Sodium malonate

Conduct the preparation in the fume cupboard. Dissolve 250 g. of redistilled chloroacetic acid (Section 111,125) in 350 ml. of water contained in a 2 -5 litre round-bottomed flask. Warm the solution to about 50°, neutralise it by the cautious addition of 145 g. of anhydrous sodium carbonate in small portions cool the resulting solution to the laboratory temperature. Dissolve 150 g. of sodium cyanide powder (97-98 per cent. NaCN) in 375 ml. of water at 50-55°, cool to room temperature and add it to the sodium chloroacetate solution mix the solutions rapidly and cool in running water to prevent an appreciable rise in temperature. When all the sodium cyanide solution has been introduced, allow the temperature to rise when it reaches 95°, add 100 ml. of ice water and repeat the addition, if necessary, until the temperature no longer rises (1). Heat the solution on a water bath for an hour in order to complete the reaction. Cool the solution again to room temperature and slowly dis solve 120 g. of solid sodium hydroxide in it. Heat the solution on a water bath for 4 hours. Evolution of ammonia commences at 60-70° and becomes more vigorous as the temperature rises (2). Slowly add a solution of 300 g. of anhydrous calcium chloride in 900 ml. of water at 40° to the hot sodium malonate solution mix the solutions well after each addition. Allow the mixture to stand for 24 hours in order to convert the initial cheese-Uke precipitate of calcium malonate into a coarsely crystalline form. Decant the supernatant solution and wash the solid by decantation four times with 250 ml. portions of cold water. Filter at the pump. 

In the second step a second molecule of sodium malonic ester exchanges its sodium with the substituted malonic ester and a second molecule of NaBi is then removed. 

Anschutz 1 treated aceto-salicylic chloride with sodium-malonic ester, with the formation of ethyl acetate and y3-hydroxy-coumarin-alpha-car-hoxylic ethyl ester—... 

Sodium malonate attacks almost exclusively the sterically hindered site, whereas /i-oxo esters, 1,3-diketones, and the C-mcthylated analogs of dimethyl malonate lead exclusively to terminal attack. 

A solution of 600 g. of anhydrous calcium chloride in 1800 cc. of water warmed to 40° is added slowly with rapid mixing to the hot sodium malonate solution. A cheese-like precipitate of calcium malonate is formed immediately and becomes coarsely crystalline on standing for twenty-four hours. After the supernatant solution is decanted, the calcium malonate is washed by decantation four or five times with 500-cc. portions of cold water. It is then transferred to a filter, sucked as dry as possible, and dried in the air, or at 45-50°, to constant weight. The yield is 800-900 g. 

Examination of the effect of pH on the rates of protodeboronation of the 2,6-dimethoxy compound at 90 °C in malonic acid-sodium malonate buffer solutions of ionic strength 0.14 gave the data in Table 199. A plot of these data revealed the curve shown in Fig. 3 (one of the points was misplotted on the original) and the linear portions of the plot were attributed to acid and base catalysis as shown on Fig. 3, and since the rates in the region of pH 4-5 are higher than would be... 

The effect of metal-ion catalysis (especially that of cadmium ion) in the above reaction has been studied628, and in Table 201 are listed the first-order rate coefficients for protodeboronation of 2,6-dimethoxybenzeneboronic acid in malonic acid-sodium malonate buffer or perchloric acid, observed in the absence ( ) or presence ( ) of cadmium ion, together with the second-order rate coefficients (k2) obtained by dividing the difference of these values by the cadmium ion concentration. The data of the first ten rows of Table 201 are plotted in Fig. 4 and the... 

Hermann and colleagues218,219 found that treatment of ketene thioacetal monoxides 172 and 173, with enamines, sodium malonates, /J-dicarbonyl compounds and lithio-... 

Years earlier, Nicholas and Ladoulis had found another example of reactions catalyzed by Fe2(CO)9 127. They had shown that Fe2(CO)9 127 can be used as a catalyst for allylic alkylation of allylic acetates 129 by various malonate nucleophiles [109]. Although the regioselectivites were only moderately temperature-, solvent-, and substrate-dependent, further investigations concerned with the reaction mechanism and the catalytic species were undertaken [110]. Comparing stoichiometric reactions of cationic (ri -allyl)Fe(CO)4 and neutral (rj -crotyl ace-tate)Fe(CO)4 with different types of sodium malonates and the results of the Fe2(CO)9 127-catalyzed allylation they could show that these complexes are likely no reaction intermediates, because regioselectivites between stoichiometric and catalytic reactions differed. Examining the interaction of sodium dimethylmalonate 75 and Fe2(CO)9 127 they found some evidence for the involvement of a coordinated malonate species in the catalytic reactions. With an excess of malonate they... 

Allylic alkylations of cinnamyl carbonate by sodium malonate have been studied with a series of ruthenium catalysts, obtained from the azohum salts 126-128 and the ruthenium complex 129 (Scheme 2.25) in MeCN or THF to give moderate yields of mixtures of alkylated products in the allylic and ipi o-carbons (90 10 to 65 35). The observed regioselectivity is inferior to similar ruthenium systems with non-NHC co-ligands. The stereoelectronic factors which govern the observed regioselectivity were not apparent [102]. 

Stoichiometric reaction with matched S-carbamate having the D atom in the Z-position 733) in the presence of S,S-ligand 64 without a nucleophile solely formed (no other isomer was observed by NMR) the Mo-complex 74 without transposition of the label. The structure of 74 was probed based on NMR studies by comparison with NMR studies and the X-ray structure of the protio complex 71. Nucleophilic attack of sodium malonate on the Mo complex 74 provided the S-product 75, where the D atom remained at the Z-position. On the other hand, stoichiometric reaction with mismatched R-carbamate having the D atom in the Z-position 76 without a nucleophile generated the Mo complex 80 as sole product, based on NMR studies. The structure of the complex 80 was elucidated by NMR. In 80, Mo is located on the same face as in 74 but the D atom is transposed from the Z to the E position. The transposition could be explained as follows. Initially the n-allyl Mo-complex 77 (unobserved) must form with retention. Mo complex 77 is equilibrated into the more stable Mo complex 80, where the D atom is moved... 

There was still some room for uncertainty on this retention-retention mechanism. The argument was, if the unobserved tt-allyl Mo complex (such as 77 or B in Scheme 2.18) was more highly reactive towards sodium malonate than experimentally observed tt-allyl Mo complexes (such as 71, 74, and 80), the reaction should proceed through inversion (since there is an equilibrium between the two tt-allyl Mo complexes via the o-allyl complex.) If so, when the isolated Mo-complex 71 was subjected to the reaction, 71 must be equilibrated to the enantiomer of 71 via the o-allyl complex prior to reaction with a nucleophile. Therefore, reaction from the Mo complex 71 should proceed with less stereoselectivity than that from a mismatched branched carbonate. This hypothesis was examined, as shown in Scheme 2.26. 

Reaction of mismatched 3-fluoro R-carbonate 83 with catalytic amounts of 70 (derived from S,S-ligand 64) proceeded with sodium malonate in acetonitrile at 60 °C and the S-adduct 84 and the R-adduct 85 were obtained in a ratio of 88.7 11.3. Complex 71 (20-30 mol%) was added to the reaction mixture of83, 70, and sodium... 

The reaction of 1,2-allenyl sulfoxides with sodium malonate also afforded 2-[bis (methoxycarbonyl)methyl]-2-alkenyl sulfoxides 177, which upon further transformation would provide an efficient access to butenolide derivatives 180 [90, 91]. 

If the oxidation is slower than the decomposition, oxygen may affect the nature of reaction products. Thus, treating p-nitrocumyl chloride with sodium malonate ester in a flow of pure dry nitrogen yields a product of C-alkylation (route a in Scheme 5.12) the yield is 90%. Oxygen completely inhibits the C-alkylation, and the reaction gives p-nitrocumyl alcohol in the same yield (route b in Scheme 5.12) (Kornblum et al. 1968). 

Diethyl Malonate. 200 kilos of the above powder (sodium malonate can be purchased cheaply without alarming DBA officials. I gave the above formula for do-it-yourselfers) is stirred with 160 kilos of ethanol (industrial spirit) and 500 kilos of benzene in an esterification kettle. About 240 kilos of coned sulfuric acid are added, at such a rate that the temp of this well stirred mixture never exceeds 25° (this will take several hours for a formula this big). The temp is then raised to 60° and maintained for at least 8 hours and then cooled. The top benzene layer is removed and the lower acid layer is extracted with benzene repeatedly. The combined benzene layers are washed free of acid, with dilute sodium hydroxide, and dried over anhydrous sodium carbonate and then distilled under vacuo (20 mm). The fraction boiling at 96-98° is collected as commercially pure diethyl malonate. Yield 85-90% of theoretical. 

Just a year before E. Fischer obtained this compound by the hydrolysis of caseinogen, it was synthesised by Willstatter in 1900 from sodium malonic ester and trimethylene bromide by the following reactions —... 

Leuchs, in 1905, synthesised two stereoisomeric-7-oxy-prolines, one of which is probably the inactive form of the natural oxyproline. Epichlorhydrin and sodium malonic ester yield 7-chlor-/8-oxy-propyl-malonic ester,... 

Ellinger s further work did not confirm this supposition. By condensing yS-chloropropionacetal with sodium malonic ester he obtained propionacetal malonic ester,... 

Fully conjugated species are somewhat rare in the 1,2-thiazine class of heterocycles. These molecules are comprised of two separate subclasses, the first of which includes the highly reactive 1,2-thiazinylium salts. Although these salts, such as 27, have in some cases been isolated, they readily react regioselectively at C-6 with a variety of nucleophiles including sodium alkoxides 76, silyl enol ethers 77, sodium malonates 78, and sodium thiophenoxide 79 (Scheme 10) <2001T8965>. 

Isoxazolo[5,4-3]pyridine 95 reacted in the dark to give different addition products 96-98 (Equation 9 Table 16), depending on the number of equivalents of organometallic compound and on the reaction temperature <2002TL9527>. The same authors found that sodium malonate, thermally unreactive toward the isoxazolo[5,4-/ ]-pyridine 95, can be used as a photochemical trapping agent <2002TL9527>. 

In 2001, Takahashi and his co-workers developed the first asymmetric ruthenium-catalyzed allylic alkylation of allylic carbonates with sodium malonates which gave the corresponding alkylated compounds with an excellent enantioselectivity (Equation (Sy)). Use of planar-chiral cyclopentadienylruthenium complexes 143 with an anchor phosphine moiety is essential to promote this asymmetric allylic alkylation efficiently. The substituents at the 4-position of the cyclopentadienyl ring play a crucial role in controlling the stereochemistry. A kinetic resolution of racemic allylic carbonates has been achieved in the same reaction system (up to 99% ee). ... 

Trinitroanisole Complex, CHj O-CgHjtNOjJj -[ 3CHAcNaCOaC1Hs, red amor ppt, expl on j heating sol in ale or acet. It was obtained on I treating a benzolic soln of TNAns with a ben2olic soln of ethyl sodium acetate. Another expl complex was obtained on treating TNAns with ethyl sodium malonate Ref C.L. Jackson Si F.H.Gazzolo, Amer Chem-J 23, 376(1900) JCS 78, I, 433-4(1900)... 

Respiration Studies in Isolated Mitochondria Cellular respiration can be studied in isolated mitochondria by measuring oxygen consumption under different conditions. If 0.01 m sodium malonate is added to actively respiring mitochondria that are using pyruvate as fuel source, respiration soon stops and a metabolic intermediate accumulates. 

This acid is considered to be the trane form largely because of lte Physical properties. Jt is possible that the other form has bssn prepared by Perkin by heating a 1,1,2,3 acid which he prepared from dlbromsuccinlc ester and sodium malonic ester. The acid differed in melting point from the one prepared by Buchner and formed no anhydride. A repetition of Perkin s work by Buchner gave negative results, (over)... 

The esters of both these acius are obtained by similar reactions,tne I iist by the action of sodium i,.al-onic ester on dioroLiSuccinic ester1 or broiamaleic ester,3 a the second from sodium malonic ester and either diorombutyric or brom (or cnlor) crotonic... 

This reaction with sodium malonic ester is entirely in accord with what would be expected from the rela-... 

These researches,which are due to iiichae 1,show that in all probability the reactions oetween many at, dibromides and sodium malonic ester should be interpreted as follows the dibromlde first loses hydro-... 

Sodium malonic ester and dibromcinnarnic ester react and a compound results which analyses for phenylcyclopropane 2,2,3 triester and is not oxidized... 

Without postulating the formation of dichloronaphthalide 368, one may explain using Scheme 7 the reaction of naphthaloyl dichloride 367 with two molecules of sodium malonic ester, which does not result in the expected 1,8-dimalonylnaphthyl diketone 372, but leads to a 2-malonylydene derivative of naphtho[cd]pyran-9-one 373 (36MI3). However, we do not insist on the suggested mechanisms for the reactions of naphthaloyldichloride 367 with aromatic compounds or sodium malonic ester one can assume the alternative course via dichloronaphthalide 368. Moreover, hemo-... 

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