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有机氟化合物

1896年,氟代乙酸乙酯的合成标志着有机氟化学研究的开端,至今已整整一个世纪。在此期间,几次重要的突破极大地推动了这一领域的发展,例如20世纪30年代氟里昂在制冷工业中的应用、二战期间曼哈顿工程的实施以及50年代高生理活性5-氟脲嘧啶的合成等。

我国拥有丰富的氟资源,已探明萤石储量约占世界总量的四分之一。然而直到20世纪50年代,中国在此领域的研究一片空白。当时国际形势的变化促使我国开始自主开发原子能技术,并急需一批特殊的含氟材料。从此,有机氟化学在中国的研究逐渐展开。中国科学院上海有机化学研究所因其在有机氟化学基础研究方面的卓越成就,被国际氟化学界誉为“上海氟化学”。

有机氟化合物又称氟碳化合物,是指分子结构中含C-F键的化合物,如四氟乙烯(CF2=CF2)。若碳氢化合物中的所有氢原子均被氟原子取代,则称为全氟化合物。由于氟是元素周期表中最电负、氧化性最强的原子,因此氟聚合物不易发生氧化裂解。此外,氟原子半径接近C-C键原子间距的一半,能紧密排列在碳原子周围,形成对C-C键的保护屏障,确保化学稳定性。C-F键具有极高的键能,赋予有机氟化物良好的热稳定性和抗氧化性。

许多含氟化合物被用于药物中,如全身麻醉剂氟烷、抗癌药5-氟尿嘧啶、镇静药氟奋乃静和抗精神病药氟哌啶醇等。根据结构不同,有机氟化合物大致可分为三类:

  1. 氟氯代烷,主要用于制冷剂和气雾剂(如氟利昂)。
  2. 全氟烃类及全氟醚、酸、叔胺,其中全氟烷烃表现出极高的化学稳定性。例如,全氟庚烷是一种耐氧化剂、耐高温的润滑油;四氟乙烯作为聚四氟乙烯的单体;而全氟萘烷和全氟叔胺等饱和有机化合物经乳化后形成的白色乳液(称为“白色血液”)被成功用作临床血液替代品。
  3. 含氟高聚物具有优异的耐高温、低温以及化学腐蚀性能。例如,聚四氟乙烯俗称“塑料王”,由偏氟乙烯和全氟丙烯共聚而成;而维通橡胶则是一种以全氟烷基为单体合成的全氟橡胶,在国防、航天、石油、化工及机械等领域广泛应用,如用于制作登月服的防火涂层、耐腐蚀管道与容器、服装耐磨轴瓦以及公路铁路桥梁滑动衬垫和密封垫等。
中文名称 英文名称 CAS号 化学式 结构式图片
—— diphenyliodonium hexafluoroarsenate 62613-15-4 AsF6*C12H8I
diphenyliodonium hexafluoroarsenate
—— 3-fluoronitrobenzene radical anion 34470-17-2 C6H4FNO2
3-fluoronitrobenzene radical anion
—— (2E)-methyl 3-(cinnamyloxy)acrylate 147460-94-4 C13H14O3
(2E)-methyl 3-(cinnamyloxy)acrylate
—— 6-fluoro-7-methylisatin 3-oxime 275374-94-2 C9H7FN2O2
6-fluoro-7-methylisatin 3-oxime
—— <(S)-pyrrolidin-2-yl>benzyl alcohol 74936-95-1 C11H15NO
<(S)-pyrrolidin-2-yl>benzyl alcohol
—— methyl 5,5-difluoropiperidine-2-carboxylate 1255663-85-4 C7H11F2NO2
methyl 5,5-difluoropiperidine-2-carboxylate
—— 3,3-difluoro-1-phenylcyclobutanecarboxylic acid 1780846-70-9 C11H10F2O2
3,3-difluoro-1-phenylcyclobutanecarboxylic acid
—— 1,3-dibromo-4,6-bis(trifluoromethyl)benzene 241151-55-3 C8H2Br2F6
1,3-dibromo-4,6-bis(trifluoromethyl)benzene
—— (3S,5S,6R)-6-methyl-2-oxo-5-phenyl-1-(2,2,2-trifluoroethyl)piperidin-3-aminium hydrochloride 1375470-88-4 C14H17F3N2O*ClH
(3S,5S,6R)-6-methyl-2-oxo-5-phenyl-1-(2,2,2-trifluoroethyl)piperidin-3-aminium hydrochloride
—— 3-(benzyloxy)-4-fluorobenzonitrile 1351862-19-5 C14H10FNO
3-(benzyloxy)-4-fluorobenzonitrile
—— Methyl 3-(2,4-dichloro-5-fluorophenyl)-2-[(4-fluorophenyl)iminomethyl]-3-hydroxyprop-2-enoate 176637-98-2 C17H11Cl2F2NO3
Methyl 3-(2,4-dichloro-5-fluorophenyl)-2-[(4-fluorophenyl)iminomethyl]-3-hydroxyprop-2-enoate
—— N-methyl-N-(2,2,2-trifluoroethyl)piperidin-4-amine hydrochloride 1432678-56-2 C8H16ClF3N2
N-methyl-N-(2,2,2-trifluoroethyl)piperidin-4-amine hydrochloride
—— 1-(2,2-difluoroethyl)-1H-pyrazol-3-amine 1006462-38-9 C5H7F2N3
1-(2,2-difluoroethyl)-1H-pyrazol-3-amine
—— 3-[2-(4-acetyl-2-chloro-phenoxy)-ethoxy]-7-chloro-2-(3,4-difluoro-phenyl)-1-methyl-1H-quinolin-4-one 851135-07-4 C26H19Cl2F2NO4
3-[2-(4-acetyl-2-chloro-phenoxy)-ethoxy]-7-chloro-2-(3,4-difluoro-phenyl)-1-methyl-1H-quinolin-4-one
—— N-(2,2-difluoroethyl)-1-methylpiperidin-4-amine 1184221-15-5 C8H16F2N2
N-(2,2-difluoroethyl)-1-methylpiperidin-4-amine
—— 1-[8-(4-Fluorophenyl)-1,4-dioxaspiro[4.5]dec-8-yl]methanamine 78228-02-1 C15H20FNO2
1-[8-(4-Fluorophenyl)-1,4-dioxaspiro[4.5]dec-8-yl]methanamine
—— 3-(α,α,α-Trifluoromethyl)nitrobenzene radical anion 34526-71-1 C7H4F3NO2
3-(α,α,α-Trifluoromethyl)nitrobenzene radical anion
—— 8-bromo-1,1,1-trifluorooctane 407-67-0 C8H14BrF3
8-bromo-1,1,1-trifluorooctane
—— 1-(difluoromethyl)-1H-pyrazole-4-carbaldehyde 1216244-84-6 C5H4F2N2O
1-(difluoromethyl)-1H-pyrazole-4-carbaldehyde
—— potassium trifluoro(prop-1-yn-1-yl)borate 1500106-31-9 C3H3BF3*K
potassium trifluoro(prop-1-yn-1-yl)borate
—— tert-butyl 4-[(2,2,2-trifluoroethyl)amino]piperidine-1-carboxylate 1146289-88-4 C12H21F3N2O2
tert-butyl 4-[(2,2,2-trifluoroethyl)amino]piperidine-1-carboxylate
—— 1-hexyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide 380497-19-8 C2F6NO4S2*C11H24N
1-hexyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide
—— 2-fluoro-5-[(E)-(3-oxo-2-benzofuran-1-ylidene)methyl]benzonitrile 763114-25-6 C16H8FNO2
2-fluoro-5-[(E)-(3-oxo-2-benzofuran-1-ylidene)methyl]benzonitrile
—— Sodium 1-(dimethoxyphosphoryl)-3,3-difluoro-3-phenylprop-1-en-2-olate 1055985-86-8 C11H12F2O4P*Na
Sodium 1-(dimethoxyphosphoryl)-3,3-difluoro-3-phenylprop-1-en-2-olate
—— 1-(2-fluorophenyl)-2-methylpropan-2-amine 1840-77-3 C10H14FN
1-(2-fluorophenyl)-2-methylpropan-2-amine
—— (Trifluoromethylthio) silver(I) 811-68-7 CHAgF3S
(Trifluoromethylthio) silver(I)
—— 2-Bromo-4-chloro-6-fluorotoluene 1082040-50-3 C7H5BrClF
2-Bromo-4-chloro-6-fluorotoluene
—— Sodium 2,4-difluorobenzoate 83198-07-6 C7H3F2O2*Na
Sodium 2,4-difluorobenzoate
—— Diphenyliodonium hexafluoroarsenate(1-) 62613-15-4 C12H10AsF6I
Diphenyliodonium hexafluoroarsenate(1-)
—— Propane, 2,3-dibromo-1,1,1-trifluoro- 431-21-0 C3H3Br2F3
Propane, 2,3-dibromo-1,1,1-trifluoro-
—— 4-(difluoromethylidene)piperidine hydrochloride 208245-66-3 C6H9F2N*ClH
4-(difluoromethylidene)piperidine hydrochloride
—— 2,3,4,5-tetrafluorobenzoic acid sodium salt 67852-79-3 C7HF4O2*Na
2,3,4,5-tetrafluorobenzoic acid sodium salt
—— 1-(4-Fluoro benzyl)cyclopropylamine 864961-01-3 C10H12FN
1-(4-Fluoro benzyl)cyclopropylamine
—— N-(2,2-Difluoroethyl)piperidin-4-amine 1378792-60-9 C7H14F2N2
N-(2,2-Difluoroethyl)piperidin-4-amine
—— (E)-3-Chloro-3-(4-fluoro-phenyl)-acrylonitrile 126417-76-3 C9H5ClFN
(E)-3-Chloro-3-(4-fluoro-phenyl)-acrylonitrile
—— (E)-N-[(2-chloro-6-fluorophenyl)methylidene]hydroxylamine 443-33-4 C7H5ClFNO
(E)-N-[(2-chloro-6-fluorophenyl)methylidene]hydroxylamine
—— Dichloromethyl(3,3,4,4,5,5,6,6,6-nonafluorohexyl)silane 38436-16-7 C7H5Cl2F9Si
Dichloromethyl(3,3,4,4,5,5,6,6,6-nonafluorohexyl)silane
—— (trans-4-(trifluoromethyl)cyclohexyl)methanol 1202577-61-4 C8H13F3O
(trans-4-(trifluoromethyl)cyclohexyl)methanol
—— 2-Methyl-6-(trifluoromethyl)benzoic acid 1104383-68-7 C9H7F3O2
2-Methyl-6-(trifluoromethyl)benzoic acid
—— 4-(difluoromethoxy)-2-fluoroaniline 1003865-65-3 C7H6F3NO
4-(difluoromethoxy)-2-fluoroaniline
—— (S)-2-((tert-butoxycarbonyl)amino)-4,4,4-trifluorobutanoic acid 181128-25-6 C9H14F3NO4
(S)-2-((tert-butoxycarbonyl)amino)-4,4,4-trifluorobutanoic acid
—— 4-bromo-3-fluoro-2-methoxyaniline 1137869-95-4 C7H7BrFNO
4-bromo-3-fluoro-2-methoxyaniline
—— 2-(3-bromophenyl)-2,2-difluoroethan-1-ol 915133-40-3 C8H7BrF2O
2-(3-bromophenyl)-2,2-difluoroethan-1-ol
—— sodium salt of 2,3,4-trifluorobenzoic acid 402955-41-3 C7H2F3O2*Na
sodium salt of 2,3,4-trifluorobenzoic acid
—— methylpiperidin-4-amine hydrochloride 1193-03-9 C6H14N2*ClH
methylpiperidin-4-amine hydrochloride
—— milvexian 1802425-99-5 C28H23Cl2F2N9O2
milvexian
—— (1R)-1-cyclopropyl-2,2,2-trifluoroethanamine hydrochloride 1160756-75-1 C5H8F3N*ClH
(1R)-1-cyclopropyl-2,2,2-trifluoroethanamine hydrochloride
—— 2-bromo-4-chloro-1-(difluoromethyl)benzene 1261476-50-9 C7H4BrClF2
2-bromo-4-chloro-1-(difluoromethyl)benzene
—— Boronic acid, B-[3-[[(2-bromo-4-methylphenyl)amino]carbonyl]-2-fluorophenyl]- 2096336-37-5 C14H12BBrFNO3
Boronic acid, B-[3-[[(2-bromo-4-methylphenyl)amino]carbonyl]-2-fluorophenyl]-
—— 1-Benzyl-4-(bromomethyl)-2,3,5,6-tetrafluorobenzene 776-40-9 C14H9BrF4
1-Benzyl-4-(bromomethyl)-2,3,5,6-tetrafluorobenzene