Malonic acid methyl ester

HYDROXY-ENT-BEYER-15-EN-MALONIC ACID (METHYL ESTER)... 

C3H5S 870-23-5) see Altizide allyl(l-methyl-2-pentynyl)malonic acid diethyl ester (C16H24O4 101448-52-6) see Methohexital 4-allyloxy-3-chlorobenzaldehyde (CigH Cl02, 58236-91-2) see Alclofenac 4-allyloxy-3-chlorobenzyl chloride (C Hi()Cl20 20788-43-6) see Alclofenac 4-allyloxy-3-chlorobenzyl cyanide (C, H C1N0 20788-44-7) see Alclofenac... 

The application of 3-aminopropyl phosphine (3) [41,46] as a building block for incorporation into -COOH functionalized frameworks provides an excellent example of the utility of preformed primary phosphine frameworks (Scheme 8) [46]. The reactions involved Michael addition of ferf-butyl acrylate to malonic acid dimethyl ester to produce the intermediate adduct, 2-methoxycarbonyl-pentanedioc acid 5-ferf-butyl ester 1-methyl ester, which upon treatment with trifluro-acetic acid (TFA) produced the corresponding diester acid,2-methoxy-carbonyl-pentanedioic acid 1-methyl ester, in near quantitative yield. It is remarkable to note that the reaction of NH2(CH2)3PH2 (3) with the diester acid is highly selective as the -COOH group remained unattacked whereas the reaction occurred smoothly and selectively at the -COOMe groups to pro-... 

Butanoic acid, methyl ester Malonic acid, dimethyl ester 1,1-Dimethylpropanoic acid, 1,1-dimethylester... 

Isobutyryl chloride (8) Propanoyl chloride, 2-methyl (9) (79-30-1) Potassium monoethylmalonate Malonic acid, monoethyl ester, potassium salt (8) Propanedioic acid, monoethyl ester, potassium salt (9) (6148-64-7)... 

Indanones are very useful and versatile intermediates in the synthesis of metallocene catalysts. Scheme 1 has the synthetic scheme originally used for the preparation of 2-alkyl-4-aryl-substituted ansa metallocenes [9-11]. In the first part of this sequence, the biaryl unit is assembled and the missing carbon atoms are introduced as a side chain. The reaction of 2-phenylbenzyl bromide with malonic acid ethyl ester under basic conditions, followed by a decarboxylation, affords the 2-(2-phenylbenzyl)propionic acid. Chlorination and Friedel-Crafts acylation yields the 2-methyl-4-phenylindanone in 93 % yield. From here, only a few standard transformations are required to complete the synthesis, finally yielding the desired metallocene. 

Meprobamate has been synthesized by several procedures (See Figure U). The first step is to synthesize 2-methyl-2-propyl-1,3-propanediol. This has been done1 1 by reacting 2-methyl pentanal and formaldehyde in presence of KOH. The diol has also been prepared by reducing 2-methyl-2-n-propyl malonic acid, diethyl ester with lithium aluminum... 

The cyanoacetic acid obtained from monochloroacetic acid and sodium cyanide, is treated with hydrochloric acid and ethanol to yield the diethyl ester of malonic acid. The ester, in absolute ethanol, is reacted with the stoichiometric proportion of metallic sodium so as to replace only one active hydrogen of the methylene (CH2) group. Thereupon, a slight excess of the calculated amount of allyl bromide is added. The second replaceable hydrogen is abstracted with 1-methyl butyl bormide and the resulting product is made to react with a theoretical amount of thiourea to yield thiamylal. The free acid thus obtained is conveniently transformed into the official sodium salt by neutralization with a stoichiometric proportion of sodium hydroxide (1 1). 

TABLE 1.42. 2-SUBSTITUTED 4-OXAZOLECARBOXYLIC ACID METHYL ESTERS FROM DIMETHYL AMINO[PHENYLTHIO)METHYL]MALONATE ... 

Synonyms Dimethyl propanedioate Dimethyl 1,3-propanedioate Malonic acid, dimethyl ester Methyl malonate Propanedioic acid, dimethyl ester... 

To a flame-dried test tube equipped with a magnetic stirring bar was added 2-(2,3-butadienyl)-2-(5-methyl-3-hexynyl)malonic acid diethyl ester (365a) (0.0480 g, 0.16 mmol) and toluene (0.5 mL). The test tube was evacuated and charged with CO for three times and [Rh(CO)2Cl]2 (3.2 mg, 0.008 mmol) was added. The mixture was stirred and heated at 90 C overnight under CO atmosphere (1 atm). The solvent was removed in vacuo and the residue was purified by preparative TLC (Si02, hexanes ether = 75 25, Rf = 0.4) to afford 366a as a pale yellow oil, which solidified in the freezer to afford a colorless solid (0.0400 g, 76%). 

A different strategy providing access to linear polyesters derived from fatty acids in which their aliphatic sequences dangle from macromolecular chains (i.e., a type of structure very different to that of linear PE) has been described recently [73]. Various saturated fatty acid methyl esters were malonated to the corresponding methyl diesters, which were polymerised by transesterification with 1,6-hexanediol (Scheme 4.17). 

A number of new routes to a-methylene esters (121) have been developed (see also ref. 110). Perhaps the simplest involves the treatment of malonic acid half-esters with formaldehyde in pyridine containing piperidine. Yields are ca. 80%. A somewhat less efficient scheme utilizes a reaction between silyl keten acetals and chloromethyl methyl ether followed by pyrolytic removal of methanol (160 °C, KHS04). Esters (121) can also be obtained in 31—83% yield by alkylation of the Diels-Alder adduct of dimethylfulvene and methyl acrylate followed by a retro-Diels-Alder reaction. " ... 

C12H22O4 2-(2-methyl-butyl)-malonic acid diethyl ester 1561-12-2... 

C6H10O4 2-methyl-malonic acid dimethyl ester 609-02-9... 

Methyl Malonate.—This ester is an artificially prepared body, having a fruity odour, somewhat similar to the above-described esters of the fatty acids. It has the formula CH2(C02CHg)2, and boils at 181°. It may be prepared by treating potassium cyan-acetate with methyl alcohol and hydrochloric acid. On saponification with alcoholic potash it yields malonic acid, which melts at 132°, and serves well for the identification of the ester. 

This ester (70 g) and diethyl carbonate (250 mg) were stirred at 90°C to 100°C while a solution of sodium ethoxide [from sodium (7.8 g) and ethanol (1 54 ml)] was added over 1 hr. During addition, ethanol was allowed to distill and after addition distillation was continued until the column heat temperature reached 124°C. After cooling the solution to 90°C, dimethyl sulfate (33 ml) was followed by a further 85 ml of diethyl carbonate. This solution was stirred and refluxed for 1 hr and then, when Ice cool, was diluted with water and acetic acid (10 ml). The malonate was isolated in ether and fractionally distilled to yield a fraction boiling at 148°C to 153°C/0.075 mm, identified as the alpha-methyl malonate. This was hydrolyzed by refluxing for 1 hr at 2.5N sodium hydroxide (350 ml) and alcohol (175 ml), excess alcohol was distilled and the residual suspension of sodium salt was acidified with hydrochloric acid to give a precipitate of the alpha-methyl malonic acid. This was decarboxylated by heating at 180°C to 200°Cfor 30 minutes and recrystallized from petroleum ether (BP 80°C to 100°C) to give 2-(2-fluoro-4-biphenylyl)propionic acid, MP 110°C to 111°C. 

MalONIC ACID, ETHYLHYDROXY, DIETHYL ESTER, BENZOATE, 45, 37 Mfsitaidehydf, 47, 1 Mesitylcne, condensation with dichloro methyl methyl ether, 47, 1 Methalljl chloride in alkylation of 2,4-pentanedione with potassium carbonate, 47, 87... 

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