Dicarboxylic acid-type compound

The Israeli company Levgum have patented a process (US 6831109) based on a chemical method using a combination of two types of chemical compound a urea-type compound and a dicarboxylic acid-type compound. The former componnd dissociates to produce an organic cation and an amine, and the latter as a promoter of this... 

The most common reaction of this type is the cyclization of various derivatives of hydrazine and substituted hydrazines with pyridine o-dicarboxylic acids and related compounds. Reactions in which the acid derivative reacts directly with the hydrazine are dealt with as [4 + 2] reactions in Section 2.15.10.6.1. 

Russell and coworkers147 had found that treatment of dimsyl anion 88 or of a similar methylsulfonyl carbanion with 1,2-, 1,3- and 1,4-dicarboxylic acid esters can give five- to seven-membered cyclic compounds. By this type of cyclization, they prepared ninhydrin hydrate 106 from diethyl phthalate148,149. 

The scope of this reaction is similar to that of 10-21. Though anhydrides are somewhat less reactive than acyl halides, they are often used to prepare carboxylic esters. Acids, Lewis acids, and bases are often used as catalysts—most often, pyridine. Catalysis by pyridine is of the nucleophilic type (see 10-9). 4-(A,A-Dimethylamino)pyridine is a better catalyst than pyridine and can be used in cases where pyridine fails. " Nonbasic catalysts are cobalt(II) chloride " and TaCls—Si02. " Formic anhydride is not a stable compound but esters of formic acid can be prepared by treating alcohols " or phenols " with acetic-formic anhydride. Cyclic anhydrides give monoesterified dicarboxylic acids, for example,... 

Special emphasis has been laid on structural studies of Cd compounds with dicarboxylic acids, because these combinations form coordination polymers of differing dimensionalities depending on the carboxylate component and on coligands coordinated to Cd. The simplest compound of this type, namely Cd oxalate CdC204, adopts a 3-D framework structure, with CdOe octahedra linked by oxalate groups.272 Further interesting structures containing Cd, oxalate and other components have been described recently.273,274... 

Now and then, projectiles from outer space cause excitement and surprises, as in January 2000, when a meteorite impacted the frozen surface of Lake Targish in Canada. It was a new type of C-chondrite with a carbon concentration of 4-5%, and probably came from a D-type asteroid (Hiroi et al., 2001). More exact analysis of the Targish meteorite showed the presence of a series of mono- and dicarboxylic acids as well as aliphatic and aromatic hydrocarbons (Pizzarello et al., 2001). Aromatic compounds and fullerenes were detected in the insoluble fraction from the extraction this contained planetary helium and argon, i.e., the 3He/36Ar ratio was... 

A powerful and efficient method for the preparation of poly(ketone)s is the direct polycondensation of dicarboxylic acids with aromatic compounds or of aromatic carboxylic acids using phosphorus pentoxide/methanesulfonic acid (PPMA)16 or polyphosphoric acid (PPA)17 as the condensing agent and solvent. By applying both of these reagents to the synthesis of hexafluoroisopropylidene-unit-containing aromatic poly(ketone)s, various types of poly(ketone)s such as poly(ether ketone) (11), poly(ketone) (12), poly(sulfide ketone) (13), and poly-... 

Oppenauer-type oxidation of secondary alcohols can be a convenient procedure for obtaining the corresponding carbonyl compounds. It was found recently [19], that Ir(I)- and Rh(I)-complexes of 2,2 -biquinoline-4,4 -dicarboxylic acid dipotassium salt (BQC) efficiently catalyze the oxidation of secondary alcohols with acetone in water/acetone 2/1 mixtures (Scheme 8.5). The reaction proceeds in the presence of Na2C03 and affords medium to excellent yields of the isolated ketones. The process is much faster in largely aqueous solutions, such as above, than in wet organic solvents in acetone, containing only 0.5 % water, low yields were observed (15 % vs. 76 % in case of cyclohexanol). 

The well documented oxidation of 1,10-phenanthroline (4) to 2,2 -bipyridyl-3,3 -dicarboxylic acid (53) by alkaline permanganate has been repeated. It is now found that 4,5-diazafluoren-9-one (54) is consistently a coproduct of the reaction in 20% yield.253 This provides a convenient route to this hitherto difficultly accessible compound. The formation of 4,5-diazafluoren-9-one almost certainly occurs by way of the intermediate, but not isolated, l,10-phenanthroline-5,6-dione, which is known to undergo a benzilic acid type rearrangement in the presence of hydroxide ions to give the diazafluorenone. This rearrangement of l,10-phenanthroline-5,6-dione has recently been studied further.115 Under some conditions 5,6-dihydro-5,6-dihydroxy- 1,10-phenanthroline can be isolated with the diazafluorenone. 

As for the unsaturated carbonyl compounds, the most significant groups are the oc,/ -unsaturated acids or esters. Some of their methods of formation are closely analogous, for example, (a) the Horner-Emmons or Wadsworth-Emmons reaction, and (b) the aldol-type reactions. Rather more specific methods are considered below for the formation of a,/ -acetylenic acids, and for the conversion of the unsaturated dicarboxylic acid, maleic acid, into its anhydride or into fumaric acid. 

In the NMR spectrum of 81 the C-12 and C-13 (C-l and C-2) methylene protons showed an A2B2-type signal at <5 2.83 ppm. Another active methylene at C-10 (C-4) absorbed as a triplet at 3 2.32 ppm. The remaining protons resonated at 3 1.0-1.8 ppm. Compound 81 was oxidized with permangamate under the alkaline conditions to yield a mixture of C6 to C9 dicarboxylic acids. These were analyzed as methyl esters by gas chromatography. Thus, the presence in the molecule of seven methylene groups between the carbonyl groups was established. 

Pyrazine-2,3-dicarboxylic acid anhydride (180) serves as the basis for the preparation of a series of pyrrolo[3,4-6]pyrazine derivatives <89JSC233>. Thus, treatment with a series of amino acids yields compounds of the type (181) (Equation (62)). 

Malonate and the dianions of the other aliphatic dicarboxylic acids H02 C(CH2 ) CO,H (n = 1-8) have been isolated as crystalline hydrates, and some of these have been dehydrated.293 X-Ray structural analyses have been reported for the malonate dihydrate,294 which has trans H2Os and bridging malonates of type (110), and for the succinate tetrahydrate and adipate dihydrate 295 the succinate reputedly has a trans- fAn02 (H2 0)4 ] polyhedron with bridging dicarboxylate, presumably as in (109). The monoanion of maleic acid (111) is only unidentate in crystalline [Mn(H-maleate)2-(H20)4] 296 but the equivalent compound of phthalic acid is a bis-chelated octahedral [Mn(0,0)2 (H2 0)2] species.297 Clearly other interactions in the solids, as well as the bonding interactions with Mn", define structure in the carboxylate compounds. 

Silyl-tethered stilbazole derivatives 349 were synthesized and subjected to intramolecular photocycloaddition in benzene at room temperature to give compounds of type 350 with stereochemistry cis-trans-ris and cis-trans-trans (Equation 66). It was shown that complexation of pyridine-containing stilbazoles 349 with dicarboxylic acid or catechol enhanced both the efficiency and stereoselectivity of the photocycloaddition <2006TL7865>. 

Though many open-chain diacyl peroxides have been described, very few cyclic compounds of this type are known. Monomeric cyclic phthaloyl peroxide (84) is prepared by treatment of phthaloyl chloride in chloroform with aqueous sodium peroxide solution in the presence of phosphate buffer, or by reaction of phthaloyl chloride with ethereal hydrogen peroxide in the presence of sodium carbonate.70-72 Russell71 has also obtained cyclic diacyl peroxides from the dichlorides of the C10, C12, and C14 dicarboxylic acids. Only polymeric diacyl peroxides were obtained from lower dicarboxylic acids. 

The intramolecular Wurtz-type coupling of dihaloorganic compounds with use of metallic zinc is a classical synthetic route to cyclic compounds. For example, cyclopropane derivatives can be prepared from 1,3-dihalo-propanes (29, 189a, 248, 451), and cyclobutane derivatives from 1,4-dihalobutanes (71). These reactions presumably proceed via the intermediate formation of organozinc compounds. The reaction of diethylzinc with esters of a,a -dibrominated aliphatic dicarboxylic acids leads to the... 

Commercially important polyesters, e.g. poly[l-(2-ethylenyl)-2,2,6,6-tetramethyl-4-piperidinylbutane dioate] (146) [190] were synthesized from l-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidines and suitable dicarboxylic acids. Another polymeric HALS was prepared by transesterification of oligoesters of tetramethyl-butane-l,2,3,4-tetracarboxylate with 22,6,6-tetramethyl-4-hydroxypiperidine and 1,10-decanediol [191]. Compound 147 is a similar polyester type HALS. An ester-amide chain is created during esterification of 2-(2,2,6,6-tetramethyl-4-piperidinylamino)ethanol and dimethyl adipate [192]. 

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