Carbon dioxide methanol → HCID 67349161, compound

HRID 1472999Notes

Reaction equation

HRID 1472999 reaction equation
[CH3:1][C:2]([CH2:14][CH2:15][CH:16]=[C:17]([CH3:34])[CH2:18][CH2:19][CH:20]=[C:21]([CH3:33])[CH2:22][CH2:23][CH:24]=[C:25]([CH3:32])[CH2:26][CH2:27][CH:28]=[C:29]([CH3:31])[CH3:30])=[CH:3][CH2:4][S:5]([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)(=[O:7])=[O:6].C(=O)=O.CO.[Li]CCCC.Br[CH2:46][C:47]([CH3:70])=[CH:48][CH2:49][CH2:50][C:51]([CH3:69])=[CH:52][CH2:53][C:54]1[C:63]([CH3:64])=[C:62]([O:65][CH3:66])[C:61]2[C:56](=[CH:57][CH:58]=[CH:59][CH:60]=2)[C:55]=1[O:67][CH3:68]>C1COCC1>[C:8]1([S:5]([CH:4]([CH:3]=[C:2]([CH3:1])[CH2:14][CH2:15][CH:16]=[C:17]([CH3:34])[CH2:18][CH2:19][CH:20]=[C:21]([CH3:33])[CH2:22][CH2:23][CH:24]=[C:25]([CH3:32])[CH2:26][CH2:27][CH:28]=[C:29]([CH3:31])[CH3:30])[CH2:46][C:47]([CH3:70])=[CH:48][CH2:49][CH2:50][C:51]([CH3:69])=[CH:52][CH2:53][C:54]2[C:63]([CH3:64])=[C:62]([O:65][CH3:66])[C:61]3[C:56](=[CH:57][CH:58]=[CH:59][CH:60]=3)[C:55]=2[O:67][CH3:68])(=[O:6])=[O:7])[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1

Participants

6

Reactant 4

HCID 21973728Carbon dioxide methanolHCID 67328998HCID 67328998, compoundHCID 67331259HCID 67331259, compoundHCID 178418339Butyllithium

Product 1

HCID 67349161HCID 67349161, compoundYield 135.9%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

9.06 g (18.76 mmol) (3,7,11,15,19-pentamethyl-eicosa-2,6,10,14,18-pentaene-1-sulfonyl)-benzene were dissolved in 80 ml of dry THF and the solution was cooled to −78° C. with CO2/MeOH. At −78° C., 11.80 ml (18.88 mmol) BuLi (1.6 M solution in hexane) was added drop wise via septum and syringe over 10 min. The orange solution was stirred for 2.5 h at −78° C. 6.07 g (14.56 mmol) 2-(8-bromo-3,7-dimethyl-octa-2,6-dienyl)-1,4-dimethoxy-3-methyl-naphtalene dissolved in 30 ml of dry THF was added via dropping funnel over 10 min. The brown reaction mixture was stirred at −78° C. for 1.5 h. At −78° C., the reaction was quenched by addition of 50 ml of a Et2O/MeOH mixture (1:1 v/v). The mixture was allowed to reach room temperature and after that 100 ml of saturated NH4Cl solution was added. The layers were separated and the aqueous layer was extracted with Et2O. The combined organic extracts were washed with brine, dried over Na2SO4, filtered and concentrated in vacuo by rotary evaporation at 30° C. to give 16.21 g of 2-(9-benzenesulfonyl-3,7,11,15,19,23,27-heptamethyl-octacosa-2,6,10,14,18,22,26-heptaenyl)-1,4-dimethoxy-3-methyl-naphtalene as a brownish yellow oil, which was used in the next step without further purification.

Workup

  1. additionwas added
  2. customover 10 min
  3. stirringThe brown reaction mixture was stirred at −78° C. for 1.5 h
  4. customAt −78° C., the reaction was quenched by addition of 50 ml of a Et2O/MeOH mixture (1:1 v/v)
  5. customto reach room temperature
  6. additionafter that 100 ml of saturated NH4Cl solution was added
  7. customThe layers were separated
  8. extractionthe aqueous layer was extracted with Et2O
  9. washThe combined organic extracts were washed with brine
  10. dry with materialdried over Na2SO4
  11. filtrationfiltered
  12. concentrationconcentrated in vacuo by rotary evaporation at 30° C.

Sources & evidence

ORD record
ord-0fe55d3825914020bd6c03aaaf8f0498
Source dataset
uspto-grants-2015_04
Patent number
US09012693B2

Reaction notes

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