CN110003061A - A kind of method of the hydrocarbon direct aminatin of methyl aromatic compound benzyl of iron catalysis - Google Patents
A kind of method of the hydrocarbon direct aminatin of methyl aromatic compound benzyl of iron catalysis Download PDFInfo
- Publication number
- CN110003061A CN110003061A CN201910371428.XA CN201910371428A CN110003061A CN 110003061 A CN110003061 A CN 110003061A CN 201910371428 A CN201910371428 A CN 201910371428A CN 110003061 A CN110003061 A CN 110003061A
- Authority
- CN
- China
- Prior art keywords
- iron
- aromatic compound
- methyl
- compound
- methyl aromatic
- 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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 19
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 15
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 12
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 12
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 12
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 11
- -1 methyl aromatic compound Chemical class 0.000 claims abstract description 29
- JRLTTZUODKEYDH-UHFFFAOYSA-N 8-methylquinoline Chemical class C1=CN=C2C(C)=CC=CC2=C1 JRLTTZUODKEYDH-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 150000002506 iron compounds Chemical class 0.000 claims abstract description 11
- 238000010898 silica gel chromatography Methods 0.000 claims abstract description 8
- 150000003939 benzylamines Chemical class 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 8
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 claims description 7
- 239000003480 eluent Substances 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 7
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 5
- 238000005576 amination reaction Methods 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 238000004440 column chromatography Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000005485 electric heating Methods 0.000 claims description 3
- 229940062993 ferrous oxalate Drugs 0.000 claims description 3
- YQJOBFVDPYXNCW-UHFFFAOYSA-N fluoroimino(diphenyl)-$l^{4}-sulfane Chemical compound C=1C=CC=CC=1S(=NF)C1=CC=CC=C1 YQJOBFVDPYXNCW-UHFFFAOYSA-N 0.000 claims description 3
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 3
- LWLURCPMVVCCCR-UHFFFAOYSA-N iron;4-methylbenzenesulfonic acid Chemical compound [Fe].CC1=CC=C(S(O)(=O)=O)C=C1 LWLURCPMVVCCCR-UHFFFAOYSA-N 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- ZBTMRBYMKUEVEU-UHFFFAOYSA-N 1-bromo-4-methylbenzene Chemical group CC1=CC=C(Br)C=C1 ZBTMRBYMKUEVEU-UHFFFAOYSA-N 0.000 claims description 2
- ZZLCFHIKESPLTH-UHFFFAOYSA-N 4-Methylbiphenyl Chemical group C1=CC(C)=CC=C1C1=CC=CC=C1 ZZLCFHIKESPLTH-UHFFFAOYSA-N 0.000 claims description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- KEHCHOCBAJSEKS-UHFFFAOYSA-N iron(2+);oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[Ti+4].[Fe+2] KEHCHOCBAJSEKS-UHFFFAOYSA-N 0.000 claims description 2
- 150000003891 oxalate salts Chemical class 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 229910000859 α-Fe Inorganic materials 0.000 claims description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims 2
- AXHVNJGQOJFMHT-UHFFFAOYSA-N 1-tert-butyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C(C)(C)C AXHVNJGQOJFMHT-UHFFFAOYSA-N 0.000 claims 1
- 239000003205 fragrance Substances 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 239000007800 oxidant agent Substances 0.000 abstract description 8
- 230000001590 oxidative effect Effects 0.000 abstract description 8
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 abstract description 6
- 239000003446 ligand Substances 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- RLKHFSNWQCZBDC-UHFFFAOYSA-N n-(benzenesulfonyl)-n-fluorobenzenesulfonamide Chemical compound C=1C=CC=CC=1S(=O)(=O)N(F)S(=O)(=O)C1=CC=CC=C1 RLKHFSNWQCZBDC-UHFFFAOYSA-N 0.000 abstract description 5
- 150000003613 toluenes Chemical class 0.000 abstract description 3
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 238000004809 thin layer chromatography Methods 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 125000003170 phenylsulfonyl group Chemical group C1(=CC=CC=C1)S(=O)(=O)* 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 4
- QCWXDVFBZVHKLV-UHFFFAOYSA-N 1-tert-butyl-4-methylbenzene Chemical compound CC1=CC=C(C(C)(C)C)C=C1 QCWXDVFBZVHKLV-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- 241000255964 Pieridae Species 0.000 description 1
- 241000907661 Pieris rapae Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- AUEMEEMVNBYZLM-UHFFFAOYSA-N bromine;toluene Chemical compound [Br].CC1=CC=CC=C1 AUEMEEMVNBYZLM-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 150000002497 iodine compounds Chemical class 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C311/48—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups having nitrogen atoms of sulfonamide groups further bound to another hetero atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/12—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A kind of method of the hydrocarbon direct aminatin of methyl aromatic compound benzyl of iron catalysis: being catalyst by raw material, iron compound of methyl aromatic compound, use o-dichlorohenzene as solvent, a certain amount of NFSI is added, heating reaction 4-28 hours, after fully reacting, it is separated through silica gel column chromatography, benzyl amine derivative is made；The present invention realize for the first time it is abundant, be easy to get, the methyl aromatic compound of environment amenable iron compound catalysis hydrocarbon direct aminatin of benzyl under conditions of not adding oxidant additionally, without using metal being the spring, synthesized benzyl amine derivative.Its advantage is as follows: iron catalyst used is cheap, environmentally friendly, nontoxic, is not necessarily to oxidant and ligand, and toluene derivative and 8- methylquinoline derivatives can be catalyzed by same iron catalyst occurs aminating reaction, applied widely.
Description
Technical field
The invention belongs to technical field of organic synthetic chemistry, the methyl aromatic compound benzyl carbon of specifically a kind of iron catalysis
The method of hydrogen direct aminatin.
Background technique
Selling in best drug has much all containing benzyl amine structural unit, in natural products and has bioactivity
Small molecule compound benzyl introduce nitrogen-atoms be possible to it is fierce change the compound bioactivity (J. R. Clark,
K. Feng, A. Sookezian, M. C. White, Nature Chem., 10, 583(2018))；In addition, benzyl amine
It can be also used for the preparation of new material etc., therefore methyl aromatic compound direct aminatin that is cheap, being easy to get is carried out one-step synthesis to have
The benzyl amine derivative of very high value has very important significance.Currently, the hydrocarbon direct aminatin of benzyl can be by metal the spring or
Additional addition peroxide is realized using the method for N- fluoro-diphenyl sulfimide, however, metal is the generation needs in spring
The azido compound or hypervalent iodine compounds of explosive, the peroxide additionally added have the possibility of explosion during use
Property, it the use of N- fluoro-diphenyl sulfimide is that the avoidable additional addition oxidant of amination reagent (waits a kind of " toluene derivative before
The hydrocarbon direct aminatin method of benzyl ", 102408285 B of CN; Z. Ni, Q. Zhang, T. Xiong, Y. Zheng,
Y. LI, H. Zhang, J. Zhang, QQ. Liu, Angew. Chem. Int. Ed., 51, 1244(2012); Á.
Iglesias, R. Álvarez, Á. R. D. Lera, K. Muñiz, Angew. Chem. Int. Ed., 51,
2225(2012)); T. Xiong, Y. Li, Y. Lv, Q. Zhang, Chem. Commun., 46, 6831
(2010)), but this method is needed with toxic, expensive copper catalyst (also needing with ligand) or expensive palladium catalyst.It is aobvious
So, up to the present, also unrealized use is cheap, is easy to get, is nontoxic, environment amenable compound for catalysis methyl aromatic compound
The hydrocarbon direct aminatin of benzyl, its significance lies in that for the first time that iron compound catalyst is double for methyl aromatic compound and N- fluoro
The reaction of benzenesulfonimide does not have to that oxidant and ligand is still further added.
Summary of the invention
The purpose of the present invention be based on above-mentioned prior art situation and provide a kind of iron catalysis methyl aromatics
The new method of the hydrocarbon direct aminatin of the benzyl of object, has synthesized a variety of benzyl amine derivatives.This method no longer needs to additionally add oxidant
And ligand.The present invention realize for the first time iron catalysis methyl aromatic compound benzyl it is hydrocarbon not additionally add oxidant, do not make
Direct aminatin under conditions of being the spring with metal.
The purpose of the present invention is achieved through the following technical solutions:
A kind of method of the hydrocarbon direct aminatin of methyl aromatic compound benzyl of iron catalysis, is with methyl aromatic compound for original
Material, iron compound are catalyst, use o-dichlorohenzene as solvent, a certain amount of NFSI, heating reaction 4-28 hours, reaction is added
It after completely, is separated through silica gel column chromatography, benzyl amine derivative is made；
The molar ratio of methyl aromatic compound and iron compound is 1: 0.05-0.2, preferably 1: 0.1；
The molar ratio of methyl aromatic compound and NFSI are 1: 1-3, preferably 1: 1.5.
Its reaction equation is as follows:
Ar for phenyl ring or can be connected with the phenyl ring of alkyl, halogen, cyano, carbonyl, nitro, phenyl, sulfuryl, trifluoromethyl, can also
Think naphthalene nucleus, quinoline ring；
The methyl aromatic compound includes first benzene and its derivative, 8- methylquinoline and its derivative, such as: toluene, to bromine
Toluene, p-tert-butyltoluene, 4- methyl-1,1 '-biphenyl, 8- methylquinoline.
The iron compound is six water ferric oxalates, ferrous oxalate, nine water ferric nitrates, nine carbonyls close two iron, nanometer four aoxidizes
Three-iron, ferric acetyl acetonade, hexafluorophosphate ferrocene, hexafluoro sodium ferrite, iron titanium oxide, six water p-methyl benzenesulfonic acid iron, ferrocene
Tetrafluoroborate.
The heating reaction is heated to reflux for electric heating cover, and 4-28 hours.
The amount volume ratio of the substance of methyl aromatic compound and solvent is 1: 20-40, unit mmol/mL.
Eluant, eluent used is ethyl acetate: petroleum ether=1:1.5-8 when column chromatography for separation.
Specific charging reaction process is as follows: mentioned above to being added in organic solvent o-dichlorohenzene (10.0-20.0 milliliters)
Methyl aromatic compound (0.5 mM), a kind of catalyst (0.05 mM) of mentioned above certain is added, above-mentioned mentions is added
NFSI(0.75 mMs arrived).It finishes, electric heating cover is heated to reflux, stirs 4-28 hours, isolated through silica gel column chromatography
Benzyl amine derivative, yield is in 47-80%.
The present invention having the prominent advantages that compared with prior art: the methyl aromatic compound benzyl of iron catalysis is realized for the first time
Hydrocarbon direct aminatin under conditions of additionally not adding oxidant, being the spring without using metal.Its advantage is as follows: with cheap, nothing
Malicious, environment amenable iron compound is catalyst；Due to using the NFSI with oxidisability be amination reagent, ferric oxalate is to urge
Agent is not necessarily to oxidant and ligand, reduces reaction cost, reduce the influence to environment；Toluene derivative and 8- methyl quinoline
Quinoline derivant can be catalyzed by same iron catalyst occurs aminating reaction, applied widely.
Detailed description of the invention
Fig. 1 is N- benzyl-N- (benzenesulfonyl) benzsulfamide1H-NMR nuclear magnetic resoance spectrum (product is made in embodiment 1)；
Fig. 2 is N-(4- bromobenzyl)-N- (benzenesulfonyl) benzsulfamide1H-NMR nuclear magnetic resoance spectrum (product is made in embodiment 2)；
Fig. 3 is N-(4- t-butylbenzyl)-N- (benzenesulfonyl) benzsulfamide1(embodiment 3 is made to be produced H-NMR nuclear magnetic resoance spectrum
Object)；
Fig. 4 is N-(4- phenylbenzyl)-N- (benzenesulfonyl) benzsulfamide1(embodiment 4 is made to be produced H-NMR nuclear magnetic resoance spectrum
Object).
Fig. 5 is N-(4- benzenesulfonyl)-N- (8- methylquinoline base) benzsulfamide1H-NMR nuclear magnetic resoance spectrum (embodiment 5
Product is made).
Specific embodiment
The present invention is described further with reference to embodiments (attached drawing):
Embodiment 1
In 50mL round-bottomed flask be added 0.0072g ferrous oxalate (0.05 mM), 10mL organic solvent o-dichlorohenzene,
0.053mL toluene (0.5 mM), 0.241gN- fluoro-diphenyl sulfimide (0.75 mM), are heated to reflux 24 hours, until
Fully reacting (thin-layer chromatography TLC detection).By reaction mixture, with silica gel column chromatography separation, (eluant, eluent is ethyl acetate: petroleum
Ether=1:6) obtain white solid 0.1055g, yield 54%, nmr spectrum such as Fig. 1.
Embodiment 2
In 50mL round-bottomed flask be added six water ferric oxalate of 0.0242g (0.05 mM), 10mL organic solvent o-dichlorohenzene,
0.061mL parabromotoluene (0.5 mM), 0.241gN- fluoro-diphenyl sulfimide (0.75 mM), it is small to be heated to reflux 23
When, until fully reacting (thin-layer chromatography TLC detection).By reaction mixture with silica gel column chromatography separate (eluant, eluent is ethyl acetate:
Petroleum ether=1:6.5) obtain white solid 0.1761g, yield 76%, nmr spectrum such as Fig. 2.
Embodiment 3
Six water ferric oxalate of 0.0242g (can also be six water p-methyl benzenesulfonic acid iron) (0.05 mmoles are added in 50mL round-bottomed flask
You), 10mL organic solvent o-dichlorohenzene, 0.091mL p-tert-butyltoluene (0.5 mM), the double benzene sulfonyls of 0.241gN- fluoro
Imines (0.75 mM), is heated to reflux 6 hours, until fully reacting (thin-layer chromatography TLC detection).By reaction mixture silica gel
Column chromatography for separation (eluant, eluent is ethyl acetate: petroleum ether=1:8) obtains white solid 0.1782g, yield 80%, nuclear magnetic resonance
Spectrogram such as Fig. 3.
Embodiment 4
Six water ferric oxalate of 0.0242g (can also be ferrocene tetrafluoroborate) (0.05 mmoles are added in 50mL round-bottomed flask
You), 10mL organic solvent o-dichlorohenzene, 0.085g4- methyl-1, the double benzene sulphurs of 1 '-biphenyl (0.5 mM), 0.241gN- fluoro
Acid imide (0.75 mM), is heated to reflux 6 hours, until fully reacting (thin-layer chromatography TLC detection).By reaction mixture silicon
Plastic column chromatography separation (eluant, eluent is ethyl acetate: petroleum ether=1:4.5) obtains white solid 0.1517g, yield 66%, nuclear-magnetism
Resonate spectrogram such as Fig. 4.
Embodiment 5
Six water ferric oxalate of 0.0242g (can also be ferrocene tetrafluoroborate) (0.05 mmoles are added in 50mL round-bottomed flask
You), 10mL organic solvent o-dichlorohenzene, 0.068mL 8- methylquinoline (0.5 mM), the double benzene sulfonyls of 0.241gN- fluoro it is sub-
Amine (0.75 mM), is heated to reflux 6 hours, until fully reacting (thin-layer chromatography TLC detection).By reaction mixture silicagel column
Chromatography (eluant, eluent is ethyl acetate: petroleum ether=1:1.5) obtains white solid 0.1034g, yield 47%, nuclear magnetic resonance
Spectrogram such as Fig. 5.
Claims (8)
1. a kind of method of the hydrocarbon direct aminatin of methyl aromatic compound benzyl of iron catalysis, it is characterised in that: with methyl fragrance
Compound is raw material, iron compound is catalyst, uses o-dichlorohenzene as solvent, is with N- fluoro-diphenyl sulfimide (NFSI)
Amination reagent, heating reaction 4-28 hours, after fully reacting, separates through silica gel column chromatography, and benzyl amine derivative is made；
The molar ratio of methyl aromatic compound and iron compound is 1: 0.05-0.2,
The molar ratio of methyl aromatic compound and NFSI are 1: 1-3.
2. according to the method described in claim 1, it is characterized by: the molar ratio of methyl aromatic compound and iron compound is 1:
0.1, the molar ratio of methyl aromatic compound and NFSI are 1: 1.5.
3. according to the method described in claim 1, it is characterized by: the methyl aromatic compound includes toluene and its derivative
Object, 8- methylquinoline and its derivative.
4. according to the method described in claim 3, it is characterized by: the first benzene and its derivative be toluene, it is parabromotoluene, right
T-butyltoluene or 4- methyl-1,1 '-biphenyl；The 8- methylquinoline and its derivative are 8- methylquinoline.
5. according to the method described in claim 1, it is characterized by: the iron compound is six water ferric oxalates, ferrous oxalate, nine
Water ferric nitrate, nine carbonyls close two iron, nano ferriferrous oxide, ferric acetyl acetonade, hexafluorophosphate ferrocene, hexafluoro sodium ferrite,
Iron titanium oxide, six water p-methyl benzenesulfonic acid iron, ferrocene tetrafluoroborate.
6. according to the method described in claim 1, it is characterized by: the heating reaction be heated to reflux for electric heating cover, 4-28
Hour。
7. according to the method described in claim 1, it is characterized by: when column chromatography for separation eluant, eluent used is ethyl acetate: stone
Oily ether=1:1.5-8.
8. method according to claim 1 or 3, it is characterised in that: the amount body of the substance of methyl aromatic compound and solvent
Product is than being 1: 20-40, unit mmol/mL.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910371428.XA CN110003061B (en) | 2019-05-06 | 2019-05-06 | Method for direct amination of methyl aromatic compound benzyl hydrocarbon under catalysis of iron |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910371428.XA CN110003061B (en) | 2019-05-06 | 2019-05-06 | Method for direct amination of methyl aromatic compound benzyl hydrocarbon under catalysis of iron |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110003061A true CN110003061A (en) | 2019-07-12 |
| CN110003061B CN110003061B (en) | 2021-04-02 |
Family
ID=67175733
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910371428.XA Expired - Fee Related CN110003061B (en) | 2019-05-06 | 2019-05-06 | Method for direct amination of methyl aromatic compound benzyl hydrocarbon under catalysis of iron |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110003061B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116063209A (en) * | 2023-02-07 | 2023-05-05 | 上海沃凯生物技术有限公司 | Method for preparing benzylamine derivative by catalyzing amination of benzyl C-H bond through nickel under promotion of visible light |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102408285A (en) * | 2011-09-15 | 2012-04-11 | 东北师范大学 | Method for directly aminating benzyl hydrocarbon of methylbenzene derivative |
| CN107266414A (en) * | 2017-08-18 | 2017-10-20 | 宁夏大学 | A kind of synthetic method of aminomethyl thiophenes |
-
2019
- 2019-05-06 CN CN201910371428.XA patent/CN110003061B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102408285A (en) * | 2011-09-15 | 2012-04-11 | 东北师范大学 | Method for directly aminating benzyl hydrocarbon of methylbenzene derivative |
| CN107266414A (en) * | 2017-08-18 | 2017-10-20 | 宁夏大学 | A kind of synthetic method of aminomethyl thiophenes |
Non-Patent Citations (4)
| Title |
|---|
| LIU HAI-HONG等: ""Transition Metal-Free Regioselective C-3 Amidation of Indoles with N-Fluorobenzenesulfonimide"", 《ADV. SYNTH. CATAL.》 * |
| NI ZHIKUN等: ""Highly Regioselective Copper-Catalyzed Benzylic C-H Amination by N-Fluorobenzenesulfonimide"", 《ANGEW. CHEM. INT. ED.》 * |
| YANG YAOCHENG等: ""Metal-free remote oxidative benzylic C-H amination of 4-methylanilides with N-fuorobenzenesulfonimide"", 《TETRAHEDRON》 * |
| ZHANG XIAOLEI等: ""Copper-catalyzed intermolecular amidation of 8-methylquinolines with N-fluoroarylsulfonimides via Csp3-H activation"", 《ORG. BIOMOL. CHEM.》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116063209A (en) * | 2023-02-07 | 2023-05-05 | 上海沃凯生物技术有限公司 | Method for preparing benzylamine derivative by catalyzing amination of benzyl C-H bond through nickel under promotion of visible light |
| CN116063209B (en) * | 2023-02-07 | 2024-04-09 | 上海沃凯生物技术有限公司 | Method for preparing benzylamine derivative by catalyzing amination of benzyl C-H bond through nickel under promotion of visible light |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110003061B (en) | 2021-04-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Huang et al. | Cooperative Effect of Two Metals: CoPd (OAc) 4‐Catalyzed C H Amination and Aziridination | |
| Santos et al. | Chemoselective Synthesis of Substituted Imines, Secondary Amines, and β‐Amino Carbonyl Compounds from Nitroaromatics through Cascade Reactions on Gold Catalysts | |
| US6051704A (en) | Synthesis of macrocyclic tetraamido-N ligands | |
| Mofakham et al. | Cellulose-SO3H as a biodegradable solid acid catalyzed one-pot three-component Ugi reaction: Synthesis of α-amino amide, 3, 4-dihydroquinoxalin-2-amine, 4H-benzo [b][1, 4] thiazin-2-amine and 1, 6-dihydropyrazine-2, 3-dicarbonitrile derivatives | |
| Pratihar et al. | Tetradentate amido azo Schiff base Cu (II), Ni (II) and Pd (II) complexes: Synthesis, characterization, spectral properties, and applications to catalysis in C–C coupling and oxidation reaction | |
| Chen et al. | A simple and straightforward approach toward selective C= C bond reduction by hydrazine | |
| Manikandan et al. | Synthesis, spectral characterization and crystal structure of Ni (II) pyridoxal thiosemicarbazone complexes and their recyclable catalytic application in the nitroaldol (Henry) reaction in ionic liquid media | |
| Benniston et al. | Synthesis and Binding Properties of Hybrid Cyclophane− Azamacrocyclic Receptors | |
| CN102408285B (en) | Method for directly aminating benzyl hydrocarbon of methylbenzene derivative | |
| Yuan et al. | Ruthenium (ii)-catalysed selective C (sp 2)–H bond benzoxylation of biologically appealing N-arylisoindolinones | |
| Bakherad et al. | Rapid, green, and catalyst-free one-pot three-component syntheses of 5-substituted 1 H-tetrazoles in magnetized water | |
| CN109320489A (en) | A kind of color alkyl compound and preparation method thereof | |
| CN110003061A (en) | A kind of method of the hydrocarbon direct aminatin of methyl aromatic compound benzyl of iron catalysis | |
| CN106000465A (en) | Method for oxidative coupling reaction of aldehyde and secondary amide | |
| Puzari et al. | An unsymmetrical Schiff-base derived recyclable Pd-catalyst for Suzuki–Miyaura and Sonogashira reactions in aqueous media | |
| CN106111190B (en) | A kind of chirality biaryl skeleton pyridoxamine class catalyst and its synthetic method and application | |
| Boland et al. | New ditopic and tripodal 1, 2, 4-triazole-and tetrazole-based ligands for coordination chemistry | |
| CN104788337B (en) | The synthetic method of imide analog compounds | |
| Albrecht et al. | Simple preparation of O-substituted hydroxylamines from alcohols | |
| CN107556262A (en) | A kind of preparation method of 2 substituent Fang Bing oxazoles | |
| CN109369448A (en) | A kind of method that bimetal composite oxide catalyzes and synthesizes azobenzene compound | |
| CN108440373B (en) | Iron-catalyzed cyanoalkylindoline and preparation method thereof | |
| Wang et al. | Palladium-Catalyzed Semihydrogenation of Alkynes with EtOH: Highly Stereoselective Synthesis of E-and Z-Alkenes | |
| CN113072470B (en) | N-acetonitrile bis-benzenesulfonylimine derivative and preparation method and application thereof | |
| Liu et al. | Zinc-mediated radical reactions of per-(or poly) fluorophenyl aromatic aldimines in aqueous media |
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: 20210402 |