반응 #316322

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(2E)-3-{4-[(4-hydroxyphenyl)(3,3,5,5-tetramethylcyclohexylidene)methyl]phenyl}-2-propenoic acid

(2E)-3-{4-[(4-Hydroxyphenyl)(3,3,5,5-tetramethylcyclohexylidene)methyl]phenyl}-2-propenoic acid

oxalyl chloride

Ammonia

→

compound 17

수율 15.0%

(2E)-3-{4-[(4-Hydroxyphenyl)(3,3,5,5-tetramethylcyclohexylidene)methyl]phenyl}-2-propenamide

수율 15.0%

용매

CH2Cl2

반응 조건

후처리

1. 1
   농축concentrated in vacuo
2. 2
   workup.ADDITIONToluene was added to the crude acid chloride
3. 3
   기타the solvent was removed in vacuo
4. 4
   workup.ADDITIONTo the crude acid chloride was added ammonia (0.5 M in 1,4-dioxane) (6 mL)
5. 5
   기타the turbid reaction mixture
6. 6
   workup.STIRRINGstirred at room temperature under a nitrogen atmosphere for 3 h
7. 7
   workup.STIRRINGstirring
8. 8
   workup.WAITwas continued overnight at room temperature under a nitrogen atmosphere
9. 9
   농축The reaction mixture was concentrated in vacuo
10. 10
    workup.ADDITIONAmmonia (0.5 M in 1,4-dioxane) (8 mL) and CH2Cl2 (8 mL) were added to the residue
11. 11
    기타The flask was equipped with a rubber septum
12. 12
    workup.STIRRINGthe reaction mixture was stirred at room temperature for 2 d
13. 13
    기타The reaction mixture was transferred to a separatory funnel
14. 14
    기타partitioned between CH2Cl2 and H2O
15. 15
    기타The layers were separated
16. 16
    추출the aqueous phase was extracted with CH2Cl2
17. 17
    세척washed with brine
18. 18
    건조dried (MgSO4)
19. 19
    여과filtered
20. 20
    농축the filtrate was concentrated
21. 21
    기타to give the crude product as an amorphous solid
22. 22
    기타The crude product was purified by flash chromatography on silica gel with CH2Cl2:MeOH (100:0 to 19:1) as eluant
23. 23
    기타to provide the product which
24. 24
    기타was dried

실험 절차

To a stirred suspension of (2E)-3-{4-[(4-hydroxyphenyl)(3,3,5,5-tetramethylcyclohexylidene)methyl]phenyl}-2-propenoic acid (16) (0.18 g, 0.46 mmol) in CH2Cl2 (6 mL) at room temperature was added oxalyl chloride (0.15 mL, 0.218 g, 1.72 mmol, 3.7 eq) followed by several drops of DMF (Note: vigorous bubbling occurred upon addition of DMF). The reaction mixture was stirred under a nitrogen atmosphere for 1 h and concentrated in vacuo. Toluene was added to the crude acid chloride and the solvent was removed in vacuo. To the crude acid chloride was added ammonia (0.5 M in 1,4-dioxane) (6 mL) and the turbid reaction mixture stirred at room temperature under a nitrogen atmosphere for 3 h. Ammonia (0.5 M in 1,4-dioxane) (2 mL) was added to the reaction mixture and stirring was continued overnight at room temperature under a nitrogen atmosphere. The reaction mixture was concentrated in vacuo. Ammonia (0.5 M in 1,4-dioxane) (8 mL) and CH2Cl2 (8 mL) were added to the residue. The flask was equipped with a rubber septum and the reaction mixture was stirred at room temperature for 2 d. The reaction mixture was transferred to a separatory funnel and partitioned between CH2Cl2 and H2O. The layers were separated and the aqueous phase was extracted with CH2Cl2. The organic extracts were combined, washed with brine, dried (MgSO4) filtered, and the filtrate was concentrated to give the crude product as an amorphous solid. The crude product was purified by flash chromatography on silica gel with CH2Cl2:MeOH (100:0 to 19:1) as eluant to provide the product which was dried to give 0.026 g (15%) of compound 17 as a pale yellow solid. 1H NMR (400 MHz, DMSO-d6): δ 0.87 (s, 6H), 0.88 (s, 6H), 1.25 (s, 2H), 1.89 (s, 2H), 1.92 (s, 2H), 6.53 (d, J=15.8 Hz, 1H), 6.66 (d, J=8.5 Hz, 2H), 6.93 (d, J=8.5 Hz, 2H), 7.06 (br s, 1), 7.14 (d, J=8.1 Hz, 2H), 7.35 (d, J=15.9 Hz, 1H), 7.45 (d, J=8.1 Hz, 2H), 7.50 (br s, 1H), 9.30 (s, 1). HRMS (ESI) Calcd for C26H32 NO2: 390.2433 (M+H)+. Found: 390.2427.

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