Allylamine → HCID 2832220, compound

Temperature

2 °C

Step 1′ A 2-L, three-necked, round-bottomed flask equipped with a magnetic stirring bar, a 24/40 adapter fitted with a thermometer, an argon inlet adapter, and a 250-mL pressure-equalizing addition funnel fitted with a glass stopper was purged with argon. The flask was charged with 3-nitrobenzoyl chloride (J) 112.0 g (0.6035 mol) and 850 mL of dichloromethane, and then cooled with an ice-water bath. The addition funnel was charged with triethylamine 93.0 mL (0.667 mol) and allylamine (K) 50.0 mL (0.666 mol), and this solution was then added dropwise to the reaction mixture over ca. 2.5 h while the reaction temperature was maintained at 0-4° C. The addition funnel was then rinsed with two 5-mL portions of dichloromethane. The resulting turbid pale orange-pink reaction mixture was allowed to slowly warm to and stir at room temperature. After 16.5 h, 600 mL of 1N HCL was added to the turbid bright yellow solution over 30 sec and the biphasic mixture was transferred to a separatory funnel. The reaction flask was rinsed with three 100-mL portions of 1:1 CH2Cl2: 1N HCl and the organic phase was separated and washed with 500 mL of saturated sodium chloride solution, dried over sodium sulfate, filtered, and concentrated under reduced pressure to afford 122 g (98% crude yield) of a pale yellow solid. The crude product was recrystallized from 450 mL of toluene to afford 113 g (91 % yield) of N-allyl-3-nitrobenzamide (L) as a powdery pale yellow solid.

1. customa 24/40 adapter fitted with a thermometer, an argon inlet adapter, and a 250-mL pressure-equalizing addition funnel
2. customfitted with a glass stopper
3. customwas purged with argon
4. temperaturecooled with an ice-water bath
5. additionthis solution was then added dropwise to the reaction mixture over ca. 2.5 h while the reaction temperature
6. washThe addition funnel was then rinsed with two 5-mL portions of dichloromethane
7. temperatureto slowly warm to and
8. addition600 mL of 1N HCL was added to the turbid bright yellow solution over 30 sec
9. customthe biphasic mixture was transferred to a separatory funnel
10. washThe reaction flask was rinsed with three 100-mL portions of 1:1 CH2Cl2
11. custom1N HCl and the organic phase was separated
12. washwashed with 500 mL of saturated sodium chloride solution
13. dry with materialdried over sodium sulfate
14. filtrationfiltered
15. concentrationconcentrated under reduced pressure
16. customto afford 122 g (98% crude yield) of a pale yellow solid
17. customThe crude product was recrystallized from 450 mL of toluene

ORD record

ord-83e7e14891bf415a9e3e6e61501030a8

Source dataset

uspto-grants-2003_04

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US06555711B1