Sodium hydride → HCID 21569045, compound

HRID 1579702Notes

Reaction equation

HRID 1579702 reaction equation
[H-].[Na+].[CH3:3][N:4]([C:16]([O:18][CH2:19][C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1)=[O:17])[NH:5][C:6]([O:8][CH2:9][C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1)=[O:7].[H][H].[Na].C[O:30][C:31](=[O:40])[C:32]1[CH:37]=[CH:36][C:35]([CH2:38]Br)=[CH:34][CH:33]=1>CN(C)C=O.CCOCC>[CH3:3][N:4]([C:16]([O:18][CH2:19][C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1)=[O:17])[N:5]([CH2:38][C:35]1[CH:36]=[CH:37][C:32]([C:31]([OH:40])=[O:30])=[CH:33][CH:34]=1)[C:6]([O:8][CH2:9][C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1)=[O:7]

Participants

8

Reactant 5

HCID 24758Sodium hydrideHCID 255687Dibenzyl 1-methylhydrazine-1,2-dicarboxylateHCID 256687Methyl 4-(bromomethyl)benzoateHCID 5360545SodiumHCID 178418361HCID 178418361, compound

Product 1

HCID 21569045HCID 21569045, compound

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 6228DimethylformamideSolvent3×

Procedure

309 g. of a 27% suspension of sodium hydride in an inert solvent were treated with 300 ml. of dimethylformamide, and a solution of 1095 g. of 1-methyl-1,2-dicarbobenzoxy-hydrazine in dimethylformamide was added thereto. When all the material had been added and the hydrogen evolution had nearly come to a standstill, the mixture was heated for an hour at about 80° in order to carry the formation of the sodium salt to completion. A mixture of 759 g. of 4-(bromo-methyl)-benzoic acid methyl ester in 700 ml. of dimethylformamide was then dropped in, and finally the reaction mixture was heated for an hour at 80°. After cooling, the reaction mixture was poured into 10 liters of ice water and the condensation products taken up in ether. The thereby obtained crude methyl ester (nD24 = 1.1558) was used without further purification for the next step. It was dissolved in about 2200 ml. of dioxane, treated with a solution of 133 g. of sodium hydroxide in 870 ml. of water, and the resulting mixture stirred for about 24 hours at room temperature. It was then poured into about 10 liters of ice water and neutral materials were extracted with ether. The aqueous phase was rendered acid with concentrated hydrochloric acid (weak congo red) and the separated acid taken up in ether. The isolated crude acid was recrystallized from dibutyl ether, yielding colorless crystals of 4-[(2-methyl-1,2-dicarbobenzoxy-hydrazino)-methyl]-benzoic acid, which melted at 112°. The so-obtained product was sufficiently pure for further reaction.

Workup

  1. additionWhen all the material had been added
  2. temperaturethe mixture was heated for an hour at about 80° in order
  3. additionA mixture of 759 g
  4. temperaturewas heated for an hour at 80°
  5. temperatureAfter cooling
  6. customThe thereby obtained crude methyl ester (nD24 = 1.1558)
  7. customwas used without further purification for the next step
  8. dissolutionIt was dissolved in about 2200 ml
  9. additionof dioxane, treated with a solution of 133 g
  10. additionIt was then poured into about 10 liters of ice water and neutral materials
  11. extractionwere extracted with ether
  12. customThe isolated crude acid
  13. customwas recrystallized from dibutyl ether

Sources & evidence

ORD record
ord-3b42d60d89ae44a59b2c322b4faab80b
Source dataset
uspto-grants-1976_01
Patent number
US03931268

Reaction notes

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