“3-Hydroxytetrahydrofuran”的意思、由来-开放百科全书

3-Hydroxytetrahydrofuran was prepared in 1910 by Pariselle^[5] via cyclization and hydrolysis of 3,4-Dibromo-1-methoxybutane. Chiral 3-hydroxytetrahydrofuran (both (S) – and (R)-forms) has been synthesized in high enantiomeric purity from (S)- and (R)-1,2,4-butanetriol, respectively, obtained from chiral feedstocks. Thus, the chiral (S)-1,2,4-butanetriol intermediate was cyclized to chiral (S)-3-hydroxytetrahydrofuran in the presence of p-toluenesulfonic acid (PTSA) catalyst at temperatures of 180−220 °C.^[6]

Similarly, (S)-3-hydroxytetrahydrofuran was prepared in 95.8% optical purity from L-malic acid via an esterification-reduction-cyclodehydration sequence.^[7] 3-hydroxytetrahydrofuran has been synthesized via hydroboration of 2,3- and 2,5-dihydrofuran employing various borane reagents^[8] and chiral 3-hydroxytetrahydrofurans have also been prepared by catalytic asymmetric hydroboration of 2,3- and 2,5-dihydrofurans with a borane in the presence of a homogeneous chiral platinum complex, followed by oxidation.^[9] Racemic 3-hydroxytetrahydrofuran may be prepared in analogous fashion from racemic butanetriol, employing PTSA catalyst for the dehydrocyclization. Alternatively, 1,2,4-butanetriol may be converted to 3-hydroxytetrahydrofuran by treating with ethylene carbonate, followed by pyrolysis of the resulting carbonate ester.^[10]

Applications

3-Hydroxytetrahydrofuran is an intermediate to the AIDS drugs amprenavir and fosamprenavir.^[4] Additionally, 3-OH THF has been an intermediate to developmental drug substances, such as chemotherapy agents. For example, reaction of phosphorus pentasulfide with 3-hydroxytetrahydrofuran has been used in the synthesis of bis(O,O-di(tetrahydrofuran-3-yl)hydrogen dithiophosphate)platinum(II), a cisplatin analog.^[11] 3-hydroxytetrahydrofuran may be converted into a range of tetrahydrofuran derivatives, many of which also serve as intermediates to compounds of pharmaceutical interest. For example, tetrahydrofuran-3-one (3-ketotetrahydrofuran)^[12] and 3-aminotetrahydrofuran^[13] have been synthesized from 3-hydroxytetrahydrofuran and used in pharmaceutical syntheses. Additionally, additive amounts (0.05-0.15 weight %) of the nitrate ester manufactured by sulfuric acid-nitric acid nitration of 3-hydoxytetrahydrofuran have been found to increase the quality (cetane number) of diesel fuel.^[14]

References

1. ^{{cite journal |title=none| author = J. Lesage | journal = Bulletin de la Societe Chimique de France | volume = 11 | pages = 4147–4151 | year = 1969}}
2. ^{{cite journal |title=none| author = Rostylaw Dowbenko | journal = Chemistry & Industry | volume = 50 | pages = 2097–2098| year = 1966}}
3. ^{{cite journal | author = Sigurd Olsen | journal = Acta Chemica Scandinavica | volume = 4 | pages = 462–472 | year = 1950 | doi = 10.3891/acta.chem.scand.04-0462 | title = Über die Umsetzung von Formaldehyd mit Allylacetat. I. Eine neue Synthese des 1,2,4-Butantriols und des 3-Oxytetrahydrofurans}}
4. ^¹Venkata Mandava, et al., "Preparation of fosamprenavir calcium" U.S. Pat. Appl., 20110224443 (2011)
5. ^{{cite journal | author = Pariselle| title = Derivatives of Butanetriol (1,2,4)| journal = Comptes Rendus| volume = 149| pages =295–8| year = 1910}}
6. ^{{cite journal | author = Vishnu K. Tandon | title = Synthesis of enantiomerically pure (S)-(+)-3-hydroxytetrahydrofuran, and its (R)-enantiomer, from malic or tartaric acid | journal = Journal of Organic Chemistry | volume = 48 | pages = 2767–2769| year = 1983 |last2 = Van Leusen | first2 = Albert M.| last3 = Wynberg | first3 = Hans | issue = 16 | doi = 10.1021/jo00164a027}}
7. ^{{cite journal | author = Xiaoqin Wang | title = Study on synthesis of drug intermediates (S)-3-hydroxytetrahydrofuran | journal = Huaxue Yanjiu Yu Yingyong | volume = 21| pages = 1070–1072 | year = 2009 |last2 = Zhu | first2 = Derong | last3 = He | first3 = Minghua | issue = 7}}
8. ^{{cite journal | author = Herbert C. Brown | title = Hydroboration. 71. Hydroboration of representative heterocyclic olefins with borane-methyl sulfide, 9-borabicyclo[3.3.1]nonane, dicyclohexylborane, and disiamylborane. Synthesis of heterocyclic alcohols | journal = Journal of Organic Chemistry | volume = 50 | pages = 1582–1589 | year = 1985 |last2 = Prasad | first2 = J. V. N. Vara | last3 = Zee | first3 = Sheng Hsu | issue = 10 | doi = 10.1021/jo00210a004}}
9. ^Anita Schnyder, et al., "Preparation of optically active 3-hydroxytetrahydrofurans by catalytic asymmetric hydroboration of dihydrofurans" Ger. Offen., 19807330 (1998)
10. ^{{cite journal | author = Dexter B. Pattison | title = Cyclic ethers made by pyrolysis of carbonate esters | journal = Huaxue Yanjiu Yu Yingyong | volume = 79| pages = 3455–3456| year = 1957}}
11. ^Anthony Lowe, et al., "Dithiophosphato platinum complexes for the treatment of cancers" PCT Int. Appl., 2005095425 (2005)
12. ^{{cite journal | author = H. Wynberg | title = Tetrahydrofuran-3-one, spirans, and dithienyls | journal = Angewandte Chemie | volume = 75 | pages = 453| year = 1963 | issue = 10 | doi = 10.1002/ange.19630751014}}
13. ^Liren Jin, et al., "Process for preparation of (R)-3-aminotetrahydrofuran" Faming Zhuanli Shenqing Gongkai Shuomingshu, CN 1660829 A 20050831 (2005)
14. ^Allen H. Filbey, "Diesel fuel composition" U.S. Pat., 4406665 (1983)