A Novel Synthesis of Diethyl Malonate

Diethyl malonate (DEM) is an important starting material in pharmaceutical and agricultural chemical industries. Traditional synthetic method by reaction mono chloroacetic acid with sodium cyanide1 is unfriendly to environment and involves complicated procedures. Therefore, green synthesis routes of diethyl malonate were investigated actively in past decade. There have been proposed various processes for preparing DEM by carbonylation of ethyl chloroacetate catalyzed by Co2(CO)82, 3. Howev…     

相转移催化羰基化合成丙二酸二乙酯的研究

在相转移催化剂存在下，使用原位制备的钴催化剂实现了氯乙酸乙酯的常压羰基化，丙二酸二乙酯收率达８０％以上。讨论了溶剂、相转移催化剂等对反应的影响。     

PHOTOLYSIS OF ETHYL CHLOROACETATE IN LIQUID PHASE AT 2537 A°R

Abstract— Results on the photolysis of ethyl chloroacetate, CICH₂COOC₂H₅, at A°≅ 254 nm in liquid phase are presented. GLC and i.r. methods revealed as products: hydrogen chloride and ethyl acetate; in smaller quantities–ethyl succinate and ethyl oxalate; in traces–ethyl malonate, CO₂, CO and CH₃CI; yet other, unidentified products with higher boiling points. Quantum yields are determined for some products. Similar studies were performed in the presence of I₂ as a radical scavenger. In the present case, ethyl iodoacetate I – CH₂COOC₂H₅ was found to arise in the system. The following primary process may be written on the basis of the experimental data:
CICH₂COOC₂H₅← CI + CH₂COOC₂H₅
Attempts to explain the production of these compounds are based mainly on the properties of the CH₂COOC₂H₅ radical.     

四羰基钴/咪唑离子液体在羰基化合成丙二酸二甲酯反应中的催化性能

采用原位法合成了不同类型的四羰基钴/咪唑离子液体催化剂, 并考察了其在氯乙酸甲酯羰基化反应中的催化性能. 研究了咪唑环上不同支链对催化活性的影响. 结果表明, 1-丁基-3-甲基咪唑羰基钴离子液体[Bmim][Co(Co)₄]不仅催化活性高, 选择性好, 而且对空气和水有较好的稳定性能. 在p_CO=2.0 MPa, 85 ℃, 反应3 h的条件下, [Bmim][Co(Co)₄]催化剂循环使用4次, 氯乙酸甲酯的平均转化率为94.3%, 丙二酸二甲酯的平均选择性和平均产率分别为98.5%和92.9%. 与传统的Na[Co(Co)₄]催化剂相比, [Bmim][Co(Co)₄]催化剂在保证高活性的条件下可以实现羰基钴催化剂的直接循环使用.     

A Novel Synthesis of Dimethyl Malonate by Carbonylation of Methyl Chloroacetate Catalyzed by Cobalt Complex

Dimethyl malonate (DMM) is an important organic synthesis intermediate. Traditional synthetic method by reaction of mono-chloroacetic acid with sodium cyanide1 is poisonous and complicated. Therefore, an interest in green synthesis routes of DMM has risen greatly. The several processes for preparing DMM by carbonylation of methyl chloroacetate catalyzed by Co2(CO)8 have been reported2~5. However, Co2(CO)8 is unstable and must be prepared under high pressure (12 Mpa). Moreover, the yield…     

A new method for the synthesis of levulinic acid

A two- step method is described for the synthesis of levulinic acid from ethyl acetoacetate and ethyl chloroacetate in 70% yield.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 474–475, February, 1990.     

Synthesis of some new fused coumarin derivatives

2-Hydrazino-4-hydroxy-5H- [1] -benzopyrano- [ 4,3-d ] -pyrim-idin-5-one (3) was prepared via condensation of 2 with hy-drazine hydrate. Treatment of 3 with methylene chloride, ethyl chloroformate, ethyl chloroacetate and benzaldehyde yielded the corresponding 2 - ( substituted ) hydrazino - 4 -hydro-xy-5H-[1]-benzopyrano-[4, 3-d]-pyrimidin-5-one (4, 5, 6, and 10), followed by cyclization of 4, 5 and 6 with dimethyl fonnamide and fused sodium acetate under reflux, while compound 10 was cyclized with bromine and sodium acetate in acetic acid. Compound 3 reacted with β-(toloyl) acrylic acid, ethyl α-cyano-p-methoxytinnamate, diethyl mal-onate and acetyl chloride affording the corresponding 2-(substituted) hydrazino-4-hydroxy-5H-[1]-benzopyrano-[4, 3-d]-pyrimidin-5-one (12, 13, 14, 15 and 16).     

The Synthesis of Some New Sulfur-Bearing Various Heterocyclic Systems Derived from Asymmetrical N,N′-Disubstituted Thiourea Derivatives

The heterocyclization of an asymmetrical N,N′-disubstituted thiourea (1a–d) in ring closure reactions with Br₂/AcOH, ethyl chloroacetate, diethyl oxalate, diethyl malonate, and hydrazine hydrate led to the direct formation of sulfur-bearing various heterocyclic systems (2–8) in which the thiaenolization is toward the aryl group. The synthetic work and reactivity investigations have been well supported by standard modern spectroscopic techniques (IR, ¹ H NMR, ¹³ C NMR, mass spectrum, and microanalysis).     

An efficient method for the preparation of mono α-aryl derivatives of diethyl malonate and ethyl cyanoacetate using ethyl-1-imidazole carbamate (EImC)

An efficient method for the synthesis of mono α-aryl derivatives of diethyl malonate and ethyl cyanoacetate using ethyl-1-imidazole carbamate (EImC) has been described. Using this method many sterically hindered and highly substituted mono α-aryl derivatives of diethyl malonate and ethyl cyanoacetate were synthesized in high yield.     

Synthesis of [60]fullerene adducts bearing carbazole moieties by Bingel reaction and their properties

Carbazole-linked [60]fullerene adducts were successfully prepared by the Bingel reactions using carbazole derivatives bearing one or two ethyl malonate moieties. In the latter cases, specific bisadduct regioisomers were obtained, depending on the spacer unit between two ethyl malonate moieties. [reaction: see text]     

Synthesis and Transformations of Oxy Amides Derived from Cycloalka[c]- and Pyrano[3,4-c]pyridines

Russian Journal of Organic Chemistry - The alkylation of 3-hyroxycycloalka[c]- and 6-hydroxypyrano[3,4-c]pyridines with ethyl chloroacetate and ethyl 4-chlorobutanoate gave the corresponding oxy...     

Chloroacetate‐Promoted Selective Oxidation of Heterobenzylic Methylenes under Copper Catalysis

The efficient selective oxidation and functionalization of C? H bonds with molecular oxygen and a copper catalyst to prepare the corresponding ketones was achieved with ethyl chloroacetate as a promoter. In this transformation, various substituted N‐heterocyclic compounds were well tolerated. Preliminary mechanistic investigations indicated that organic radical species were involved in the overall process. The N‐heterocyclic compounds and ethyl chloroacetate work synergistically to activate C? H bonds in the methylene group, which results in the easy generation of free radical intermediates, thus leading to the corresponding ketones in good yields.     

New approach to the synthesis of 4-phosphorylated 1,2,3-trisubstituted pyrroles

New synthetic method for preparation of previously unknown 1,2,3-trisubstituted pyrroles based on the reaction of the available phosphorus-containing 4-arylaminoacrylonitriles with chloroacetonitrile or ethyl chloroacetate is developed.     

Chloroacetate Promotes and Participates in the Oxidative Annulation of Pyridines/Isoquinoline by Using Oxygen as the Oxidant

The aerobic oxidative annulation of chalcones, pyridines/isoquinoline and ethyl chloroacetate to indolizines was achieved by cascade reaction. Various functional groups on chalcones were tolerated. And different pyridines derivatives could also be suitable substrates. Ethyl chloroacetate is an essential component in participating of the oxidative annulation process. Overall, this protocol is very practical and efficient by using molecular oxygen as oxidant with high selectivity for the annulation product.     

Synthesis of some new pyrimidine selanyl derivatives

The targeted synthesis of 2-(methylsulfanyl)-6-(furan-2-yl)-4(3H)-selenoxo -pyrimidine-5-carbonitrile failed due to the formation 1-methyl-2-methylsulfanyl-6-oxo -4-(furan-2-yl)-1,6-dihydropyrimidine-5-carbonitrile. A new series of 5,6,7,8-tetrahydro-1-benzo thieno[2,3-d]pyrimidine-4-yl substituted selanyl derivatives were prepared by the reaction of sodium diselenide with 4-chloro-5,6,7,8-tetrahydro-1-benzothieno[2,3-d]pyrimidine followed by the reaction with chloroacetic acid derivatives such as ethyl chloroacetate, chloroacetamide or chloroacetonitrile. Hydrazinolysis of ethyl (5,6,7,8-tetrahydro-1-benzothieno[2,3-d]pyrimidine- 4-ylselanyl)acetate with hydrazine hydrate gave the corresponding hydrazino derivative. The latter reacted with ethyl acetoacetate, acetylacetone, diethyl malonate, ethoxymethylenemalononitrile or ethyl 2-cyano-3-ethoxyacetate to afford 5-methyl-2-[2-(5,6,7,8-tetrahydro-1-benzothieno [2,3-d]pyrimidine-4-ylselanyl)acetyl]-2,4-dihydropyrazol-3-one, 1-(3,5-dimethylpyrazol-1-yl)-2- (5,6,7,8-tetrahydro-1-benzothieno[2,3-d]pyrimidin-4-ylselanyl)ethanone, 1-[2-(5,6,7,8-tetrahydro -1-benzothieno[2,3-d]pyrimidine-4-ylselanyl)acetyl]-2,4-dihydropyrazolidine-3,5-dione and 5-Amino-1-[2-(5,6,7,8-tetrahydro-1-benzothieno[2,3-d]pyrimidin-4-ylselanyl)acetyl]-1H-pyrazol -4-yl substituted carbonitrile or ethyl carboxylate, respectively. The structure of the novel compounds was confirmed by spectroscopic tools (IR, ¹H NMR ¹³C NMR and mass spectra) and elemental analysis.     

A facile one step synthesis of novel ethyl 2,6-bis(trifluoromethyl)-4-hydroxypyrimidine-5-carboxylate

Trifluoroacetonitrile was condensed with diethyl malonate to give a novel ethyl 2,6-bis(trifluoromethyl)-4-hydroxypyrimidine-5-carboxylate ( 2 ) in 88% yield. Derivations of 2 are also described.     

Regioselective single and double conjugate additions to substituted cyclohexa-2,5-dienone monoacetals

[reaction: see text]. A series of quinone monoacetals bearing electron-withdrawing groups was treated with diethyl malonate and other bifunctional nucleophiles in the presence of KO-t-Bu in THF. Reactions of ethyl 3-nitropropionate or diethyl malonate resulted in single conjugate addition adducts. When ethyl acetoacetate was used as a nucleophile, bridged bicyclic products were obtained in good yields. The regiochemistry of conjugate addition was dependent on the quinone monoacetal substitution.     

(Vapour + liquid) equilibria,volumetric and compressibility behaviour of binary and ternary aqueous solutions of 1-hexyl-3-methylimidazolium chloride,methyl potassium malonate,and ethyl potassium malonate

(Vapour + liquid) equilibrium data (water activity, vapour pressure, osmotic coefficient, and activity coefficient) of binary aqueous solutions of 1-hexyl-3-methylimidazolium chloride ([C₆mim][Cl]), methyl potassium malonate, and ethyl potassium malonate and ternary {[C₆mim][Cl] + methyl potassium malonate} and {[C₆mim][Cl] + ethyl potassium malonate} aqueous solutions were obtained through the isopiestic method at T = 298.15 K. These results reveal that the ionic liquid behaves as surfactant-like and aggregates in aqueous solutions at molality about 0.4 mol · kg⁻¹. The constant water activity lines of all the ternary systems investigated show small negative deviations from the linear isopiestic relation (Zdanovskii–Stokes–Robinson rule) derived using the semi-ideal hydration model. The density and speed of sound measurements were carried out on solutions of methyl potassium malonate and ethyl potassium malonate in water and of [C₆mim][Cl] in aqueous solutions of 0.25 mol · kg⁻¹ methyl potassium malonate and ethyl potassium malonate at T = (288.15 to 308.15) K at atmospheric pressure. From the experimental density and speed of sound data, the values of the apparent molar volume, apparent molar isentropic compressibility and excess molar volume were evaluated and from which the infinite dilution apparent molar volume and infinite dilution apparent molar isentropic compressibility were calculated at each temperature. Although, there are no clear differences between the values of the apparent molar volume of [C₆mim][Cl] in pure water and in methyl potassium malonate or ethyl potassium malonate aqueous solutions, however, the results show a positive transfer isentropic compressibility of [C₆mim][Cl] from pure water to the methyl potassium malonate or ethyl potassium malonate aqueous solutions. The results have been interpreted in terms of the solute–water and solute–solute interactions.     

Synthesis of c-17 trans β-lactams of the androstane series

3,3′-Ethylenedioxyandrost-4-en-17β-ol 1 was converted into the ethyl ester 2 by reaction with potassium metal and ethyl chloroacetate. The ethyl ester 2 on reaction with hydrazine gave the hydrazide 3 . Condensation of 3 with aryl aldehydes gave the Schiff bases 4 . The reaction of Schiff bases 4 with mono-chloroacetyl chloride in the presence of triethylamine afforded the β-lactams 5 .     

一种制备带有酯基基团杯[4]芳烃的简便方法

采用更为经济和毒性较小的氯乙酸乙酯-碱金属碘化物体系作烷基化试剂,方便地制得了下缘带有酯基基团的杯[4]芳烃.