2, 7-Dihydroxy-9-fluorenone

Cov cuab yeej siv tom qab

2, 7-dihydroxy-9-fluorenone yog ib qho tseem ceeb ntawm cov organic synthesis, uas tuaj yeem siv los npaj cov khoom siv fluorescent silicone polymeric. Nws kuj tseem siv tau los npaj fluorenyl polyether sulfone ketone thermoplastic cob. Tsis tas li ntawd, nws tuaj yeem siv los ua ib qho tseem ceeb nruab nrab rau kev sib txuas ntawm cov kab mob interferon (diethylamino-9- fluorenone) thiab 2-hydroxylamino-acetyl-9- fluorenone ua ib qho tshuaj antispasmodic. Yog li ntawd, cov synthesis ntawm 2, 7-dihydroxy-9-fluorenone muaj txiaj ntsig tshawb fawb tseem ceeb.

Lub synthesis ntawm 2, 7-dihydroxy-9-fluorenone tau tshaj tawm thawj zaug los ntawm Krishna hauv xyoo 1967 (Journal of Medicinal Chemistry, 1967,10:99-101). Siv fluorene ua raw khoom, 2, 7-dihydroxy-9-fluorenone tau txais los ntawm sulfonation, oxidation, alkali melting thiab kaw-voj cov tshuaj tiv thaiv. Txoj kev no yooj yim kom tau txais cov khoom siv raw thiab tus nqi qis. Txawm li cas los xij, nyob rau hauv cov txheej txheem kev npaj, poov tshuaj permanganate raug xaiv los ua cov oxidant, muaj ntau cov khoom pov tseg ntawm manganese dioxide, uas nyuaj rau kev daws, thiab ob theem kawg ntawm cov tshuaj tiv thaiv yog cov tshuaj tiv thaiv kub kub, hom kev ua haujlwm thiab cov txheej txheem hloov pauv loj hauv cov txheej txheem tshuaj tiv thaiv yog qhov nyuaj, thiab cov khoom siv tshuaj tiv thaiv yog siab thiab nws nyuaj rau tswj cov qib ntawm cov tshuaj tiv thaiv.

Xyoo 1973, Horner et al. (Justus Liebigs Annalen der Chemie, 1973,6(5):910-935.) qhia tias methyl 2-bromo5-methoxybenzoate thiab p-iodoanisole tau siv los ua raw khoom hauv catalysis ntawm tooj liab hmoov. 4-dimethyl ether biphenyl-2-formic acid thiab 4,4' -dimethyl ether dibenzoic acid. 2, 7-dihydroxy-9-fluorenone tau txais los ntawm kev hloov pauv ntawm methoxy pawg mus rau hydroxyl pawg los ntawm hydrobromic acid nyob rau hauv lub voj kaw nyob rau hauv kev ua ntawm polyphosphate. Cov xwm txheej ntawm txoj kev no yog me me, tab sis tus nqi raw khoom yog siab, thiab thawj kauj ruam muaj nws tus kheej coupling khoom, thiab cov tawm los yog tsawg.

Xyoo 2008, Jeffrey et al. (Journal of Materials Chemistry, 2008,18(28):3361-3365.) qhia tias fluorene tau siv los ua cov khoom pib thiab acetic anhydride ua acylation reagent, thiab Fu-g acylation tau ua raws li catalysis ntawm anhydrous. A1C1. Tom qab ntawd cov khoom tau raug rau Baeyer-Villiger oxidation rearrangement los ntawm m-CPBA thiab trifluoroacetic acid nyob rau hauv chloroform hnyav. Cov khoom tau oxidized nrog sodium dichromate thiab thaum kawg hydrolyzed rau 2, 7-dihydroxy-9-fluorenone. Tus nqi ntawm txoj kev no yog siab, kev siv cov peroxide ntau lawm yuav tsum tau xyuam xim rau kev nyab xeeb, thiab sodium bichromate tom qab kho yog nyuaj.

Tam sim no, cov txheej txheem tsim khoom ntawm 2, 7-dihydroxy-9- fluorenone muaj cov teeb meem hauv qab no: 1) Vim qhov tsis zoo ntawm cov nqi siab, kev ua haujlwm txaus ntshai, tsis yooj yim thiab hnyav hnyav, nws nyuaj rau tau txais txiaj ntsig zoo hauv kev npaj ua lag luam; 2) Txoj kev no muaj tus nqi raw khoom siab, tsis tshua muaj txiaj ntsig thiab kev ua kom huv ntawm cov khoom nyuaj; 3) Ob kauj ruam kawg ntawm cov tshuaj tiv thaiv yog cov tshuaj tiv thaiv kub kub, kev ua haujlwm hom thiab cov txheej txheem hloov loj hauv cov txheej txheem tshuaj tiv thaiv yog qhov nyuaj, thiab kev tsim khoom yuav tsum muaj cov khoom siv tshuaj tiv thaiv siab thiab nws nyuaj rau kev tswj cov qib ntawm cov tshuaj tiv thaiv.

Txoj kev npaj

1. Ntxiv 50g fluorene, 79g benzoic acid, 124g silver oxide, 2g palladium acetate thiab 350g toluene rau hauv cov tshuaj tiv thaiv hlab ntsha nruab nrog lub ntsuas kub, agitator thiab dej separator, tswj cov tshuaj tiv thaiv kub ntawm 115 degree, fractiate cov dej tsim los ntawm cov tshuaj tiv thaiv thaum reacting, txias nws mus rau 70 degree tom qab 10-15 teev cov tshuaj tiv thaiv, lim nws thaum nws kub, txo lub siab thiab mloog zoo rau cov organic txheej kom txog rau thaum ib tug loj tus naj npawb ntawm cov khib nyiab yog precipitated. Ntxiv 100g methanol, kub txog 50 degree, do rau 1h, txias rau 10 degree, rho tawm thiab lim kom tau 9h-fluoren{15}}, 7-diacyldibenzoate methyl ester, qhuav 105.3g ntawm 70 degree , 85.4%.

2. Ntxiv 100g9h-fluoren-2, 7-diacyldibenzoate methyl ester, 8.2g tooj liab acetate thiab 650g dichloroethane rau hauv lub reactor uas muaj tus pas ntsuas kub, stirrer thiab lub twj tso kua mis tas li. Maj mam ua kom sov li 50 degree, thiab maj mam ntxiv 118.6g70% tert-butyl peroxide. Tom qab dej ntws tawm, ua kom sov li 10 teev. Thaum kawg ntawm cov tshuaj tiv thaiv, qhov kub tau txo qis rau 10 degree, thiab cov khoom ntub dej ntawm 9-oxy-9h-fluoren-2, 7-diacyldibenzoate methyl ester tau txais los ntawm extraction thiab filtration. Cov khoom ntub dej tau ntxuav nrog 20g sodium disulfite thiab 115g dej rau 1h, thiab cov khoom tiav ntawm 9-oxy-9h-fluoren-2, 7-diacyldibenzoate tau muab rho tawm thiab qhuav. kom tau 96.8g, nrog rau 94.0%.

3. Ntxiv 700g dej, 60g ntawm sodium carbonate, thiab 100G9-oxy-9h-fluoren-2, 7-diacyldibenzoate rau cov hlab ntsha hauv qab tiv thaiv nitrogen. Tshav kub li 90 degree nyob rau hauv nitrogen cua thiab tuav rau 7h. Thaum kawg ntawm cov tshuaj tiv thaiv, qhov kub thiab txias tau txo qis rau 5 degree, thiab 47g concentrated hydrochloric acid tau maj mam ntxiv rau cov tshuaj tiv thaiv. Tom qab tso tawm, cov kua tau khaws cia sov ntawm 5 degree rau 1h, thiab tom qab ntawd nqus thiab lim kom tau 52g ntawm 2, 7-dihydroxy-9- fluorenone cov khoom ntub dej. Cov khoom ntub dej ces ntxuav nrog 52g methanol ntawm 15-20 degree rau 1h, txias rau 5 degree, lim thiab qhuav kom tau 47.1g ntawm 2, 7-dihydroxy-9-fluorenone. HPLC purity yog 99.8% thiab tawm los 94.2%.