Hydrochloric Acid → HCID 86056334, compound

HRID 749323Notes

Reaction equation

HRID 749323 reaction equation
[CH2:1]([CH:11]([CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH:24]=[CH2:25])[C:12]([OH:14])=[O:13])[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH:9]=[CH2:10].[C:26]([O-])([O-])=O.[K+].[K+].CI.Cl>C(OCC)(=O)C.CC(C)=O>[CH2:1]([CH:11]([CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH:24]=[CH2:25])[C:12]([O:14][CH3:26])=[O:13])[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH:9]=[CH2:10]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 6328Methyl iodideHCID 11430Potassium CarbonateHCID 59752448HCID 59752448, compound

Product 1

HCID 86056334HCID 86056334, compoundYield 97.5%

Reagents, catalysts & solvents 2

HCID 180AcetoneSolventHCID 8857Ethyl AcetateSolvent

Procedure

2-(Dec-9-enyl)-tridec-12-enoic acid (63 mg, 0.18 mmol, Example 67) was added to a 100 mL three-neck round-bottom flask fitted with a reflux condenser (cooled with ice cold water) followed by 15 mL of reagent-grade acetone. The resulting solution was vigorously stirred and 0.062 g K2CO3 (0.45 mmol, 2.5 eq.) was added in one portion and the mixture was stirred for 5 minutes at room temperature. An excess of methyl iodide (˜2.0 mL) was then added and the mixture was refluxed under argon for 24 hours, after which TLC analysis (5:95 ethyl acetate:hexanes) indicated complete reaction. The mixture was acidified to pH 5 with 3N aqueous HCl and extracted with CH2Cl2. This solution was dried over MgSO4 and a small amount of Na2S2O3 (to destroy iodine). The solvent was then evaporated to afford methyl 2-(dec-9-enyl)-tridec-12-enoate (64 mg, quantitative yield) as a clear oil. 1H NMR (300 MHz, CDCl3): δ 5.80 (m, 2H), 4.93 (m, 4H), 3.65 (s, 1H), 2.35 (m, 1H), 2.03 (q, 4H), 1.58 (m, 2H) 1.42, 1.35, and 1.27 (m, 28H) ppm. 13C NMR (75 MHz, CDCl3): δ 177.04, 139.17, 139.15, 114.08, 114.06, 51.23, 45.68, 33.78 (2 C, unresolved), 32.48, 29.51, 29.50, 29.48 (2 C, unresolved), 29.42 (2 C, unresolved), 29.37 (2 C, unresolved), 29.09, 29.06, 28.90, 28.88, 27.44 (2 C, unresolved) ppm. Analysis calculated for C24H44O2: C, 79.06; H, 12.16. Found: C, 78.83; H, 12.16. HRMS-FAB: Theoretical: 365.3420; Found: 365.3399 [M]+. A copolymer of methyl 2-(dec-9-enyl)-tridec-12-enoate and 1,9-decadiene, prepared similarly to polymer 21, would have the following features: The end groups R2 and R3 would be H. For this polymer, e and f would be derived from methyl 2-(dec-9-enyl)-tridec-12-enoate and would equal 9 and 10, respectively; d would derive from 1,9-decadiene and would equal 8. The run length distribution would therefore be: rHH=(9+0)+8z; rHT=(9+10)+8z; and rTT=(10+10)+8z; therefore rtotal=(18+8z), (19+8z), (20+8z).

Workup

  1. customfitted with a reflux condenser
  2. temperature(cooled with ice cold water)
  3. stirringthe mixture was stirred for 5 minutes at room temperature
  4. temperaturethe mixture was refluxed under argon for 24 hours
  5. customreaction
  6. extractionextracted with CH2Cl2
  7. dry with materialThis solution was dried over MgSO4
  8. customThe solvent was then evaporated

Sources & evidence

ORD record
ord-1378131bfcc842b5b4e08084633e7bd5
Source dataset
uspto-grants-2008_07
Patent number
US07402642B2

Reaction notes

Loading…