CN113831216A - 一种以醛类化合物为原料制备单氟代烯烃的合成方法 - Google Patents
一种以醛类化合物为原料制备单氟代烯烃的合成方法 Download PDFInfo
- Publication number
- CN113831216A CN113831216A CN202111219330.6A CN202111219330A CN113831216A CN 113831216 A CN113831216 A CN 113831216A CN 202111219330 A CN202111219330 A CN 202111219330A CN 113831216 A CN113831216 A CN 113831216A
- Authority
- CN
- China
- Prior art keywords
- preparing
- monofluoroalkene
- reaction
- taken
- amount
- 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.)
- Granted
Links
- -1 aldehyde compound Chemical class 0.000 title claims abstract description 20
- 239000002994 raw material Substances 0.000 title claims abstract description 15
- 238000010189 synthetic method Methods 0.000 title claims abstract description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims abstract description 12
- TYCFGHUTYSLISP-UHFFFAOYSA-N 2-fluoroprop-2-enoic acid Chemical compound OC(=O)C(F)=C TYCFGHUTYSLISP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 7
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- 239000007800 oxidant agent Substances 0.000 claims abstract description 4
- 230000001590 oxidative effect Effects 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 30
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 150000001336 alkenes Chemical class 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 3
- 238000004519 manufacturing process Methods 0.000 claims 3
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 21
- 238000001228 spectrum Methods 0.000 description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- 229910052731 fluorine Inorganic materials 0.000 description 10
- 239000011737 fluorine Substances 0.000 description 10
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 9
- KVFDZFBHBWTVID-UHFFFAOYSA-N cyclohexanecarbaldehyde Chemical compound O=CC1CCCCC1 KVFDZFBHBWTVID-UHFFFAOYSA-N 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 238000005859 coupling reaction Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 239000003480 eluent Substances 0.000 description 4
- QDPMQZGIASGJAP-UHFFFAOYSA-N 3-(3,4-dimethoxyphenyl)-2-fluoroprop-2-enoic acid Chemical compound COC1=CC=C(C=C(F)C(O)=O)C=C1OC QDPMQZGIASGJAP-UHFFFAOYSA-N 0.000 description 3
- 239000007818 Grignard reagent Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- FTZILAQGHINQQR-UHFFFAOYSA-N 2-Methylpentanal Chemical compound CCCC(C)C=O FTZILAQGHINQQR-UHFFFAOYSA-N 0.000 description 2
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 150000001350 alkyl halides Chemical class 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005262 decarbonization Methods 0.000 description 2
- 238000006114 decarboxylation reaction Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- JRTIUDXYIUKIIE-KZUMESAESA-N (1z,5z)-cycloocta-1,5-diene;nickel Chemical compound [Ni].C\1C\C=C/CC\C=C/1.C\1C\C=C/CC\C=C/1 JRTIUDXYIUKIIE-KZUMESAESA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- GPCDGGKVBPVZCT-UHFFFAOYSA-N 1,1-difluorocyclopropane Chemical compound FC1(F)CC1 GPCDGGKVBPVZCT-UHFFFAOYSA-N 0.000 description 1
- ORIJMCDIKDQQCW-UHFFFAOYSA-N 2-fluoro-3-(3-iodophenyl)prop-2-enoic acid Chemical compound OC(=O)C(F)=Cc1cccc(I)c1 ORIJMCDIKDQQCW-UHFFFAOYSA-N 0.000 description 1
- NOJXPGXFDASWEI-UHFFFAOYSA-N 3-ethylsulfanylprop-1-ene Chemical compound CCSCC=C NOJXPGXFDASWEI-UHFFFAOYSA-N 0.000 description 1
- GAGWJHPBXLXJQN-UORFTKCHSA-N Capecitabine Chemical compound C1=C(F)C(NC(=O)OCCCCC)=NC(=O)N1[C@H]1[C@H](O)[C@H](O)[C@@H](C)O1 GAGWJHPBXLXJQN-UORFTKCHSA-N 0.000 description 1
- GAGWJHPBXLXJQN-UHFFFAOYSA-N Capecitabine Natural products C1=C(F)C(NC(=O)OCCCCC)=NC(=O)N1C1C(O)C(O)C(C)O1 GAGWJHPBXLXJQN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 101710160107 Outer membrane protein A Proteins 0.000 description 1
- 102000034527 Retinoid X Receptors Human genes 0.000 description 1
- 108010038912 Retinoid X Receptors Proteins 0.000 description 1
- 229940127395 Ribonucleotide Reductase Inhibitors Drugs 0.000 description 1
- 210000001744 T-lymphocyte Anatomy 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000005599 alkyl carboxylate group Chemical group 0.000 description 1
- 239000002246 antineoplastic agent Substances 0.000 description 1
- 229940041181 antineoplastic drug Drugs 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 229960004117 capecitabine Drugs 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000006606 decarbonylation reaction Methods 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 238000005796 dehydrofluorination reaction Methods 0.000 description 1
- 238000007876 drug discovery Methods 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- 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
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/26—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids
- C07C303/30—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids by reactions not involving the formation of esterified sulfo groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
-
- 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
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
- C07D307/79—Benzo [b] furans; Hydrogenated benzo [b] furans with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D309/04—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/10—1,4-Dioxanes; Hydrogenated 1,4-dioxanes
- C07D319/14—1,4-Dioxanes; Hydrogenated 1,4-dioxanes condensed with carbocyclic rings or ring systems
- C07D319/16—1,4-Dioxanes; Hydrogenated 1,4-dioxanes condensed with carbocyclic rings or ring systems condensed with one six-membered ring
- C07D319/18—Ethylenedioxybenzenes, not substituted on the hetero ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/12—Radicals substituted by halogen atoms or nitro or nitroso radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J1/00—Normal steroids containing carbon, hydrogen, halogen or oxygen, not substituted in position 17 beta by a carbon atom, e.g. estrane, androstane
- C07J1/0051—Estrane derivatives
- C07J1/0059—Estrane derivatives substituted in position 17 by a keto group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明属于有机合成领域，公开了一种以醛类化合物为原料制备单氟代烯烃的合成方法，以氟代丙烯酸与醛类物质为原料，乙酸亚铁为催化剂、二叔丁基过氧化物为氧化剂，氯苯为溶剂，在110℃下反应16小时，得到具有Z构型单氟代烯烃化合物，该方法原料来源易得，价格便宜，产物选择性高，操作简单，无需使用危险的化学药品，方法经济、成本低，合成应用价值高。
Description
技术领域
本发明涉及化合物制备，属于有机合成领域。具体涉及以醛类化合物为原料制备单氟代烯烃的合成方法。
背景技术
单氟代烯烃是一类重要的有机化合物，广泛存在于各类生物活性分子和药物分子中，具有广泛的应用潜力。其是酰胺键的电子等排体，因此在药物发现和材料科学上有重要的应用价值。如核苷酸还原酶抑制剂、视黄醛X受体调节器、T细胞表面抗原抑制剂和抗肿瘤药物卡培他滨(式1)等都存在单氟代烯烃结构片段。因此单氟代烯烃的合成是有机合成的重要研究领域。
式1.含有单氟代烯烃的活性药物分子
合成单氟代烯烃可以通过二氟环丙烷的开环偶联反应、消除反应等。其中应用最多的是谐二氟烯烃脱氟偶联反应。如Cao Song课题组报道的谐二氟烯烃与烷基格氏试剂反应(Org.Lett.2016，18，4284-4287)，构建单氟代烯烃。然而格氏试剂活性高，官能团兼容性差(式2)。
式2.谐二氟烯烃与烷基格氏试剂反应
近来Fu Yao课题组报道了谐二氟烯烃与烷基卤化物的偶联反应，用于构建单氟代烯烃(式3)，该反应需要使用昂贵的双-(1，5-环辛二烯)镍为催化剂，当量的联硼酸频那醇酯作为还原剂，而外添加碱性很强的磷酸钾作为反应的碱(J.Am.Chem.Soc.2017，139，12632-12637)。
式3.谐二氟烯烃与烷基卤化物反应
近来谐二氟烯烃与烷基羧酸的偶联反应构建谐二氟烯烃的方法也被报道(式4，Org.Lett.2018，20，4579-4583)。但该反应需要使用三个当量的锌粉，然而锌粉是管制药品，活性高，与水、酸类或碱金属氢氧化物接触能放出易燃的氢气。与氧化剂反应会引起燃烧或爆炸。粉末与空气能形成爆炸性混合物。
式4.谐二氟烯烃与烷基羧酸酯的反应
Fu和Li组实现了光催化谐二氟烯烃与烷基羧酸的脱羧偶联，但该反应底物类型有限对于单芳基底物产物反应选择性低，得到了顺、反烯烃混合物，产物分离困难(式5，Org.Chem.Front.2019，6，2365；Chem.Commun.2017，53，10299)。
式5.谐二氟烯烃与烷基羧酸的反应
醛类化合物是丰富、廉价、易得的有机原料，且广泛用于香料行业。以醛类化合物为原料，通过脱羰反应直接构建单氟代烯烃有着重要的应用价值，且该类反应未见报道。因此发展新颖的可用于与醛类化合物为原料的脱碳反应构建单氟代烯烃的方法有着重要的意义。
发明内容
本发明针对醛类化合物为原料，未实现脱碳反应用于构建单氟代烯烃，发明了以氟代丙烯酸为原料与醛类的脱羧、脱羰反应，可以高效的合成单氟代烯烃。
为解决上述技术问题，本发明采用如下技术方案：一种以醛类化合物为原料制备单氟代烯烃的合成方法，其特征在于：以氟代丙烯酸与烷基醛为原料，乙酸亚铁为催化剂、二叔丁基过氧化物(DTBP)为氧化剂，氯苯为溶剂按下述反应式在110℃下反应16小时，得到具有通式(I)的Z构型单氟代烯烃化合物，该方法原料来源易得，产物选择性高，操作简单，无需使用危险的化学药品，合成应用价值高。
其中R1为芳基或者烯基取代基；R2，R3为烷基取代基；
优选地，乙酸亚铁的量为氟代丙烯酸的物质的量的10％；
优选地，烷基醛的物质的量为氟代丙烯酸的物质的量的3倍；
优选地，二叔丁基过氧化物的物质的量为氟代丙烯酸的物质的量的3倍；
该方法提供了一种原料廉价易得、操作简单、无需使用危险化学试剂的合成单氟代烯烃的合成方法。该方法产物顺反异构体比例高。为单氟代烯烃提供了高效、便捷、经济的合成方法。
具体实施方式
下面通过具体实施方式对本发明的技术方案进行做进一步说明：
实施例1，该实施例的反应式如下所示：
(1)在空气下，α-氟代肉桂酸(0.2mmol)，Fe(OAc)2(10mol％)和一个磁子加入到带支管的反应管中，抽充氩气三次，加入1mL氯苯，环己烷甲醛(0.6mmol)和二叔丁基过氧化物(0.6mmol)，在110℃下反应16小时；
(2)将步骤(1)中所得物料加入乙酸乙酯充分混合，用短硅胶柱柱层析，洗脱剂为石油醚，分离收率为80％，产物纯度100％。
实施例2
该实施例的反应式如下所示：
(1)在空气下，α-氟代-3-碘肉桂酸(0.2mmol)，Fe(OAc)2(10mol％)和一个磁子加入到带支管的反应管中，抽充氩气三次，加入1mL氯苯，环己烷甲醛(0.6mmol)和二叔丁基过氧化物(0.6mmol)，在110℃下反应16小时；
(2)将步骤(1)中所得物料加入乙酸乙酯充分混合，用短硅胶柱柱层析，洗脱剂为石油醚，分离收率为77％，产物纯度100％。
实施例3
该实施例的反应式如下所示：
(1)在空气下，α-氟代-3，4-二甲氧基肉桂酸(0.2mmol)，Fe(OAc)2(10mol％)和一个磁子加入到带支管的反应管中，抽充氩气三次，加入1mL氯苯，环己烷甲醛(0.6mmol)和二叔丁基过氧化物(0.6mmol)，在110℃下反应16小时；
(2)将步骤(1)中所得物料加入乙酸乙酯充分混合，用短硅胶柱柱层析，洗脱剂为石油醚，分离收率为80％，产物纯度100％。
实施例4
该实施例的反应式如下所示：
(1)在空气下，α-氟代-3，4-二甲氧基肉桂酸(0.2mmol)，Fe(OAc)2(10mol％)和一个磁子加入到带支管的反应管中，抽充氩气三次，加入1mL氯苯，异丁醛(0.6mmol)和二叔丁基过氧化物(0.6mmol)，在110℃下反应16小时；
(2)将步骤(1)中所得物料加入乙酸乙酯充分混合，用短硅胶柱柱层析，洗脱剂为石油醚，分离收率为81％，产物纯度100％。
实施例5
该实施例的反应式如下所示：
(1)在空气下，α-氟代-3，4-二甲氧基肉桂酸(0.2mmol)，Fe(OAc)2(10mol％)和一个磁子加入到带支管的反应管中，抽充氩气三次，加入1mL氯苯，2-甲基戊醛(0.6mmol)和二叔丁基过氧化物(0.6mmol)，在110℃下反应16小时；
(2)将步骤(1)中所得物料加入乙酸乙酯充分混合，用短硅胶柱柱层析，洗脱剂为石油醚，分离收率为82％，产物纯度100％。
以上已将本发明做一详细说明，以上所述，仅为本发明之较佳实施例而已，当不能限定本申请实施范围，即凡依本申请范围所作均等变化与修饰，皆应仍属本发明涵盖范围。
以下是以此方法合成的单氟代烯烃的具体实例。
附图说明
附图1为合成的单氟代烯烃1的核磁共振氢谱图；
附图2为合成的单氟代烯烃1的核磁共振氟谱图；
附图3为合成的单氟代烯烃1的核磁共振碳谱图；
附图4为合成的单氟代烯烃2的核磁共振氢谱图；
附图5为合成的单氟代烯烃2的核磁共振氟谱图；
附图6为合成的单氟代烯烃2的核磁共振碳谱图；
附图7为合成的单氟代烯烃3的核磁共振氢谱图；
附图8为合成的单氟代烯烃3的核磁共振氟谱图；
附图9为合成的单氟代烯烃3的核磁共振碳谱图；
附图10为合成的单氟代烯烃4的核磁共振氢谱图；
附图11为合成的单氟代烯烃4的核磁共振氟谱图；
附图12为合成的单氟代烯烃4的核磁共振碳谱图；
附图13为合成的单氟代烯烃5的核磁共振氢谱图；
附图14为合成的单氟代烯烃5的核磁共振氟谱图；
附图15为合成的单氟代烯烃5的核磁共振碳谱图；
附图16为合成的单氟代烯烃21的核磁共振氢谱图；
附图17为合成的单氟代烯烃21的核磁共振氟谱图；
附图18为合成的单氟代烯烃21的核磁共振碳谱图；
附图19为合成的单氟代烯烃22的核磁共振氢谱图；
附图20为合成的单氟代烯烃22的核磁共振氟谱图；
附图21为合成的单氟代烯烃22的核磁共振碳谱图；
附图22为合成的单氟代烯烃23的核磁共振氢谱图；
附图23为合成的单氟代烯烃23的核磁共振氟谱图；
附图24为合成的单氟代烯烃23的核磁共振碳谱图；
附图25为合成的单氟代烯烃24的核磁共振氢谱图；
附图26为合成的单氟代烯烃24的核磁共振氟谱图；
附图27为合成的单氟代烯烃24的核磁共振碳谱图；
附图28为合成的单氟代烯烃25的核磁共振氢谱图；
附图29为合成的单氟代烯烃25的核磁共振氟谱图；
附图30为合成的单氟代烯烃25的核磁共振碳谱图。
Claims (4)
1.一种以醛类化合物为原料制备单氟代烯烃的合成方法，其特征在于：以氟代丙烯酸与烷基醛为原料，以乙酸亚铁为催化剂、二叔丁基过氧化物(DTBP)为氧化剂，氯苯为溶剂按下述反应式在110℃下反应16小时，得到具有通式(I)的Z构型单氟代烯烃化合物。
2.根据权利要求1所述的一种以醛类化合物为原料制备单氟代烯烃的合成方法，其特征在于：乙酸亚铁的量为氟代丙烯酸的物质的量的10％。
3.根据权利要求1所述的一种以醛类化合物为原料制备单氟代烯烃的合成方法，其特征在于：烷基醛的物质的量为氟代丙烯酸的物质的量的3倍。
4.根据权利要求1所述的一种以醛类化合物为原料制备单氟代烯烃的合成方法，其特征在于：二叔丁基过氧化物的物质的量为氟代丙烯酸的物质的量的3倍。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111219330.6A CN113831216B (zh) | 2021-10-15 | 2021-10-15 | 一种以醛类化合物为原料制备单氟代烯烃的合成方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111219330.6A CN113831216B (zh) | 2021-10-15 | 2021-10-15 | 一种以醛类化合物为原料制备单氟代烯烃的合成方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113831216A true CN113831216A (zh) | 2021-12-24 |
| CN113831216B CN113831216B (zh) | 2024-05-24 |
Family
ID=78965408
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111219330.6A Active CN113831216B (zh) | 2021-10-15 | 2021-10-15 | 一种以醛类化合物为原料制备单氟代烯烃的合成方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113831216B (zh) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101326150A (zh) * | 2005-12-13 | 2008-12-17 | 住友化学株式会社 | 制备烯烃化合物的方法 |
| CN102746076A (zh) * | 2012-07-24 | 2012-10-24 | 苏州大学 | 一种取代烯烃的制备方法 |
| CN105121392A (zh) * | 2013-04-23 | 2015-12-02 | 花王株式会社 | 烯烃的制造方法 |
| CN107501055A (zh) * | 2017-08-22 | 2017-12-22 | 中国科学技术大学 | 基于镍催化制备氟代烯烃化合物的方法 |
| CN107602320A (zh) * | 2017-10-18 | 2018-01-19 | 滁州学院 | 一种基于镍催化制备三取代烯烃的合成方法 |
| CN108658716A (zh) * | 2017-03-30 | 2018-10-16 | 清华大学 | 一种光诱导一锅法合成烯烃类化合物的方法 |
| CN109879731A (zh) * | 2019-02-27 | 2019-06-14 | 华东师范大学 | 一类二芳基甲烷卤代烯烃衍生物及制备方法 |
| CN111004094A (zh) * | 2019-12-18 | 2020-04-14 | 中山大学 | 一种顺式二芳基单氟烯烃类化合物的制备方法 |
| CN111170856A (zh) * | 2020-02-08 | 2020-05-19 | 云南民族大学 | 一种氟代烯烃的制备方法及应用 |
| WO2020242046A1 (ko) * | 2019-05-28 | 2020-12-03 | 전남대학교산학협력단 | 불소알켄화합물 전구체, 상기 전구체 합성방법 및 상기 전구체를 이용한 불소알켄화합물 제조방법 |
| JP2021014433A (ja) * | 2019-07-12 | 2021-02-12 | ダイキン工業株式会社 | フルオロオレフィン化合物の製造方法 |
-
2021
- 2021-10-15 CN CN202111219330.6A patent/CN113831216B/zh active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101326150A (zh) * | 2005-12-13 | 2008-12-17 | 住友化学株式会社 | 制备烯烃化合物的方法 |
| CN102746076A (zh) * | 2012-07-24 | 2012-10-24 | 苏州大学 | 一种取代烯烃的制备方法 |
| CN105121392A (zh) * | 2013-04-23 | 2015-12-02 | 花王株式会社 | 烯烃的制造方法 |
| CN108658716A (zh) * | 2017-03-30 | 2018-10-16 | 清华大学 | 一种光诱导一锅法合成烯烃类化合物的方法 |
| CN107501055A (zh) * | 2017-08-22 | 2017-12-22 | 中国科学技术大学 | 基于镍催化制备氟代烯烃化合物的方法 |
| CN107602320A (zh) * | 2017-10-18 | 2018-01-19 | 滁州学院 | 一种基于镍催化制备三取代烯烃的合成方法 |
| CN109879731A (zh) * | 2019-02-27 | 2019-06-14 | 华东师范大学 | 一类二芳基甲烷卤代烯烃衍生物及制备方法 |
| WO2020242046A1 (ko) * | 2019-05-28 | 2020-12-03 | 전남대학교산학협력단 | 불소알켄화합물 전구체, 상기 전구체 합성방법 및 상기 전구체를 이용한 불소알켄화합물 제조방법 |
| JP2021014433A (ja) * | 2019-07-12 | 2021-02-12 | ダイキン工業株式会社 | フルオロオレフィン化合物の製造方法 |
| CN111004094A (zh) * | 2019-12-18 | 2020-04-14 | 中山大学 | 一种顺式二芳基单氟烯烃类化合物的制备方法 |
| CN111170856A (zh) * | 2020-02-08 | 2020-05-19 | 云南民族大学 | 一种氟代烯烃的制备方法及应用 |
Non-Patent Citations (5)
| Title |
|---|
| HUAN ZHANG, 等: "Experimental and Computational Studies of the Iron-Catalyzed Selective and Controllable Defluorosilylation of Unactivated Aliphatic gem-Difluoroalkenes", ANGEWANDTE CHEMIE, vol. 60, no. 18, pages 10211 - 10218 * |
| XIAOYU LU, 等: "Iron-catalyzed decarboxylative and oxidative decarbonylative cross-coupling: a new strategy for the synthesis of monofluoroalkenes", ORGANIC CHEMISTRY FRONTIERS, vol. 09, no. 03, pages 831 - 837 * |
| 何世江, 等: "镍催化氟代烯烃硼酯与烷基卤化物Suzuki偶联反应", 化学学报, vol. 76, no. 12, pages 956 - 961 * |
| 廖富民;等: "三或四取代单氟烯烃的高立体选择性合成研究进展", 有机化学, vol. 37, no. 09, pages 2175 - 2186 * |
| 谢丽梅;等: "单氟烯烃的合成研究进展", 广东化工, vol. 47, no. 16, pages 83 - 85 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113831216B (zh) | 2024-05-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Guo et al. | Silver tungstate: a single-component bifunctional catalyst for carboxylation of terminal alkynes with CO 2 in ambient conditions | |
| Zhang et al. | Metal-free tandem oxidative C (sp 3)–H bond functionalization of alkanes and dearomatization of N-phenyl-cinnamamides: access to alkylated 1-azaspiro [4.5] decanes | |
| CN104169265B (zh) | 使用烷基乙酸铵制备5-乙酰氧基甲基糠醛的新方法 | |
| Jiang et al. | Ultrasound accelerated synthesis of O-alkylated hydroximides under solvent-and metal-free conditions | |
| CN108658717B (zh) | 一种脱羧反应制备三取代烯烃的合成方法 | |
| CN107915630B (zh) | 一种琥珀酸二酯或琥珀酸二酯衍生物的制备方法 | |
| CN116496316A (zh) | 一种氟烯基磷的合成方法 | |
| CN113831216A (zh) | 一种以醛类化合物为原料制备单氟代烯烃的合成方法 | |
| CN114716353B (zh) | 一种4-碘-2,3-二烯砜类化合物的合成方法 | |
| CN107915653B (zh) | 催化酯和胺进行反应制备酰胺的方法 | |
| Kang et al. | n-Butyllithium as a highly efficient precatalyst for cyanosilylation of aldehydes and ketones | |
| CN102060659A (zh) | 高烯丙基醇的制备方法 | |
| Masuda et al. | The formation of alkyl acetate in the reaction of trialkylborane with lead (IV) acetate or phenyliodoso acetate. | |
| CN108727179B (zh) | 一种α-烯丙基取代的α,β-不饱和酮、酯或腈化合物的合成方法 | |
| CN113773167B (zh) | 一种单氟代烯烃的合成方法 | |
| CN116253659B (zh) | 一种酰胺基烯胺类化合物及其制备方法与应用 | |
| CN114315874B (zh) | 一种制备四取代烯基硼酸酯衍生物的方法 | |
| CN102432425B (zh) | 1，3－二取代－3－芳基丙烯类化合物制备方法及应用 | |
| CN114773229B (zh) | 一种1,6二烯类化合物及其制备方法与应用 | |
| CN102659624A (zh) | 一种制备苯腈类化合物的方法 | |
| RU2678208C1 (ru) | Аддукты триаллилборанов с аммиаком и аминами в качестве аллилирующих реагентов | |
| CN110483291B (zh) | 一种(E)-β-芳基-β,γ-不饱和酯化合物的合成方法 | |
| CN111018830B (zh) | 一种多取代共轭二烯化合物及其合成方法 | |
| Jia et al. | Me3Ga-mediated alkynylation of aldehydes | |
| CN110015946B (zh) | 一种1,5-二芳基-4-戊烯-1-醇化合物的制备方法 |
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 |