N,N,N',N'-Tetramethylethylenediamine → 1-phenyl-2-methyl-6-chloro-2,3-dihydro-1H-2,1-benzazaphosphole-1-oxide

온도

-70 °C

Under a static nitrogen atmosphere at 0° C., a solution of n-butyllithium (7.87 g, 0.123 mol) in hexane was added to a solution of tetramethylethylenediamine (14.3 g, 0.123 mol) in 60 ml. of anhydrous cyclohexane with constant stirring. The resulting mixture was stirred for an additional 15 minutes and then cooled to -70° C. using a solid carbon dioxide-acetate bath. A solution of N-methyl-4-chloro-benzylamine (9.6 g, 0.06 mol) in 60 ml. of anhydrous cyclohexane was added to the reaction mixture to produce a suspension containing a dilithio compound. This suspension was stirred for 2 hours at 26° C. and then cooled to -70° C. using a solid carbon dioxide-acetone bath. A solution of phenylphosphonic dichloride (12.5 g, 0.064 mol) in 60 ml. of anhydrous cyclohexane was rapidly added to the suspension causing the temperature of the reaction to increase to -20° C. The reaction mixture was allowed to cool to -70° C., after which time the solid carbon dioxide-acetone bath was removed and the reaction mixture was stirred for 2.5 hours. The reaction mixture was cooled to 0° C. and then quenched with the rapid addition of 12 ml. of acetic acid. The cyclohexane was removed on a rotary evaporator, and the resulting residue was partitioned between methylene chloride and water. The layers were separated and the methylene chloride layer was dried over magnesium sulfate and concentrated in vacuo to yield a red oil. Distillation of the red oil at 180° C. and 0.25 mm yielded a yellow solid which was slurried in ether to yield 1-phenyl-2-methyl-6-chloro-2,3-dihydro-1H-2,1-benzazaphosphole-1-oxide (2.2 g, 13% yield) as a pale yellow solid having a melting point of 159°-162° C. and the following analysis:

1. customto produce a suspension
2. stirringThis suspension was stirred for 2 hours at 26° C.
3. temperaturecooled to -70° C.
4. customthe temperature of the reaction
5. temperatureto increase to -20° C
6. temperatureto cool to -70° C.
7. customafter which time the solid carbon dioxide-acetone bath was removed
8. stirringthe reaction mixture was stirred for 2.5 hours
9. temperatureThe reaction mixture was cooled to 0° C.
10. customquenched with the rapid addition of 12 ml
11. customThe cyclohexane was removed on a rotary evaporator
12. customthe resulting residue was partitioned between methylene chloride and water
13. customThe layers were separated
14. dry with materialthe methylene chloride layer was dried over magnesium sulfate
15. concentrationconcentrated in vacuo
16. customto yield a red oil
17. distillationDistillation of the red oil at 180° C.
18. custom0.25 mm yielded a yellow solid which

ORD 기록

ord-8aceb9363d544d8cb5f722fec53879bb

출처 데이터셋

uspto-grants-1982_03

DOI

10.6084/m9.figshare.5104873.v1

특허 번호

US04319913