bicyclo[2.2.2]octane-1-carboxylic acid

bicyclo[2.2.2]octane-1-carboxylic acid Property

Melting point:

140.8-141.3 °C

Boiling point:

274.3±8.0 °C(Predicted)

Density 

1.186±0.06 g/cm3(Predicted)

storage temp. 

Sealed in dry,Room Temperature

pka

5.07±0.10(Predicted)

Appearance

White to off-white Solid

InChI

InChI=1S/C9H14O2/c10-8(11)9-4-1-7(2-5-9)3-6-9/h7H,1-6H2,(H,10,11)

InChIKey

PUNFICOCZAPAJV-UHFFFAOYSA-N

SMILES

C12(C(O)=O)CCC(CC1)CC2

Safety

HS Code 

2916200090

Hazard and Precautionary Statements (GHS)

Symbol(GHS)

Signal word

Warning

Hazard statements

H315Causes skin irritation

H319Causes serious eye irritation

H335May cause respiratory irritation

Precautionary statements

P260Do not breathe dust/fume/gas/mist/vapours/spray.

P280Wear protective gloves/protective clothing/eye protection/face protection.

P301+P312IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell.

bicyclo[2.2.2]octane-1-carboxylic acid Chemical Properties,Usage,Production

Synthesis

To a round-bottomed flask was added 4-(methoxycarbonyl)bicyclo[2.2.2]octane-1-carboxylic acid (1 g, 4.71 mmol), 2,2'-disulfonylbis(pyridine 1-oxide) (1.427 g, 5.65 mmol) and dichloromethane (50 mL). The flask was wrapped in aluminum foil to protect from light. The suspension was cooled to 0 °C and tributylphosphine (1.453 mL, 5.89 mmol) was added dropwise. The ice bath was removed and the reaction mixture continued to be stirred for 2 hours. The reaction system was again cooled to 0 °C and 2-methylpropane-2-thiol (4.7 mL, 41.7 mmol) was added. The reaction mixture was irradiated using a 300W tungsten lamp for 1.25 hours. The reaction was quenched by adding a suspension of calcium hypochlorite (10 g) in water (100 mL). The mixture was diluted with ether and stirred at 0°C for 5 min and then at room temperature for 20 min. Diatomaceous earth was added to assist in stratification and the mixture was filtered. The filtrate was transferred to a partition funnel and the organic layer was separated. The organic phase was washed with brine, dried over magnesium sulfate and concentrated. The residue was dissolved in a methanol/water (1:1, 100 mL) solution of potassium hydroxide (5 g) and stirred overnight at room temperature. The reaction solution was concentrated to remove most of the methanol, and the by-products were removed by extraction with ether (2×) (discarded). The aqueous phase was acidified with concentrated hydrochloric acid to pH acidic and a white precipitate was precipitated. The precipitate was collected by filtration to give 530 mg of product (66% yield).1H NMR (CDCl3) δ: 11.13 (br.s, 1H), 1.73-1.84 (m, 6H), 1.64-1.68 (m, 1H), 1.53-1.64 (m, 6H).

References

[1] Patent: WO2015/54103, 2015, A1. Location in patent: Page/Page column 27; 28