CN109053536A - The fluoroform seleno method of electron rich aromatic hydrocarbons or the miscellaneous hydrocarbon of virtue - Google Patents
The fluoroform seleno method of electron rich aromatic hydrocarbons or the miscellaneous hydrocarbon of virtue Download PDFInfo
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- CN109053536A CN109053536A CN201810982010.8A CN201810982010A CN109053536A CN 109053536 A CN109053536 A CN 109053536A CN 201810982010 A CN201810982010 A CN 201810982010A CN 109053536 A CN109053536 A CN 109053536A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/30—Indoles; Hydrogenated indoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to carbon atoms of the hetero ring
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C391/00—Compounds containing selenium
- C07C391/02—Compounds containing selenium having selenium atoms bound to carbon atoms of six-membered aromatic rings
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- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/44—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members
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- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D233/90—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
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- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
- C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
- C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
- C07D317/62—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring 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 atoms of the carbocyclic ring
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D495/04—Ortho-condensed systems
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Abstract
The invention discloses the fluoroform seleno methods of electron rich aromatic hydrocarbons or the miscellaneous hydrocarbon of virtue, the following steps are included: fluoroform seleno ammonium salt or metal salt, oxidant are added in a solvent, electron rich aromatic hydrocarbons or the miscellaneous hydrocarbon of virtue are added at -80 DEG C to 100 DEG C, it is stirred to react 0.1~48h, water quenching is added to go out, column chromatographs to obtain fluoroform seleno product.The present invention is fluoroform seleno source using fluoroform seleno ammonium salt or metal salt, it is proposed the oxidation fluoroform seleno new method of electron rich aromatic hydrocarbons or the miscellaneous hydrocarbon of virtue, the oxidation fluoroform seleno for realizing electron rich aromatic hydrocarbons or the miscellaneous hydrocarbon of virtue in very mild conditions, by c h bond direct construction C-SeCF3Key, not only easy to operate, mild condition, yield are higher, functional group tolerance is fine, but also raw material is cheap and easy to get.
Description
Technical field
The invention belongs to technical field of organic synthesis, and in particular to the fluoroform seleno of a kind of electron rich aromatic hydrocarbons or fragrant miscellaneous hydrocarbon
Change method.
Background technique
Fluorinated organic compound has great application study in fields such as medicine, pesticide and materials with its unique performance
Value.Introduced in drug molecular structure fluorine atom or fluoro-containing group be change parent drug bioactivity most efficient method it
One, therefore, extensive concern of the method by chemist of fluorochemical is constructed, by-SeCF3It is introduced into substrate, can be allowed to
As potential more effectively selenium-supply product or new anticancer drug.Currently, introducing the side of fluoroform seleno into organic molecule
Method is broadly divided into two classes: indirect method and direct method.Indirect Method refers to the trifluoro realized on selenium atom to selenium-containing compound
Methylation.Cause step relatively complicated since this method needs to prepare reactant containing selenium in advance, so what is developed in recent years is big
Mostly it is direct method, i.e., introduces fluoroform seleno directly into molecule.There are several types of the reaction types of representative for direct method at present:
The bipyridyl fluoroform seleno developed with Weng Zhiqiang seminar of University of Fuzhou is cuprous to match object ([(bpy) CuSeCF3]2)
For fluoroform seleno reagent.Using trifluoromethyl trimethylsilane, elemental selenium, potassium fluoride, in cuprous iodide and bipyridyl
[(bpy) CuSeCF is obtained with moderate yield under effect3]2.It is successfully that class substrate realizes trifluoro to one using the complex
First seleno, including aryl or heteroaryl halides, halogenated alkyl object, β-bromo- α, β-insatiable hunger ketone, α-bromo- α, β-insatiable hunger ketone, α-
Brominated carbonyl compound, terminal alkyne and acyl chlorides etc..Although the complex adapts to, substrate spectrum is wide and yield is good, needs thing
First synthesize the complex, using a large amount of metal and ligand, and much reaction require to be heated to higher temperature (100 degree with
On), it reacts 16 hours.Therefore its application is limited by very large.
With fluoroform seleno tetramethyl-ammonium ([Me4N][SeCF3]) it is fluoroform seleno reagent.The reagent earliest by
The separation that Yagupolskii seminar is higher than 65% by trifluoromethyl trimethylsilane, elemental selenium, Methanaminium, N,N,N-trimethyl-, fluoride produces
Rate is prepared.In recent years, [Me is utilized4N][SeCF3] fluoroform seleno reagent is used as to have more reports, wherein
Successfully realize the fluoroform seleno aoxidized under copper trifluoromethanesulfcomposite catalysis to terminal alkyne and aryl boric acid or borate
Change reaction.It, also can be with preferable yield under the catalysis of cuprous sulfocyanide for aryl diazonium salts and α-diazonium ketone compounds
Obtain fluoroform seleno product.Use tri-tert-butylphosphine palladium iodide dimer that aryl iodide also may be implemented as catalyst for object
Fluoroform selenium glycosylation reaction.In addition there are also realize aryl iodide for object, bromo-derivative, chloro using fluoroform seleno tetramethyl-ammonium
The fluoroform selenium glycosylation reaction of object under mild conditions.
Electrophilic fluoroform seleno reagent: fluoroform seleno chlorine (CF3SeCl).Nearest Billard seminar will be in situ
The fluoroform seleno chlorine of generation is applied in the fluoroform selenium glycosylation reaction of electron rich aromatic hydrocarbons, is obtained with higher yield a series of
Fluoroform seleno product.But fluoroform seleno chlorine is a high poison and mordant gas, is had to the application of this method
Certain limitation.
Summary of the invention
It is an object of that present invention to provide one kind mild and participated in without transition metal under conditions of realize electron rich aromatic hydrocarbons or
The fluoroform seleno method of the miscellaneous hydrocarbon of virtue.
In order to achieve the above objectives, as follows using technical solution:
The fluoroform seleno method of electron rich aromatic hydrocarbons or the miscellaneous hydrocarbon of virtue, comprising the following steps:
Fluoroform seleno ammonium salt or metal salt, oxidant are added in a solvent, electron rich is added at -80 DEG C to 100 DEG C
Aromatic hydrocarbons or the miscellaneous hydrocarbon of virtue, are stirred to react 0.1~48h, water quenching are added to go out, column chromatographs to obtain fluoroform seleno product.
Reaction temperature and it is time-optimized for -30 DEG C to 60 DEG C, 5-24h.
According to the above scheme, the electron rich aromatic hydrocarbons or the miscellaneous hydrocarbon/fluoroform seleno ammonium salt of virtue or metal salt/oxidant mole
Than for 1:(0.2-5): (0.2-5).
According to the above scheme, the electron rich aromatic hydrocarbons has following structure formula:
Wherein, Y is O or S or CH or NR6；And R3、R4、R6Respectively hydrogen atom, fluorine atom, chlorine atom, bromine atom,
Iodine atom, methyl, trifluoromethyl, methoxyl group, trifluoromethoxy, ethyl, propyl, butyl, phenyl, 4- methoxyphenyl, nitro,
Cyano, amino, carboxyl, boronate, ester group, ketone carbonyl, aldehyde carbonyl groups, any one in amide groups.
According to the above scheme, the miscellaneous hydrocarbon of the electron rich virtue has following structure formula:
Wherein, X is CH or NR7；And R1、R2、R5、R7Respectively hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine are former
Son, methyl, trifluoromethyl, methoxyl group, trifluoromethoxy, ethyl, propyl, butyl, phenyl, 4- methoxyphenyl, nitro, cyanogen
Base, amino, carboxyl, boronate, ester group, ketone carbonyl, aldehyde carbonyl groups, any one in amide groups.
According to the above scheme, the fluoroform seleno ammonium salt is [Me4N][SeCF3]、[Et4N][SeCF3]、[Pr4N]
[SeCF3]、[Bu4N][SeCF3] in any one.
According to the above scheme, the metal salt is AgSeCF3、CuSeCF3、Hg(SeCF3)2、NaSeCF3、KSeCF3、
CsSeCF3In any one.
According to the above scheme, the oxidant is metachloroperbenzoic acid (m-CPBA), benzoyl hydroperoxide, Peracetic acid, uncle
Butylhydroperoxide (TBHP), hydrogen peroxide (H2O2), wear this Martin's oxidant (DMP), iodobenzene acetate (PhI (OAc)2)、2,3-
Two chloro- 5,6- dicyanoquinones (DDQ), N- N-iodosuccinimide (NIS), N- bromo-succinimide (NBS), N- chloro fourth
Imidodicarbonic diamide (NCS), 2,2,6,6- tetramethyl piperidine nitrogen oxides (TEMPO), potassium permanganate (KMnO4), potassium peroxydisulfate
(K2S2O8), silver nitrate (AgNO3), silver tetrafluoroborate (AgBF4), iodine (I2), oxygen (O2), the fluoro- 1,4- of 1- chloromethyl -4-
It is any in bis- (tetrafluoro boric acid) salt (Selectfluor) of two ring 2.2.2 octane of diazotising, N- fluoro bis benzene sulfonamide (NSFI)
It is a kind of.
According to the above scheme, the solvent be acetonitrile, n,N-Dimethylformamide, N-Methyl pyrrolidone, dimethyl sulfoxide,
Ethyl acetate, methylene chloride, chloroform, 1,2- dichloroethanes, tetrahydrofuran, ether, methyl tertiary butyl ether(MTBE), glycol dinitrate
Ether, 1,4- dioxane, methanol, ethyl alcohol, propyl alcohol, butanol, trifluoroethanol, hexafluoroisopropanol, acetic acid, water, benzene, toluene, diformazan
Any one in benzene.
The product reaction equation that the present invention prepares the seleno containing fluoroform is as follows:
For indoles and its derivative, when having electron substituent group on pyrrole ring or phenyl ring, the reaction time is relatively short,
Yield is higher；When there is electron-withdrawing group substitution, then the longer reaction time is needed, and yield is relatively low.Particularly, the N of indoles is former
On son when substituted base, use NIS reaction can be made to go on smoothly as oxidant, and the substituent group is if donor residues, then
Yield is higher, and if electron-withdrawing group, yield is lower.
For phenol analog derivative, the yield of fluoroform seleno is higher when reaction site is single, when reaction has multidigit point
When, what is obtained is mixture.
The present invention has the beneficial effect that compared with the existing technology:
The present invention is fluoroform seleno source using fluoroform seleno ammonium salt or metal salt, proposes electron rich aromatic hydrocarbons or the miscellaneous hydrocarbon of virtue
Oxidation fluoroform seleno new method, realize the oxidation trifluoro of electron rich aromatic hydrocarbons or the miscellaneous hydrocarbon of virtue in very mild conditions
First seleno, by c h bond direct construction C-SeCF3Key, not only easy to operate, mild condition, yield be higher, functional group tolerance
Very well, and raw material is cheap and easy to get.
Specific embodiment
Following embodiment further illustrates technical solution of the present invention, but not as limiting the scope of the invention.
Embodiment 1:
Under nitrogen protection, by [Me4N][SeCF3] (67mg, 0.3mmol) and oxidant m-CPBA (45mg, 85%,
It 0.22mmol) is dissolved in 1mL acetonitrile, is cooled to 0 DEG C, the acetonitrile that 1mL indoles (23.4mg, 0.2mmol) is then added dropwise is molten
Liquid, and reacted 8 hours at 0 DEG C.Instillation two, which is dripped, after reaction is quenched, and then revolving removes solvent, uses petroleum ether
With ethyl acetate (10:1) as eluant, eluent, column chromatographs to obtain fluoroform seleno product: (brown is solid for 3- fluoroform selenoindoles
Body 49.3mg, yield 93%),1H NMR(500MHz,CDCl3)δ8.49(brs,1H),7.81-7.79(m,1H),7.51(d,J
=2.7Hz, 1H), 7.45-7.43 (m, 1H), 7.31 (m, 2H)；19F NMR(471MHz,CDCl3)δ-35.9(s,3F)；13C
NMR(126MHz,CDCl3) δ 136.1,132.9,130.0,123.4,122.3 (q, J=335.4Hz), 121.5,120.1,
(111.5,93.3 q, J=1.5Hz)
Embodiment 2:
Under nitrogen protection, by AgSeCF3(77mg, 0.3mmol) and oxidant m-CPBA (45mg, 85%,
It 0.22mmol) is dissolved in 1mL acetonitrile, is cooled to 0 DEG C, 1mL 2 methyl indole (26.2mg, 0.2mmol) is then added dropwise
Acetonitrile solution, and reacted 8 hours at 0 DEG C.Instillation two, which is dripped, after reaction is quenched, and then revolving removes solvent, uses
As eluant, eluent, column chromatographs to obtain fluoroform seleno product: 3- fluoroform seleno -2- first for petroleum ether and ethyl acetate (10:1)
Base indoles (white solid 54.1mg, yield 97%),1HNMR(500MHz,CDCl3)δ8.30(brs,1H),7.70-7.69(m,
1H),7.33-7.31(m,1H),7.25-7.22(m,2H),2.60(s,3H)；19F NMR(471MHz,CDCl3)δ-37.4(s,
3F)；13C NMR(126MHz,CDCl3) δ 142.8,135.5,131.3,122.7 (q, J=336.1Hz), 122.6,121.2,
(119.5,110.7,91.7 q, J=1.1Hz), 13.0.
Embodiment 3:
Under nitrogen protection, by CuSeCF3(63mg, 0.3mmol) and oxidant m-CPBA (45mg, 85%,
It 0.22mmol) is dissolved in 1mL acetonitrile, the acetonitrile solution of 1mL4- fluoro indole (27.0mg, 0.2mmol) is then added dropwise, and
It is reacted 24 hours at 80 DEG C.Instillation two, which is dripped, after reaction is quenched, and then revolving removes solvent, uses petroleum ether and acetic acid
Ethyl ester (10:1) is as eluant, eluent, and column chromatographs to obtain fluoroform seleno product: (white is solid for 3- fluoroform seleno -4- fluoro indole
Body 50.2mg, yield 89%)1H NMR(500MHz,CDCl3)δ8.67(brs,1H),7.47(s,1H),7.24-7.21(m,
2H),6.93-6.89(m,1H)；19F NMR(471MHz,CDCl3) δ -38.5 (d, J=3.3Hz, 3F), -124.7 (m, 1F)；13C
NMR(126MHz,CDCl3) δ 156.8 (d, J=250.7Hz), 139.0 (d, J=9.5Hz), 133.7,123.9 (d, J=
7.9Hz), 122.1 (q, J=335.4Hz), 118.5 (d, J=18.1Hz), 107.8 (d, J=3.8Hz), 106.9 (d, J=
19.1Hz), 89.3 (q, J=2.3Hz)
Embodiment 4:
Under nitrogen protection, by CsSeCF3(84mg, 0.3mmol) and oxidant m-CPBA (45mg, 85%,
It 0.22mmol) is dissolved in 1mL acetonitrile, is cooled to 0 DEG C, 1mL 7- azaindole (23.6mg, 0.2mmol) is then added dropwise
Acetonitrile solution, and reacted 8 hours at 0 DEG C.Instillation two, which is dripped, after reaction is quenched, and then revolving removes solvent, uses
As eluant, eluent, column chromatographs to obtain fluoroform seleno product: 3- fluoroform seleno -7- nitrogen for petroleum ether and ethyl acetate (5:1)
Miscellaneous indoles (white solid 46.2mg, yield 87%)1H NMR(500MHz,CDCl3) δ 12.52 (brs, 1H), 8.35 (d, J=
4.2Hz, 1H), 8.03 (s, 1H), 7.98 (d, J=7.8Hz, 1H), 7.27-7.24 (m, 1H)；19F NMR(471MHz,CDCl3)
δ-37.5(s,3F)；13C NMR(126MHz,CDCl3) δ 149.0,144.5,135.9,127.7,122.9 (q, J=
335.4Hz), 122.6,117.7,89.5 (q, J=1.5Hz)
Embodiment 5:
Under nitrogen protection, by [Me4N][SeCF3] (67mg, 0.3mmol) and oxidant m-CPBA (45mg, 85%,
It 0.22mmol) is dissolved in 1mL acetonitrile, the acetonitrile solution of 1mL 5- cyanoindole (28.4mg, 0.2mmol) is then added dropwise,
And it is reacted 0.5 hour at 25 DEG C.Instillation two, which is dripped, after reaction is quenched, and then revolving removes solvent, uses petroleum ether
With ethyl acetate (5:1) as eluant, eluent, column chromatographs to obtain fluoroform seleno product: 3- fluoroform seleno -5- cyanoindole
(white solid 48.2mg, yield 83%)1HNMR(500MHz,(CD3)2CO)δ11.62(brs,1H),8.08(s,1H),8.03
(s, 1H), 7.77 (d, J=8.5Hz, 1H), 7.58 (dd, J=8.5,1.5Hz, 1H)；19F NMR(471MHz,(CD3)2CO)δ-
38.9(s,3F)；13C NMR(126MHz,(CD3)2CO) δ 138.7,137.1,130.1,125.5,124,6,122.4 (q, J=
334.5Hz), 119.6,113.7,104.3,92.2 (q, J=1.5Hz)
Embodiment 6:
Under nitrogen protection, by [Me4N][SeCF3] (67mg, 0.3mmol) and oxidant m-CPBA (45mg, 85%,
0.22mmol) be dissolved in 1mL tetrahydrofuran and be cooled to -60 DEG C, be then added dropwise 1mL 7- methyl indol (26.2mg,
Tetrahydrofuran solution 0.2mmol), and reacted 24 hours at -60 DEG C.Instillation two, which is dripped, after reaction is quenched, then
Revolving removes solvent, uses petroleum ether and ethyl acetate (10:1) as eluant, eluent, column chromatographs to obtain fluoroform seleno product:
3- fluoroform seleno -7- methyl indol (white solid 46.8mg, yield 84%)1H NMR(500MHz,CDCl3)δ8.47
(brs, 1H), 7.65 (d, J=8.0Hz, 1H), 7.51 (d, J=2.7Hz, 1H), 7.22 (d, J=7.4Hz, 1H), 7.12 (d, J
=7.1Hz, 1H), 2.52 (s, 3H)；19F NMR(471MHz,CDCl3)δ-37.6(s,3F)；13C NMR(126MHz,CDCl3)δ
(135.7,132.5,129.7,123.9,122.3 q, J=335.7Hz), 121.7,120.7,117.8,93.7 (q, J=
1.1Hz),16.4.
Embodiment 7:
Under nitrogen protection, by [Me4N][SeCF3] (67mg, 0.3mmol) and iodobenzene acetate (71mg, 0.22mmol) it is molten
In 1mL acetonitrile, it is cooled to 0 DEG C, the acetonitrile solution of 1mL 6- chloro-indole (30.2mg, 0.2mmol) is then added dropwise, and
It is reacted 12 hours at 0 DEG C.Instillation two, which is dripped, after reaction is quenched, and then revolving removes solvent, uses petroleum ether and acetic acid
Ethyl ester (10:1) is as eluant, eluent, and column chromatographs to obtain fluoroform seleno product: 3- fluoroform seleno -6- chloro-indole is (faint yellow
Liquid 53.7mg, yield 90%)1H NMR(500MHz,CDCl3) δ 8.57 (brs, 1H), 7.69 (d, J=8.5Hz, 1H),
7.52 (s, 1H), 7.45 (s, 1H), 7.27 (d, J=8.5Hz, 1H)；19F NMR(471MHz,CDCl3)δ-37.5(s,3F)；13C
NMR(126MHz,CDCl3) δ 136.4,133.5,129.4,128.7,122.3,122.2 (q, J=335.2Hz), 121.1,
(111.5,117.8,92.6 q, J=1.5Hz)
Embodiment 8:
Under nitrogen protection, by [Me4N][SeCF3] (67mg, 0.3mmol) and oxidant m-CPBA (45mg, 85%,
It 0.22mmol) is dissolved in 1mL toluene, is cooled to 0 DEG C, be then added dropwise 1mL 2,6- xylenol (24.4mg,
Toluene solution 0.2mmol), and reacted 8 hours at 0 DEG C.Instillation two, which is dripped, after reaction is quenched, and then revolving removes
Solvent uses petroleum ether and ethyl acetate (10:1) as eluant, eluent, and column chromatographs to obtain fluoroform seleno product: 4- fluoroform
Seleno -2.6- xylenol (white solid 41.4mg, yield 77%)1H NMR(500MHz,CDCl3)δ7.32(s,2H),
4.88(s,1H),2.26(s,6H)；19F NMR(471MHz,CDCl3)δ-37.1(s,3F)；13C NMR(126MHz,CDCl3)δ
154.4,137.7,124.5,122.6 (q, J=333.0Hz), 112.2 (q, J=1.2Hz), 15.7.
Embodiment 9:
Under nitrogen protection, by [Me4N][SeCF3] (67mg, 0.3mmol) and oxidant m-CPBA (123mg, 85%,
It 0.6mmol) is dissolved in 1mL acetonitrile, is cooled to 0 DEG C, be then added dropwise 1mL 2,6- DI-tert-butylphenol compounds (41.2mg,
Acetonitrile solution 0.2mmol), and reacted 8 hours at 0 DEG C.Instillation two, which is dripped, after reaction is quenched, and then revolving removes
Solvent uses petroleum ether and ethyl acetate (20:1) as eluant, eluent, and column chromatographs to obtain fluoroform seleno product: 4- fluoroform
Seleno -2.6- DI-tert-butylphenol compounds (white solid 48.1mg, yield 68%)1H NMR(500MHz,CDCl3)δ7.53(s,
2H),5.49(s,1H),1.46(s,18H)；19F NMR(471MHz,CDCl3)δ-37.1(s,3F)；13C NMR(126MHz,
CDCl3) δ 155.9,137.3,134.4,122.7 (q, J=333.6Hz), 112.6,34.4,30.1.
Embodiment 10:
Under nitrogen protection, by [Me4N][SeCF3] (67mg, 0.3mmol) and oxidant NIS (59mg, 0.26mmol) it is molten
In 1mL acetonitrile, it is cooled to 0 DEG C, the acetonitrile solution of 1mL sesamol (27.6mg, 0.2mmol) is then added dropwise, and 0
It is reacted 8 hours at DEG C.Instillation two, which is dripped, after reaction is quenched, and then revolving removes solvent, uses petroleum ether and ethyl acetate
(10:1) as eluant, eluent, column chromatographs to obtain fluoroform seleno product: 2- fluoroform seleno sesamol (white solid
47.2mg, yield 74%)1H NMR(500MHz,CDCl3)δ7.05(s,1H),6.64(s,1H),6.07(s,1H),5.98(s,
2H)；19F NMR(471MHz,CDCl3)δ-37.6(s,3F)；13C NMR(126MHz,CDCl3)δ153.9,152.5,142.0,
121.7 (q, J=336.5Hz), 117.7,101.9,97.8,97.4.
Typical reaction product of the invention simultaneously is as follows, and preparation process no longer enumerates:
Claims (8)
1. the fluoroform seleno method of electron rich aromatic hydrocarbons or the miscellaneous hydrocarbon of virtue, it is characterised in that the following steps are included:
Fluoroform seleno ammonium salt or metal salt, oxidant are added in a solvent, electron rich aromatic hydrocarbons is added at -80 DEG C to 100 DEG C
Or the miscellaneous hydrocarbon of virtue, it is stirred to react 0.1~48h, water quenching is added to go out, column chromatographs to obtain fluoroform seleno product.
2. the fluoroform seleno method of electron rich aromatic hydrocarbons as described in claim 1 or the miscellaneous hydrocarbon of virtue, it is characterised in that the rich electricity
Sub- aromatic hydrocarbons or the miscellaneous hydrocarbon/fluoroform seleno ammonium salt of virtue or metal salt/oxidant molar ratio are 1:(0.2-5): (0.2-5).
3. the fluoroform seleno method of electron rich aromatic hydrocarbons as described in claim 1 or the miscellaneous hydrocarbon of virtue, it is characterised in that the rich electricity
Sub- aromatic hydrocarbons has following structure formula:
Wherein, Y is O or S or CH or NR6；And R3、R4、R6Respectively hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine are former
Son, methyl, trifluoromethyl, methoxyl group, trifluoromethoxy, ethyl, propyl, butyl, phenyl, 4- methoxyphenyl, nitro, cyanogen
Base, amino, carboxyl, boronate, ester group, ketone carbonyl, aldehyde carbonyl groups, any one in amide groups.
4. the fluoroform seleno method of electron rich aromatic hydrocarbons as described in claim 1 or the miscellaneous hydrocarbon of virtue, it is characterised in that the rich electricity
The sub- miscellaneous hydrocarbon of virtue has following structure formula:
Wherein, X is CH or NR7；And R1、R2、R5、R7Respectively hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, first
Base, trifluoromethyl, methoxyl group, trifluoromethoxy, ethyl, propyl, butyl, phenyl, 4- methoxyphenyl, nitro, cyano, ammonia
Base, carboxyl, boronate, ester group, ketone carbonyl, aldehyde carbonyl groups, any one in amide groups.
5. the fluoroform seleno method of electron rich aromatic hydrocarbons as described in claim 1 or the miscellaneous hydrocarbon of virtue, it is characterised in that the trifluoro
First seleno ammonium salt is [Me4N][SeCF3]、[Et4N][SeCF3]、[Pr4N][SeCF3]、[Bu4N][SeCF3] in any one.
6. the fluoroform seleno method of electron rich aromatic hydrocarbons as described in claim 1 or the miscellaneous hydrocarbon of virtue, it is characterised in that the metal
Salt is AgSeCF3、CuSeCF3、Hg(SeCF3)2、NaSeCF3、KSeCF3、CsSeCF3In any one.
7. the fluoroform seleno method of electron rich aromatic hydrocarbons as described in claim 1 or the miscellaneous hydrocarbon of virtue, it is characterised in that the oxidation
Agent is metachloroperbenzoic acid, benzoyl hydroperoxide, Peracetic acid, tert-butyl hydroperoxide, hydrogen peroxide, wears this Martin oxidation
Agent, iodobenzene acetate, the chloro- 5,6- dicyanoquinone of 2,3- bis-, N- N-iodosuccinimide, N- bromo-succinimide, N- chloro
Succimide, 2,2,6,6- tetramethyl piperidine nitrogen oxides, potassium permanganate, potassium peroxydisulfate, silver nitrate, silver tetrafluoroborate, list
The double benzene sulfonyls of bis- (tetrafluoro boric acid) salt of the fluoro- two ring 2.2.2 octane of 1,4- diazotising of matter iodine, oxygen, 1- chloromethyl -4-, N- fluoro
Any one in amine.
8. the fluoroform seleno method of electron rich aromatic hydrocarbons as described in claim 1 or the miscellaneous hydrocarbon of virtue, it is characterised in that the solvent
For acetonitrile, N,N-dimethylformamide, N-Methyl pyrrolidone, dimethyl sulfoxide, ethyl acetate, methylene chloride, chloroform,
1,2- dichloroethanes, tetrahydrofuran, ether, methyl tertiary butyl ether(MTBE), glycol dimethyl ether, 1,4- dioxane, methanol, ethyl alcohol,
Propyl alcohol, butanol, trifluoroethanol, hexafluoroisopropanol, acetic acid, water, any one in benzene,toluene,xylene.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110372565A (en) * | 2019-08-09 | 2019-10-25 | 武汉理工大学 | The acylated fluoroform seleno difunctionality dough method of the N- of indole derivatives |
| CN110407727A (en) * | 2019-07-30 | 2019-11-05 | 武汉理工大学 | A method of preparing alkyl trifluoromethyl selenide |
| CN110452146A (en) * | 2019-08-29 | 2019-11-15 | 武汉理工大学 | Trifluoromethyl seleno-amino acids derivative and preparation method thereof |
| CN111018765A (en) * | 2019-12-27 | 2020-04-17 | 武汉理工大学 | Direct trifluoromethylselenylation method of alcohol |
| CN114605299A (en) * | 2022-03-17 | 2022-06-10 | 浙江师范大学 | Electrophilic trifluoromethyl selenium-based reagent, preparation method and application thereof |
| CN114805239A (en) * | 2022-04-08 | 2022-07-29 | 山东农业大学 | Preparation method and application of trifluoromethylselenylation reagent |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103193803A (en) * | 2013-04-25 | 2013-07-10 | 福州大学 | Copper trifluoromethseleno (I) reagent for aryl halides/alkanes |
| CN105153003A (en) * | 2015-08-11 | 2015-12-16 | 覃继波 | Synthetic method of trifluoromethyl seleno-alkyne compound |
| CN107118143A (en) * | 2017-06-23 | 2017-09-01 | 武汉理工大学 | The preparation method of the trifluoromethyl diaryliodonium of nickel catalysis |
-
2018
- 2018-08-27 CN CN201810982010.8A patent/CN109053536B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103193803A (en) * | 2013-04-25 | 2013-07-10 | 福州大学 | Copper trifluoromethseleno (I) reagent for aryl halides/alkanes |
| CN105153003A (en) * | 2015-08-11 | 2015-12-16 | 覃继波 | Synthetic method of trifluoromethyl seleno-alkyne compound |
| CN107118143A (en) * | 2017-06-23 | 2017-09-01 | 武汉理工大学 | The preparation method of the trifluoromethyl diaryliodonium of nickel catalysis |
Non-Patent Citations (1)
| Title |
|---|
| TAO DONG，ET AL.: "Catalyst- and Additive-Free Trifl uoromethylselenolation with [Me4N][SeCF3]", 《ACS SUSTAINABLE CHEMISTRY ENGINEERING》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110407727A (en) * | 2019-07-30 | 2019-11-05 | 武汉理工大学 | A method of preparing alkyl trifluoromethyl selenide |
| CN110407727B (en) * | 2019-07-30 | 2020-07-31 | 武汉理工大学 | Method for preparing alkyl trifluoromethyl selenide |
| CN110372565A (en) * | 2019-08-09 | 2019-10-25 | 武汉理工大学 | The acylated fluoroform seleno difunctionality dough method of the N- of indole derivatives |
| CN110452146A (en) * | 2019-08-29 | 2019-11-15 | 武汉理工大学 | Trifluoromethyl seleno-amino acids derivative and preparation method thereof |
| CN111018765A (en) * | 2019-12-27 | 2020-04-17 | 武汉理工大学 | Direct trifluoromethylselenylation method of alcohol |
| CN114605299A (en) * | 2022-03-17 | 2022-06-10 | 浙江师范大学 | Electrophilic trifluoromethyl selenium-based reagent, preparation method and application thereof |
| CN114605299B (en) * | 2022-03-17 | 2023-08-25 | 浙江师范大学 | Electrophilic trifluoro methyl seleno reagent, preparation method and application thereof |
| CN114805239A (en) * | 2022-04-08 | 2022-07-29 | 山东农业大学 | Preparation method and application of trifluoromethylselenylation reagent |
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