Hydrochloric Acid → Methyl 2-chloro-5-methylnicotinate

HRID 704447Notes

Reaction equation

HRID 704447 reaction equation
C([C:3]([C:11]([O:13][CH3:14])=[O:12])=[CH:4][C:5]([CH3:10])=[CH:6][N:7](C)[CH3:8])#N.[ClH:15]>ClCCCl>[CH3:14][O:13][C:11](=[O:12])[C:3]1[CH:4]=[C:5]([CH3:10])[CH:6]=[N:7][C:8]=1[Cl:15]

Participants

4

Reactant 2

HCID 313Hydrochloric AcidHCID 46390831-Cyano-4-(N,N-dimethylamino)-1-methoxycarbonyl-3-methyl-1,3-butadiene

Product 1

HCID 11636946Methyl 2-chloro-5-methylnicotinate

Reagents, catalysts & solvents 1

HCID 111,2-DichloroethaneSolvent

Conditions

Temperature
50 °C

Procedure

1-Cyano-4-(N,N-dimethylamino)-1-methoxycarbonyl-3-methyl-1,3-butadiene (33.6 g, 0.173 mol) prepared in a manner analogous to that described in Example 1(i) above was suspended in 1,2-dichloroethane (330 ml) and heated to 50° C. with stirring whereupon a steady stream of hydrogen chloride was passed through the mixture. After 21/4 hours, the clear solution was concentrated. The residue was dissolved in water and this solution was extracted with dichloromethane (3×100 ml). The pooled organic layers were dried with sodium sulphate and evaporated. Crystallisation of the residue from petrol yielded colourless crystals of 2-chloro-5-methylnicotinic acid methyl ester (30.0g, 93.4% of theoretical yield) with m.pt. 31° C.-33° C.

Workup

  1. concentrationAfter 21/4 hours, the clear solution was concentrated
  2. dissolutionThe residue was dissolved in water
  3. extractionthis solution was extracted with dichloromethane (3×100 ml)
  4. dry with materialThe pooled organic layers were dried with sodium sulphate
  5. customevaporated
  6. customCrystallisation of the residue from petrol yielded colourless crystals of 2-chloro-5-methylnicotinic acid methyl ester (30.0g, 93.4% of theoretical yield) with m.pt. 31° C.-33° C.

Sources & evidence

ORD record
ord-109d9ff0ecce471992c755816654aaa2
Source dataset
uspto-grants-1991_01
Patent number
US04987232

Reaction notes

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