000, PD=3>.A general method for alkylating norbornadiene in the 2-position was developed.Treatment of norbornadiene with tert-BuOK, tetramethylethylenediamine (TMEDA), n-BuLi, and tributylchlorostannane (in that order) afforded 2-(tributylstannyl)norbornadiene in excellent yield.On the other hand, carbon electrophiles required the generation of the 2-(lithiocyanocuprate) in order to effect clean alkylation.Treatment of 2-norbornadiene (8a) with RMgX in the presence of (dppp)NiCl2 afforded the cross-coupling products 2-(XCH2)-norbornadiene in high yield.Polymerization of 9 in THF initiated by n-BuLi resulted in an elastomeric polymer (12) n=18,000, PD=1.5>.Photolysis of 12 in the presence of (Ph3P)2CuBr converted the pendant norbornadiene to quadricyclane (13).Heating of the photoisomerized sample to 180 deg C caused an exothermic (by DSC) reaction which corresponded to 59percent of theory (using the value 26 kcal/mol: quadricyclane -> norbornadiene).

1, 1-cyclopropane dicarboxylic acid amide compound as well as preparation method and application thereof

The invention discloses a 1, 1-cyclopropane dicarboxylic acid amide compound as well as a preparation method and application thereof, and the structural formula of the 1, 1-cyclopropane dicarboxylic acid amide compound is as shown in a formula (I): in the formula (I), the structures of two substituted benzene rings are the same, the number of substituents R on each substituted benzene ring is 1-3,and the substituent R is selected from H, halogen, C1-C4 alkyl, C2-C4 ester group or C1-C3 alkoxy. The 1, 1-cyclopropane dicarboxylic acid amide compound provided by the invention is a novel compoundwith an efficient weeding effect, and provides a basis for research and development of novel herbicides.

A 4, 7 - diaza spiro [2.5] octane -7 - formic acid tert-butyl synthetic method

The invention belongs to the technical field of chemical synthesis of N-heterocycle-containing drug intermediates, and particularly relates to a synthesis method of tert-butyl 4,7-diazaspiro[2.5]octyl-7-formate. By using diethyl malonate as a raw material, cyclization reaction, Hofmann reaction, hydrolysis reaction, acylation reaction for recyclization, reduction reaction and the like are performed to conveniently synthesize the target compound product. The method has the advantages of simple synthesis technique, cheap and accessible raw materials, mild reaction conditions, high controllability, low cost and high yield, and is convenient to operate.

Preparation method of compound

The invention discloses a preparation method of a compound shown in the formula (I). The method is characterized by including the following steps of firstly, mixing the compound shown in the formula (I), a compound shown in the formula (III), strong alkali and weak acid salt and a catalyst to obtain a mixed solution; secondly, conducting heating and refluxing on the mixed solution obtained in the first step, and conducting post-processing to obtain the compound shown in the formula (I), wherein X is Cl, Br or I. The method can effectively improve the yield and safety of the compound shown in the formula (I). Please see the formula in the description.