Triethylamine → HCID 53706937, compound

HRID 465116Notes

Reaction equation

HRID 465116 reaction equation
[C:1](Cl)(=O)C(Cl)=O.Cl.[N:8]1[CH:13]=[CH:12][CH:11]=[C:10]([CH2:14][C:15](O)=O)[CH:9]=1.[C:18]([CH2:20][C:21]([O:23][C:24]([CH3:27])([CH3:26])[CH3:25])=[O:22])#[N:19].[CH2:28]([N:30](CC)[CH2:31]C)C>C(Cl)Cl.CN(C)C=O.O>[C:18]([C:20](=[CH:1][C:14]([C:10]1[CH:9]=[N:8][CH:13]=[CH:12][CH:11]=1)=[CH:15][N:30]([CH3:31])[CH3:28])[C:21]([O:23][C:24]([CH3:27])([CH3:26])[CH3:25])=[O:22])#[N:19]

Participants

8

Reactant 4

HCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 70693tert-Butyl cyanoacetateHCID 27237243-Pyridineacetic acid, hydrochloride (1:1)

Product 1

HCID 53706937HCID 53706937, compound

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6228DimethylformamideSolvent3×HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
20 °C

Procedure

A 13.4 ml portion of N,N-dimethylformamide in 300 ml of methylene chloride was cooled to 0° C. An 11.1 ml portion of oxalyl chloride in 50 ml of methylene chloride was added dropwise over 10 minutes. The solution was allowed to warm to 20° C. and stirred for 30 minutes. The volatiles were removed at reduced pressure leaving a flocculent white powder. A 10.0 g portion of 3-pyridineacetic acid hydrochloride salt was added followed by 50 ml of N,N-dimethylformamide. This solution was stirred at 20° C. for 30 minutes and then warmed to 80° C. for 72 hours. The black solution was cooled to 20° C., 8.13 g of t-butyl cyanoacetate in 50 ml of N,N-dimethylformamide was added and the solution was cooled to 0° C. A 36 ml portion of triethylamine was added over 5 minutes and the solution was allowed to warm to 20° C. and was stirred for one hour. The solution was then poured onto 500 ml of water and extracted with three 150 ml portions of methylene chloride. The organic layers were combined, washed with brine, dried and the volatiles removed at reduced pressure. The residue was purified by chromatography, using a Waters 500 HPLC, two columns and eluting with acetone:hexane (2:3). The resulting oil was crystallized from ether-hexane, giving 1,1-dimethylethyl 2-cyano-5-(dimethylamino)-4-(3-pyridinyl)-2,4-pentanedienoate as yellow crystals, mp 161°-63° C.

Workup

  1. customThe volatiles were removed at reduced pressure
  2. customleaving a flocculent white powder
  3. stirringThis solution was stirred at 20° C. for 30 minutes
  4. temperaturewarmed to 80° C. for 72 hours
  5. temperatureThe black solution was cooled to 20° C.
  6. temperaturethe solution was cooled to 0° C
  7. temperatureto warm to 20° C.
  8. stirringwas stirred for one hour
  9. extractionextracted with three 150 ml portions of methylene chloride
  10. washwashed with brine
  11. customdried
  12. customthe volatiles removed at reduced pressure
  13. customThe residue was purified by chromatography
  14. washeluting with acetone:hexane (2:3)
  15. customThe resulting oil was crystallized from ether-hexane

Sources & evidence

ORD record
ord-6b28f9628d584227bbb88dacbe9c2612
Source dataset
uspto-grants-1985_10
Patent number
US04550166

Reaction notes

Loading…