【结 构 式】 |
【分子编号】64525 【品名】diethyl {3-[(allyloxy)methyl]phenyl}(difluoro)methylphosphonate 【CA登记号】 |
【 分 子 式 】C15H21F2O4P 【 分 子 量 】334.2999084 【元素组成】C 53.89% H 6.33% F 11.37% O 19.14% P 9.27% |
合成路线1
该中间体在本合成路线中的序号:(VI)Condensation of dibromide (I) with allyl alcohol (II) in the presence of NaH gives rise to a mixture of mono- and diallylated compounds (III) and (IV) which, without separation, is subjected to Arbuzov reaction with triethyl phosphite, to furnish the desired phosphonate (V). Electrophilic fluorination of (V) using N-fluorobenzenesulfonimide provides the difluoro phosphonate (VI). Then, basic hydrolysis of phosphonate (VI) affords acid (VII). Compound (VII) is attached to a functionalized non-crosslinked polystyrene soluble polymer under Mitsunobu conditions to produce the polymer-bound phosphonate (VIII). Then, removal of the allyl group in the presence of p-toluenesulfinic acid and Pd(PPh3)4 yields the benzylic alcohol (IX). Oxidation of (IX) employing the Dess-Martin periodinane reagent leads to aldehyde (X) (1).
【1】 Hum, G.; Lee, J.; Taylor, S.D.; Synthesis of [difluoro-(3-alkenylphenyl)-methyl]-phosphonic acids on non-crosslinked polystyrene and their evaluation as inhibitors of PTP1B. Bioorg Med Chem Lett 2002, 12, 23, 3471. |
中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
---|---|---|---|---|---|---|
(VII), (VIII) | 64570 | ethyl hydrogen {3-[(allyloxy)methyl]phenyl}(difluoro)methylphosphonate | C13H17F2O4P | 详情 | 详情 | |
(I) | 64521 | 1,3-bis(bromomethyl)benzene | C8H8Br2 | 详情 | 详情 | |
(II) | 12234 | 2-Propen-1-ol; Allyl alcohol | 107-18-6 | C3H6O | 详情 | 详情 |
(III) | 64522 | allyl 3-(bromomethyl)benzyl ether; 1-[(allyloxy)methyl]-3-(bromomethyl)benzene | C11H13BrO | 详情 | 详情 | |
(IV) | 64523 | 1,3-bis[(allyloxy)methyl]benzene; allyl 3-[(allyloxy)methyl]benzyl ether | C14H18O2 | 详情 | 详情 | |
(V) | 64524 | diethyl 3-[(allyloxy)methyl]benzylphosphonate | C15H23O4P | 详情 | 详情 | |
(VI) | 64525 | diethyl {3-[(allyloxy)methyl]phenyl}(difluoro)methylphosphonate | C15H21F2O4P | 详情 | 详情 | |
(IX) | 64572 | ethyl hydrogen difluoro[3-(hydroxymethyl)phenyl]methylphosphonate | C10H13F2O4P | 详情 | 详情 | |
(X) | 64573 | ethyl hydrogen difluoro(3-formylphenyl)methylphosphonate | C10H11F2O4P | 详情 | 详情 |