CN111303089B - 一种α-卤代三氟甲基取代烷烃的制备方法 - Google Patents
一种α-卤代三氟甲基取代烷烃的制备方法 Download PDFInfo
- Publication number
- CN111303089B CN111303089B CN202010163061.5A CN202010163061A CN111303089B CN 111303089 B CN111303089 B CN 111303089B CN 202010163061 A CN202010163061 A CN 202010163061A CN 111303089 B CN111303089 B CN 111303089B
- Authority
- CN
- China
- Prior art keywords
- trifluoromethyl
- alpha
- halogenated
- preparation
- substituted alkane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 title claims abstract description 26
- 150000001335 aliphatic alkanes Chemical class 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000001350 alkyl halides Chemical class 0.000 claims abstract description 9
- 230000001590 oxidative effect Effects 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- XGPOMXSYOKFBHS-UHFFFAOYSA-M sodium;trifluoromethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(F)(F)F XGPOMXSYOKFBHS-UHFFFAOYSA-M 0.000 claims abstract description 8
- -1 olefin compound Chemical class 0.000 claims abstract description 7
- 239000007800 oxidant agent Substances 0.000 claims abstract description 7
- ONJSLAKTVIZUQS-UHFFFAOYSA-K manganese(3+);triacetate;dihydrate Chemical compound O.O.[Mn+3].CC([O-])=O.CC([O-])=O.CC([O-])=O ONJSLAKTVIZUQS-UHFFFAOYSA-K 0.000 claims abstract description 4
- KAVUKAXLXGRUCD-UHFFFAOYSA-M sodium trifluoromethanesulfinate Chemical compound [Na+].[O-]S(=O)C(F)(F)F KAVUKAXLXGRUCD-UHFFFAOYSA-M 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 30
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 238000004440 column chromatography Methods 0.000 claims description 7
- 238000010791 quenching Methods 0.000 claims description 6
- 230000000171 quenching effect Effects 0.000 claims description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000003480 eluent Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000012074 organic phase Substances 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 5
- 239000000741 silica gel Substances 0.000 claims description 5
- 229910002027 silica gel Inorganic materials 0.000 claims description 5
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 5
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims 2
- KIAYWZXEAJWSGJ-BQYQJAHWSA-N 1,3,7-trimethyl-8-[(e)-2-(3,4,5-trimethoxyphenyl)ethenyl]purine-2,6-dione Chemical compound COC1=C(OC)C(OC)=CC(\C=C\C=2N(C=3C(=O)N(C)C(=O)N(C)C=3N=2)C)=C1 KIAYWZXEAJWSGJ-BQYQJAHWSA-N 0.000 claims 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims 1
- 239000012467 final product Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 abstract description 9
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 230000002194 synthesizing effect Effects 0.000 abstract description 4
- 229940079593 drug Drugs 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 3
- 150000004820 halides Chemical class 0.000 abstract description 3
- AHSBSUVHXDIAEY-UHFFFAOYSA-K manganese(iii) acetate Chemical compound [Mn+3].CC([O-])=O.CC([O-])=O.CC([O-])=O AHSBSUVHXDIAEY-UHFFFAOYSA-K 0.000 abstract description 3
- 229930014626 natural product Natural products 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 6
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
- 238000006692 trifluoromethylation reaction Methods 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- KTOXGWMDJYFBKK-UHFFFAOYSA-L manganese(2+);diacetate;dihydrate Chemical compound O.O.[Mn+2].CC([O-])=O.CC([O-])=O KTOXGWMDJYFBKK-UHFFFAOYSA-L 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000005051 trimethylchlorosilane Substances 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001723 carbon free-radicals Chemical class 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- HVAPLSNCVYXFDQ-UHFFFAOYSA-N 3,3-dimethyl-1-(trifluoromethyl)-1$l^{3},2-benziodoxole Chemical compound C1=CC=C2C(C)(C)OI(C(F)(F)F)C2=C1 HVAPLSNCVYXFDQ-UHFFFAOYSA-N 0.000 description 1
- WCCVEGGNHCGFGB-UHFFFAOYSA-N C1[IH]C(C2=C1C=CC=C2)=O Chemical compound C1[IH]C(C2=C1C=CC=C2)=O WCCVEGGNHCGFGB-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 238000007342 radical addition reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- QXXHXTRTGZBOGD-UHFFFAOYSA-M trifluoromethanesulfonate;5-(trifluoromethyl)dibenzothiophen-5-ium Chemical compound [O-]S(=O)(=O)C(F)(F)F.C1=CC=C2[S+](C(F)(F)F)C3=CC=CC=C3C2=C1 QXXHXTRTGZBOGD-UHFFFAOYSA-M 0.000 description 1
- MWKJTNBSKNUMFN-UHFFFAOYSA-N trifluoromethyltrimethylsilane Chemical compound C[Si](C)(C)C(F)(F)F MWKJTNBSKNUMFN-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/69—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to carbon-to-carbon double or triple bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B39/00—Halogenation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three 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
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及一种α‑卤代三氟甲基取代烷烃的制备方法,本发明通过二水合三醋酸锰促进非活化烯烃的卤代三氟甲基化反应,在温和的反应条件下直接生成含有三氟甲基的化合物,达到高效构建α‑卤代三氟甲基取代烷烃的目的。本发明提供的技术方案如下:将烯烃类化合物、氧化剂、三氟甲基亚磺酸钠和三甲基卤烷加入有机溶剂中,在室温下反应24小时,即可得到α‑卤代三氟甲基取代烷烃。本发明提供的制备方法,反应稳定,收率良好,使用的三醋酸锰、三氟甲基亚磺酸钠、三甲基卤烷为易得产品,且易于存贮,适用范围广泛,所制备的三氟甲基化产物的α位有卤化物,易于被其它官能团取代,对于合成含三氟甲基基团的天然产物或药物具有良好的应用前景。
Description
技术领域
本发明属于有机合成领域,具体涉及一种α-卤代三氟甲基取代烷烃的制备方法。
背景技术
由于三氟甲基基团有着较强的吸电子性和疏水性,三氟甲基基团在药物化学中有着重要且广泛的应用。化合物中引入三氟甲基基团,化合物的亲油性,生物利用度,代谢稳定性,化学键结合选择性等因素会发生明显的改变,所以发展新的三氟甲基合成方法是十分有意义的。在众多的三氟甲基合成方法中,烯烃的三氟甲基化反应被认为是最有效的引入三氟甲基基团的方法之一。在这些方法中,Togni试剂(例如:1-(三氟甲基)-1,2-苯碘酰-3(1H)-酮),Umemoto试剂(例如:S-(三氟甲基)二苯并噻吩三氟甲基磺酸盐),Ruppert试剂(TMSCF3)和卤代三氟甲基烷试剂都是烯烃的三氟甲基化反应中常见的三氟甲基化试剂。在众多三氟甲基化试剂中,CF3SO2Na在三氟甲基化反应中有着广泛的应用,例如光敏催化剂体系催化的三氟甲基化反应。
基于上述的观点,研究三氟甲基化合成方法成为重要的课题,烯烃结构中碳碳双键的三氟甲基化反应是一种有效且应用价值广泛的方法。
发明内容
本发明的目的是提供一种烯烃的双键同时进行三氟甲基化与卤(溴、氯)化,可高效构建α-卤代三氟甲基取代烷烃的制备方法。
本发明是通过如下技术方案实现的:一种α-卤代三氟甲基取代烷烃的制备方法,将结构式如(I)所示的烯烃类化合物、氧化剂、三氟甲基亚磺酸钠和三甲基卤烷加入有机溶剂中,在室温下反应24小时,得到如(II)所示的α-卤代三氟甲基取代烷烃,反应式如下:
所述的三甲基卤烷结构式为:
其中,R1、R2、R3、R4为烷基或氢原子,X为溴原子或氯原子;
其中,所述烯烃类化合物、氧化剂、三氟甲基亚磺酸钠、三甲基卤烷的摩尔比为1:2:1.2:1.2;
其中,所述有机溶剂为乙腈(MeCN)(MeCN),所述氧化剂为二水合三醋酸锰。
反应首先通过三醋酸锰氧化三氟甲基磺酸钠得到三氟甲基自由基,三氟甲基自由基与双键进行自由基加成反应得到碳自由基,碳自由基被三醋酸锰氧化得到碳正离子,最后被三甲基卤硅烷捕获得到α-卤代三氟甲基化产物。
其中,对上述反应所得的产物进行处理,依次进行淬灭、萃取、有机相经洗涤、干燥和柱层析分离。
淬灭:使用硫代硫酸钠水溶液进行淬灭;
萃取:使用乙酸乙酯作为萃取剂。
洗涤:采用饱和食盐水洗涤。
干燥:使用无水硫酸镁和无水氯化钙干燥。
柱层析分离:300-400目硅胶层析柱,洗脱液为体积比10比1的石油醚与乙酸乙酯的混合液。
本发明的有益效果为:
1、制备三氟甲基化产物的方法所使用的二水合三醋酸锰、三氟甲基亚磺酸钠、三甲基卤烷均为易得产品,且易于存贮。
2、反应得到的三氟甲基化产物的α位有卤化物,易于被其它官能团取代,为合成多种类型的活性天然产物与药物提供新的方法。
3、反应在常温常压下进行,所需条件简单,反应稳定,收率良好,通过直接在烯烃上引入三氟甲基基团,不仅合成的步骤简化,操作方便,适用范围广泛,对于合成含三氟甲基基团的天然产物或药物具有良好的应用前景。
具体实施方式
下面对本发明实施例中的技术方案进行清楚、完整地描述。在下面的描述中阐述了很多具体细节以便于充分理解本发明,但是本发明还可以采用其他不同于在此描述的其它方式来实施,本领域技术人员可以在不违背本发明内涵的情况下做类似推广,因此本发明不受下面公开的具体实施例的限制。
实施例一
取一支干燥的反应管,称入反应式中所示的烯烃(88.1mg,0.5mmol)、二水合醋酸锰(268.1mg,1.0mmol)、三氟甲基亚磺酸钠(93.6mg,0.6mmol)、三甲基氯硅烷(65.2mg,0.6mmol),然后加入6mL乙腈(MeCN)(MeCN)。反应在室温下搅拌24h后,加入10mL硫代硫酸钠水溶液淬灭,用乙酸乙酯(10mL)萃取三次,合并后用饱和食盐水洗涤有机相,无水硫酸镁干燥。使用旋转蒸发仪除去有机溶剂至没有溶剂蒸出为止,最后用硅胶(300-400目)柱层析分离(洗脱液:石油醚/乙酸乙酯的体积比为10/1)得到115.1mg无色液体,收率82%。
表征数据-核磁产物分析:
1HNMR(400MHz,Chloroform-d)δ9.82(s,1H),7.79–7.76(m,2H),6.97–6.93(m,2H),4.41–4.33(m,1H),4.26–4.14(m,2H),2.73–2.53(m,2H),2.41–2.31(m,1H),2.15–2.04(m,1H).13CNMR(101MHz,Chloroform-d)δ189.7,162.4,131.0,129.3,124.1(q,1J(C,F)=277.6Hz),113.7,63.2,49.7(q,2J(C,F)=3.3Hz),41.6(q,J=28.7Hz),36.3.IR(KBr):2917,2848,2360,2342,1685,1601,1509,1258,1156,830,616cm-1.HRMS-ESI(m/z):[M+H]+calcdforC12H12ClF3O2,281.0556;found:281.0558.
实施例二
取一支干燥的反应管,称入反应式中所示的烯烃(97.1mg,0.5mmol)、二水合醋酸锰(268.1mg,1.0mmol)、三氟甲基亚磺酸钠(93.6mg,0.6mmol)、三甲基氯硅烷(65.2mg,0.6mmol),然后加入6mL乙腈(MeCN)(MeCN)。反应在室温下搅拌24h后,加入10mL硫代硫酸钠水溶液淬灭,用乙酸乙酯(10mL)萃取三次,合并后用饱和食盐水洗涤有机相,无水硫酸镁干燥。使用旋转蒸发仪除去有机溶剂至没有溶剂蒸出为止,最后用硅胶(300-400目)柱层析分离(洗脱液:石油醚/乙酸乙酯的体积比为100/1)得到97.1mg无色液体,收率65%。
表征数据-核磁产物分析:
1HNMR(500MHz,Chloroform-d)δ7.58(s,1H),7.18(d,J=3.5Hz,1H),6.52(dd,J=3.5,1.7Hz,1H),4.33(t,J=6.4Hz,2H),4.16–4.10(m,1H),2.70–2.60(m,1H),2.60–2.50(m,1H),1.97–1.87(m,1H),1.86–1.68(m,4H),1.65–1.55(m,1H).13CNMR(126MHz,Chloroform-d)δ158.8,146.4,144.8,125.3(q,1J(C,F)=277.6Hz),118.0,111.9,64.5,54.0(q,2J(C,F)=3.0Hz),42.5(q,3J(C,F)=28.5Hz),37.6,28.1,22.6.IR(KBr):2963,2361,2343,1718,1261,1079,1016,800,669cm-1.HRMS-ESI(m/z):[M+H]+calcdforC12H14ClF3O3,299.0662;found:299.0661.
实施例三
取一支干燥的反应管,称入反应式中所示的烯烃(95.1mg,0.5mmol)、二水合醋酸锰(268.1mg,1.0mmol)、三氟甲基亚磺酸钠(93.6mg,0.6mmol)、三甲基氯硅烷(65.2mg,0.6mmol),然后加入6mL乙腈(MeCN)(MeCN)。反应在室温下搅拌24h后,加入10mL硫代硫酸钠水溶液淬灭,用乙酸乙酯(10mL)萃取三次,合并后用饱和食盐水洗涤有机相,无水硫酸镁干燥。使用旋蒸旋转蒸发仪除去有机溶剂至没有溶剂蒸出为止,最后用硅胶(300-400目)柱层析分离(洗脱液:石油醚/乙酸乙酯的体积比为100/1)得到134.0mg无色液体,收率79%。
表征数据-核磁产物分析:
1HNMR(500MHz,Chloroform-d)δ7.34(d,J=5.7Hz,4H),7.31–7.25(m,1H),4.50(s,2H),4.17–4.10(m,1H),3.48(t,J=5.8Hz,2H),2.82–2.72(m,1H),2.71–2.61(m,1H),1.94–1.81(m,2H),1.72–1.52(m,4H).13CNMR(126MHz,Chloroform-d)δ138.5,128.4,127.7,127.6,125.4(q,1J(C,F)=278.0Hz),73.0,69.9,44.9(q,2J(C,F)=2.9Hz),43.1(q,3J(C,F)=28.4Hz),38.3,28.9,24.1.
显然,所描述的实施例仅仅是本发明的一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
Claims (3)
2.根据权利要求1所述的一种α-卤代三氟甲基取代烷烃的制备方法,其特征在于,所述纯化处理的过程为将终产物混合物依次进行淬灭、萃取、有机相经洗涤、干燥和柱层析分离。
3.根据权利要求2所述的一种α-卤代三氟甲基取代烷烃的制备方法,其特征在于,
淬灭:使用硫代硫酸钠水溶液进行淬灭;
萃取:使用乙酸乙酯作为萃取剂;
洗涤:采用饱和食盐水洗涤;
干燥:使用无水硫酸镁干燥;
柱层析分离:300-400目硅胶层析柱,洗脱液为体积比10比1的石油醚与乙酸乙酯的混合液。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010163061.5A CN111303089B (zh) | 2020-03-10 | 2020-03-10 | 一种α-卤代三氟甲基取代烷烃的制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010163061.5A CN111303089B (zh) | 2020-03-10 | 2020-03-10 | 一种α-卤代三氟甲基取代烷烃的制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN111303089A CN111303089A (zh) | 2020-06-19 |
CN111303089B true CN111303089B (zh) | 2022-04-26 |
Family
ID=71151573
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010163061.5A Expired - Fee Related CN111303089B (zh) | 2020-03-10 | 2020-03-10 | 一种α-卤代三氟甲基取代烷烃的制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111303089B (zh) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108640808A (zh) * | 2018-04-28 | 2018-10-12 | 河北工业大学 | 一种邻位三氟甲基取代的叠氮化合物制备方法 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105503688B (zh) * | 2016-01-07 | 2018-03-13 | 武汉大学 | 一种烯烃的卤化三氟甲基化反应的方法 |
CN106892800B (zh) * | 2016-02-19 | 2020-08-28 | 湖北工程学院 | 一种未活化烯烃氢三氟甲基化的制备方法及应用 |
CN109320489A (zh) * | 2018-10-08 | 2019-02-12 | 信阳师范学院 | 一种色烷类化合物及其制备方法 |
CN109972165B (zh) * | 2019-01-17 | 2020-07-17 | 五邑大学 | 一种β-三氟甲基酰胺类化合物的电化学制备方法 |
-
2020
- 2020-03-10 CN CN202010163061.5A patent/CN111303089B/zh not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108640808A (zh) * | 2018-04-28 | 2018-10-12 | 河北工业大学 | 一种邻位三氟甲基取代的叠氮化合物制备方法 |
Non-Patent Citations (2)
Title |
---|
Anodically Coupled Electrolysis for the Heterodifunctionalization of Alkenes;Ke-Yin Ye 等;《J.Am.Chem.Soc.》;20180206;第140卷;第2438-2441页 * |
Mn(OAc)3-Mediated Addition Reactions of NaSO2CF3 and Perhalogenated Carboxylic Acids with Unactivated Alkenes Conjectured by a Single Electron Transfer and Halogen Abstraction Mechanism;Hui Sun 等;《J.Org.Chem.》;20201117;第85卷;第15241-15255页 * |
Also Published As
Publication number | Publication date |
---|---|
CN111303089A (zh) | 2020-06-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4435586A (en) | Etherification process for hexitols and anhydrohexitols | |
CN111269074A (zh) | 一种α-卤代三氟甲基取代烷烃的制备方法 | |
CN110041235A (zh) | 一种n-苯基-n-对甲苯磺酰基三氟乙酰胺及应用 | |
CN111303089B (zh) | 一种α-卤代三氟甲基取代烷烃的制备方法 | |
CN109734571B (zh) | α-F-β-OH-羰基化合物的合成方法 | |
CN111662147B (zh) | 制备二炔及其类似物的方法 | |
CN113816837A (zh) | 一种4,4`-二甲氧基三苯基氯甲烷的合成方法 | |
CN107628926B (zh) | 一种单氟乙基取代芳香化合物的制备方法 | |
CN109265385B (zh) | 一种手性催化剂的合成工艺 | |
CN111320664B (zh) | 一种24-胆烯烯酸乙酯的制备方法 | |
CN108659028B (zh) | 一种(z)式氟烷基化烯基硼酸酯及其制备方法和应用 | |
CN112194559A (zh) | 一种手性及非手性2,2’-二卤代联芳基化合物的合成方法 | |
CN111269114A (zh) | 草地贪夜蛾性信息素活性成分的合成方法 | |
CN110015946B (zh) | 一种1,5-二芳基-4-戊烯-1-醇化合物的制备方法 | |
CN108586209A (zh) | 一种1,2-二(2-(2,6-二甲基苯氧基)乙氧基)乙烷的合成方法 | |
CN113072448B (zh) | 一种芳基吉非罗齐衍生物高价碘化合物及其制备方法 | |
CN111732508B (zh) | 一种螺环化合物的合成方法 | |
CN113800998B (zh) | 一种(2-溴乙炔基)苯类化合物的制备方法 | |
CN115626861B (zh) | 合成三氟甲基芳香化合物的方法 | |
CN111848552B (zh) | 一种3-(取代苯基)氧杂环丁烷-3-羧酸及其中间体的制备方法及应用 | |
CN104418707B (zh) | 一种天然产物补骨脂酚及其对映体的不对称合成方法 | |
CN1332930C (zh) | 制备乙氰菊酯前体的方法 | |
WO2001083419A1 (fr) | Procede de preparation de cetones alicycliques et d'esters alicycliques substitues par alkyle | |
JPH03112940A (ja) | (±)―4―ホルミル―α―アルキルベンジルアルコール類の製造方法 | |
CN115819207A (zh) | 镍催化合成1,1-二取代联烯的方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20220426 |