Putrescine → HCID 131715472, compound

HRID 231716Notes

Reaction equation

HRID 231716 reaction equation
[CH3:1][Si](C)(C)N[Si](C)(C)C.C([Li])CCC.CCCCCC.Br[C:22]1[N:36]([Si:37]([C:40]([CH3:43])([CH3:42])[CH3:41])([CH3:39])[CH3:38])[C:35]2[C:44]3[C:23]=1[CH2:24][C@@H:25]1[C:30]([C:31]=3[CH:32]=[CH:33][CH:34]=2)=[CH:29][C@H:28]([NH:45][C:46](=[O:52])[N:47]([CH2:50][CH3:51])[CH2:48][CH3:49])[CH2:27][N:26]1[CH3:53].NCCCCN.C([Li])(C)(C)C.FC(F)(F)S(O)(=O)=O>O.C1(C)C=CC=CC=1>[Si:37]([N:36]1[C:35]2[C:44]3[C:23]([CH2:24][C@@H:25]4[C:30]([C:31]=3[CH:32]=[CH:33][CH:34]=2)=[CH:29][C@H:28]([NH:45][C:46](=[O:52])[N:47]([CH2:50][CH3:51])[CH2:48][CH3:49])[CH2:27][N:26]4[CH3:53])=[C:22]1[CH3:1])([C:40]([CH3:43])([CH3:42])[CH3:41])([CH3:39])[CH3:38]

Participants

9

Reactant 6

HCID 1045PutrescineHCID 13838HexamethyldisilazaneHCID 62406Trifluoromethanesulfonic acidHCID 131715473HCID 131715473, compoundHCID 178418244HCID 178418244, compoundHCID 178418306HCID 178418306, compound

Product 1

HCID 131715472HCID 131715472, compoundYield 27.4%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 1140TolueneSolvent2×

Conditions

Temperature
0 °C

Procedure

Under argon, 0.3 ml (1.5 mmol) of distilled hexamethyldisilazane is added to 4 ml of absolute, freshly distilled toluene, and the mixture is cooled to 0° C. Then 0.85 ml (1.4 mmol) of 15% butyllithium/hexane is added dropwise and the mixture is stirred for 15 minutes at 0° C. To this mixture is added 531 mg (1 mmol) of 3-[2-bromo-1-(tert-butyldimethylsilyl)-9,10-didehydro-6-methyl-8α-ergolinyl]-1,1-diethylurea in 50 ml of absolute, freshly distilled toluene and agitation is continued for another 15 minutes at 0° C. After adding 1 ml of distilled tetramethylenediamine, the batch is cooled to -90° C. At this temperature, 5 ml (7 mmol) of 1.4M tert-butyllithium is added and the mixture is agitated for 2 minutes before 0.6 ml (5.4 mmol) of the methyl ester of trifluoromethanesulfonic acid is added thereto. After 11/2 hours of agitation at -70° C., water is added to work up the reaction mixture. Extraction is performed with ethyl acetate. The organic phases are washed with saturated sodium bicarbonate solution and water. The combined ethyl acetate phases are dried over sodium sulfate and concentrated. Crystallization from methanol produces 128 mg of 3-[1-(tert-butyldimetylsilyl)-9,10-didehydro-2,6-dimethyl-8α-ergolinyl]-1,1-diethylurea (27% yield).

Workup

  1. waitis continued for another 15 minutes at 0° C
  2. temperaturethe batch is cooled to -90° C
  3. additionis added
  4. extractionExtraction
  5. washThe organic phases are washed with saturated sodium bicarbonate solution and water
  6. dry with materialThe combined ethyl acetate phases are dried over sodium sulfate
  7. concentrationconcentrated
  8. customCrystallization from methanol

Sources & evidence

ORD record
ord-4964fdd357d5471c88e6627b50f5025d
Source dataset
uspto-grants-1989_07
Patent number
US04847262

Reaction notes

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