Chloroform → HCID 21518377, compound

HRID 1283574Notes

Reaction equation

HRID 1283574 reaction equation
C[O:2][C:3]([CH:5]1[C:9]([CH3:11])([CH3:10])[CH2:8]C(=O)C1C)=O.[CH:14](Cl)(Cl)Cl.[CH:18]([SH:21])([SH:20])[CH3:19].B(F)(F)F.[CH3:26][CH2:27]OCC>O>[OH:2][CH2:3][CH:5]1[C:9]([CH3:11])([CH3:10])[CH2:8][C:18]2([S:21][CH2:27][CH2:26][S:20]2)[CH:19]1[CH3:14]

Participants

6

Reactant 4

HCID 6212ChloroformHCID 8000Boron trifluoride etherateHCID 336451,1-EthanedithiolHCID 21518374HCID 21518374, compound

Product 1

HCID 21518377HCID 21518377, compound

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

4 g. of 1-methoxycarbonyl-3-oxo-2,5,5-trimethyl-cyclopentane are dissolved in 60 ml. of chloroform. After the addition of 10 ml. of ethane dithiol, the solution is treated with 1.5 ml. of boron trifluoride etherate, stirred for 2 hours at room temperature, introduced into water and extracted with ether. The ether extract is evaporated. The remaining 7-methoxycarbonyl-6,8,8-trimethyl-1,4-dithia-spiro[4,4]nonane is purified by adsorption on silica gel. The oil obtained has the following I.R. absorption spectrum: 1737 cm-1 [ester CO]; 1434 cm-1 [--CH2 --S--]; 1254 and 1173 cm-1 [ester]. 3.1 g. of the 7-methoxycarbonyl-6,8,8-trimethyl-1,4-dithiaspiro[4,4]nonane are dissolved in 30 ml. of toluene. The solution is treated at 0°C. with 28 ml. of a 1.12-M solution of diisobutylaluminum hydride in benzene, stirred for 4 hours and, after the addition of ethyl acetate, introduced into water. The organic phase is separated and evaporated. There is obtained 7-hydroxymethyl-6,8,8-trimethyl-1,4-dithia-spiro[4,4]nonane which, after recrystallization from ether/hexane, has a melting point of 72°-74°C. 2 g. of the 7-hydroxymethyl-6,8,8-trimethyl-1,4-dithia-spiro-[4,4]nonane are dissolved in 280 ml. of acetone and 14 ml of water. After the addition of 3.5 g. of cadmium carbonate and 3.5 g. of mercury (II) chloride, the solution is stirred for 24 hours at room temperature. The mixture is subsequently filtered and and the filtrate evaporated. There is obtained 1-hydroxymethyl-3-oxo-2,5,5-trimethyl-cyclopentane as an oil, whose 2,4-dinitrophenlhydrazone has a melting point of 144°-146°C. A solution of 9.5 g of pyridine in 150 ml of methylene chloride is treated with 6,0 g of chromium trioxide, stirred for 15 minutes at room temperature and, after the solution of 1.56 g of the 1-hydroxymethyl-3-oxo-2,5,5-trimethyl-cyclopentane dissolved in a small amount of methylene chloride, stirred for a further 15 minutes at room temperature. The mixture is then introduced into water and extracted with ether. The ether extract is evaporated. The remaining 1-formyl-3-oxo-2,5,5-trimethyl-cyclopentane is purified by adsorption on silica gel and converted into the desired methyl-(3-oxo-2,5,5-trimethyl-cyclopent-1-en-1-yl)-triphenylphosphonium bromide via the intermediate steps described in Example 2.

Workup

  1. additionAfter the addition of 10 ml
  2. extractionextracted with ether
  3. extractionThe ether extract
  4. customis evaporated
  5. customThe remaining 7-methoxycarbonyl-6,8,8-trimethyl-1,4-dithia-spiro[4,4]nonane is purified by adsorption on silica gel
  6. customThe oil obtained
  7. customabsorption spectrum
  8. dissolutionof the 7-methoxycarbonyl-6,8,8-trimethyl-1,4-dithiaspiro[4,4]nonane are dissolved in 30 ml
  9. additionThe solution is treated at 0°C. with 28 ml
  10. additionafter the addition of ethyl acetate
  11. additionintroduced into water
  12. customThe organic phase is separated
  13. customevaporated

Sources & evidence

ORD record
ord-ef7211f7d6664c9ca718f8c101228d57
Source dataset
uspto-grants-1976_08
Patent number
US03975445

Reaction notes

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