Methyl malonate chloride

Methyl malonate chloride Potassium acetate Bromobenzene... 

Decenoic acid (143), easily prepared from the same telomer 142, was cyclized via acid chloride using A1C13 to give 2-pentyl-2-cyclopentenone (144). Michael addition of methyl malonate followed by removal of one ester group produced methyl dihydrojasmonate (145) (129) ... 

Chloride is a poor nucleophile, but it is more reactive in DMSO by which it cannot be solvated. And, as soon as the carboxylate is substituted, the high temperature encourages (entropy again) irreversible decarboxylation, and the other by-product, MeCl, is also lost as a gas. The decarboxylation (in fact, removal of a C02Me group, not CO2) is known as the Krapcho decarboxylation. Because of the S 2 step, it works best with methyl malonate esters. 

Carbene precursor 16 was prepared from phthalimide 11. Ozonolysis of the olefin gave aldehyde 12. An acetylide addition gave 13 as a racemic mixture. Semihydrogenation of the alkyne, esterfication of 14 with methyl malonyl chloride, and diazotization of mixed malonate 15 gave 16. The car-benoid insertion reaction proceeded according to plan to give 18. 

Tlie bifunctional sulfenyl chloride 213 was obtained by chlorination of 144 in good yield, although excessive chlorination led to the saturated compound 214 (94CB533). A series of compounds 215-220 were obtained from 213 by reactions with secondary amines ferf-butyl methyl ketone hexane-2,4-dione 2,6-dimethylcyclohexanone diethyl malonate and acetylacetone, respectively. 

Methyl- and 3-phenyl-4-hydroxy-2-oxo-2//-pyrido[2,1 -Z)]oxazinium inner salts were prepared in the reaction of 2-pyridone and 2-substituted malonyl chloride, prepared in situ from 2-substituted malonic acid with PCI5 in CH2CI2 (00JCS(P2)2096). 

The reaction mixture is acidified with N hydrochloric acid (200 cc) and the oil formed is extracted with methylene chloride (200 cc). The methylene chloride solution is washed with water (210 cc), treated with decolorizing charcoal (5 grams), dried over anhydrous sodium sulfate and concentrated to dryness under reduced pressure (20 mm Hg) giving an oil (77 grams) which is crystallized from methanol (300 cc) to yield methyl ethyl (7-meth-oxy-10-methyl-3-phenthiazinyl)-malonate (62.4 grams) melting at 80°-82°C. 

Methyl ethyl (7-methoxy-10-methyl-3-phenthiazinyl)malonate (62.2 grams) followed by methyl iodide (45.7 grams) is added to a solution of sodium (4.45 grams) in anhydrous ethanol (500 cc). The reaction mixture is heated under reflux for 1 hour at 45°C, then for 6 hours at 55°C, and finally concentrated to dryness under reduced pressure (20 mm Hg). The residue is taken up in methylene chloride (300 cc) and water (250 cc), filtered in the presence of a filtration adjuvant, washed with methylene chloride (150 cc) and water (150 cc), and decanted. The aqueous solution is extracted once again with methylene chloride (100 cc), and the combined organic solutions washed with water (100 cc), aqueous 0.1 N sodium hyposulfite solution (200 cc) and finally with water (200 cc). After drying over anhydrous sodium sulfate and evaporation to dryness under reduced pressure (20 mm Hg), there is obtained an oil (64.8 grams) which is dissolved in methylene chloride (100 cc) and... 

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... 

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 diazo transfer reaction between p-toluenesulfonyl azide and active methylene compounds is a useful synthetic method for the preparation of a-diazo carbonyl compounds. However, the reaction of di-tert-butyl malonate and p-toluenesulfonyl azide to form di-tert-butyl diazomalonate proceeded to the extent of only 47% after 4 weeks with the usual procedure." The present procedure, which utilizes a two-phase medium and methyltri-n-octylammonium chloride (Aliquat 336) as phase-transfer catalyst, effects this same diazo transfer in 2 hours and has the additional advantage of avoiding the use of anhydrous solvents. This procedure has been employed for the preparation of diazoacetoacetates, diazoacetates, and diazomalonates (Table I). Ethyl and ten-butyl acetoacetate are converted to the corresponding a-diazoacetoacetates with saturated sodium carbonate as the aqueous phase. When aqueous sodium hydroxide is used with the acetoace-tates, the initially formed a-diazoacetoacetates undergo deacylation to the diazoacetates. Methyl esters are not suitable substrates, since they are too easily saponified under these conditions. 

Calcium-selective electrodes have long been in use for the estimation of calcium concentrations - early applications included their use in complexometric titrations, especially of calcium in the presence of magnesium (42). Subsequently they have found use in a variety of systems, particularly for determining stability constants. Examples include determinations for ligands such as chloride, nitrate, acetate, and malonate (mal) (43), several diazacrown ethers (44,45), and methyl aldofuranosides (46). Other applications have included the estimation of Ca2+ levels in blood plasma (47) and in human hair (where the results compared satisfactorily with those from neutron activation analysis) (48). Ion-selective electrodes based on carboxylic polyether ionophores are mentioned in Section IV.B below. Though calcium-selective electrodes are convenient they are not particularly sensitive, and have slow response times. 

Amino-3-benzyloxypyridine (X = CH)and4-amino-5-benzyloxypyri-midine (X = N) were reacted with Meldrum s acid (421) and methyl orthoformate in the presence of zinc chloride to give (hetarylamino)methylene-malonates (447) (89TL1529). 

Condensation of 3-chloromethylbenzo[6]thiophene with diethyl malonate followed by hydrolysis, decarboxylation, Arndt-Eistert homo-logization, hydrolysis, and cyclization of the derived acid chloride with anhydrous stannic chloride yielded 2-methyl-4-keto-l,2,3,4-tetrahy-drodibenzothiophene (47). ... 

Methylbenzofuran-3-carbaldehydes undergo ready condensation with Meldrum s acid (isopropylidene malonate) to afford arylmethylene derivatives 83. These on flash vacuum pyrolysis at 500-600 C give 3-dibenzofuranols 84 (Scheme 21). The arylmethylene derivative, e.g., 85, presumably undergoes conversion to a methylene ketene (86, Scheme 22) on pyrolysis, which undergoes a [1,5-H] shift and subsequent cyclization and tautomerization, yielding the dibenzofuranol 87. The derived methyl ether 88 has been converted by mild acetylation with acetyl chloride and aluminum chloride and subsequent boron trichloride-induced demethylation to the natural product ruscodibenzofuran (8). A limitation is imposed on this method because 3-acetyl-2-methyldibenzofurans fail to condense with Meldrum s acid so that l-methyl-3-dibenzofuranols are not available by this method. ... 

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