CN114702364A - 一种多氟烷基芳香烃的制备方法 - Google Patents
一种多氟烷基芳香烃的制备方法 Download PDFInfo
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- CN114702364A CN114702364A CN202210509223.5A CN202210509223A CN114702364A CN 114702364 A CN114702364 A CN 114702364A CN 202210509223 A CN202210509223 A CN 202210509223A CN 114702364 A CN114702364 A CN 114702364A
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- substituted
- membered heterocycle
- oxime
- aromatic hydrocarbon
- polyfluoroalkyl
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B47/00—Formation or introduction of functional groups not provided for in groups C07B39/00 - C07B45/00
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/32—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by introduction of halogenated alkyl groups into ring compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
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- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
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Abstract
本申请公开了一种多氟烷基芳香烃的制备方法,所述多氟烷基芳香烃具有式I所示的结构:R‑Ar‑Rf式I;至少包括以下步骤:将含有具有式II所示结构的化合物、具有式III所示结构的化合物、具有式Ⅳ所示结构的肟、光催化剂和溶剂的原料混合,发生光催化反应,得到所述多氟烷基芳香烃;R‑Ar式III;其中,R选自C1~C5的烷基、C1~C5的烷氧基、频哪醇硼烷基、C2~C10的酯基、氰基、羧基、羧酸氨基、卤素原子、五元杂环、取代的五元杂环、苯环、取代的苯环、六元杂环、取代的六元杂环或氧原子中的至少一种;Ar选自五元杂环、苯环或六元杂环中的一种;Rf选自CF3、C2F5、C3F7、C4F9、CF2Cl或CF2H中的一种。
Description
技术领域
本申请涉及一种多氟烷基芳香烃的制备方法,属于有机合成领域。
背景技术
有机氟化物在工业生产、医药卫生、农业生产和居民生活等国计民生的各个方面都发挥着重要作用。虽然氟元素在地壳中的含量较为丰富,但含氟化合物主要以萤石及氟磷灰石等矿物盐形式存在,极少有天然存在的可利用的有机氟化物。在前辈们从自然界成功提取了氟酸和单质氟后,1896年Swarts等人利用氟卤交换反应合成了一氟乙酸乙酯,开创了有机化学分支学科有机氟化学。1954年前后,医药学家发现部分药物通过氟化大幅提高了药物活性。这是由于氟元素具有小的原子半径和较大的电负性,还能形成有效氢键。有机分子引入含氟基团后,由于氟原子与氢原子大小相近,使药物具有“拟态”效应(氟取代氢不影响药物进入代谢系统的能力)的同时,由于氟原子的电负性强,C-F键键能大,较稳定,能够增加药物有机分子的稳定性和亲脂性、降低生物代谢率、增强膜的通透性及增加靶标蛋白结合能力等,最终达到药效好、用量小、副作用小的功效。这一发现激发了化学家对有机氟化合物合成方法学的研究兴趣。
随着对有机氟化物的深入研究和广泛应用,有机氟化物在农业、医药、工程等产业都展现了特殊的作用和魅力。中国自70年代起先后开发了多种适用性广,效能稳定、杀伤力强的多种类含氟除草剂和杀虫剂,30%-40%的农药至少含有一个氟原子,它们多数是农药中的明星产品。以杂环类化合物为原料的农药本身具有较强的性能,氟的引入使其性能更进一步得到了提高。如含氟吡啶衍生物制成的除草剂吡氟禾草灵(稳杀特)的性能提高了1倍多;杀虫剂氯氟脲(定虫隆)兼有杀虫和不育功能。有机氟化物在制药工业中也占据及其重要的地位。目前市售的药物中高达20%带有氟原子。其中,三氟甲基以其独有的物理性质和化学性质,诸如亲脂性、代谢稳定性和生物利用率等备受关注。在2012年度全美销售前200名的药物中就有多种带有三氟甲基,比如常见的抗抑郁药百忧解和镇痛药西乐葆等。因此,三氟甲基反应成为有机方法学的研究热点之一。近年来,生物医学研究的热点技术正电子发射断层照相术使包括三氟甲基化合物的含氟有机物的需求量不断提高。氢二氟甲基化合物在调节药物的代谢稳定性和脂溶性方面也具有突出的效果。此外,在工业领域,除了熟知的冷冻试剂氟利昂是含氟烷烃外,含氟烯烃聚合而成的聚合物具有刚性强、弹性大、稳定高和防水力强的特点,可以作为人体骨骼,也可以作为多种场合适用的特种工程塑料,应用广泛。鉴于含氟化合物在多个关系到国运民生领域的重要价值和独特作用,发展简单便捷、绿色环保且具有实现规模化生产潜力的含氟化合物的合成方法势在必行。
常用的三氟甲基化试剂虽然反应活性高、选择性好,但是由于其自身高昂的价格、制备的复杂性、毒性以及反应副产物对环境的污染,极大地限制了深入研究和大规模应用;三氟乙酸及其衍生物最廉价丰富,三氟乙酸和三氟乙酸盐又因其高稳定性导致了苛刻的活化条件,三氟乙酸酐成为理想的三氟甲基试剂。
在此背景下,国内外先后建立了几个典型的三氟乙酸酐及类似物作为三氟甲基源合成三氟甲基芳香烃的光催化体系。2015年,Corey R.J.Stephenson报道了一例以吡啶氮氧化合物活化三氟乙酸酐产生的三氟甲基自由基进攻芳香烃和杂环芳烃的体系。该方法也适用于三氟甲基自由基对烯烃底物的双官能团化的反应。反应使用的活性试剂为芳香化合物,可以在流动态的反应体系中光照下实施克级规模合成。2019年,南京大学王毅、梁勇等教授报道了利用氯离子和苯甲腈离去降低体系能量的方法,使预合成的含三氟甲基的氯肟酯分解生成三氟甲基自由基,参与后续的自由基迁移反应或不饱和烯烃的加成反应。该体系设计巧妙,但反应需要将底物三氟乙酸酐预合成生成活性的含三氟甲基的氯肟酯再进行后续反应,步骤繁琐。2018年,中国科学院上海有机所卿凤翎教授团队曾报道一个以吡啶活化三氟甲磺酸酐对芳香烃、杂环芳烃以及炔烃进行三氟甲基化的体系。三氟甲磺酸酐也是一类重要、常见的三氟甲基源,较三氟乙酸酐更活泼易活化,但其释放的是有毒的二氧化硫副产物,环保效益差。
芳烃的多氟烷基化通常使用氟烷基专用试剂作为氟烷基化的原料试剂,在计量的或催化量的金属催化剂作用下完成。反应的转化率和选择性较高,但是由于其自身高昂的价格、制备的复杂性、毒性以及反应副产物对环境的污染,很大地限制深入研究和大规模应用。
发明内容
氟烷基的酸酐廉价易得,以可见光催化的温和条件实现氟烷基酸酐的活化,是理想的芳香烃氟烷基合成方法,这既是实验室合成的便捷路径,也具有规模合成的巨大潜力。
在本发明申请的方法使用的两种原料氟烷酸酐和肟廉价易得,光催化反应条件下,氟烷酸酐通过肟活化试剂转化生成氟烷基自由基,可以实现对芳香烃的氟烷基修饰。反应在室温和可见光照射下完成,条件温和;反应收率高,产品氟烷基官能团的区域选择性高,副产物是无毒的小分子;光催化剂是廉价常见的过渡金属钌配合物;溶剂是常见的有机溶剂乙腈、乙酸乙酯、二氯甲烷、二氯乙烷,活化试剂是常见的结构简单的肟,无需外加氧化剂及还原剂。反应过程温和,原子经济,副产品环保无毒。
本申请以三氟乙酸酐为三氟甲基源,肟为活化试剂,光催化剂参与,在可见光照射的室温条件下实现对芳香烃的三氟甲基官能团修饰。
根据本申请的一个方面,提供一种多氟烷基芳香烃的制备方法,所述多氟烷基芳香烃具有式I所示的结构:
R-Ar-Rf
式I;
至少包括以下步骤:将含有具有式II所示结构的化合物、具有式III所示结构的化合物、肟、光催化剂和溶剂的原料混合,发生光催化反应,得到所述多氟烷基芳香烃;
R-Ar
式III;
其中,R选自C1~C5的烷基、C1~C5的烷氧基、频哪醇硼烷基、C2~C10的酯基、氰基、羧基、羧酸氨基、卤素原子、五元杂环、取代的五元杂环、苯环、取代的苯环、六元杂环、取代的六元杂环或氧原子中的至少一种;
Ar选自五元杂环、苯环或六元杂环中的一种;
Rf选自CF3、C2F5、C3F7、C4F9、CF2Cl或CF2H中的一种。
所述羧酸氨基选自甲酸氨基、乙酸胺基、丙酸氨基或丁酸氨基中的至少一种;
所述卤素原子选自氟原子、氯原子、溴原子或碘原子中的至少一种;
所述五元杂环、取代的五元杂环、六元杂环或取代的六元杂环中的杂原子选自S、N或O中的一种;
可选地,所述五元杂环选自吡咯、呋喃、噻吩、吡唑、咪唑、噁唑或噻唑;
可选地,所述六元杂环选自吡啶、嘧啶、吡嗪或哒嗪;
所述取代的五元杂环或取代的六元杂环中的取代基选自C1~C5的烷基、C1~C5的烷氧基、C2~C10的酯基、氰基、羧基或氧原子中的至少一种。
所述肟选自芳香烃取代的肟或脂肪烃取代的肟;
可选地,所述肟选自丙酮肟、苯乙酮肟、环戊酮肟或甲丙酮肟中的至少一种。
所述光催化剂选自Ru(bpy)3Cl2、Ru(phen)3Cl2、Ir(ppy)3、Ir[(dtbpy)(ppy)2]PF6或Ir[dF(CF3)ppy]2(dtbpy)PF6中的至少一种。
所述溶剂选自乙腈、乙酸乙酯、二氯甲烷或二氯乙烷中的至少一种。
所述具有式II所示结构的化合物与所述肟的摩尔比为10:1~1:5;
所述具有式II所示结构的化合物与具有式III所示结构的化合物的摩尔比为10:1~1:10;
所述光催化剂的摩尔量占所述具有式III所示结构的化合物摩尔量的0.1~10mol%;所述光催化剂的摩尔量占所述具有式III所示结构的化合物摩尔量的上限为10mol%、9mol%、8mol%、7mol%、6mol%、5mol%、4mol%、3mol%、2mol%、1mol%;下限为0.1mol%、1mol%、2mol%、3mol%、4mol%、5mol%、6mol%、7mol%、8mol%、9mol%;
所述溶剂的用量与所述具有式III所示结构的化合物摩尔量的比为1~20L:1mol。
所述光催化反应采用可见光;
所述可见光的波长为390~500nm。
所述光催化反应的时间为8~72h;
所述光催化反应的温度为15~35℃。
所述多氟烷基芳香烃经过旋蒸和柱层析分离。
所述多氟烷基芳香烃包括单取代的多氟烷基芳香烃和双取代的多氟烷基芳香烃。
该反应原理如图1所示,酸酐被肟活化生成肟酯的同时放出羧酸,羧酸的质子和肟酯的氮结合,并由羧酸阴离子稳定该中间体,光作用下氮氧键断裂,生成的氟烷基羧酸根自由基放出二氧化碳后生成三氟甲基自由基。三氟甲基自由基和另一个底物芳香化合物结合生成目标产品芳烃的三氟甲基化产品。该机制中,原位生成的酸引发的肟酯物种在氮氧键两端的极性倒转是产生氟烷基自由基的重要步骤。外加的碱会导致反应活性不同程度的减弱。
本申请能产生的有益效果包括:
1、能实现多种官能团兼容的芳香烃以及杂环芳烃的三氟甲基化。
2、能实现多种官能团兼容的芳香烃以及杂环芳烃的全氟甲基化(包括但不限于五氟丙基、七氟丁基)、氯二氟烷基化和氢二氟烷基化。
3、本两种原料氟烷基酸酐和肟廉价易得、性质温和。
4、反应的副产品以季铵盐或者丙酮、氨气、氟烷酸等挥发性的小分子形式离开。
5、该合成路线使用温和的合成条件,可以实现对各类芳香烃的氟烷基修饰,转化率高,氟烷基官能团的区域选择性高。
附图说明
图1本申请技术方案氟烷酸酐经肟原位活化合成氟烷基芳香烃的光催化体系反应过程图(a)及其原理图(b)。
图2为实施例5的核磁测试19F NMR分析图。
具体实施方式
下面结合实施例详述本申请,但本申请并不局限于这些实施例。
如无特别说明,本申请的实施例中的原料和催化剂均通过商业途径购买。
本发明方法的具体操作为:在手套箱的氮气保护下,向35mL的Schlenk玻璃反应管内加入光催化剂Ru(bpy)3Cl2(2.6mg,0.004mmol,0.02equiv.)和丙酮肟(29.2mg,0.4mmol,2.0equiv.),以橡胶塞密封。接着在氮气保护下,加入其它原料氟烷基酸酐(0.4mmol,2.0equiv.)、芳香化合物(0.20mmol,1.0equiv.)和溶剂二氯乙烷(2.0mL)。用聚四氟乙烯塞密封反应管。以2个3W的紫色LED光源照射装有原料的反应管,同时在室温下进行磁力搅拌。反应一段时间后,反应结束。以硅藻土过滤反应混合物,用20mL二氯乙烷洗涤三次,将滤液收集并旋转蒸发处理。将该样品使用硅胶进行柱层析分离,洗脱液为正己烷。
将分离得到的产品称重,可计算得到产品收率(收率=产品的质量/(产品的摩尔质量X芳香化合物投料量的摩尔数)X100%)。
反应后混合物经19F NMR测试得到产品选择性(内标为对三氟甲氧基苯甲醚)。
产品经过核磁测试,确定产品结构。
本申请提供18个实施例。
表1实施例1~18的反应物
表2实施例1~18中原料投料量及产品的质量和收率
其中,a:光催化反应时间为72h。
以实施例1为例说明具体过程。
实施例1
在手套箱的氮气保护下,向35mL的Schlenk玻璃反应管内加入光催化剂Ru(bpy)3Cl2(2.6mg,0.004mmol,0.02equiv.)和丙酮肟(29.2mg,0.4mmol,2.0equiv.),以橡胶塞密封。接着在氮气保护下,加入其它原料三氟乙酸酐(56uL,0.4mmol,2.0equiv.)、芳香化合物均三甲苯(28uL,0.20mmol,1.0equiv.)和溶剂二氯乙烷(2.0mL)。用聚四氟乙烯塞密封反应管。以2个3W的紫色LED光源照射装有原料的反应管,同时在室温下进行磁力搅拌。22小时后,反应结束。以硅藻土过滤反应混合物,用20mL二氯乙烷洗涤三次,将滤液收集并旋转蒸发处理。将该样品使用硅胶进行柱层析分离,洗脱液为正己烷。分离产品为无色油状物。将产品称重,产品为32.0mg,计算相应的收率为80%。反应后混合物加入内标对三氟甲氧基苯甲醚(30μL,0.20mmol),经19F NMR测试得到其单取代和双取代产品的比例为4.9:1。
产品经过核磁测试,表征结果为:1a-mono:1H NMR(400MHz,Chloroform-d)δ6.90(s,2H),2.45(q,J=3.4Hz,6H),2.30(s,3H).13C NMR(101MHz,Chloroform-d)δ140.79,137.22(q,J=2.2Hz),130.78,126.13(q,J=274.7Hz),124.70(q,J=28.4Hz),21.25(q,J=4.0Hz),20.78.19F NMR(376MHz,Chloroform-d)δ-53.70.1a-bis:1H NMR(400MHz,Chloroform-d)δ6.99(s,1H),2.54-2.47(m,9H);13C NMR(101MHz,Chloroform-d)δ140.03,137.81(q,J=2.0Hz),134.42,127.81(q,J=28.0Hz),125.40(q,J=276.2Hz),21.98(q,J=4.8Hz),17.27(hept,J=4.4Hz).19F NMR(376MHz,Chloroform-d)δ-52.90(s,3F)。
实施例2~18
以与实施例1相同的方法,改变反应物或反应条件。
实施例2~3
产品经过核磁测试,产品结构表征结果和实施例1一致。
产物结构与实施例1相同。
实施例4
产品经过核磁测试,表征结果为:1H NMR(400MHz,Chloroform-d)δ6.87(s,1H),2.52(q,J=3.0Hz,3H),2.43(q,J=3.8Hz,3H),2.37(s,3H),1.41(s,12H).13C NMR(101MHz,Chloroform-d)144.28,140.79(d,J=2.2Hz),137.99(d,J=2.1Hz),131.15,126.47(q,J=276.1Hz),124.87(q,J=27.9Hz),84.18,25.03,21.87(d,J=3.9Hz),21.85,20.91(q,J=4.0Hz).19F NMR(376MHz,Chloroform-d)δ-52.71(s,3F)。
实施例5
反应后混合物加入内标对三氟甲氧基苯甲醚(15μL,0.10mmol),产品分布由核磁测试19F NMR分析确定。
图2为实施例5的核磁测试19F NMR分析图。从图中可以看出19F NMR(376MHz,Chloroform-d)δ-62.85(s,3F),-62.62(s,3F),-62.54(s,3F),-58.4(s,3F),4个峰分别对应间位(m-)、邻位(o-)和对位(p-)取代的苯三氟甲基氯苯以及内标对三氟甲氧基苯甲醚的三氟甲氧基的氟信号。将谱图积分处理后,总收率为59%,三个不同取代位置的产品苯三氟甲基氯苯之间的比例为o:m:p=2.2:1:1.2。
实施例6
产品经过核磁测试,表征结果为:1H NMR(400MHz,Chloroform-d)δ7.72(d,J=8.3Hz,1H),6.32(d,J=8.3Hz,1H),4.02(s,3H),3.96(s,3H).13C NMR(101MHz,)δ165.12,160.42,138.82(q,J=4.6Hz),123.71(q,J=270.1Hz),104.37(q,J=33.5Hz),100.75,53.92,53.87.19F NMR(376MHz,Chloroform-d)δ-62.81(s,3F)。
实施例7
产品经过核磁测试,表征结果为:1H NMR(400MHz,)δ8.41(s,1H),6.44(d,J=2.1Hz,1H),6.32(d,J=2.1Hz,1H),3.93(s,3H),3.89(s,3H).13C NMR(101MHz,Chloroform-d)δ166.17,158.24,157.77,156.84,138.93(d,J=4.9Hz),122.13(q,J=271.2Hz),111.65(q,J=33.3Hz),102.33,95.49,92.87,56.29,56.17.19F NMR(376MHz,Chloroform-d)δ-65.25(s)。
实施例8
产品经过核磁测试,表征结果为:1H NMR(400MHz,Chloroform-d)δ10.18(s,1H),6.97–6.84(m,1H),6.76–6.57(m,1H).13C NMR(101MHz,Chloroform-d)δ125.80(q,J=40.3Hz),120.42,119.78(q,J=268.2Hz),112.85,110.79(m),103.55.19F NMR(376MHz,Chloroform-d)δ-60.49(s).HRMS(DART):Calcd.for C6H4N2F3([M+H]+):161.0321,Found:161.0320。
实施例9
产品经过核磁测试,表征结果为:1H NMR(400MHz,Chloroform-d)δ7.86(d,J=4.1Hz,1H),7.71(s,1H),7.41(d,J=5.4Hz,1H),2.20(s,3H).13C NMR(101MHz,Chloroform-d)δ167.75,137.02(q,J=2.7Hz),127.37,124.09,122.98(q,J=268.3Hz),112.43(q,J=33.8Hz),24.20.19F NMR(376MHz,Chloroform-d)δ-53.34(s)。
实施例10
产品经过核磁测试,表征结果为:1H NMR(400MHz,Chloroform-d)δ8.68(s,1H),6.78(s,1H),2.42(s,3H).13C NMR(101MHz,Chloroform-d)δ163.75,144.25(q,J=43.4Hz),141.09,133.32,118.35(q,J=268.5Hz),116.03(d,J=2.9Hz),11.71.19F NMR(376MHz,Chloroform-d)δ-64.68(s).HRMS(DART):Calcd.for C7H6F3O3([M+H]+):
195.0264,Found:195.0262。
实施例11
产品经过核磁测试,表征结果为:3-11-mono:1H NMR(400MHz,Chloroform-d)δ6.92(s,2H),2.43(t,J=4.8Hz,6H),2.29(s,3H).19F NMR(376MHz,Chloroform-d)δ-84.02(t,J=3.3Hz,3F),-103.81(q,J=3.1Hz,2F).HRMS(EI)m/z:[M]+Calcd forC11H11F5238.0775,Found:238.0773.3-11-bis:1H NMR(400MHz,Chloroform-d)δ7.07(s,1H),2.46-2.49(m,9H).19F NMR(376MHz,Chloroform-d)δ-82.27(t,J=3.1Hz,3F),-99.88(q,J=3.3Hz,2F).13C NMR(101MHz,Chloroform-d)δ142.69,141.08,139.02(t,J=3.3Hz),136.18,131.65,126.54–113.35(carbons for C2F5),22.72–22.51(m),22.01–21.85(m),20.80,14.14。
实施例12
产品经过核磁测试,表征结果为:1H NMR(400MHz,Chloroform-d)δ6.99(s,1H),4.05(t,J=1.80Hz,3H),3.85(s,3H).13C NMR(101MHz,Chloroform-d)δ160.26,126.88,121.60(t,J=27.5Hz),120.89,118.96(qt,J=287.1,39.7Hz),111.06(tq,J=256.25,40.16Hz),100.61(t,J=3.31Hz),51.88,34.92.19F NMR(376MHz,Chloroform-d)δ-84.40(s,3F),-108.76(s,2F).HRMS(EI):Calcd.for C9H7O2NBrF5([M]+):334.9575,Found:334.9581。
实施例13
产品经过核磁测试,表征结果为:1H NMR(400MHz,Chloroform-d)δ7.24(dt,J=3.7,1.1Hz,1H),6.94(dt,J=3.7,1.0Hz,1H),3.93(s,3H).13C NMR(101MHz,Chloroform-d)δ158.14,147.46,143.75(t,J=33.5Hz),119.46-107.5(carbons of CF2CF2CF3),117.92,115.20,52.52.19F NMR(376MHz,Chloroform-d)δ-80.45(t,J=9.2Hz,3F),
-112.60(q,J=8.2Hz,2F),-126.82(s,2F).HRMS(DART):Calcd.for C9H6F7O3([M+H]+):295.0200,Found:295.0197。
实施例14
产品经过核磁测试,表征结果为:1H NMR(400MHz,Chloroform-d)δ7.23(d,J=4.3Hz,1H),6.94(d,J=3.7Hz,1H),3.92(s,3H).13C NMR(101MHz,Chloroform-d)δ158.12,147.47,143.84(t,J=33.5Hz),119.11-107.35(carbons of CF2CF2CF2CF3),117.88,115.24,52.45.19F NMR(376MHz,Chloroform-d)δ-81.06(tt,J=9.7,2.7Hz,3F),-111.98(t,J=12.1Hz,2F),-122.89–-123.66(m,2F),-125.49–-126.50(m,2F).HRMS(DART):Calcd.for C10H6F9O3([M+H]+):345.0168,Found:345.0165。
实施例15
产品经过核磁测试,表征结果为:1H NMR(400MHz,Chloroform-d)δ6.67(t,J=54.5Hz,1H),2.99-2.77(m,4H),2.68(s,3H),1.39-1.19(m,6H).13C NMR(101MHz,Chloroform-d)δ157.34(t,J=1.6Hz),
152.16(t,J=1.1Hz),148.99,142.10(t,J=26.4Hz),116.76(t,J=239.7Hz),27.54,26.80,20.17(t,J=2.3Hz),13.03,12.79.19F NMR(376MHz,Chloroform-d)δ-114.24(d,J=55.5Hz)。
实施例16
产品经过核磁测试,表征结果为:1H NMR(400MHz,Chloroform-d)δ4.14(s,3H),3.52(s,3H),3.34(s,3H).13C NMR(101MHz,Chloroform-d)δ155.42,151.27,146.87,137.67(t,J=28.7Hz),118.15(qt,J=286.7,35.9Hz),109.32(tq,J=254.5,40.3Hz),110.04,33.62,29.87,28.15.19F NMR(376MHz,Chloroform-d)δ-82.52(t,J=2.8Hz,3F),-111.36(p,J=2.4Hz,2F).HRMS(DART):Calcd.for C10H10F5N4O2([M+H]+):313.0718,Found:313.0715。
实施例17
产品经过核磁测试,表征结果为:1H NMR(400MHz,Chloroform-d)δ4.13(s,3H),3.54(s,3H),3.36(s,3H).13C NMR(101MHz,Chloroform-d)δ155.55,151.36,146.34,142.54(t,J=32.9Hz),119.71(t,J=288.2Hz),109.64,33.52,29.96,28.24.19F NMR(376MHz,Chloroform-d)δ-50.97(s)。
实施例18
产品经过核磁测试,表征结果为:1H NMR(400MHz,Chloroform-d)δ6.74(t,J=52.2Hz,1H),4.15(s,3H),3.56(s,3H),3.40(s,3H).13C NMR(101MHz,Chloroform-d)δ155.66,151.53,146.98,142.89(t,J=27.3Hz),109.85(t,J=238.0Hz),109.59,32.99,29.87,28.22.19F NMR(376MHz,Chloroform-d)δ-114.83(d,J=52.2Hz)。
以上所述,仅是本申请的若干个实施例,并非对本申请做任何形式的限制,虽然本申请以较佳实施例揭示如上,然而并非用以限制本申请,任何熟悉本专业的技术人员,在不脱离本申请技术方案的范围内,利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例,均属于技术方案范围内。
Claims (10)
1.一种多氟烷基芳香烃的制备方法,其特征在于,
所述多氟烷基芳香烃具有式I所示的结构:
R-Ar-Rf
式I;
至少包括以下步骤:将含有具有式II所示结构的化合物、具有式III所示结构的化合物、肟、光催化剂和溶剂的原料混合,发生光催化反应,得到所述多氟烷基芳香烃;
R-Ar
式III;
其中,R选自C1~C5的烷基、C1~C5的烷氧基、频哪醇硼烷基、C2~C10的酯基、氰基、羧基、羧酸氨基、卤素原子、五元杂环、取代的五元杂环、苯环、取代的苯环、六元杂环、取代的六元杂环或氧原子中的至少一种;
Ar选自五元杂环、苯环或六元杂环中的一种;
Rf选自CF3、C2F5、C3F7、C4F9、CF2Cl或CF2H中的一种。
2.根据权利要求1所述的制备方法,其特征在于,
所述羧酸氨基选自甲酸氨基、乙酸胺基、丙酸氨基或丁酸氨基中的至少一种;
所述卤素原子选自氟原子、氯原子、溴原子或碘原子中的至少一种;
所述五元杂环、取代的五元杂环、六元杂环或取代的六元杂环中的杂原子选自S、N或O中的一种;
所述取代的五元杂环或取代的六元杂环中的取代基选自C1~C5的烷基、C1~C5的烷氧基、C2~C10的酯基、氰基、羧基或氧原子中的至少一种。
3.根据权利要求1所述的制备方法,其特征在于,
所述肟选自芳香烃取代的肟或脂肪烃取代的肟;
优选地,所述肟选自丙酮肟、苯乙酮肟、环戊酮肟或甲丙酮肟中的至少一种。
4.根据权利要求1所述的制备方法,其特征在于,
所述光催化剂选自Ru(bpy)3Cl2、Ru(phen)3Cl2、Ir(ppy)3、Ir[(dtbpy)(ppy)2]PF6或Ir[dF(CF3)ppy]2(dtbpy)PF6中的至少一种。
5.根据权利要求1所述的制备方法,其特征在于,
所述溶剂选自乙腈、乙酸乙酯、二氯甲烷或二氯乙烷中的至少一种。
6.根据权利要求1所述的制备方法,其特征在于,
所述具有式II所示结构的化合物与所述肟的摩尔比为10:1~1:5;
优选地,所述具有式II所示结构的化合物与具有式III所示结构的化合物的摩尔比为10:1~1:10;
优选地,所述光催化剂的摩尔量占所述具有式III所示结构的化合物摩尔量的0.1~10mol%;
优选地,所述溶剂的用量与所述具有式III所示结构的化合物摩尔量的比为1~20L:1mol。
7.根据权利要求1所述的制备方法,其特征在于,
所述光催化反应采用可见光;
优选地,所述可见光的波长为390~500nm。
8.根据权利要求1所述的制备方法,其特征在于,
所述光催化反应的时间为8~72h;
优选地,所述光催化反应的温度为15~35℃。
9.根据权利要求1所述的制备方法,其特征在于,
所述多氟烷基芳香烃经过旋蒸和柱层析分离。
10.根据权利要求1所述的制备方法,其特征在于,
所述多氟烷基芳香烃包括单取代的多氟烷基芳香烃和双取代的多氟烷基芳香烃。
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