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

HRID 1048844

反応式

HRID 1048844 の反応式
[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]

参加物

10

反応物 4

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

生成物 1

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

試薬・触媒・溶媒 5

HCID 16683746Diacetyloxymercury触媒HCID 178502985HCID 178502985、化合物触媒HCID 887Methanol溶媒2 回HCID 8028Tetrahydrofuran溶媒2 回HCID 21881883Oxolane--water (1/1)溶媒

反応条件

温度
0 °C

実験手順

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).

後処理

  1. customat room temperature

出典と根拠

ORDレコード
ord-7b64a73616104fb9aa7e1fb77b004b3b
出典データセット
uspto-grants-2016_07
特許番号
US09382213B2

関連ノート

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