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

HRID 1089161노트

반응식

HRID 1089161 반응식
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]

참가 물질

8

반응물 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

생성물 1

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

시약·촉매·용매 3

HCID 8028Tetrahydrofuran용매HCID 8857Ethyl Acetate용매HCID 12679Hexamethylphosphoramide용매

실험 절차

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)hydroxyme thyl)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-benzo dioxole-2-carboxylic acid) is dissolved in 100 ml of methylene chloride, 10 g of pyridinium dichromate 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.

후처리

  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-benzo dioxole-2-carboxylic acid) is dissolved in 100 ml of methylene chloride
  6. addition10 g of pyridinium dichromate 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

출처 및 근거

ORD 기록
ord-ce35af19dca24368979c76709ace75f4
출처 데이터셋
uspto-grants-1990_10
특허 번호
US04965282

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