ChemicalBook CAS DataBase List 4-ETHYNYLBENZYL ALCOHOL 97

4-ETHYNYLBENZYL ALCOHOL 97 synthesis

14synthesis methods

Product Name:4-ETHYNYLBENZYL ALCOHOL 97
CAS Number:10602-04-7
Molecular formula:C9H8O
Molecular Weight:132.16

275386-60-2

10602-04-7

General steps: 1. To an anhydrous triethylamine (TEA) solution of (4-bromophenyl)methanol (935 mg, 5 mmol), Pd(PPh3)2Cl2 (175 mg, 0.25 mmol), CuI (48 mg, 0.25 mmol), and P(t-Bu)3 (51 mg, 0.25 mmol) were sequentially added under nitrogen protection. 2. After stirring the reaction mixture for 5 minutes, ethynyltrimethylsilane (980 mg, 10 mmol) was added dropwise. 3. The reaction mixture was microwaved at 130 °C for 4 hours and subsequently cooled to room temperature. 4. The reaction mixture was filtered through diatomaceous earth and the filtrate was concentrated under reduced pressure. 5. The residue was extracted three times with a mixture of ethyl acetate (EtOAc) and water and the organic layers were combined. 6. The organic layer was washed with brine, dried over anhydrous sodium sulfate (Na2SO4), filtered and purified by silica gel column chromatography (petroleum ether/ethyl acetate=4/1) to afford (4-((trimethylmethylsilyl)ethynyl)phenyl)methanol as a brown oil (670 mg, 66% yield). [0633] 1. To a solution of (4-((trimethylmethylsilyl)ethynyl)phenyl)methanol (250 mg, 1.23 mmol) in tetrahydrofuran (THF) was added tetrabutylammonium fluoride (TBAF, 500 mg, 2.45 mmol) in one portion at 0 °C. 2. The reaction mixture was stirred from 0 °C to room temperature for 3 hours. 3. The reaction mixture was concentrated under reduced pressure and the residue was extracted three times with a mixture of ethyl acetate (EtOAc) and water and the organic layers were combined. 4. The organic layer was washed with brine, dried over anhydrous sodium sulfate (Na2SO4), filtered and purified by silica gel column chromatography (petroleum ether/ethyl acetate=4/1) to afford (4-ethynylphenyl)methanol as a brown oil (170 mg, 100% yield). 1H NMR (400 MHz, CDCl3) δ 7.45-7.49 (m, 2H), 7.21-7.26 (m, 2H), 4.69 (s, 1H), 4.65 (s, 2H).

275386-60-2 Synthesis

275386-60-2
76 suppliers
$10.00/100mg

10602-04-7
131 suppliers
$24.00/100mg

Yield:10602-04-7 100%

Reaction Conditions:

with tetrabutyl ammonium fluoride in tetrahydrofuran at 0 - 20; for 3 h;

Steps:

1 Step 1. Preparation of (4-ethynylphenyl) methanol (122-01) :
To a solution of (4-bromophenyl) methanol (935mg, 5mmol) in dry TEA was added Pd (PPh₃) ₂Cl₂ (175mg, 0.25mmol) , CuI (48mg, 0.25mmol) and P (t-Bu) ₃ (51mg, 0.25mmol) under N₂ atmosphere. The reaction mixture was stirred for 5mins, followed by addition of ethynyltrimethylsilane (980mg, 10mmol) dropwise. The reaction mixture was then microwaved at 130 for 4hrs. The reaction mixture was cooled to room temperature, filtered over celite. Solvents were removed from the filtrate in vacuo, then the residue was extracted by EtOAc/H₂O 3 times. The organic layer was combined, washed with brine, dried over Na₂SO₄ and further pufrified by silica gel column chromatography (PE/EA4/1) to give 670mg of (4- ( (trimethylsilyl) ethynyl) phenyl) methanol as a brown oil (66) .[0633]To a solution of (4- ( (trimethylsilyl) ethynyl) phenyl) methanol (250mg, 1.23mmol) in THF was added TBAF (500mg, 2.45mmol) in portions at 0. The reaction mixture was stirred at 0 to room temperature for 3hrs. Solvents were removed from the mixture in vacuo, and the residue was extracted by EtOAc/H₂O 3 times. The organic layer was combined, washed with brine, dried over Na₂SO₄ and further pufrified by silica gel column chromatography (PE/EA4/1) to give 170mg of (4-ethynylphenyl) methanol as a brown oil (100) . ¹H NMR (400Hz, CDCl3) δ7.45-7.49 (m, 2H) , 7.21-7.26 (m, 2H) , 4.69 (s, 1H) , 4.65 (s, 2H) .

References:

NATIONAL INSTITUTE OF BIOLOGICAL SCIENCES, BEIJING;ZHANG, Zhiyuan;WANG, Xiaodong;HUANG, Shaoqiang;JIANG, Xian;LI, Li;ZHANG, Zhaolan;HAN, Jianguang WO2018/14802, 2018, A1 Location in patent:Paragraph 0364

FullText

63697-96-1 Synthesis