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Ammonium Chloride → 1-(1,3-Benzodioxol-5-yl)-3-(1,3-dioxol-2-yl)-1-propanone

HRID 486527
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HRID 486527 반응식
Br[CH2:2][CH2:3][CH:4]1[O:8][CH2:7][CH2:6][O:5]1.[Mg].[Cl-].[Mg+2].[Cl-].CON(C)[C:16]([C:18]1[CH:26]=[CH:25][C:21]2[O:22][CH2:23][O:24][C:20]=2[CH:19]=1)=[O:17].[Cl-].[NH4+]>O1CCCC1.O>[O:22]1[C:21]2[CH:25]=[CH:26][C:18]([C:16](=[O:17])[CH2:2][CH2:3][CH:4]3[O:8][CH:7]=[CH:6][O:5]3)=[CH:19][C:20]=2[O:24][CH2:23]1
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참가 물질

8

반응물 5

HCID 25517Ammonium ChlorideHCID 877762-(2-Bromoethyl)-1,3-dioxolaneHCID 5360315Magnesium ChlorideHCID 5462224MagnesiumHCID 10921728N-methoxy-N-methylbenzo[d][1,3]dioxole-5-carboxamide

생성물 1

HCID 190952701-(1,3-Benzodioxol-5-yl)-3-(1,3-dioxol-2-yl)-1-propanone수율 72%

시약·촉매·용매 2

HCID 962Water용매HCID 8028Tetrahydrofuran용매

실험 절차

2-(2-Bromoethyl)-1,3-dioxolane (4.5 ml) was added dropwise within 15 minutes under argon and while stirring at a maximum 30° C. to a suspension of Rieke magnesium, prepared from 5.1 g of magnesium chloride, in 150 ml of absolute tetrahydrofuran. The suspension was stirred at room temperature for 30 minutes, cooled to -70° C. and treated within 10 minutes with 6.1 g of N-methoxy-N-methyl-1,3-benzodioxol-5-carboxamide. The reaction mixture was stirred at -70° C. for 30 minutes and at room temperature for 2 hours and subsequently hydrolyzed with 100 ml of saturated ammonium chloride solution while cooling at a maximum 20° C. After the addition of 50 ml of water the mixture was extracted once with 150 ml of ethyl acetate and twice with 100 ml of ethyl acetate each time. The combined organic extracts were dried over MgSO4 and freed from solvent. The residue, 8.0 g of yellow oil, was chromatographed on 490 g of silica gel with ethyl acetate/hexane (1:5) as the eluent. 5.3 g (72%) of 1-(1,3-benzodioxol-5-yl)-3-(1,3-dioxol-2-yl)-1-propanone were isolated as a colourless solid. A sample crystallized colourless from a 20-fold amount of diethyl ether and melted at 94°-96° C.

후처리

  1. temperaturecooled to -70° C.
  2. temperaturewhile cooling at a maximum 20° C
  3. extractionwas extracted once with 150 ml of ethyl acetate and twice with 100 ml of ethyl acetate each time
  4. dry with materialThe combined organic extracts were dried over MgSO4
  5. customThe residue, 8.0 g of yellow oil, was chromatographed on 490 g of silica gel with ethyl acetate/hexane (1:5) as the eluent

출처 및 근거

ORD 기록
ord-7ae7d278f1024e268d3e07302079e164
출처 데이터셋
uspto-grants-1994_03
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US05292732

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