1-(Methoxymethyl)-1H-pyrazole → 4,5-Dichloro-6-(1-methoxymethyl-5-pyrazolylcarbonyl)-1,3-benzodioxole-2-carboxylic acid

HRID 1074178Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1074178
COCN1C=CC=N1.C([Li])CCC.ClC1C2OC(C([O-])=O)OC=2C=C(C=O)C=1Cl.[Li+].[Cl:31][C:32]1[C:40]2[O:39][CH:38]([C:41]([OH:43])=[O:42])[O:37][C:36]=2[CH:35]=[C:34]([CH:44]([C:46]2[N:50]([CH2:51][O:52][CH3:53])[N:49]=[CH:48][CH:47]=2)[OH:45])[C:33]=1[Cl:54]>CN(C)P(=O)(N(C)C)N(C)C.C(OCC)(=O)C.O1CCCC1>[Cl:31][C:32]1[C:40]2[O:39][CH:38]([C:41]([OH:43])=[O:42])[O:37][C:36]=2[CH:35]=[C:34]([C:44]([C:46]2[N:50]([CH2:51][O:52][CH3:53])[N:49]=[CH:48][CH:47]=2)=[O:45])[C:33]=1[Cl:54]

Komponenten

8

Edukt 4

HCID 147197681-(Methoxymethyl)-1H-pyrazoleHCID 157144034,5-Dichloro-6-((1-methoxymethyl-pyrazol-5-yl)hydroxyme thyl)1,3-benzodioxole-2-carboxylic acidHCID 23683076Lithium 4,5-dichloro-6-formyl-1,3-benzodioxole-2-carboxylateHCID 178418339Butyllithium

Produkt 1

HCID 147486174,5-Dichloro-6-(1-methoxymethyl-5-pyrazolylcarbonyl)-1,3-benzodioxole-2-carboxylic acid

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 8028TetrahydrofuranLösungsmittelHCID 8857Ethyl AcetateLösungsmittelHCID 12679HexamethylphosphoramideLösungsmittel

Versuchsvorschrift

A mixture of 1.12 g of 1-methoxymethyl-pyrazole, 25 ml of tetrahydrofuran, 6.88 ml of 1.6M n-butyl lithium and a solution of 2.69 g of lithium 4,5-dichloro-6-formyl-1,3-benzodioxole-2-carboxylate in 12 ml of hexamethylphosphoric triamide is treated in the same manner described in Example 11-(1) to give an ethyl acetate solution containing 4,5-dichloro-6-[(1-methoxymethyl-pyrazol-5-yl)hydroxymethyl)-1,3-benzodioxole-2-carboxylic acid. The ethyl acetate solution is washed with water, dried and evaporated to remove solvent under reduced pressure. The residue (crude 4,5-dichloro-6-[(1-methoxymethyl-pyrazol-5-yl)hydroxymethyl]-1,3-benzodioxole-2-carboxylic acid) is dissolved in 100 ml of methylene chloride, 10 g of pyridinium dicromate are added thereto and the mixture is stirred at room temperature for 17 hours. Insoluble materials are filtered off and washed with methylene chloride. The filtrate and the washing solution are combined and evaporated under reduced pressure to remove solvent. Ethyl acetate is added to the residue and insoluble materials are filtered off. The filtrate is washed, dried and evaporated under reduced pressure to remove solvent. The residue is recrystallized from ethyl acetate-n-hexane to give 1.57 g of 4,5-dichloro-6-(1-methoxymethyl-5-pyrazolylcarbonyl)-1,3-benzodioxole-2-carboxylic acid.

Aufarbeitung

  1. washThe ethyl acetate solution is washed with water
  2. customdried
  3. customevaporated
  4. customto remove solvent under reduced pressure
  5. dissolutionThe residue (crude 4,5-dichloro-6-[(1-methoxymethyl-pyrazol-5-yl)hydroxymethyl]-1,3-benzodioxole-2-carboxylic acid) is dissolved in 100 ml of methylene chloride
  6. addition10 g of pyridinium dicromate are added
  7. filtrationInsoluble materials are filtered off
  8. washwashed with methylene chloride
  9. customevaporated under reduced pressure
  10. customto remove solvent
  11. additionEthyl acetate is added to the residue and insoluble materials
  12. filtrationare filtered off
  13. washThe filtrate is washed
  14. customdried
  15. customevaporated under reduced pressure
  16. customto remove solvent
  17. customThe residue is recrystallized from ethyl acetate-n-hexane

Quellen und Nachweise

ORD-Eintrag
ord-203156cb89b447d2989fc69517505c2d
Quelldatensatz
uspto-grants-1990_11
Patentnummer
US04973600

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