Pyridine → (4aR,8aS)-2,6-Bis(hydroxymethylidene)octahydronaphthalene-1,5-dione

HRID 2163560Notes

Reaction equation

HRID 2163560 reaction equation
[C:1]1(=[O:12])[C@H:10]2[C@@H:5]([C:6](=[O:11])[CH2:7][CH2:8][CH2:9]2)[CH2:4][CH2:3][CH2:2]1.[O:13]([CH3:15])[Na].[CH:16](OCC)=[O:17].N1C=CC=CC=1>O.CC(O)=O>[OH:17][CH:16]=[C:7]1[CH2:8][CH2:9][C@H:10]2[C@@H:5]([CH2:4][CH2:3][C:2](=[CH:15][OH:13])[C:1]2=[O:12])[C:6]1=[O:11]

Participants

7

Reactant 4

HCID 1049PyridineHCID 8025Ethyl formateHCID 11126638HCID 11126638, compoundHCID 178418582HCID 178418582, compound

Product 1

HCID 70605315(4aR,8aS)-2,6-Bis(hydroxymethylidene)octahydronaphthalene-1,5-dione

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 962WaterSolvent

Procedure

A mixture of 1.66 g (10 mmole) of trans-decalin-1,5-dione, 2.16 g (40 mmole) of NaOCH3, 9.2 ml (130 mmole) of ethyl formate, and 70 ml of dry pyridine was stirred under nitrogen at room temperature for 21 hr. After the mixture was adjusted to a pH between 5 and 6 with the aid of 51 ml of AcOH and 471 ml of water, it was extracted with benzene several times. The benzene layers were thoroughly washed with water and then were extracted with 2% KOH solution. The basic extracts were washed with ether and then after reacidification with AcOH they were thoroughly extracted again with benzene. The benzene extracts were dried (Na2SO4) and then were reduced to dryness to give 2 g (90%) of crude product. Recrystallization from ethanol afforded trans-2,6-Bis(hydroxymethylene)decalin-1,5-dione as a fine yellow powder, mp 155°-157°; ir (nujol) 1640 and 1570 cm-1 ; nmr (CDCl3)δ2.3 (broad multiplet, 10), 9.00 (s,2), and 14.50 (s,2); mass spectrum m/e 222(M+.).

Workup

  1. extractionwas extracted with benzene several times
  2. washThe benzene layers were thoroughly washed with water
  3. extractionwere extracted with 2% KOH solution
  4. washThe basic extracts were washed with ether
  5. extractionafter reacidification with AcOH they were thoroughly extracted again with benzene
  6. dry with materialThe benzene extracts were dried (Na2SO4)
  7. customto give 2 g (90%) of crude product
  8. customRecrystallization from ethanol

Sources & evidence

ORD record
ord-e295da5d60e749ed92b3c5ca6ec88463
Source dataset
uspto-grants-1979_01
Patent number
US04135048

Reaction notes

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