Imidazole → 3-(4-Chlorophenyl)-3-methyl-1-iodo-1-tributylstannylbutane

HRID 1441007Notes

Reaction equation

HRID 1441007 reaction equation
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N1C=CN=C1.[I:25]I.[Cl:27][C:28]1[CH:33]=[CH:32][C:31]([C:34]([CH3:52])([CH3:51])[CH2:35][CH:36]([Sn:38]([CH2:47][CH2:48][CH2:49][CH3:50])([CH2:43][CH2:44][CH2:45][CH3:46])[CH2:39][CH2:40][CH2:41][CH3:42])O)=[CH:30][CH:29]=1>C(Cl)Cl.C(#N)C>[Cl:27][C:28]1[CH:33]=[CH:32][C:31]([C:34]([CH3:52])([CH3:51])[CH2:35][CH:36]([I:25])[Sn:38]([CH2:47][CH2:48][CH2:49][CH3:50])([CH2:43][CH2:44][CH2:45][CH3:46])[CH2:39][CH2:40][CH2:41][CH3:42])=[CH:30][CH:29]=1

Participants

7

Reactant 4

HCID 795Imidazole2×HCID 807Iodine2×HCID 11776TriphenylphosphineHCID 153325673-(4-Chlorophenyl)-3-methyl-1-tributylstannylbutanol

Product 1

HCID 153325683-(4-Chlorophenyl)-3-methyl-1-iodo-1-tributylstannylbutaneYield 40.4%

Reagents, catalysts & solvents 2

HCID 6342AcetonitrileSolventHCID 6344DichloromethaneSolvent2×

Procedure

A solution of 14.0 grams (0.053 mole) of triphenylphosphine in about 54 mL of methylene chloride was stirred, and 3.6 grams (0.053 mole) of imidazole was added. Upon completion of addition, the reaction mixture was stirred about 45 minutes until the imidazole dissolved. The reaction mixture was then cooled in an ice bath, and 13.6 grams (0.053 mole) iodine was added portionwise. Upon completion of addition, the reaction mixture was allowed to warm to ambient temperature, where it stirred for about 15 minutes until the iodine dissolved. After this time the reaction mixture was cooled to 0° C., and a solution of 17.4 grams (0.036 mole) of 3-(4-chlorophenyl)-3-methyl-1-tributylstannylbutanol in about 36 mL of methylene chloride was added dropwise while maintaining the reaction mixture temperature below 5° C. Upon completion of addition, the reaction mixture was allowed to warm to ambient temperature where it stirred for about 18 hours. The reaction mixture was then taken up in about 100 mL of acetonitrile and extracted with three 150 mL portions of hexane. The combined extracts were concentrated under reduced pressure to a residue. The residue was subjected to column chromatography on silica gel, using petroleum ether as the eluant. The product-containing fractions were combined and concentrated under reduced pressure, yielding 8.7 grams of 3-(4-chlorophenyl)-3-methyl-1-iodo-1-tributylstannylbutane. The NMR spectrum was consistent with the proposed structure.

Workup

  1. additionUpon completion of addition
  2. dissolutiondissolved
  3. temperatureThe reaction mixture was then cooled in an ice bath
  4. additionUpon completion of addition
  5. dissolutiondissolved
  6. temperatureAfter this time the reaction mixture was cooled to 0° C.
  7. temperaturewhile maintaining the reaction mixture temperature below 5° C
  8. additionUpon completion of addition
  9. temperatureto warm to ambient temperature where it
  10. extractionextracted with three 150 mL portions of hexane
  11. concentrationThe combined extracts were concentrated under reduced pressure to a residue
  12. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-2a703bf2efa649b4aae849c11a91c3e1
Source dataset
uspto-grants-1996_03
Patent number
US05502054

Reaction notes

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