Sulfuric Acid → 1-(1,3-dioxolan-2-ylidene)-1H-indene-3-carbonitrile

HRID 10080

반응식

HRID 10080 반응식
CC(C)([O-])C.[Na+].Br[C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][C:9]=1[CH2:14][C:15]#[N:16].[CH2:17]([O:19][C:20](=[O:26])[CH:21]=[CH:22]OCC)[CH3:18].S(=O)(=O)(O)O>O1CCCC1.O.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(P(C2CCCCC2)C2CCCCC2)CCCCC1.C(O)CO>[O:19]1[CH2:17][CH2:18][O:26][C:20]1=[C:21]1[C:8]2[C:9](=[CH:10][CH:11]=[CH:12][CH:13]=2)[C:14]([C:15]#[N:16])=[CH:22]1

참가 물질

10

반응물 4

HCID 1118Sulfuric AcidHCID 296252-Bromobenzyl cyanideHCID 221780Ethyl 3-ethoxy-2-propenoateHCID 23676156Sodium t-butoxide

생성물 1

HCID 98343201-(1,3-dioxolan-2-ylidene)-1H-indene-3-carbonitrile수율 80%

시약·촉매·용매 5

HCID 75806Tricyclohexylphosphine촉매HCID 167845palladium(II) acetate촉매HCID 174Ethylene Glycol용매HCID 962Water용매HCID 8028Tetrahydrofuran용매2회

반응 조건

온도
0 °C

실험 절차

A solution of tricyclohexylphosphine (536 mg, 1.91 mmol) in tetrahydrofuran (25 mL) was charged with palladium (II) acetate (287 mg, 1.27 mmol) under nitrogen. After 1 hour the reaction mixture was cooled to 0° C. and charged with sodium tert-butoxide (31.6 g, 319 mmol). After 5 minutes a solution of 2-bromo-phenylacetonitrile (25.0 g, 128 mmol) and β-ethoxyacrylic acid ethyl ester (18.4 mL, 128 mmol) in tetrahydrofuran (75 mL) was added dropwise over 15 minutes. The reaction was heated to 60° C. After 2 hours 30 minutes the reaction mixture was cooled to room temperature and charged with ethylene glycol (200 mL) over 5 minutes and then charged with sulfuric acid (18.8 M, 36 mL) added dropwise over 15 minutes. After 15 hours the reaction was diluted with water (90 ml) and a solid product was filtered through a glass frit. The solid was dried under vacuum affording 3-[1,3]dioxolan-2-ylidene-3H-indene-1-carbonitrile (21.6 g, 102 mmol, 80%) as a light tan solid. The crude material was slurried in isopropanol (50 mL) for 2 hours, filtered and dried under vacuum affording 3-[1,3]dioxolan-2-ylidene-3H-indene-1-carbonitrile (20.8 g, 98.5 mmol, 77%) as a light tan solid. 1H NMR (400 MHz, d6-DMSO) δ 7.75 (s, 1H), 7.74 (d, 1H, J=7.9), 7.50 (d, 1H, J=7.1), 7.22 (m, 2H), 4.97 (t, 2H, J=7.8), 4.85 (t, 2H, J=7.8); 13C NMR (100 MHz, d6-DMSO) 167.4, 136.7, 135.7, 133.1, 124.7, 123.9, 121.1, 119.4, 118.1, 97.8, 92.7, 71.1, 69.9; mp (decomposition) 228° C.

후처리

  1. temperatureThe reaction was heated to 60° C
  2. temperatureAfter 2 hours 30 minutes the reaction mixture was cooled to room temperature
  3. additionadded dropwise over 15 minutes
  4. filtrationa solid product was filtered through a glass frit
  5. customThe solid was dried under vacuum

출처 및 근거

ORD 기록
ord-764b14b9941241a4aa26e7910f5f2e10
출처 데이터셋
uspto-grants-2006_08
특허 번호
US07091372B2

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