Malonic acid, bis

DIETHYL BIS(HYDROXYMETHYL)MALONATE (Malonic acid, bis(hydroxymethyl)-, diethyl ester)... 

Ethyl a-(bromomethyl)acrylate Acrylic acid, 2-(bromomethyl)-, ethyl ester (8) 2-Propenoic acid, 2-(bromomethyl)-, ethyl (9) (17435-72-2) Diethyl bis(hydroxymethyl)malonate Malonic acid, bis(hydroxymethyl)-, diethyl ester (8) (20605-01-0)... 

C24H44O4 2-cyclopentyl-malonic acid bis-(2-ethyl-hexyl) ester 102809-00-7... 

Not only 2,4,7-trinitro-9-fluorenone (TNF) but also other electron acceptors, for example, TCNQ, 1,2,4,5-tetracyanoben-zene, the enantiomers of 2-(2,4,5,7-tetrani-tro-9-fluorenylideneaminooxy)-propionic acid (TAPA) or 2,4,5,7-tetranitro-9-fluore-none, and derivatives of the latter one, are effective in this type of mesophase induction [50]. In particular, a TNF derivative carrying two hexadecanoyl side chains (2,4,7-trinitrofluorenylidene-9-malonic acid bis(hexadecyl) ester) is remarkable because of the induction of a nematic columnar type (Ncoi) mesophase with hexakispen-... 

Figure 13.5 2-(4-Dodecyloxy-bei zylidene)-malonic acid bis-(2,3-dihy-droxy-propyl) ester (1)...

C19H36O4 malonic acid bis-(l-methyl-heptyl ester) 89837-79-6... 

Several procedures for making glutaric acid have been described in Organic Syntheses starting with trimethylene cyanide (28), methylene bis (malonic acid) (29), y-butyrolactone (30), and dihydropyran (31). Oxidation of cyclopentane with air at 140° and 2.7 MPa (400 psi) gives cyclopentanone and cyclopentanol, which when oxidized further with nitric acid at 65—75° gives mixtures of glutaric acid and succinic acid (32). 

Di-fcr(-butyl diazomalonate Malonic acid, diazo-, di-(erf-butyl ester (8) Propanedioic acid, diazo-, bis(l,l-dimethylethyl)ester (9) (35207-75-1)... 

One of the most recent developments in the field of Ni-catalyzed reactions of alkyl halides with organozinc derivatives is a study of Terao et al.411 They reported the use of three additives in the couplings 1,3-butadiene, N,N-bis(penta-2,4-dienyl)benzylamine 308a, and 2,2-bis(penta-2,4-dienyl)malonic acid dimethyl ester 308b. Addition of tetraene 308b to the reaction mixtures significantly increased the product yields (Scheme 157). The remarkable effect of these additives was explained by the formation of the bis-7r-allylic complex 309 as the key intermediate (Scheme 158). 

N,)V -Bis(cyclohexylaminocarbonyl)formamidine (310) was reacted with diethyl malonate in ethanol at 70°C for 60 hr to give N-(cyclohexylami-nocarbonyl)aminomethylenemalonate (311, R = Et) in 24% yield (53-JA671). The similar reaction of malonic acid at room temperature for 3-4 min afforded (cyclohexylaminocarbonyl)aminomethylenemalonic acid (311, R = H) in 65% yield. When bis(cyclohexylaminocarbonyl)for-mamidine (310) was reacted with 1 1 molar mixture of diethyl malonate and malonic acid in ethanol at 70°C for 5 min, only malonic acid (311, R = H) was obtained, in 76% yield. 

Bis-acceptor-substituted diazomethanes are most conveniently prepared by diazo group transfer to CH acidic compounds either with sulfonyl azides under basic conditions [949,950] or with l-alkyl-2-azidopyridinium salts [951] under neutral or acidic conditions [952-954]. Diazo group transfer with both types of reagents usually proceeds in high yield with malonic acid derivatives, 3-keto esters and amides, 1,3-diketones, or p, y-unsaturated carbonyl compounds [955,956]. Cyano-, sulfonyl, or nitrodiazomethanes, which can be unstable or sensitive to bases, can often only be prepared with 2-azidopyridinium salts, which accomplish diazo group transfer under neutral or slightly acidic reaction conditions. Other problematic substrates include amides of the type Z-CHj-CONHR and P-imino esters or the tautomeric 3-amino-2-propenoic esters, which upon diazo group transfer cyclize to 1,2,3-triazoles [957-959]. 

After treatment of (130a) with sulfuric acid in ethanol, bis(4-amino-5-cyanopyridine-2-yl)-disulfide (131) was isolated as the only product in 69% yield. However, if (130b,c) are treated with sulfuric acid in ethanol under otherwise identical conditions the corresponding tetrazolyl-methylene malonic acid derivatives (132) could be isolated in 45% and 48% yields respectively. 

On their side, Yin and Linker [216] made use of a 2-C-branched hexopyranoside, the synthesis of which was achieved by addition of dimethyl malonate to tri-O-benzyl-D-glucal (TUPAC name 3,4,6-tri-0-benzyl-l,5-anhydro-2-deoxy-D-araZtino-hex-l-enitol, Scheme 45) [217], Thus, saponification of the 2-C-[bis(meth-oxycarbonyl)]methyl derivative 184 to the corresponding malonic acid 185 was followed by heating in refluxing toluene. This led to decarboxylation and lactoniza-tion giving 186. The method was optimized and applied to the synthesis of pentoses and disaccharides. 

Bis-p-nitrophenyl malonate (55M29) reacts with a-alkylamino-isobutyr-onitriles in xylene to give derivatives (16b) of tetramic acids with yields of 30-50% (86UP1 88UP1). The reaction of derivatized malonic acids with a-amino acid esters to 3-alkoxycarbonyl-l,5-dihydro-4-hydroxy-2-pyrrolones presents the same problems (see Section III). (See Fig. 8.)... 

Verdini and co-workers 71,81 107 were able to silylate the amine with Af,0-bis(trimethylsilyl)-acetamide 108 (BTMSA) and to ring-open Meldrum s acid in a one-pot procedure without isolating the labile Af-silyl derivative. Additional, less frequently employed methods for the synthesis of C2-substituted malonic acids are summarized in a review. 73 ... 

Several procedures for making glularic acid have been described in Organic Syntheses starting with trimcthylcne cyanide, methylene bis (malonic acid), g-butyrolactone. and dihydropyran. 

Apart from the diols examined so far there are other bis-O nucleophiles that also react with carbonyl compounds following the mechanisms discussed, as illustrated by Figure 9.21. The result is acetal analogs such as the compounds D (from hydroxy carboxylic acid A), E (from enol carboxylic acid wo-B) or F ( Meldrum s acid from malonic acid). Each of these acetal analogs is used as a reagent in organic synthesis. 

The treatment of alkenes with iodine(III) reagents usually results in functionalization of the carbon-carbon double bond. However, 1,1-diphenylethylene affords a low yield of (l,l-diphenylethenyl)phenyliodonium tosylate with HTIB (equation 181)11,138. The cyclic dithiolylidene derivative of malonic acid, shown in equation 182, undergoes decarboxylation with [bis(trifiuoroacetoxy)iodo]benzene in methanol and gives an unusual vinyliodo-nium trifluoroacetate139. Finally, when the allenylphosphonate shown in equation 183 is added to a mixture of (difluoroiodo)benzene and BF3-etherate in dichloromethane, a... 

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