Pentane-3,3-dicarboxylic acid

Diethyl 2-butylmalonate Pentane-1,1-dicarboxylic acid, diethyl ester C11H20O4 133-08-4 216.276 238 0.9764 1.4260 vs EtOH, eth... 

Pimelic Acid (Heptanedioic Acid or 1,5-Pentane-dicarboxylic Acid). HOOC.(CH2)s-COOH mw 160.17 white prisms mp 106° bp 272° at 100mm (subl), and 212° at 10mm d 1.329 g/cc at 15°. Sol in w, ethanol, eth and hot benz. Prepn is by oxidn of cycloheptanone, capric acid or oleic acid treatment of salicylic acid with Na in amyl ale, or bydecarboxylating 1,1,5,5-pentanetetracarboxylic acid with heat Pimelic acid has been combined with cis and trans-1,4-cyclohexanediol to give polyesters, and with m-xylene-a,a -diamine or poly-methylenediamines to form polyamides. With diperoxides, the acid forms resins. It is also used as the parent compd to form the expls presented below... 

Synonims 1,2-cyclohexanedicarboxylic, acid calcium salt octacosanoic acid, calcium salt (2 1) calcium difluoride propanedioic acid, calcium salt (1 1) 1,5-pentane dicarboxylic acid, calcium salt (lR,2R,3S,4S)-rel-bicyclo[2.2.1]heptane-2,3-dicarboxylic acid, disodium salt mixture of polycarbonic acid salt and inorganic carbonate in a polymeric carrier, sodium 2,2 -methylene-bis-(4,6-di-tert-butylphenyl)phosphate bicyclic (2,2,1) heptane di-carboxylate 1,2-cyclohexanedicarboxylic acid, calcium salt -i- zinc stearate bicyclo[2.2.1]heptane-2,3-dicarbo lic acid, disodium salt, (IR, 2R, 3S, 4S)-rel-and a blend of amorphous silicon dioxide coated wilh 13-docosenamide in a 1 1 ratio proprietary zinc compound octacosanoic acid, calcium salt (2 1) benzoic acid, lithium salt zinc monoglycerolate sodium benzoate encapsulated sodium salts of carbonic and poly-carboxylic acids with styrene and SEES rubber carrier resins zinc,[l,2,3-propanetriolato(2-)-k01,k02]homopolymer, stereoisomer... 

In a modified procedure the free carboxylic acid is treated with a mixture of mercuric oxide and bromine in carbon tetrachloride the otherwise necessary purification of the silver salt is thereby avoided. This procedure has been used in the first synthesis of [1.1.1 ]propellane 10. Bicyclo[l.l.l]pentane-l,3-dicarboxylic acid 8 has been converted to the dibromide 9 by the modified Hunsdiecker reaction. Treatment of 9 with t-butyllithium then resulted in a debromination and formation of the central carbon-carbon bond thus generating the propellane 10." ... 

A mixture of 2,2 -diaminobiphenyl-4,4 -dicarboxylic acid (10 g. 36.8 mmol) and benzil (10 g, 47.6 mmol) in glacial HOAc (300 mL) was heated underlux for 24 h. After cooling the solution, the resulting product was collected, washed with small portions of pentane, and recrystallized (EtOH), which gave a pale yellow solid yield 12 g (73%) mp 348-352"C. 

Photochemical Synthesis of Bicyclo[1.1.1]pentane-1,3-dicarboxylic Acid. 

A magnetically stirred mixture of cyclobutane-1,1-dicarboxylic acid (1.6 g, 11.1 mmol), HgO (3.3 g, 15.7 mmol), and Br2 (1.14 mL, 3.55 g, 22.2 mmol) in CH2C12 (40 mL) was heated at reflux for 80 min, cooled in an ice bath, treated with pentane (15 mL), and suction filtered. Following rinsing of the filter cake with pentane, the filtrate was concentrated by simple distillation. Pentane was added, the solids were removed by filtration, and the filtrate was washed with 1 M NaOH and brine prior to drying. The pentane was distilled to leave a residue, which in turn was bulb-to-bulb distilled to give the product yield 1.1 g (46%) bp 80-120 "C (bath)/31 Torr. 

PHOTOCHEMICAL SYNTHESIS OF BICYCLO[1.1.1)PENTANE-1,3-DICARBOXYLIC ACID... 

B. Bicyclo[1.1.1]pentane-1,3-dicarboxylic acid (3). A 1-L, three-necked, round-bottomed flask, equipped with a mechanical stirrer, addition funnel, and thermometer is charged with a solution of 43.3 g (1.08 mol) of sodium hydroxide in 315 mL of water and 25.5 mL (79.1 g, 0.495 mol) of bromine. The mixture is cooled to 0°C. A solution of the diketone (10 g, 0.066 mol) obtained in Part A in 36 mL of dioxane is added dropwise at such a rate that the temperature does not exceed 3°C (Note 7). After the addition is finished, the reaction mixture is stirred for 1 hr at 0°C, then overnight at room temperature. Sodium bisulfite (1.8 g) is added and the solution is extracted with chloroform (3 x 50 mL). Subsequently, 36 mL of coned hydrochloric acid is added to the aqueous layer. After the acidified solution is cooled to room temperature, the mixture is continuously extracted with diethyl ether for 50 hr (Note 8) in an extraction apparatus. Evaporation of ether from the extract yields 9.68 g (94.5% from diketone 2) of pure diacid 3, mp 302-305°C, with decomposition [lit.4 mp, 305°C (d)] (Note 9). 

C. 5 -Methoxycyclohexan- -one- > A -dicarboxylic acid anhydride. To 3.00 g (0.174 mol) of 1-methoxy-3-trimethylsiloxy- 1,3-butadiene at 0°C (ice bath) is added a total of 980 mg (0.01 mol) of freshly sublimed maleic anhydride in portions of 70-80 mg each over a period of 25 min. When the addition is complete, the ice bath is removed and the clear solution is stirred for 15 min at room temperature (Note 7). Three 5-mL portions of a solution of tetrahydrofuran (35 mL) and 0.1 N hydrochloric acid (15 mL) are added and the solution is stirred for 1 min. The remaining acid solution (35 mL) is added all at once and the resulting solution is poured into 100 mL of chloroform and treated with 25 mL of water. The organic layer is separated and the aqueous layer is extracted four times with 100-mL portions of chloroform. The extracts are combined and dried over anhydrous magnesium sulfate. The solvent is then removed under reduced pressure (Note 8) to provide 2.0 g of an oil which solidifies. Pentane (10 mL) is added to the oily solid and small portions... 

Carboxyl-labeled dicarboxylic acid 68 has been prepared from l,5-di(bromomagnesio) pentane and labeled carbon dioxide [Eq. (27) 51]. However, when the di-Grignard reagent 67 was heated with isotopically labeled barium carbonate, labeled 4-f-butylcyclohexanone 69 was isolated [52]. 

In a beaker-type cell (Figure 2) equipped with two platinum electrodes (area 10 cm, thickness 0.05 mm, supported on a teflon frame), a solution of 14.3 mmol 5-decynoic acid and 86 mmol methyl sube-rate in 40 mL methanol, neutralized to 5% with KOH, was electrolyzed at 22 C and a current density of 100 mA cm 2, provided from a regulated d.c. power supply, until a pH of 8-9 was reached. After evaporation of the methanol the crude product was refluxed with equimolar amounts of KOH in 100-200 mL methanol for 24 h thereafter the mixture was evaporated to dryness and extracted with petroleum ether. The remaining salt was dissolved in water, acidified with 15% HCl, and continuously extracted with petroleum ether. The precipitated tetradecanoic dicarboxylic acid (72%, m.p. 126 C) was filtered off, and after evaporation of the petroleum ether 8.43 mmol (59%) 11-hexadecynoic acid was isolated by bulb to bulb distillation m.p, (from pentane) 40-41... 

Oxotricyclo 2.1.0.0 pentane-l,5-dicarboxylic Acid Typical Procedure ... 

Latifolic 3,4-Dihydroxy pentan-2,3-dicarboxylic acid lactone Latifoline 1Q5-166 + 94.0d... 

O Acetylmonocrotalic 2 -Hydroxy 3 - acetoxy - 3 -methyl - pentan-2,4-dicarboxylic acid lactone Spectabiline — — ... 

Jean-Pierre Deprds and Andrew E. Greene 41 VICINAL DICARBOXYLATION OF AN ALKENE cis-l-METHYLCYCLO-PENTANE-1,2-DICARBOXYLIC ACID... 

Chuman, T, H. Kaneko, and M. Noguchi Structure of a new terpenoid acid, l-Xi-methyl-3-Xi-isopropylcyclo-pentane-l-Xi, 2-Xi-dicarboxylic acid Agr. Biol. Chem. 

The original preparation of [l.l.l]propellane (177) involved Hunsdiecker degradation of bicyclo[1.1.0]pentane-l,3-dicarboxylic acid (178) to the dibromide 179 and then treatment of 179 with an alkyllithium. Unfortunately, 178 was only accessible with difficultyand [l.l.l]propellane remained effectively unavailable until Szeimies and coworkers reported a remarkable two-step synthesis in 1985. The commercially... 

Methylisobutylmalonic Acid (2.Methyl-pentane-i i-dicarboxylic acid)... 

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