Fluorotrimethylsilane → 1,4,7-Tris(trimethylsilyl)-1,4,7-triazacyclododecane

HRID 1288215

반응식

HRID 1288215 반응식
Cl.Cl.Cl.[NH:4]1[CH2:15][CH2:14][CH2:13][CH2:12][CH2:11][NH:10][CH2:9][CH2:8][NH:7][CH2:6][CH2:5]1.C([Li])CCC.F[Si:22]([CH3:25])([CH3:24])[CH3:23]>ClC1C=CC=CC=1>[CH3:23][Si:22]([CH3:25])([CH3:24])[N:4]1[CH2:15][CH2:14][CH2:13][CH2:12][CH2:11][N:10]([Si:22]([CH3:25])([CH3:24])[CH3:23])[CH2:9][CH2:8][N:7]([Si:22]([CH3:25])([CH3:24])[CH3:23])[CH2:6][CH2:5]1

참가 물질

5

반응물 3

HCID 9869FluorotrimethylsilaneHCID 214862991,4,7-Triazacyclododecane trishydrochlorideHCID 178418339Butyllithium

생성물 1

HCID 215042021,4,7-Tris(trimethylsilyl)-1,4,7-triazacyclododecane

시약·촉매·용매 1

HCID 7964Chlorobenzene용매

실험 절차

1,4,7-Tris(trimethylsilyl)-1,4,7-triazacyclododecane was prepared from 1,4,7-triazacyclododecane trishydrochloride with six equivalents of n-butyllithium essentially by the procedure of Example 1 (A). In a 50 ml flask a solution of 0.675 g of the tris silyl compound (distilled bulb-to-bulb at 95°-125°/0.1 mm) in 2.5 ml of chlorobenzene was frozen, evacuated, and pressured with 40 ml of phosphorus oxyfluoride gas. The flask was sealed and the mixture heated overnight at 100°. Then the mixture was refluxed under a nitrogen atmosphere for 4 hours. A sample indicated (by nmr) that two-thirds of the silyl groups had reacted. Refluxing was continued for 5.8 hours under a nitrogen pressure of 960- 1040 mm of mercury. A sample at this time showed almost complete displacement of the silyl groups as fluorotrimethylsilane. The mixture remaining (about 80-85% of the original) was concentrated under vacuum and distilled bulb-to-bulb under vacuum (0.1 mm). The fraction collected at 80°-100° oven temperature consisted of solidified condensate in the mouth of the receiver, mp 78°-86.5°. This sample (~30 mg) was used for ir and mass spectroscopy which identify this material as 13-oxo-1,4,7-triaza-13-phosphatricyclo[5.5.1.04,13 ]-tridecane. It was recrystallized in part from cyclohexane giving needles, mp 86°-87.5°.

후처리

  1. customevacuated
  2. customThe flask was sealed
  3. temperaturethe mixture heated overnight at 100°
  4. temperatureThen the mixture was refluxed under a nitrogen atmosphere for 4 hours
  5. customhad reacted
  6. temperatureRefluxing
  7. concentrationwas concentrated under vacuum
  8. distillationdistilled bulb-to-bulb under vacuum (0.1 mm)
  9. customThe fraction collected at 80°-100° oven temperature
  10. customIt was recrystallized in part from cyclohexane giving needles, mp 86°-87.5°

출처 및 근거

ORD 기록
ord-852154e6c6864917a419c5131b7ae959
출처 데이터셋
uspto-grants-1976_10
특허 번호
US03987128

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