반응 #536363

반응 방정식

acetic acid

methyl carbamate

2-oxo-4-(hydroxymethylphosphinyl)-butanoic acid

→

objective compound

수율 80.7%

(Z)-2-methoxycarbonylamino-4-(hydroxymethylphosphinyl)-2-butenoic acid

수율 80.7%

용매

toluene

toluene

반응 조건

후처리

1. 1
   workup.DISSOLUTIONAfter being dissolved
2. 2
   온도by heating
3. 3
   온도the solution was refluxed with vigorous stirring
4. 4
   기타was from 106 to 108 deg. C
5. 5
   기타Three hours
6. 6
   기타After removing about 60 mL of the solvent under a reduced pressure
7. 7
   workup.ADDITIONby adding 20 mL of acetic acid
8. 8
   workup.STIRRINGthe resultant was stirred for 1 hour at 80 deg. C
9. 9
   기타The precipitate which was obtained
10. 10
    workup.STIRRINGstirring over-night
11. 11
    여과was filtered
12. 12
    세척the filtrate was washed with acetic acid
13. 13
    세척After being washed with acetone
14. 14
    기타dried for 5 hours from 40 to 50 deg. C

실험 절차

7.085 g of methyl carbamate, 0.275 g of p-toluenesulfonic acid monohydrate and 10.000 g of 2-oxo-4-(hydroxymethylphosphinyl)-butanoic acid prepared by the method described in Japanese Patent Laid-Open No. 92897/1981, were added to 16 mL of acetic acid to be suspended. After being dissolved by heating, 64 mL of toluene was added thereto and then the solution was refluxed with vigorous stirring. The internal temperature of the reaction solution was from 106 to 108 deg. C. One and a half hours later, 8 mL of toluene was further added to the reaction solution and continued stirring. Three hours later, dissipation of almost all the raw materials was confirmed by HPLC measurement. At this point, the area ratio of Z form to E form was 94:6. After removing about 60 mL of the solvent under a reduced pressure, followed by adding 20 mL of acetic acid, and then the resultant was stirred for 1 hour at 80 deg. C. The precipitate which was obtained by cooling the solution gradually to room temperature and stirring over-night, was filtered and then the filtrate was washed with acetic acid. After being washed with acetone, dried for 5 hours from 40 to 50 deg. C. under a reduced pressure, 10.625 g of the objective compound was obtained (80.7% yield, Z:E=99.6:0.4). mp 254-256 deg. C.

출처