CN109053455A - A kind of α-nitro-alpha-aryl ketones compounds synthetic method - Google Patents

A kind of α-nitro-alpha-aryl ketones compounds synthetic method Download PDF

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CN109053455A
CN109053455A CN201810876488.2A CN201810876488A CN109053455A CN 109053455 A CN109053455 A CN 109053455A CN 201810876488 A CN201810876488 A CN 201810876488A CN 109053455 A CN109053455 A CN 109053455A
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nitro
phenyl
synthetic method
aryl
alpha
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张辅民
安洋
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Lanzhou University
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Lanzhou University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered
    • C07C2601/20—Systems containing only non-condensed rings with a ring being at least seven-membered the ring being twelve-membered

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Indole Compounds (AREA)

Abstract

The present invention discloses a kind of α-nitro-alpha-aryl ketones compounds synthetic method, and this method includes that in the presence of alkali, α-nitro ketone compounds and Diaryl iodonium reactant salt obtain the α-nitro-alpha-aryl ketones compounds；Wherein, the α-nitro ketone compounds structural formula is as follows:OrThe structural formula of the diaryl iodonium salt is as follows:Orα-nitro-alpha-aryl ketones compounds structural formula is as follows:OrA is 5~12 member rings, and R is alkyl or aryl, R1For alkyl or aryl, Ar is aryl, X‑For anion.The present invention can economically and efficiently realize the synthesis of α-nitro-alpha-aromatic ring ketone compounds under the conditions of without transition metal-catalyzed, and operation is simple, safe.

Description

A kind of α-nitro-alpha-aryl ketones compounds synthetic method
Technical field
The invention belongs to organic intermediates to synthesize field, and in particular to a kind of α-nitro-alpha-aryl ketones compounds conjunction At method.
Background technique
In modern organic synthesis, material science and drug research, α-nitro-alpha-aromatic cyclic ketones with quaternary carbon center Class compound is a kind of important structural unit.Compound containing the skeleton can be used as herbicide and be widely used in agricultural production In, additionally by the skeleton nitro functions and carbonyl functional group further convert and with synthesis of natural product and can have The key intermediate of machine functional molecular can also prepare asymmetry catalysis ligand --- α-amido alcoholic compound etc..
Applicant (CN106632200A) discloses a kind of synthetic method of α-nitro cyclanone before this, and this method is With under copper-based or ferrum-based catalyst catalysis,It reacts to obtain with nitrating agent
2005087752 A2 of WO discloses one kind with 2- nitrocyclohexanone substrate, and tributylaryltin alkane is arylation examination Agent synthesizes α-(4- tert-butyl-phenyl)-α-nitrocyclohexanone under conditions of mercuric acetate and lead acetate are deposited, but the reaction needs to hold high Expensive and severe toxicity organotin, lead, mercury compound.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the existing defects, provides a kind of α-nitro-alpha-aryl ketones Close the synthetic method of object.
In order to solve the above-mentioned technical problems, the present invention provides the following technical solutions:
A kind of α-nitro-alpha-aryl ketones compounds synthetic method, comprising: in the presence of alkali, α-nitro ketone Object and Diaryl iodonium reactant salt are closed, the α-nitro-alpha-aryl ketones compounds are obtained；
Wherein, the α-nitro ketone compounds structural formula is as follows:
The structural formula of the diaryl iodonium salt is as follows:
α-nitro-alpha-aryl ketones compounds structural formula is as follows:
A is 5~12 member rings, and R is alkyl or aryl, R1For alkyl or aryl, Ar is aryl, X-For anion.
Preferably, the anion is CF3SO3 -、p-CH3C6H4SO3 -、BF4 -、PF6 -、CF3COO-Or Br-。
Preferably, the alkali be B alkali or L alkali, such as potassium tert-butoxide, sodium hydroxide, potassium carbonate, sodium bicarbonate, sodium carbonate, Cesium carbonate, potassium phosphate, triethylamine, two ring of miscellaneous nitrogen (such as 1,8- diazacyclo [5,4,0] hendecene -7) or n-BuLi.
Preferably, the molar ratio of the α-nitro ketone compounds and alkali, diaryl iodonium salt is 1:(2-20): (2- 20)。
Preferably, the aryl is phenyl, halogenophenyl, nitrobenzophenone, alkyl phenyl, alkoxyl phenyl, alkoxy acyl Phenyl or xenyl.Such as: 2- chlorphenyl, 3- chlorphenyl, rubigan, 2- fluorophenyl, 3- fluorophenyl, p-fluorophenyl, 2- bromine Phenyl, 3- bromophenyl, p-bromophenyl, 2- nitrobenzophenone, 3- nitrobenzophenone, p-nitrophenyl, 2- alkyl phenyl, 3- alkylbenzene Base, 4- alkyl phenyl, 2- alkoxyl phenyl, 3- alkoxyl phenyl, 4- alkoxyl phenyl, 2- alkoxy acyl phenyl, 3- alcoxyl acyl Base phenyl or 4- alkoxy acyl phenyl.
Preferably, the carbon number of the alkyl and/or alkoxy is 1~4, the carbon number of the alkoxy acyl 2~5, example Such as methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, methoxyl group, ethyoxyl, positive propoxy, isopropoxy, positive fourth Oxygroup, isobutoxy, methoxy acyl group, ethoxy acyl group.
Preferably, the α-nitro-alpha-aryl ketones compounds are one of the following:
Preferably, the α-nitro ketone compounds carry out in organic solvent with reacting for diaryl iodonium salt, described Organic solvent is 1,2- dichloroethanes (DCE), methylene chloride (DCM), n-hexane, hexamethylene, n -nonane, acetonitrile, normal heptane, two One or more of methyl sulfoxide (DMSO), n,N-Dimethylformamide (DMF), preferably 1,2- dichloroethanes or dichloromethane Alkane.
For the influence for avoiding air, it is preferable that the α-nitro ketone compounds are reacted with diaryl iodonium salt lazy It is carried out under property atmosphere, such as argon atmosphere.
Preferably, the α-nitro ketone compounds are carried out with reacting for diaryl iodonium salt at 0~120 DEG C, more preferably Ground is carried out at 65~100 DEG C.
The present invention can economically and efficiently realize α-nitro-alpha-aromatic cyclic ketones class chemical combination under the conditions of without transition metal-catalyzed The synthesis of object, operation are simple, safe.
Specific embodiment
Hereinafter, preferred embodiments of the present invention will be described, it should be understood that preferred embodiment described herein is only used In the description and interpretation present invention, it is not intended to limit the present invention.
Embodiment 1
Using 2- nitrocyclohexanone as raw material
2- nitrocyclohexanone (28.6mg, 0.20mmol), K are sequentially added in dry 10mL tube sealing2CO3(82.9mg, 0.60mmol) and diphenyl iodine tetrafluoroborate (Ph2IBF4, CAS:313-39-3) and (220.8mg, 0.60mmol), then in argon Atmosphere encloses lower addition 2.0mL DCE, is sealed with lid, reacts 2 hours in 100 DEG C of oil baths.After consumption of raw materials is complete, by body System is cooled to room temperature, and the dilution of 5.0mL petroleum ether, directly progress column chromatography (petrol ether/ethyl acetate=40:1) is then added.Most Light yellow solid (16.2mg, yield 37.0%) is obtained eventually.
Product detection data are as follows:
1H NMR(400MHz,CDCl3):δ7.48-7.46(m,3H),7.36-7.34(m,2H),3.10-3.03(m,1H), 2.94-2.88(m,1H),2.70-2.64(m,1H),2.59-2.52(m,1H),1.98-1.89(m,3H),1.80-1.74(m, 1H)；13C NMR(100MHz,CDCl3):δ200.5,131.8,130.0,129.0,128.2,100.9,40.0,35.0,27.0, 21.8。
Embodiment 2
Using 2- nitrocyclohexanone as raw material
2- nitrocyclohexanone (28.6mg, 0.20mmol), K are sequentially added in dry 10mL tube sealing2CO3(55.3mg, 0.30mmol) and diphenyl iodine trifluoro-methanyl sulfonate (Ph2IOTf, CAS:66003-76-7) (172.1mg, 0.40mmol), Then 4.0mL DCE is added under argon atmosphere, is sealed with lid, is reacted 3 hours in 85 DEG C of oil baths.When consumption of raw materials it is complete it Afterwards, system is cooled to room temperature, then be added 6.0mL petroleum ether dilution, directly carry out column chromatography (petrol ether/ethyl acetate= 40:1).Finally obtain light yellow solid (30.3mg, yield 69.0%).
The spectral data of product is the same as embodiment 1.
Embodiment 3
Using 2- nitrocyclohexanone as raw material
2- nitrocyclohexanone (28.6mg, 0.20mmol), Cs are sequentially added in dry 10mL tube sealing2CO3(97.7mg, 0.30mmol) and diphenyl iodine bromide (Ph2IBr then 3.0mL is added under argon atmosphere in) (180.5mg, 0.50mmol) DCE is sealed with lid, is reacted 2 hours in 65 DEG C of oil baths.After consumption of raw materials is complete, system is cooled to room temperature, then plus Enter the dilution of 6.0mL petroleum ether, directly progress column chromatography (petrol ether/ethyl acetate=40:1).Finally obtain light yellow solid (24.4mg, yield 55.6%).
The spectral data of product is the same as embodiment 1.
Embodiment 4
Using 2- nitrocyclohexanone as raw material
It is sequentially added in dry 10mL tube sealing 2- nitrocyclohexanone (28.6mg, 0.20mmol), DBU (1,8- phenodiazine Heterocycle [5,4,0] hendecene -7) (29.9uL, 0.20mmol) and diphenyl iodine hexafluorophosphate (Ph2IPF6, CAS:58109- 40-3) (225.6mg, 0.60mmol) 5.0mL DCE is then added under argon atmosphere, is sealed with lid, in 80 DEG C of oil baths Reaction 1 hour.After consumption of raw materials is complete, system is cooled to room temperature, the dilution of 6.0mL petroleum ether is then added, directly carries out Column chromatographs (petrol ether/ethyl acetate=40:1).Finally obtain light yellow solid (20.8mg, yield 47.5%).
The spectral data of product is the same as embodiment 1.
Embodiment 5
Using 2- nitrocyclohexanone as raw material
2- nitrocyclohexanone (28.6mg, 0.20mmol), Na are sequentially added in dry 10mL tube sealing2CO3(53.0mg, 0.50mmol) and diphenyl iodine trifluoro-methanyl sulfonate (215.4mg, 0.50mmol), 4.0mL then is added under argon atmosphere DCE is sealed with lid, is reacted 3 hours in 90 DEG C of oil baths.After consumption of raw materials is complete, system is cooled to room temperature, then plus Enter the dilution of 5.0mL petroleum ether, directly progress column chromatography (petrol ether/ethyl acetate=40:1).Finally obtain light yellow solid (23.3mg, yield 53.2%).
The spectral data of product is the same as embodiment 1.
Embodiment 6
Using 2- nitrocyclohexanone as raw material
2- nitrocyclohexanone (28.6mg, 0.20mmol), K are sequentially added in dry 10mL tube sealing3PO4(63.7mg, 0.30mmol) and diphenyl iodine trifluoro-methanyl sulfonate (172.1mg, 0.40mmol), 3.0mL then is added under argon atmosphere DCE is sealed with lid, is reacted 2 hours in 85 DEG C of oil baths.After consumption of raw materials is complete, system is cooled to room temperature, then plus Enter the dilution of 5.0mL petroleum ether, directly progress column chromatography (petrol ether/ethyl acetate=40:1).Finally obtain light yellow solid (14.2mg, yield 32.4%).
The spectral data of product is the same as embodiment 1.
Embodiment 7
Using 2- nitrocyclohexanone as raw material
2- nitrocyclohexanone (28.6mg, 0.20mmol), K are sequentially added in dry 10mL tube sealing2CO3(82.9mg, 0.60mmol) and diphenyl iodine trifluoro-methanyl sulfonate (86.1mg, 0.20mmol), 4.0mL then is added under argon atmosphere Toluene is sealed with lid, is reacted 1 hour in 95 DEG C of oil baths.After consumption of raw materials is complete, system is cooled to room temperature, then The dilution of 5.0mL petroleum ether, directly progress column chromatography (petrol ether/ethyl acetate=40:1) is added.Finally obtain light yellow solid (15.3mg, yield 34.8%).
The spectral data of product is the same as embodiment 1.
Embodiment 8
Using 2- nitrocyclohexanone as raw material
2- nitrocyclohexanone (28.6mg, 0.20mmol), K are sequentially added in dry 10mL tube sealing2CO3(55.3mg, 0.40mmol) and diphenyl iodine trifluoro-methanyl sulfonate (129.6mg, 0.30mmol), 2.0mL then is added under argon atmosphere DCM is sealed with lid, is reacted 3 hours in 90 DEG C of oil baths.After consumption of raw materials is complete, system is cooled to room temperature, then plus Enter the dilution of 5.0mL petroleum ether, directly progress column chromatography (petrol ether/ethyl acetate=40:1).Finally obtain light yellow solid (22.0mg, yield 50.2%).
The spectral data of product is the same as embodiment 1.
Embodiment 9
Using 2- nitrocyclohexanone as raw material
2- nitrocyclohexanone (28.6mg, 0.20mmol), K are sequentially added in dry 10mL tube sealing2CO3(124.3mg, 0.9mmol) and diphenyl iodine trifluoro-methanyl sulfonate (215.6mg, 0.50mmol), 4.0mL then is added under argon atmosphere CH3CN is sealed with lid, is reacted 2 hours in 70 DEG C of oil baths.After consumption of raw materials is complete, system is cooled to room temperature, then The dilution of 5.0mL petroleum ether, directly progress column chromatography (petrol ether/ethyl acetate=40:1) is added.Finally obtain light yellow solid (19.3mg, yield 44.0%).
The spectral data of product is the same as embodiment 1.
Embodiment 10
Using 2- nitrocyclohexanone as raw material
2- nitrocyclohexanone (1.00g), K are sequentially added in dry 100mL tube sealing2CO3(2.9g) and diphenyl iodine three 30.0mL DCE is then added under argon atmosphere, is sealed with lid for fluoromethane sulfonate (6.02g), anti-in 85 DEG C of oil baths It answers 5 hours.After consumption of raw materials is complete, system is cooled to room temperature, the dilution of 15.0mL petroleum ether, directly progress column is then added It chromatographs (petrol ether/ethyl acetate=40:1).Finally obtain light yellow solid (731mg, yield 47.6%).
The spectral data of product is the same as embodiment 1.
Embodiment 11
Using 2- nitrocyclohexanone as raw material
2- nitrocyclohexanone (28.6mg, 0.20mmol), K are sequentially added in dry 10mL tube sealing2CO3(27.6mg, 0.20mmol) and two (2- fluorophenyl) iodine trifluoro-methanyl sulfonates (139.8mg, 0.30mmol), then under argon atmosphere plus Enter 4.0mL DCE, sealed with lid, is reacted 2 hours in 80 DEG C of oil baths.After consumption of raw materials is complete, system is cooled to room Then the dilution of 5.0mL petroleum ether, directly progress column chromatography (petrol ether/ethyl acetate=40:1) is added in temperature.It finally obtains pale yellow Color solid (16.8mg, yield 35.4%).
Product detection data are as follows:
1H NMR(400MHz,CDCl3):δ7.50-7.45(m,1H),7.29-7.23(m,2H),7.21-7.16(m,1H), 2.99-2.92(m,2H),2.73-2.69(m,1H),2.65-2.58(m,1H),2.00-1.87(m,3H),1.73-1.68(m, 1H)；13C NMR(100MHz,CDCl3): δ 198.9,161.3 (J=250Hz), 132.2 (J=9.0Hz), 128.3 (J= 3.0Hz), 124.8 (J=4.0Hz), 121.2 (J=12.0Hz), 117.0 (J=23.0Hz), 99.2 (J=3.0Hz), 39.8 (J=2.0Hz), 35.9 (J=3.0Hz), 27.3,21.9.
Embodiment 12
Using 2- nitrocyclohexanone as raw material
2- nitrocyclohexanone (28.6mg, 0.20mmol), K are sequentially added in dry 10mL tube sealing2CO3(69.1mg, 0.50mmol) and two (3- chlorphenyl) iodine trifluoro-methanyl sulfonates (249.5mg, 0.50mmol), then under argon atmosphere plus Enter 3.0mL DCE, sealed with lid, is reacted 1 hour in 90 DEG C of oil baths.After consumption of raw materials is complete, system is cooled to room Then the dilution of 5.0mL petroleum ether, directly progress column chromatography (petrol ether/ethyl acetate=40:1) is added in temperature.It finally obtains pale yellow Color solid (30.5mg, yield 60.2%).
Product detection data are as follows:
1H NMR(400MHz,CDCl3): δ 7.45-7.38 (m, 2H), 7.34 (s, 1H), 7.23 (d, J=7.6Hz, 1H), 3.12-3.06(m,1H),2.81-2.75(m,1H),2.73-2.66(m,1H),2.59-2.52(m,1H),2.00-1.86(m, 3H),1.84-1.73(m,1H)；13C NMR(100MHz,CDCl3):δ199.6,135.0,133.9,130.2,128.2, 126.4,100.0,40.0,35.2,26.9,21.8。
Embodiment 13
Using 2- nitrocyclohexanone as raw material
2- nitrocyclohexanone (28.6mg, 0.20mmol), K are sequentially added in dry 10mL tube sealing2CO3(41.5mg, 0.30mmol) and two (4- bromophenyl) iodine trifluoro-methanyl sulfonates (235.2mg, 0.40mmol), then under argon atmosphere plus Enter 4.0mL DCE, sealed with lid, is reacted 3 hours in 70 DEG C of oil baths.After consumption of raw materials is complete, system is cooled to room Then the dilution of 5.0mL petroleum ether, directly progress column chromatography (petrol ether/ethyl acetate=40:1) is added in temperature.It finally obtains pale yellow Color solid (37.9mg, yield 63.5%).
Product detection data are as follows:
1H NMR(400MHz,CDCl3): δ 7.59 (d, J=8.8Hz, 2H), 7.22 (d, J=8.4Hz, 2H), 3.12- 3.05(m,1H),2.81-2.75(m,1H),2.71-2.64(m,1H),2.57-2.49(m,1H),1.99-1.86(m,3H), 1.81-1.71(m,1H)；13C NMR(100MHz,CDCl3):δ199.8,132.2,131.0,129.8,124.6,100.1, 39.9,35.1,26.9,21.8。
Embodiment 14
Using 2- nitrocyclohexanone as raw material
2- nitrocyclohexanone (28.6mg, 0.20mmol), K are sequentially added in dry 10mL tube sealing2CO3(82.9mg, 0.60mmol) and two (4- methoxyphenyl) iodine tetrafluoroborates (85.6mg, 0.20mmol), it is then added under argon atmosphere 3.0mL DCM, is sealed with lid, is reacted 1 hour in 100 DEG C of oil baths.After consumption of raw materials is complete, system is cooled to room Then the dilution of 5.0mL petroleum ether, directly progress column chromatography (petrol ether/ethyl acetate=40:1) is added in temperature.It finally obtains pale yellow Color solid (14.1mg, yield 28.2%).
Product detection data are as follows:
1H NMR(400MHz,CDCl3):δ7.31-7.28(m,2H),6.99-6.95(m,2H),3.84(s,3H),3.09- 3.02(m,1H),2.91-2.86(m,1H),2.65-2.50(m,2H),1.98-1.88(m,3H),1.80-1.73(m,1H)；13C NMR(100MHz,CDCl3):δ200.8,160.7,129.8,123.6,114.5,100.7,55.4,39.9,34.9,27.1, 22.0。
Embodiment 15
Using 2- nitrocyclohexanone as raw material
2- nitrocyclohexanone (28.6mg, 0.20mmol), Cs are sequentially added in dry 10mL tube sealing2CO3(45.6mg, 0.14mmol) and (4- nitrobenzophenone) (2,4,6- trimethylphenyl) iodine trifluoro-methanyl sulfonate (155.2mg, 0.30mmol), Then 3.0mL DCM is added under argon atmosphere, is sealed with lid, is reacted 4 hours in 85 DEG C of oil baths.When consumption of raw materials it is complete it Afterwards, system is cooled to room temperature, then be added 5.0mL petroleum ether dilution, directly carry out column chromatography (petrol ether/ethyl acetate= 40:1).Finally obtain light yellow solid (24.2mg, yield 45.8%).
Product detection data are as follows:
1H NMR(400MHz,CDCl3):δ8.31-8.28(m,2H),7.54-7.51(m,2H),3.23-3.16(m,1H), 2.79-2.69(m,2H),2.62-2.55(m,1H),2.09-2.04(m,1H),1.95-1.85(m,3H)；13C NMR (100MHz,CDCl3):δ198.7,148.6,138.8,129.1,123.9,99.6,40.1,35.8,26.8,21.7。
Embodiment 16
Using 2- nitrocyclohexanone as raw material
2- nitrocyclohexanone (28.6mg, 0.20mmol), Cs are sequentially added in dry 10mL tube sealing2CO3(58.6mg, 0.18mmol) and (4- methoxy aminosulfonylphenyl) (2,4,6- trimethylphenyl) iodine trifluoro-methanyl sulfonate (159.1mg, 0.30mmol), 4.0mL DCM is then added under argon atmosphere, is sealed with lid, is reacted 1 hour in 85 DEG C of oil baths.Work as original Material run out of after, system is cooled to room temperature, then be added 5.0mL petroleum ether dilution, directly carry out column chromatography (petroleum ether/ Ethyl acetate=40:1).Finally obtain light yellow solid (28.2mg, yield 50.9%).
Product detection data are as follows:
1H NMR(400MHz,CDCl3): δ 8.12-8.10 (m, 2H), 7.42 (d, J=8.8Hz, 2H), 3.94 (s, 3H), 3.15-3.08(m,1H),2.85-2.79(m,1H),2.73-2.68(m,1H),2.58-2.51(m,1H),2.01-1.88(m, 3H),1.82-1.77(m,1H)；13C NMR(100MHz,CDCl3):δ199.5,166.1,136.6,131.6,130.1, 128.1,100.3,52.4,40.1,35.5,26.9,21.8。
Embodiment 17
Using 2- nitrocyclohexanone as raw material
2- nitrocyclohexanone (28.6mg, 0.20mmol), K are sequentially added in dry 10mL tube sealing2CO3(27.6mg, 0.20mmol) and two (3- aminomethyl phenyl) iodine fluoroform sulphonates (274.9mg, 0.60mmol), then under argon atmosphere plus Enter 4.0mL DCE, sealed with lid, is reacted 3 hours in 100 DEG C of oil baths.After consumption of raw materials is complete, system is cooled to room Then the dilution of 5.0mL petroleum ether, directly progress column chromatography (petrol ether/ethyl acetate=40:1) is added in temperature.It finally obtains pale yellow Color solid (11.7mg, yield 15.1%).
Product detection data are as follows:
1H NMR(400MHz,CDCl3): δ 7.35 (t, J=7.6Hz, 1H), 7.27-7.25 (m, 1H), 7.16-7.13 (m, 1H),3.07-3.00(m,1H),2.93-2.88(m,1H),2.69-2.63(m,1H),2.60-2.52(m,1H),2.39(s, 3H),1.96-1.87(m,3H),1.79-1.71(m,1H)；13C NMR(100MHz,CDCl3):δ200.6,138.9,131.8, 130.8,128.9,128.8,125.2,101.0,40.1,35.1,27.1,21.9,21.5。
Embodiment 18
Using 2- nitro cyclopentanone as raw material
2- nitro cyclopentanone (28.6mg, 0.20mmol), K are sequentially added in dry 10mL tube sealing2CO3(41.5mg, 0.30mmol) and diphenyl iodine trifluoro-methanyl sulfonate (172.1mg, 0.40mmol), 3.0mL then is added under argon atmosphere DCE is sealed with lid, is reacted 2 hours in 65 DEG C of oil baths.After consumption of raw materials is complete, system is cooled to room temperature, then plus Enter the dilution of 5.0mL petroleum ether, directly progress column chromatography (petrol ether/ethyl acetate=40:1).Finally obtain light yellow solid (20.2mg, yield 49.2%).
Product detection data are as follows:
1H NMR(400MHz,CDCl3):δ7.52-7.49(m,2H),7.46-7.43(m,3H),3.22-3.15(m,1H), 2.94-2.87(m,1H),2.71-2.62(m,1H),2.51-2.42(m,1H),2.21-2.13(m,1H),1.99-1.90(m, 1H)；13C NMR(100MHz,CDCl3):δ204.7,131.1,130.1,129.0,127.9,97.6,36.3,35.2,18.2。
Embodiment 19
Using 2- nitro cycloheptanone as raw material
2- nitro cycloheptanone (28.6mg, 0.20mmol), K are sequentially added in dry 10mL tube sealing2CO3(82.9mg, 0.60mmol) and diphenyl iodine trifluoro-methanyl sulfonate (215.1mg, 0.50mmol), 4.0mL then is added under argon atmosphere DCE is sealed with lid, is reacted 2 hours in 85 DEG C of oil baths.After consumption of raw materials is complete, system is cooled to room temperature, then plus Enter the dilution of 5.0mL petroleum ether, directly progress column chromatography (petrol ether/ethyl acetate=40:1).Finally obtain light yellow solid (29.2mg, yield 62.5%).
Product detection data are as follows:
1H NMR(400MHz,CDCl3): δ 7.46-7.42 (m, 3H), 7.32-7.30 (m, 2H), 3.20 (dd, J= 15.6Hz, 8.8Hz 1H), 2.70-2.64 (m, 1H), 2.59-2.52 (m, 1H), 2.44 (dd, J=15.6Hz, 10.4Hz 1H),2.13-2.09(m,1H),1.93-1.84(m,1H),1.71-1.67(m,1H),1.46-1.42(m,1H)；13C NMR (100MHz,CDCl3):δ201.9,134.7,129.9,129.0,128.0,103.2,41.4,34.4,30.1,26.8,25.4。
Embodiment 20
Using 2- nitro cyclopentanone as raw material
2- nitro cyclopentanone (28.6mg, 0.20mmol), K are sequentially added in dry 10mL tube sealing2CO3(27.6mg, 0.20mmol) and two (4- chlorphenyl) iodine trifluoro-methanyl sulfonates (99.8mg, 0.20mmol), it is then added under argon atmosphere 3.0mL DCE, is sealed with lid, is reacted 1 hour in 95 DEG C of oil baths.After consumption of raw materials is complete, system is cooled to room temperature, Then the dilution of 5.0mL petroleum ether, directly progress column chromatography (petrol ether/ethyl acetate=40:1) is added.It finally obtains light yellow Solid (24.5mg, yield 51.1%).
Product detection data are as follows:
1H NMR(400MHz,CDCl3):δ7.59-7.57(m,2H),7.42-7.40(m,2H),3.21-3.14(m,1H), 2.87-2.81(m,1H),2.73-2.65(m,1H),2.51-2.42(m,1H),2.23-2.13(m,1H),2.02-1.94(m, 1H)；13C NMR(100MHz,CDCl3):δ204.3,132.2,130.0,129.7,124.9,96.7,36.3,35.1,18.2。
Embodiment 21
Using 2- nitro -1- indone as raw material
2- nitro -1- indone (28.6mg, 0.20mmol), K are sequentially added in dry 10mL tube sealing2CO3(41.5mg, 0.30mmol) and diphenyl iodine trifluoro-methanyl sulfonate (172.1mg, 0.40mmol), 4.0mL then is added under argon atmosphere DCE is sealed with lid, is reacted 3 hours in 70 DEG C of oil baths.After consumption of raw materials is complete, system is cooled to room temperature, then plus Enter the dilution of 5.0mL petroleum ether, directly progress column chromatography (petrol ether/ethyl acetate=40:1).Finally obtain light yellow solid (23.7mg, yield 46.7%).
Product detection data are as follows:
1H NMR(400MHz,CDCl3): δ 7.90 (d, J=7.6Hz, 2H), 7.71 (t, J=7.6Hz, 2H), 7.58- 7.56 (m, 1H), 7.53 (d, J=7.6Hz, 1H), 7.48 (t, J=7.6Hz, 1H), 7.43-7.41 (m, 3H), 4.51 (d, J= 17.6Hz, 1H), 4.00 (d, J=17.6Hz, 1H)；13C NMR(100MHz,CDCl3):δ193.5,150.2,136.8, 133.8,133.4,129.8,129.0,128.8,128.0,126.2,125.9,97.6,41.1。
Embodiment 22
Using 2- nitro -1-tetralone as raw material
2- nitro -1- indone (28.6mg, 0.20mmol), K are sequentially added in dry 10mL tube sealing2CO3(55.3mg, 0.40mmol) and diphenyl iodine trifluoro-methanyl sulfonate (258.1mg, 0.60mmol), 4.0mL then is added under argon atmosphere DCE is sealed with lid, is reacted 1 hour in 100 DEG C of oil baths.After consumption of raw materials is complete, system is cooled to room temperature, then The dilution of 5.0mL petroleum ether, directly progress column chromatography (petrol ether/ethyl acetate=40:1) is added.Finally obtain light yellow solid (32.1mg, yield 60.1%).
Product detection data are as follows:
1H NMR(400MHz,CDCl3):δ8.19-8.16(m,1H),7.53-7.49(m,1H),7.42-7.37(m,4H), 7.36-7.32 (d, 2H), 7.17 (d, J=7.6Hz, 1H), 3.46-3.38 (m, 1H), 3.12-3.05 (m, 2H), 2.85-2.77 (m,1H)；13C NMR(100MHz,CDCl3):δ188.5,142.1,134.6,131.03,131.00,130.1,129.0, 128.8,128.6,128.2,127.4,98.6,32.8,26.3。
Embodiment 23
Using 2- nitro twelve-ring as raw material
2- nitro twelve-ring (28.6mg, 0.20mmol), K are sequentially added in dry 10mL tube sealing2CO3 (82.9mg, 0.60mmol) and diphenyl iodine trifluoro-methanyl sulfonate (129.1mg, 0.30mmol), then under argon atmosphere 4.0mL DCE is added, is sealed with lid, is reacted 2 hours in 80 DEG C of oil baths.After consumption of raw materials is complete, system is cooled to Then the dilution of 5.0mL petroleum ether, directly progress column chromatography (petrol ether/ethyl acetate=40:1) is added in room temperature.It finally obtains shallow Yellow solid (36.0mg, yield 59.4%).
Product detection data are as follows:
1H NMR(400MHz,CDCl3):δ7.59-7.56(m,2H),7.43-7.39(m,2H),2.80-2.72(m,1H), 2.67-2.53(m,1H),1.80-1.71(m,1H),1.39-1.24(m,14H)；13C NMR(100MHz,CDCl3):δ201.1, 133.6,129.9,128.7,128.6,102.3,34.9,31.6,26.9,26.5,23.3,22.7,22.6,22.2,21.5, 19.9。
Embodiment 24
Using 2- nitro -1- phenyl-propane -1- ketone as raw material
2- nitro -1- phenyl-propane -1- ketone (28.6mg, 0.20mmol) is sequentially added in dry 10mL tube sealing, K2CO3(27.6mg, 0.20mmol) and diphenyl iodine trifluoro-methanyl sulfonate (86.0mg, 0.20mmol), then in argon atmosphere Lower addition 4.0mL DCE, is sealed with lid, is reacted 2 hours in 85 DEG C of oil baths.After consumption of raw materials is complete, system is cooled down To room temperature, the dilution of 5.0mL petroleum ether, directly progress column chromatography (petrol ether/ethyl acetate=40:1) is then added.It finally obtains Light yellow solid (31.5mg, yield 61.7%).
Product detection data are as follows:
1H NMR(400MHz,CDCl3):δ7.59-7.57(m,2H),7.53-7.50(m,3H),7.48-7.45(m,3H), 7.32 (t, J=7.6Hz 2H), 2.37 (s, 3H)；13C NMR(100MHz,CDCl3):δ192.3,134.4,133.5,133.2, 130.2,129.9,128.9,128.5,128.4,99.9,23.7。
Embodiment 25
Using 2- nitro -1- phenyl butane -1- ketone as raw material
2- nitro -1- phenyl butane -1- ketone (28.6mg, 0.20mmol) is sequentially added in dry 10mL tube sealing, K2CO3(27.6mg, 0.20mmol) and diphenyl iodine trifluoro-methanyl sulfonate (172.1mg, 0.40mmol), then in argon atmospher Lower addition 4.0mL DCE is enclosed, is sealed with lid, is reacted 1 hour in 100 DEG C of oil baths.After consumption of raw materials is complete, system is dropped It warms to room temperature, the dilution of 5.0mL petroleum ether, directly progress column chromatography (petrol ether/ethyl acetate=40:1) is then added.Final To light yellow solid (37.1mg, yield 68.9%).
Product detection data are as follows:
1H NMR(400MHz,CDCl3): δ 7.63 (d, J=7.2Hz, 2H), 7.54-7.51 (m, 2H), 7.47 (t, J= 7.6Hz, 1H), 7.43-7.40 (m, 3H), 7.30 (t, J=7.6Hz, 2H), 2.94-2.85 (m, 1H), 2.75-2.66 (m, 1H), 1.00 (t, J=7.2Hz 3H)；13C NMR(100MHz,CDCl3):δ191.0,134.6,134.1,133.3,129.6, 129.5,128.8,128.5,128.1,102.4,31.5,9.2。
Embodiment 26
Using 2- nitro-propione as raw material
2- nitro-propione (28.6mg, 0.20mmol), K are sequentially added in dry 10mL tube sealing2CO3(55.3mg, 0.40mmol) and diphenyl iodine trifluoro-methanyl sulfonate (172.1mg, 0.40mmol), 4.0mL then is added under argon atmosphere DCE is sealed with lid, is reacted 2 hours in 75 DEG C of oil baths.After consumption of raw materials is complete, system is cooled to room temperature, then plus Enter the dilution of 5.0mL petroleum ether, directly progress column chromatography (petrol ether/ethyl acetate=40:1).Finally obtain light yellow solid (17.9mg, yield 43.2%).
Product detection data are as follows:
1H NMR(600MHz,CDCl3):δ7.45-7.43(m,3H),7.36-7.34(m,2H),2.54-2.43(m,2H), 2.19 (s, 3H), 1.10 (t, J=7.2Hz, 3H)；13C NMR(150MHz,CDCl3):δ202.1,134.2,129.8,128.9, 127.4,99.7,31.6,21.9,8.3。
Embodiment 27
Using 2- nitro cycloheptanone as raw material
2- nitro cycloheptanone (28.6mg, 0.20mmol), K are sequentially added in dry 10mL tube sealing2CO3(82.9mg, 0.60mmol) and two (4- bromophenyl) iodine trifluoro-methanyl sulfonates (352.8mg, 0.60mmol), then under argon atmosphere plus Enter 4.0mL DCE, sealed with lid, is reacted 1 hour in 95 DEG C of oil baths.After consumption of raw materials is complete, system is cooled to room Then the dilution of 5.0mL petroleum ether, directly progress column chromatography (petrol ether/ethyl acetate=40:1) is added in temperature.It finally obtains pale yellow Color solid (40.9mg, yield 65.5%).
Product detection data are as follows:
1H NMR(400MHz,CDCl3): δ 7.59-7.56 (m, 2H), 7.21-7.17 (m, 2H), 3.14 (dd, J= 15.6Hz, 8.4Hz, 1H), 2.70-2.64 (m, 1H), 2.55-2.49 (m, 1H), 2.41 (dd, J=15.2Hz, 10.0Hz, 1H),2.11-2.03(m,1H),1.90-1.83(m,3H),1.73-1.62(m,1H),1.49-1.43(m,1H)；13C NMR (100MHz,CDCl3):δ201.5,133.4,132.2,129.6,124.5,102.4,41.3,34.2,30.0,26.7,25.3。
Commercial product or self-control can be used in diaryl iodonium salt of the invention.Self-control can refer to following methods:
Under argon atmosphere, metachloroperbenzoic acid (being used as oxidant) is added in 100mL round-bottomed flask, weight is added Steam CH2Cl2Aryl iodide is successively added in stirring and dissolving into system, is slowly added to BF3·OEt2, it is stirred at room temperature 30 minutes, It is subsequently cooled to 0 DEG C, adds aromatic hydrocarbons, temperature is warmed to room temperature after stirring 15 minutes, then reaction system is down to 0 DEG C, is added Counter ion counterionsl gegenions acid, is then warmed to room temperature stirring 1 hour for temperature.Solvent is evaporated after complete reaction, is added into reaction system Solution is stirred 15 minutes, ether phase is then decanted by ether (20mL), is washed repeatedly salt compounded of iodine 7-8 times, then vacuum is dry It is dry, obtain diaryl iodonium salt.
Trifluoromethanesulfonic acid, p-methyl benzenesulfonic acid, tetrafluoro boric acid, hexafluorophosphoric acid, trifluoroacetic acid or hydrogen can be used in counter ion counterionsl gegenions acid Bromic acid.
The preparation of diaryl iodonium salt is see also following existing literature:
“Efficient and General One‐Pot Synthesis of Diaryliodonium Triflates: Optimization, Scope and Limitations ", Marcin Bielawski, Mingzhao Zhu, Berit Olofsson,Adv.Synth.Catal.2007,349:2640-2618.
“Reaction of Arenes with Iodine in the Presence of Potassium Peroxodisulfate in Trifluoroacetic Acid.Direct and Simple Synthesis of Diaryliodonium Triflates ", Md.Delwar Hossain, Yasuyuki Ikegami, and Tsugio Kitamura, J.Org.Chem., 2006,71 (26), pp 9903-9905.
" Synthesis of functionalised unsymmetrical diaryliodonium salts ", Aneela Shah, Victor W.Pike and David A.Widdowson, J.Chem.Soc., Perkin Trans.1, 1997,0,2463-2466.
" the easy synthesis of bromination diaryl iodonium salt ", Guo Haiming etc., He'nan Normal University's journal (natural science edition), The 5th phase of volume 38 in 2010.
Finally, it should be noted that the foregoing is only a preferred embodiment of the present invention, it is not intended to restrict the invention, Although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still may be used To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features. All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in of the invention Within protection scope.

Claims (10)

1. a kind of α-nitro-alpha-aryl ketones compounds synthetic method, comprising: in the presence of alkali, α-nitro ketone chemical combination Object and Diaryl iodonium reactant salt obtain the α-nitro-alpha-aryl ketones compounds；
Wherein, the α-nitro ketone compounds structural formula is as follows:
The structural formula of the diaryl iodonium salt is as follows:
α-nitro-alpha-aryl ketones compounds structural formula is as follows:
A is 5~12 member rings, and R is alkyl or aryl, R1For alkyl or aryl, Ar is aryl, X-For anion.
2. synthetic method according to claim 1, which is characterized in that the anion is CF3SO3 -、p-CH3C6H4SO3 -、 BF4 -、PF6 -、CF3COO-Or Br-。
3. synthetic method according to claim 1, which is characterized in that the alkali is potassium tert-butoxide, sodium hydroxide, carbonic acid Potassium, sodium bicarbonate, sodium carbonate, cesium carbonate, potassium phosphate, triethylamine, two ring of miscellaneous nitrogen or n-BuLi.
4. synthetic method according to claim 1, which is characterized in that the α-nitro ketone compounds and alkali, diaryl The molar ratio of salt compounded of iodine is 1:(2-20): (2-20).
5. synthetic method according to claim 1, which is characterized in that the aryl is phenyl, halogenophenyl, nitrobenzene Base, alkyl phenyl, alkoxyl phenyl, alkoxy acyl phenyl or xenyl.
6. synthetic method according to claim 5, which is characterized in that the halogenophenyl 2- chlorphenyl, 3- chlorphenyl, right Chlorphenyl, 2- fluorophenyl, 3- fluorophenyl, p-fluorophenyl, 2- bromophenyl, 3- bromophenyl or p-bromophenyl；The nitrobenzophenone is 2- nitrobenzophenone, 3- nitrobenzophenone or p-nitrophenyl；The alkyl phenyl is 2- alkyl phenyl, 3- alkyl phenyl or 4- alkyl Phenyl；The alkoxyl phenyl is 2- alkoxyl phenyl, 3- alkoxyl phenyl or 4- alkoxyl phenyl；The alkoxy acyl phenyl For 2- alkoxy acyl phenyl, 3- alkoxy acyl phenyl or 4- alkoxy acyl phenyl.
7. synthetic method according to claim 5 or 6, which is characterized in that the carbon number of the alkoxy is 1~4, described The carbon number of alkoxy acyl 2~5.
8. according to claim 1, synthetic method described in 5 or 6, which is characterized in that the carbon number of the alkyl is 1~4.
9. synthetic method according to claim 1, which is characterized in that the α-nitro-alpha-aryl ketones compounds are Following one:
10. synthetic method according to claim 1, which is characterized in that the reaction is carried out at 0~120 DEG C, more preferably It is carried out at 65~100 DEG C.
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