Potassium Carbonate → 5-(1-Methyl-prop-2-ynyl)-2-phenyl-pyrimidine

HRID 1048844노트

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HRID 1048844 반응식
[Cl-].[CH3:2]OC[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[CH3:24][C:25]([O-])([CH3:27])[CH3:26].[Na+].[C:30]1([C:36]2[N:41]=[CH:40]C(C(=O)C)=[CH:38][N:37]=2)[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=1.C([O-])([O-])=O.[K+].[K+]>C1COCC1.C1COCC1.O.CO.[Hg](OC(C)=O)OC(C)=O.C/C(/[O-])=C(/P(OC)(OC)=O)\[N+]#N>[CH3:24][CH:25]([C:27]1[CH:38]=[N:37][C:36]([C:30]2[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=2)=[N:41][CH:40]=1)[C:26]#[CH:2]

참가 물질

10

반응물 4

HCID 11430Potassium CarbonateHCID 2723798Methoxymethyl-triphenylphosphonium chlorideHCID 226310721-(2-Phenylpyrimidin-5-yl)ethanoneHCID 23676156Sodium t-butoxide

생성물 1

HCID 1182944455-(1-Methyl-prop-2-ynyl)-2-phenyl-pyrimidine수율 725.3%

시약·촉매·용매 5

HCID 16683746Diacetyloxymercury촉매HCID 178502985HCID 178502985, 화합물촉매HCID 887Methanol용매2회HCID 8028Tetrahydrofuran용매2회HCID 21881883Oxolane--water (1/1)용매

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온도
0 °C

실험 절차

According to a general procedure for homologation, methoxymethyl triphenylphosphonium chloride (2.3 g, 6.62 mmol) in dry THF (18 mL), NaOtBu (0.797 g, 8.3 mmol), ketone 42 (0.655 g, 3.31 mmol) in THF (6 mL) were stirred at 0° C. Following the general workup, the mixture of enol ethers (0.398 g, 1.76 mmol) in THF/H2O (9:1, 6 mL) were hydrolyzed using Hg(OAc)2 (1.680 g, 5.28 mmol) at room temperature. After the general extraction procedure, aldehyde (0.300 g, 1.41 mmol) in MeOH (4 mL), Ohira-Bestmann reagent (0.407 g, 2.12 mmol) dissolved in MeOH (2 mL), powdered K2CO3 (0.410 g, 2.96 mmol) were stirred at 0° C. Following the general workup and flash chromatography (SiO2, 5 g, 5% EtOAc/hexanes) alkyne 45 was obtained as a white solid (0.066 g, 10% yield over 3 steps): TLC Rf=0.3 (5% EtOAc/hexanes); mp 75.4-76.7° C.; 1H NMR (500 MHz, CDCl3) δ 8.82 (s, 2H), 8.60-8.21 (m, 2H), 7.48-7.46 (m, 3H), 3.82 (qd, J=7.1, 2.5 Hz, 1H), 2.34 (d, J=2.5 Hz, 1H), 1.57 (d, J=7.2 Hz, 3H); 13C NMR (125 MHz, CDCl3) δ 163.7, 156.1, 137.6, 133.3, 130.9, 128.8, 128.3, 84.6, 71.9, 27.4, 23.8; IR (neat cm−1) 3205, 3059, 2978, 2934, 1584, 1547, 1425, 1296, 1175, 1094, 1069, 749, 692, 651; HRMS (DART, M++H) m/z 209.1103 (calculated for C14H13N2, 209.1079).

후처리

  1. customat room temperature

출처 및 근거

ORD 기록
ord-7b64a73616104fb9aa7e1fb77b004b3b
출처 데이터셋
uspto-grants-2016_07
특허 번호
US09382213B2

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