Toluene → HCID 13934071, compound

HRID 2308996Notes

Reaction equation

HRID 2308996 reaction equation
[CH3:1][C:2]1[S:6][C:5]([CH:7]=[C:8]([C:14]([O:16][CH2:17][CH3:18])=[O:15])[C:9]([O:11][CH2:12][CH3:13])=[O:10])=[CH:4][CH:3]=1.[C-:19]#[N:20].C([Al+]CC)C.C1(C)C=CC=CC=1>C1COCC1>[C:19]([CH:7]([C:5]1[S:6][C:2]([CH3:1])=[CH:3][CH:4]=1)[CH:8]([C:14]([O:16][CH2:17][CH3:18])=[O:15])[C:9]([O:11][CH2:12][CH3:13])=[O:10])#[N:20]

Participants

5

Reactant 3

HCID 1140TolueneHCID 1811896HCID 1811896, compoundHCID 16686413Diethyl aluminum cyanide

Product 1

HCID 13934071HCID 13934071, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A 50.60 g (0.189 moles) sample of diethyl 2-[(5-methyl-2-thienyl)methylene]propanedioate, the product of Example 1a., was taken up in 560 ml dry THF. The solution was cooled in an ice bath. 560 ml of 1N diethyl aluminum cyanide in toluene (0.57 moles) was added dropwise over one hr. The ice bath was then removed and the reaction was stirred at room temperature for 1.5 hr. After this time the reaction was cooled again in an ice bath and 168 ml of 3N sodium hydroxide was added slowly. This was stirred for one hr. The reaction was partitioned between methylene chloride and water, the organics were washed with water, brine, and dried (MgSO4). The solvents were evaporated in vacuo. The residue was distilled in a Kugelrohr at 140° C. and 0.005 mm Hg. 117.17 g of diethyl 2-[cyano(5-methyl-2-thienyl)methyl]-propanedioate was collected as an oil.

Workup

  1. temperatureThe solution was cooled in an ice bath
  2. customThe ice bath was then removed
  3. temperatureAfter this time the reaction was cooled again in an ice bath
  4. addition168 ml of 3N sodium hydroxide was added slowly
  5. stirringThis was stirred for one hr
  6. customThe reaction was partitioned between methylene chloride and water
  7. washthe organics were washed with water, brine
  8. dry with materialdried (MgSO4)
  9. customThe solvents were evaporated in vacuo
  10. distillationThe residue was distilled in a Kugelrohr at 140° C.
  11. custom117.17 g of diethyl 2-[cyano(5-methyl-2-thienyl)methyl]-propanedioate was collected as an oil

Sources & evidence

ORD record
ord-289cccade48943f6b6574e66c6e89ee9
Source dataset
uspto-grants-1987_09
Patent number
US04692460

Reaction notes

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