Iodine → HCID 15702077, compound

HRID 1590515Notes

Reaction equation

HRID 1590515 reaction equation
[Li]CCCC.[CH2:6]([C:9]1[CH:10]=[N:11][C:12]([C:15]2[CH:20]=[CH:19][C:18]([CH2:21][CH2:22][C:23]3[CH:28]=[C:27]([F:29])[CH:26]=[C:25]([F:30])[CH:24]=3)=[CH:17][CH:16]=2)=[N:13][CH:14]=1)[CH2:7][CH3:8].[CH3:31][N:32](CCN(C)C)C.II>C1COCC1.C(OCC)C.O>[CH2:6]([C:9]1[CH:14]=[N:13][C:12]([C:15]2[CH:20]=[CH:19][C:18]([CH2:21][CH2:22][C:23]3[CH:24]=[C:25]([F:30])[C:26]([C:31]#[N:32])=[C:27]([F:29])[CH:28]=3)=[CH:17][CH:16]=2)=[N:11][CH:10]=1)[CH2:7][CH3:8]

Participants

8

Reactant 4

HCID 807Iodine2×HCID 8037N,N,N',N'-TetramethylethylenediamineHCID 15702076HCID 15702076, compoundHCID 178418339Butyllithium

Product 1

HCID 15702077HCID 15702077, compound

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
170 °C

Procedure

0.1 m of n-BuLi (1,5 M in hexane) is added dropwise to a solution of 0.1 m of 1-[p-(5-n-propyl-2-pyrimidinyl)-phenyl]-2-(3,5-difluorophenyl)ethane (prepared in accordance with scheme 1) and 0.1 m of TMEDA in 300 ml of THF at approximately -90° . Stirring is carried out for a further 30 min at this temperature and then a solution of 0.1 m of I2 in 70 ml of THF is slowly added. After addition is complete, the solution is allowed to heat up to -20° and hydrolyzation is carried out with H2O. The product is completely dissolved by adding diethyl ether and excess I2 is removed by washing with sodium thiosulfate solution and H2O. After evaporating down, the product is left behind as a residue and without further purification, is heated with 0.12 m of (CuCN)x and 100 ml of NMP for 4 h at 170° C. in an oil bath. After this time, water and CH2CH2 are added to the cooled reaction mixture, and the organic phase is washed, dried and evaporated down. The pure product can be obtained by chromatography and crystallization. 1-[p-(5-n-propyl-2-pyrimidinyl)-phenyl]-2-(4-cyano-3,5difluorophenyl)ethane is obtained.

Workup

  1. additionAfter addition
  2. temperatureto heat up to -20°
  3. dissolutionThe product is completely dissolved
  4. customis removed
  5. washby washing with sodium thiosulfate solution and H2O
  6. customAfter evaporating down
  7. waitthe product is left behind as a residue and without further purification
  8. additionAfter this time, water and CH2CH2 are added to the cooled reaction mixture
  9. washthe organic phase is washed
  10. customdried
  11. customevaporated down
  12. customThe pure product can be obtained by chromatography and crystallization

Sources & evidence

ORD record
ord-39403142282f4d07adcbb44aa4065837
Source dataset
uspto-grants-1993_04
Patent number
US05204017

Reaction notes

Loading…