CN106866508B - A kind of method that catalysis oxidation heteroaromatic primary alconol prepares heteroaromatic aldehyde - Google Patents
A kind of method that catalysis oxidation heteroaromatic primary alconol prepares heteroaromatic aldehyde Download PDFInfo
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- CN106866508B CN106866508B CN201710037086.9A CN201710037086A CN106866508B CN 106866508 B CN106866508 B CN 106866508B CN 201710037086 A CN201710037086 A CN 201710037086A CN 106866508 B CN106866508 B CN 106866508B
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- heteroaromatic
- primary alconol
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- aldehyde
- oxidant
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- -1 heteroaromatic aldehyde Chemical class 0.000 title claims abstract description 23
- 125000001072 heteroaryl group Chemical group 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 18
- 230000003647 oxidation Effects 0.000 title claims abstract description 16
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 230000001590 oxidative effect Effects 0.000 claims abstract description 14
- 239000007800 oxidant agent Substances 0.000 claims abstract description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 7
- SHNUBALDGXWUJI-UHFFFAOYSA-N pyridin-2-ylmethanol Chemical compound OCC1=CC=CC=N1 SHNUBALDGXWUJI-UHFFFAOYSA-N 0.000 claims description 5
- ZPHGMBGIFODUMF-UHFFFAOYSA-N thiophen-2-ylmethanol Chemical compound OCC1=CC=CS1 ZPHGMBGIFODUMF-UHFFFAOYSA-N 0.000 claims description 5
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 3
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 claims description 3
- RFFFKMOABOFIDF-UHFFFAOYSA-N Pentanenitrile Chemical compound CCCCC#N RFFFKMOABOFIDF-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- KHCWBCVTCIXCCB-UHFFFAOYSA-N methanol;piperazine Chemical compound OC.C1CNCCN1 KHCWBCVTCIXCCB-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims 1
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 claims 1
- 150000002825 nitriles Chemical class 0.000 claims 1
- 238000006467 substitution reaction Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract description 3
- 150000003254 radicals Chemical class 0.000 abstract description 3
- 239000010953 base metal Substances 0.000 abstract description 2
- 239000010970 precious metal Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000005984 hydrogenation reaction Methods 0.000 abstract 1
- 238000004817 gas chromatography Methods 0.000 description 12
- PTMBWNZJOQBTBK-UHFFFAOYSA-N pyridin-4-ylmethanol Chemical compound OCC1=CC=NC=C1 PTMBWNZJOQBTBK-UHFFFAOYSA-N 0.000 description 12
- 238000005070 sampling Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 238000010792 warming Methods 0.000 description 12
- WDVDHJLKXYCOFS-UHFFFAOYSA-N (5-bromopyridin-3-yl)methanol Chemical compound OCC1=CN=CC(Br)=C1 WDVDHJLKXYCOFS-UHFFFAOYSA-N 0.000 description 6
- MVQVNTPHUGQQHK-UHFFFAOYSA-N 3-pyridinemethanol Chemical compound OCC1=CC=CN=C1 MVQVNTPHUGQQHK-UHFFFAOYSA-N 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 4
- KBCDOXSSYLFMHH-UHFFFAOYSA-N (3,5-dimethyl-4-nitropyridin-2-yl)methanol Chemical compound CC1=CN=C(CO)C(C)=C1[N+]([O-])=O KBCDOXSSYLFMHH-UHFFFAOYSA-N 0.000 description 2
- HYOBIUULDPLKIE-UHFFFAOYSA-N (5-methylpyridin-2-yl)methanol Chemical compound CC1=CC=C(CO)N=C1 HYOBIUULDPLKIE-UHFFFAOYSA-N 0.000 description 2
- CSDSSGBPEUDDEE-UHFFFAOYSA-N 2-formylpyridine Chemical compound O=CC1=CC=CC=N1 CSDSSGBPEUDDEE-UHFFFAOYSA-N 0.000 description 2
- NGUVGKAEOFPLDT-UHFFFAOYSA-N 5-bromopyridine-3-carbaldehyde Chemical compound BrC1=CN=CC(C=O)=C1 NGUVGKAEOFPLDT-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- VYPMWCUNCNMNOM-UHFFFAOYSA-N [2-(methylamino)pyridin-3-yl]methanol Chemical compound CNC1=NC=CC=C1CO VYPMWCUNCNMNOM-UHFFFAOYSA-N 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 230000002363 herbicidal effect Effects 0.000 description 2
- 239000004009 herbicide Substances 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- BGUWFUQJCDRPTL-UHFFFAOYSA-N pyridine-4-carbaldehyde Chemical compound O=CC1=CC=NC=C1 BGUWFUQJCDRPTL-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- KGJJYDKVEPQIKZ-UHFFFAOYSA-N (3-bromopyridin-4-yl)boronic acid Chemical compound OB(O)C1=CC=NC=C1Br KGJJYDKVEPQIKZ-UHFFFAOYSA-N 0.000 description 1
- WFOFAXCPKAZLRV-UHFFFAOYSA-N 3,5-dimethyl-4-nitropyridine-2-carbaldehyde Chemical compound CC1=CN=C(C=O)C(C)=C1[N+]([O-])=O WFOFAXCPKAZLRV-UHFFFAOYSA-N 0.000 description 1
- RBIGKSZIQCTIJF-UHFFFAOYSA-N 3-formylthiophene Chemical compound O=CC=1C=CSC=1 RBIGKSZIQCTIJF-UHFFFAOYSA-N 0.000 description 1
- SARODJOLCPBJHK-UHFFFAOYSA-N 5-methylpyridine-2-carbaldehyde Chemical compound CC1=CC=C(C=O)N=C1 SARODJOLCPBJHK-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
- 239000003810 Jones reagent Substances 0.000 description 1
- GOPYZMJAIPBUGX-UHFFFAOYSA-N [O-2].[O-2].[Mn+4] Chemical class [O-2].[O-2].[Mn+4] GOPYZMJAIPBUGX-UHFFFAOYSA-N 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 239000003098 androgen Substances 0.000 description 1
- 230000036436 anti-hiv Effects 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- NKLCNNUWBJBICK-UHFFFAOYSA-N dess–martin periodinane Chemical compound C1=CC=C2I(OC(=O)C)(OC(C)=O)(OC(C)=O)OC(=O)C2=C1 NKLCNNUWBJBICK-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- CNUDBTRUORMMPA-UHFFFAOYSA-N formylthiophene Chemical compound O=CC1=CC=CS1 CNUDBTRUORMMPA-UHFFFAOYSA-N 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 239000004030 hiv protease inhibitor Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- XWINCPYLXQTPQV-UHFFFAOYSA-N piperazine Chemical compound C1CNCCN1.C1CNCCN1 XWINCPYLXQTPQV-UHFFFAOYSA-N 0.000 description 1
- 239000005648 plant growth regulator Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- QJZUKDFHGGYHMC-UHFFFAOYSA-N pyridine-3-carbaldehyde Chemical compound O=CC1=CC=CN=C1 QJZUKDFHGGYHMC-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Substances [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- C07D213/02—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
- 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
- C07D213/24—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 with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
- C07D213/46—Oxygen atoms
- C07D213/48—Aldehydo radicals
-
- 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
- C07D213/02—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
- 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
- C07D213/60—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 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
- C07D213/61—Halogen atoms or nitro radicals
-
- 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
- C07D213/02—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
- 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
- C07D213/60—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 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
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/68—One oxygen atom attached in position 4
-
- 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
- C07D213/02—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
- 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
- C07D213/60—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 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
- C07D213/72—Nitrogen atoms
- C07D213/74—Amino or imino radicals substituted by hydrocarbon or substituted hydrocarbon radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
- C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D241/14—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having 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
- C07D241/16—Halogen atoms; Nitro radicals
-
- 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
- C07D333/22—Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
Abstract
The present invention provides a kind of methods that catalysis oxidation heteroaromatic primary alconol prepares corresponding heteroaromatic aldehyde.This method is using nitric acid vanadium acyl as catalyst, using air as oxidant, in atmospheric conditions by heteroaromatic primary alconol it is highly selective be oxidized to heteroaromatic aldehyde.This method oxidization-hydrogenation ratio is high, and by-product is water, green economy environmental protection；Reaction condition is mild, easy to operate.The catalyst system is oxidant using air, and using base metal as catalyst, reaction condition is mild, and oxidation efficiency is high, and green economy can be by heteroaromatic primary alconol efficient catalytic selective oxidation at corresponding heteroaromatic aldehyde.Compared with precious metal catalyst system and catalyst system containing NO free radical, the catalyst system oxidation reaction is low in cost, has very high application value.
Description
Technical field
The present invention relates to a kind of methods for preparing heteroaromatic aldehyde.It is catalyzed specifically related to one kind by oxygen source of molecular oxygen
The method that selective oxidation heteroaromatic primary alconol prepares corresponding heteroaromatic aldehyde.
Background technique
Heteroaromatic aldehyde compound is a kind of important organic chemical industry's intermediate, is had in Fine Chemical important
Using.Such as 2- pyridine carboxaldehyde can be used as the raw material of synthesis anti-HIV protease inhibitors, 3- thiophenecarboxaldehyde is as important medicine
Intermediate is for synthesizing fungicide, androgen inhibitors, herbicide, herbicide, plant growth regulator etc..Selective oxidation is miscellaneous
Aromatic cyclophane is the important method for preparing corresponding heteroaromatic aldehyde compound.Tradition uses the side of stoichiometric oxidant
Method, such as such as Sarrett reagent, Jones reagent, activated manganese dioxide, Dess-Martin reagent, although can be in high yield
The oxidation of realization heteroaromatic alcohol convert corresponding heteroaromatic aldehyde, but oxidation process can generate harmful waste residue, pollute environment.Make
When with oxygen being oxidant, the by-product that oxidation process generates is only water, environmentally protective (Green Chem., 2012,14,547-
564), exploitation has important application value and prospect using the efficiently catalyzing and oxidizing system that oxygen is oxygen source.But pyridine, piperazine
Piperazine, thiophene contain N, S hetero atom, and strong complexing easily inactivates metallic catalyst, heterocyclic aromatic compounds selective oxidation
It is very challenging.Such as the catalyst system based on noble metal Ru can efficiently catalyzing and oxidizing be free of heteroatomic benzylalcohol, rouge
Fat alcohol compound, but encounter the heterocyclic compound containing N, S and be easy inactivation, the practicality is very restricted
(J.Am.Chem.Soc.2001,123,6826-6833)；Catalyst system using NO free radical as key component show compared with
High catalytic activity, wherein using 2,2,6,6-tetramethylpiperidine nitroxide as representative.Such as Chinese patent CN1796349A,
CN1789225A reports NaNO respectively2/Br2/ TEMPO, NaNO2This kind of catalyst system of/HCl/TEMPO all uses TEMPO, but
TEMPO class compound is expensive.Develop one kind and use air as oxidant, and do not use noble metal, can low temperature,
Efficiently catalyzing and oxidizing heteroaromatic primary alconol prepares the new technology of corresponding heteroaromatic aldehyde under condition of normal pressure, has great importance
And application background.
Summary of the invention
The purpose of the present invention is to provide one kind to prepare phase by oxygen source catalytic selective oxidation heteroaromatic primary alconol of molecular oxygen
The oxidant of the method for answering heteroaromatic aldehyde, the method is air or oxygen, and catalyst is cheap and easy to get, and catalytic activity is high, reaction
Mild condition, by-product are few.
A kind of method that catalysis oxidation heteroaromatic primary alconol prepares heteroaromatic aldehyde, steps are as follows:
Heteroaromatic primary alconol, catalyst, oxidant are mixed with solvent, under normal pressure, reaction temperature is 20-120 DEG C, instead
It is 1-30 hours between seasonable, obtains corresponding heteroaromatic aldehyde；
The heteroaromatic primary alconol is pyridinemethanol, piperazine methanol or thenyl alcohol containing substituent group:
R1、R2、R3And R4For hydrogen, alkyl, phenyl ,-F ,-Cl ,-Br ,-NO2, methoxyl group, ethyoxyl, amino or acetyl ammonia
Base, R1、R2、R3And R4It is identical or different；
In heteroaromatic primary alconol molecule on heterocycle containing substituent group, substituting group position is one of ortho position, meta position, contraposition
Or it is two or more, substituent group type is one or more, and the number of substituent group is one or more.
The catalyst is nitric acid vanadium acyl, and the dosage of nitric acid vanadium acyl is the 0.5-20mol%, preferably 1- of heteroaromatic primary alconol
10mol%；When catalyst amount increases, complete transformation time shortens, but cost improves.
The oxidant is air or oxygen；
The solvent is mixed for one or more of acetonitrile, propionitrile, isobutyronitrile, valeronitrile, diethylamine, triethylamine
It closes, the solvent usage is the 50-300wt% of heteroaromatic primary alconol.
Beneficial effects of the present invention: the catalyst system is oxidant using air, using base metal as catalyst, reaction
Mild condition, oxidation efficiency is high, and green economy can be by heteroaromatic primary alconol efficient catalytic selective oxidation at corresponding heteroaromatic
Aldehyde.Compared with precious metal catalyst system and catalyst system containing NO free radical, the catalyst system oxidation reaction is low in cost,
With very high application value.
Specific embodiment
A specific embodiment of the invention is further illustrated below in conjunction with technical solution.
Embodiment 1
By 1.09g 4- pyridinemethanol, it is anti-to be added to 50mL for 2mol% nitric acid vanadium acyl (relative to substrate 4- pyridinemethanol)
5mL isobutyronitrile is added in Ying Guanzhong, is filled with air balls, closes and finishes reaction tube, 80 DEG C is warming up under stirring, and keep 2h, wait react
Terminate, is cooled to room temperature.Sampling is analyzed using gas-chromatography, the conversion ratio 96.5% of 4- pyridinemethanol, 4- pyridine carboxaldehyde
Selectivity be greater than 99%.
Embodiment 2
By 10g 4- pyridinemethanol, 1mol% nitric acid vanadium acyl (relative to substrate 4- pyridinemethanol) is added to 250mL reaction
20mL isobutyronitrile is added in Guan Zhong, is filled with air balls, closes and finishes reaction tube, 100 DEG C is warming up under stirring, and keep 30h, wait react
Terminate, is cooled to room temperature.Sampling is analyzed using gas-chromatography, the conversion ratio 99.2% of 4- pyridinemethanol, 4- pyridine carboxaldehyde
Selectivity be greater than 99%.
Embodiment 3
By 1.14g 2- thenyl alcohol, 0.5mol% nitric acid vanadium acyl (relative to substrate 2- thenyl alcohol) is added to 50mL
In reaction tube, 5mL acetonitrile is added, is filled with air balls, closes and finishes reaction tube, 80 DEG C are warming up under stirring, and keep 30h, wait react
Terminate, is cooled to room temperature.Sampling is analyzed using gas-chromatography, the conversion ratio 98.5% of 2- thenyl alcohol, 2 thiophene carboxaldehyde
Selectivity be greater than 99%.
Embodiment 4
By the chloro- 2- pyrazine methanol of 1.44g 3-, 2mol% nitric acid vanadium acyl (relative to the chloro- 2- pyrazine methanol of substrate 3-) adds
Enter into 50mL reaction tube, 5mL acetonitrile is added, be filled with air balls, closes and finish reaction tube, 40 DEG C are warming up under stirring, and keep
10h is cooled to room temperature to the end of reacting.Sampling is analyzed using gas-chromatography, the conversion ratio of the chloro- 2- pyrazine methanol of 3-
The selectivity of the chloro- 2- pyrazine formaldehyde of 96.1%, 3- is greater than 99%.
Embodiment 5
By 1.88g 3- bromopyridine -5- methanol, 5mol% nitric acid vanadium acyl (relative to substrate 3- bromopyridine -5- methanol) adds
Enter into 50mL reaction tube, 5mL triethylamine is added, be filled with air balls, closes and finish reaction tube, 90 DEG C are warming up under stirring, and keep
5h is cooled to room temperature to the end of reacting.Sampling is analyzed using gas-chromatography, the conversion ratio of 3- bromopyridine -5- methanol
The selectivity of 99.8%, 3- bromopyridine -5- formaldehyde is greater than 99%.
Embodiment 6
By 1.88g 3- bromopyridine -5- methanol, 5mol% nitric acid vanadium acyl (relative to substrate 3- bromopyridine -5- methanol) adds
Enter into 50mL reaction tube, 5mL acetonitrile be added, be filled with air balls, closes and finish reaction tube, 80 DEG C are warming up under stirring, and keep 8h,
To the end of reacting, it is cooled to room temperature.Sampling is analyzed using gas-chromatography, the conversion ratio 99.3% of 3- bromopyridine -5- methanol,
The selectivity of 3- bromopyridine -5- formaldehyde is greater than 99%.
Embodiment 7
By 1.09g 2- pyridinemethanol, 1mol% nitric acid vanadium acyl (relative to 2- pyridinemethanol) is added to 50mL reaction tube
In, 5mL acetonitrile is added, is filled with air balls, closes and finishes reaction tube, 80 DEG C are warming up under stirring, and keep 6h, it is cold to the end of reacting
But to room temperature.Sampling is analyzed using gas-chromatography, the conversion ratio 98.2% of 2- pyridinemethanol, the selectivity of 2- pyridine carboxaldehyde
Greater than 99%.
Embodiment 8
By 1.09g 3- pyridinemethanol, 1mol% nitric acid vanadium acyl (relative to 3- pyridinemethanol) is added to 50mL reaction tube
In, 10mL isobutyronitrile is added, is filled with air balls, closes and finishes reaction tube, 100 DEG C are warming up under stirring, and keep 10h, wait react knot
Beam is cooled to room temperature.Sampling is analyzed using gas-chromatography, the conversion ratio 99.0% of 3- pyridinemethanol, 3- pyridine carboxaldehyde
Selectivity is greater than 99%.
Embodiment 9
By 1.23g5- picoline -2- methanol, 2mol% nitric acid vanadium acyl (relative to 5- picoline -2- methanol) is added
Into 50mL reaction tube, 5mL diethylamine is added, is filled with air balls, closes and finishes reaction tube, 50 DEG C are warming up under stirring, and keep 6h,
To the end of reacting, it is cooled to room temperature.Sampling is analyzed using gas-chromatography, the conversion ratio of 5- picoline -2- methanol
The selectivity of 95.2%, 5- picoline -2- formaldehyde is greater than 99%.
Embodiment 10
By 1.38g 2- methylamino -3- pyridinemethanol, 5mol% nitric acid vanadium acyl is (relative to 2- methylamino -3- pyridine first
Alcohol), it is added in 50mL reaction tube, 10mL triethylamine is added, be filled with air balls, close and finish reaction tube, 80 DEG C are warming up under stirring,
And 5h is kept, to the end of reacting, it is cooled to room temperature.Sampling is analyzed using gas-chromatography, 2- methylamino -3- pyridinemethanol
The selectivity of conversion ratio 97.2%, 2- methylamino -3- pyridine carboxaldehyde is greater than 99%.
Embodiment 11
By 1.82g 3,5- dimethyl -4- nitropyridine -2- methanol, 5mol% nitric acid vanadium acyl is (relative to 3,5- dimethyl -
4- nitropyridine -2- methanol), it is added in 50mL reaction tube, 5mL acetonitrile is added, be filled with air balls, close and finish reaction tube, stirring
Under be warming up to 80 DEG C, and keep 6h, to the end of reacting, be cooled to room temperature.Sampling is analyzed using gas-chromatography, 3,5- diformazans
The selectivity of the conversion ratio 98.9% of base -4- nitropyridine -2- methanol, 3,5- dimethyl -4- nitropyridine -2- formaldehyde is greater than
99%.
Embodiment 12
By 1.67g 4- methoxyl group -3,5- dimethyl -2- pyridinemethanol, 5mol% nitric acid vanadium acyl is (relative to 4- methoxyl group -
3,5- dimethyl -2- pyridinemethanols), it is added in 50mL reaction tube, 5mL isobutyronitrile is added, be filled with air balls, close Bi Fanying
Pipe, is warming up to 100 DEG C, and keep 6h, to the end of reacting, is cooled to room temperature under stirring.Sampling is analyzed using gas-chromatography,
The conversion ratio 99.5% of 4- methoxyl group -3,5- dimethyl -2- pyridinemethanol, 4- methoxyl group -3,5- dimethyl -2- pyridine carboxaldehyde
Selectivity is greater than 99%.
Claims (5)
1. a kind of method that catalysis oxidation heteroaromatic primary alconol prepares heteroaromatic aldehyde, which is characterized in that steps are as follows:
Heteroaromatic primary alconol, catalyst, oxidant are mixed with solvent, under normal pressure, reaction temperature is 20-120 DEG C, when reaction
Between be 1-30 hours, obtain corresponding heteroaromatic aldehyde；
The heteroaromatic primary alconol is pyridinemethanol, piperazine methanol or thenyl alcohol containing substituent group:
R1、R2、R3And R4For hydrogen, alkyl, phenyl ,-F ,-Cl ,-Br ,-NO2, methoxyl group, ethyoxyl, amino or acetylamino, R1、
R2、R3And R4It is identical or different；
The catalyst is nitric acid vanadium acyl, and the dosage of nitric acid vanadium acyl is the 0.5-20mol% of heteroaromatic primary alconol；
The oxidant is air or oxygen；
The solvent usage is the 50-300wt% of heteroaromatic primary alconol.
2. the method according to claim 1, wherein in heteroaromatic primary alconol molecule on heterocycle containing substituent group,
Substituting group position is one or more of ortho position, meta position, contraposition, and substituent group type is one or more kinds of, substitution
The number of base is one or more.
3. method according to claim 1 or 2, which is characterized in that the dosage of the catalyst is heteroaromatic primary alconol
1-10mol%.
4. method according to claim 1 or 2, which is characterized in that the solvent is acetonitrile, propionitrile, isobutyronitrile, penta
The mixing of one or more of nitrile, diethylamine, triethylamine.
5. according to the method described in claim 3, it is characterized in that, the solvent is acetonitrile, propionitrile, isobutyronitrile, valeronitrile, two
The mixing of one or more of ethamine, triethylamine.
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| Complexes ofcis-dioxomolybdenum(VI) and oxovanadium(IV) with a tridentate ONS donor ligand: Synthesis, spectroscopic properties,X-ray crystal structure and catalytic activity;Ahmed M. Fayed，et al.;《Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy》;20141231;第129卷;第293-302页 |
| Novel oxovanadium(IV) complexes with 4-acylpyrazolone ligands: synthesis, crystal structure and catalytic activity towards the oxidation of benzylic alcohols;Sanjay Parihar，et al.;《RSC Advances》;20141231;第2014卷(第4期);第10295-10302页 |
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