Bicyclo heptane-7 -carboxylic acid

A primary halide, 1-bromooctane, reacted as expected to give 100% yield in 10 min and was converted to pivalic acid in 52% yield after 1 hr of reaction. l-Chlorobicyclo[2.2.1]heptane reacted slowly at room temperature, so this was rerun in refluxing THF. Again, the Grignard preparation was slow, giving 74% yield after 6 hr of reflux. The Grignard was then quenched with CO2 to give l-bicyclo[2.2.1]heptane-carboxylic acid in 63% yield. Bixler and Niemann [64] prepared l-bicyclo[2.2.1]-heptanecarboxylic acid from l-chlorobicyclo[2.2.l]heptane by conversion of the chloride to the lithium salt, followed by CO2 quench. The Rieke method appears to be superior, since it obviates the preparation of the lithium salt used in the procedure of Bixler and Niemann. 

Trichloroacetyl fluoride, 45, 6 2-(Trichloromethyl)bicyclo[3.3.0]octane, from reaction of chloroform and cib,o i-l,5-cyclooctadiene, 47,10 hydrolysis with phosphoric acid to c.ro-m-bicyclo[3.3.0]octane-2-carboxylic acid, 47, 11 1,1,3-Trichloro- -nonane, 46,104 Tricyclo[2.2.1,02 6]heptan-3-ol, 46,... 

A Wagner-Meerwein rearrangement via a bridged carbenium ion has been observed in the electrodecarboxylation of bicyclo[2.2.1]heptane-2-carboxylic acids (CXVIIa, CXVIIb, and CXVIIc), leading to the formation of the same products (CXVIII and CXIX) [Eq. (58)] [174]. This method has been successfully applied to synthesis of useful intermediates for natural product synthesis. Some examples are given in Eqs. (59) and (60) [175-179]. 

A ring enlargement involving rupture of a cyclopropane ring on anodic oxidation is exemplified in the transformation of bicyclo[4.1.0]heptane-7-carboxylic acid in methanol to 3-methoxycycloheptene [23]. 

Reaction. with Lithium Thiocyanate. To LiSCN (153 mg, 2.3 mmol) in anhyd Et O (1 mL) was added exo-7,8-epoxybicyclo[4.2.0]octane (166 mg, 1.3 mmol). The flask was stoppered and stirred at 4L C for 34 h. Workup as described above gave the product yield 150 mg (90%), whose H NMR spectrum was consistent with that of known bicyclo[4.1.0]heptane-en<7o-7-carbaldehyde and displayed no cxo-aldchyde signal at 5 = 9.1. Air oxidation of the carbaldehyde gave an acid identical with authentic bicyclo[4.1.0]hep-tane-enrfo-7-carboxylic acid. ... 

A solution of 3,4-dibromo-7-hydroxy-c/s-bicyclo[4.1.0]heptane-exo-7-carboxylic acid (1.25 g, 3.97 mmol) in 0.75% aq NaOH (30 mL) was stirred at 20 C under Nj for 24 h. Acidification to pH 1 with 1 M HCl and continuous extraction with EtjO gave a colorless crystalline product yield 0.95 g (93%) mp 149-150°C (sublimation). 

Decarboxylation of bicyclo[4.1.0]heptane-7,7-dicarboxylic acid (16) affords exo- and endo-hi-cyclo[4.1.0]heptane-7-carboxylic acid (17) in a relatively poor yield together with cyclohex-2-eneacetic acid (18). ... 

Various 7-carboxylic acid derivatives of bicyclo[4.1.0]heptane and -ene were reduced using a two-step procedure starting with generation of anhydride derivatives which were not isolated, but reduced directly with sodium borohydride - for example reduction of... 

Fig. 11.6 Structures of bridged bicyclic proline mimetics (22) 2-aza-bicyclo[2.2.1]hep-tane-3-carboxylic acid, (23) 2-aza-bicy-clo[2.2.1]hept-5-ene-3-carboxylic acid, (24) 7-aza-bicyclo[2.2.1]heptane-l-carboxylic acid, (25) 2-aza-bicyclo[2.2.1]hexane-l carboxylic acid, (26) 2-aza-bicyclo[2.2.1]hexane-...

Oxidation. Primary alcohols are converted to carboxylic acids using EtOAc to replace carbon tetrachloride as solvent. Bicyclo[2.2.1]heptane-2,3-diones are obtained from the Diels-Alder adducts of a 5,5-dimethoxy-l,2,3,4-tetrahalocyclopentadiene. ... 

These products are precursors of perfluoro carboxylic acids while the fluorosulfates derived from secondary and tertiary hydrofluorocarbons provide perfluoro ketones, and starting from the IH-perfluoro bicyclo[2.2.1]heptane, the corresponding perfluoro teriaiy alcohol is... 

Trimethyl-3-oxo-2-oxa-bicyclo[2.2.1]heptane-l-carboxylic acid [(-)-1 -(1 S,4R)-camphanic acid]... 

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... 

Bicyclo-(2.2.1)- heptene Bicyclo-(2.2.1)- heptane-2 carboxylic acid 80 [489]... 

C9H12O8, D-Spiro[3.3]heptane-2,6-dicarboxylic acid, 38B, 203 C9H13CIO, 2-Chlorobicyclo[3.3.1]nonan-9-one, 32B, 144 C9H13NO2, 6-endo-Hydroxy-3-endo-aminomethylbicyclo[2.2.1]heptane-2-endo-carboxylic acid lactam, 43B, 232 C9H1n02, exo-7-Hydroxybicyclo[3.3.1]nonan-3-one, 45B, 172 C9H18O2S, 6-endo-(Methylthio)bicyclo[2.2.1]heptane-2-endo-carboxylic acid, 46B, 169... 

C9H18O2S, 6-exo-(Methylthio)bicyclo[2.2.1]heptane-2-endo-carboxylic acid, 46B, 169... 

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