Synthesis Of Fluorene Derivatives Containing Bromine, Nitryl And Steroidrings

Fluorene is the products from zetar. The derivatives of fluorene have been widely applied in medicine, plastic, photoelectric materials and other realms. Derivatives of fluorene containing steroidrings have been used as the synthesis unit because of its unique structural features, and were widely used in cosmetics, liquid crystal materials, medical devices and medicine, etc. Therefore the research on this subject has not only important theoretical significance, but also has a broad prospect of application. The main research content is the synthesis of fluorene derivatives in this thesis.1. The synthesis of nitro bromination derivatives of fluorene(1) Using fluorene as raw material, by oxidation, bromination, nitrification, reduction and acylation, fluorenone(1a),2,7-dibromine fluorene(1b),2,7-dibromine-4-nityl fluorene(lc),2,7-dibromine-amino fluorene(1d),2,7-dibromine-4(N,N-dimethylacryloy l)-fluorene(1e) were respectively synthesised. The synthesis conditions of1e were ascertained by orthogonal test. The optimal synthesis condition are methylene dichloride as the solvent, triethylamine as deacid reagent, the ratio of1d and methacryloylchloride being1:2.2, room temperature for3h and88.2%yield. All the compounds above were characterized by IR, NMR spectrums.(2) Using fluorenone as raw material, by bromination, nitrification, reduction and acylation,2-bromine fluorenone(2a),2-bromine-7-nitryl fluorenone(2b),2,7-dibromine fluorenone(2c),2,7-dibromine-4-nitryl fluorenone(2d),2,7-dinitryl fluorenone(2h),2,7-di-bromine-4-amino fluorenone(2e),2,7-dibromine-4(N-methyl acroloyl)-fluorenone(2f),2,7-dibromine-4(N,N-di methyl acroloyl)-fluorenone(2g) were respectively synthsised. The synthesis conditions of2b,2d,2h,2f,2g were ascertained by orthogonal test. The optimal synthesis conditions of2b are H2O being the solvent,65%of mass fraction of nitric acid and the mass fraction of96%sulfuric acid being the nitrification reagent, n(HNO3):n(H2SO4): n(2a)=29:36:1, m(2a):m(H2O)=1:7.7, reflux for3h and92.8%yield. The optimal synthesis conditions of2d are H2O being the solvent,85%of mass fraction of nitric acid and the mass fraction of96%sulfuric acid being the nitrification reagent, n(HNO3):n(H2SO4):n(2c)=40:36:1, m(2c):m(H2O)=1:5.9, reflux for4h and90.9%yield. The optimal synthesis conditions of2h are H2O as the solvent, the mixed nitric acid and sulfuric as the nitrification reagent, n(1a):n(HNO3):n(H2SO4):=1:10:13, reflux for7h and90%yield; the optimal synthesis conditions of2f are methylene dichloride as the solvent, triethylamine as deacid reagent, the ratio of2e and methacryloylchloride being1:1.25, room temperature for3h and87%yield. The optimal synthesis conditions of2g are methylene dichloride as the solvent, triethylamine as deacid reagent, the ratio of2e and methacryloylchloride being1:2.2, room temperature for3h and86%yield. All the compounds above were characterized by IR, NMR spectrums.2. Derivatives of fluorene containing steroidringsUsing cholesterol as raw material, by condension, reduction, acidylation,2-steroid-7-bromine-4-nitryl fluorenone(3a),2-steroid-7-bromine-4-amino fluorene(3b),2-steroid-4-(N-methyl acroloyl)-7-bromine fluorene(3c) and2-steroid-4-(N,N-dimethyl acroloyl)-7-bromine fluorene(3d) were respectively synthesised. The synthesis conditions of3a,3b,3c and3d were ascertained by orthogonal test. The optimal synthesis conditions of3a are toluene as the solvent, solution of40%sodium hydroxide as alkali, tetrabutyl amonium bromide as the phase transfer catalyst, n(2d):n(cholesterol)=1:1.2and32%yield. The optimal synthesis conditions of3b are ethanol as solvent, n(3a):n(NH2NH2)=1:4, catalyst and3a are equal quality, reflux for4h and88.1%yield. The optimal synthesis conditions of3c are methylene dichloride as the solvent, triethylamine to be deacid reagent, n(3b):n (methacryloylchloride)=1:1.25, room temperature for3h and85.2%yield. The optimal synthesis conditions of3d are methylene dichloride as the solvent, triethylamine as deacid reagent, n(3b):n(methacryloylchloride)=1:2.2, room temperature for3h and87.2%yield. All the compounds above were characterized by IR, NMR spectrums.