CN106632200B - A kind of synthetic method of α-nitro cyclanone - Google Patents

A kind of synthetic method of α-nitro cyclanone Download PDF

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CN106632200B
CN106632200B CN201610871965.7A CN201610871965A CN106632200B CN 106632200 B CN106632200 B CN 106632200B CN 201610871965 A CN201610871965 A CN 201610871965A CN 106632200 B CN106632200 B CN 106632200B
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copper
synthetic method
cyclanone
nitro
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CN106632200A (en
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张辅民
彭蕊
张志强
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Lanzhou University
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Lanzhou University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/22—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4
    • C07D311/26—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3
    • C07D311/34—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3 with aromatic rings attached in position 3 only
    • 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
    • C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups
    • 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
    • C07D209/32—Oxygen atoms
    • C07D209/34—Oxygen atoms in position 2

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention discloses a kind of synthetic method of α-nitro cyclanone, and the α-nitro cyclanone structural formula is as follows:A is 5~10 member rings, and R is alkyl or aryl, and R ' is hydrogen, alkyl, aryl or fused-aryl, synthesis step include: under copper-based or ferrum-based catalyst catalysis,

Description

A kind of synthetic method of α-nitro cyclanone
Technical field
The invention belongs to organic intermediates to synthesize field, and in particular to a kind of synthetic method of α-nitro cyclanone.
Background technique
α-phenyl-α-nitrocyclohexanone and its derivative are widely present in bioactive natural product and clinical medicine molecule, It is applied to the synthesis of natural products (such as erythrina indica Alkaloid) and drug molecule used also as crucial building block.And α-benzene Base-α-nitrocyclohexanone and its derivative can be used as starting material and synthesized by way of cutting off carbon-carbon bond containing polyfunctional group Chain compound etc..
Although mercuric acetate and lead acetate can be used for synthesizing α-(4- tert-butyl-phenyl) α-nitrocyclohexanone, valuableness is needed With the organo-tin compound of toxicity, and only method (WO of an example report currently without pervasive such compound of synthesis 2005087752 A2)。
Summary of the invention
The technical problem to be solved by the present invention is to overcome the existing defects, provides a kind of synthesis side of α-nitro cyclanone Method.
In order to solve the above-mentioned technical problems, the present invention provides the following technical solutions:
A kind of synthetic method of α-nitro cyclanone, the α-nitro cyclanone structural formula are as follows: A is 5~10 member rings (such as 5 member rings, 6 member rings, 7 member rings, 8 member rings, 9 member rings, 10 member rings), and R is alkyl or aryl, and R ' is hydrogen, alkane Base, aryl or fused-aryl, synthesis step include: under copper-based or ferrum-based catalyst catalysis,With nitrating agent Reaction obtains the α-nitro cyclanone.
Preferably, the copper-based catalysts are copper acetate (Cu (OAc)2), copper sulphate, copper oxide, cupric iodide, copper bromide, Acetylacetone copper (Cu (acac)2) or copper chloride.
Preferably, the ferrum-based catalyst is ferric trichloride.
Preferably, the nitrating agent is nitric acid, copper nitrate, ferric nitrate, magnesium nitrate, bismuth nitrate, nitrite tert-butyl, nitrous Isoamyl valerate or ammonium ceric nitrate (CAN).
Preferably, describedMolar ratio with nitrating agent, catalyst is 1:(2-20): (0.05-0.3).
Preferably, the A is containing 0~3 (such as 0,1,2,3) heteroatomic 5~10 member ring of O, S, N.
Preferably, the alkyl is C1-C8 alkyl, and the aryl is phenyl, substituted-phenyl, naphthalene, benzyl.
Preferably, the substituted-phenyl is halogenophenyl, nitrobenzophenone, methoxyphenyl, xenyl.
Preferably, the α-nitro cyclanone has
Preferably, the synthetic method carries out in organic solvent, the organic solvent be 1,2- dichloroethanes (DCE), Methylene chloride (DCM), n-hexane, hexamethylene, n -nonane, acetonitrile, normal heptane, dimethyl sulfoxide (DMSO), dimethylformamide One or more of (DMF), more preferably 1,2- dichloroethanes or acetonitrile.Preferred reaction temperature is 50~120 DEG C, more excellent Selection of land is 70~120 DEG C.
The present invention can economically and efficiently realize the synthesis of α-nitro cyclanone using cheap copper-based or ferrum-based catalyst, Reaction process is simple, safe and easily operated.
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- phenyl cyclohexanone as raw material
2- phenyl cyclohexanone (34.8mg, 0.2mmol), ammonium ceric nitrate are sequentially added in dry 15mL tube sealing (330.0mg, 0.6mmol) and Cu (OAc)22.0mL DCE is then added, with lid in (16mg, 0.10mmol) under argon atmosphere Son sealing, reacts 12 hours in 120 DEG C of oil baths.After consumption of raw materials is complete, system is cooled to room temperature, is then added The dilution of 5.0mL petroleum ether, directly progress column chromatography (petrol ether/ethyl acetate=40:1).Finally obtain light yellow solid (25.8mg, yield 51.0%).
Product detection data are as follows:
1H NMR(400MHz,CDCl3):δ7.48-7.44(m,3H),7.36-7.33(m,2H),3.10-3.03(m,1H), 2.92-2.86(m,1H),2.70-2.63(m,1H),2.59-2.53(m,1H),1.97-1.87(m,3H),1.82-1.73(m, 1H)；13C NMR(100MHz,CDCl3):δ200.5,132.1,130.2,129.2,128.4,101.0,40.2,35.3,27.3, 22.1.
Embodiment 2
Using 2- phenyl cyclohexanone as raw material
2- phenyl cyclohexanone (34.8mg, 0.2mmol), ammonium ceric nitrate are sequentially added in dry 15mL tube sealing (495.0mg, 0.9mmol) and CuSO4(6.4mg, 0.04mmol) 4.0mL DCE is then added under argon atmosphere, uses lid Sealing, reacts 16 hours in 120 DEG C of oil baths.After consumption of raw materials is complete, system is cooled to room temperature, 6.0mL is then added Petroleum ether dilution, directly progress column chromatography (petrol ether/ethyl acetate=40:1).Finally obtaining light yellow solid, (20.1mg is produced Rate 46.0%).
The spectral data of product is same as above.
Embodiment 3
Using 2- phenyl cyclohexanone as raw material
2- phenyl cyclohexanone (34.8mg, 0.2mmol), ammonium ceric nitrate are sequentially added in dry 15mL tube sealing 6.0mL DCE is then added under argon atmosphere, uses lid by (495.0mg, 0.9mmol) and CuO (9.54mg, 0.06mmol) Sealing, reacts 10 hours in 120 DEG C of oil baths.After consumption of raw materials is complete, system is cooled to room temperature, 6.0mL is then added Petroleum ether dilution, directly progress column chromatography (petrol ether/ethyl acetate=40:1).Finally obtaining light yellow solid, (23.2mg is produced Rate 52.9%).
The spectral data of product is same as above.
Embodiment 4
Using 2- phenyl cyclohexanone as raw material
2- phenyl cyclohexanone (34.8mg, 0.2mmol), ammonium ceric nitrate are sequentially added in dry 15mL tube sealing (110.0mg, 0.2mmol) and Cu (acac)2(21mg, 0.04mmol) 5.0mL DCE is then added under argon atmosphere, uses Lid sealing, reacts 13 hours in 70 DEG C of oil baths.After consumption of raw materials is complete, system is cooled to room temperature, is then added The dilution of 6.0mL petroleum ether, directly progress column chromatography (petrol ether/ethyl acetate=40:1).Finally obtain light yellow solid (21.6mg, yield 49.5%).
The spectral data of product is same as above.
Embodiment 5
Using 2- phenyl cyclohexanone as raw material
2- phenyl cyclohexanone (34.8mg, 0.2mmol), ammonium ceric nitrate are sequentially added in dry 15mL tube sealing (222.0mg, 0.4mmol) and FeCl3(26mg, 0.16mmol) 4.0mL DCE is then added under argon atmosphere, uses lid Sealing, reacts 14 hours in 110 DEG C of oil baths.After consumption of raw materials is complete, system is cooled to room temperature, 5.0mL is then added Petroleum ether dilution, directly progress column chromatography (petrol ether/ethyl acetate=40:1).Finally obtaining light yellow solid, (19.7mg is produced Rate 45.0%).
The spectral data of product is same as above.
Embodiment 6
Using 2- phenyl cyclohexanone as raw material
2- phenyl cyclohexanone (34.8mg, 0.2mmol), ammonium ceric nitrate are sequentially added in dry 15mL tube sealing 3.0mL DCE is then added under argon atmosphere, uses lid by (285.0mg, 0.50mmol) and CuI (45.7mg, 0.16mmol) Sealing, reacts 16 hours in 100 DEG C of oil baths.After consumption of raw materials is complete, system is cooled to room temperature, 5.0mL is then added Petroleum ether dilution, directly progress column chromatography (petrol ether/ethyl acetate=40:1).Finally obtaining light yellow solid, (18.6mg is produced Rate 42.4%).
The spectral data of product is same as above.
Embodiment 7
Using 2- phenyl cyclohexanone as raw material
2- phenyl cyclohexanone (34.8mg, 0.2mmol), ammonium ceric nitrate are sequentially added in dry 15mL tube sealing (330.0mg, 0.6mmol) and Cu (OAc)2(160mg, 1.0mmol) 4.0mL DMSO is then added under argon atmosphere, uses Lid sealing, reacts 10 hours in 90 DEG C of oil baths.After consumption of raw materials is complete, system is cooled to room temperature, is then added The dilution of 5.0mL petroleum ether, directly progress column chromatography (petrol ether/ethyl acetate=40:1).Finally obtain light yellow solid (12.2mg, yield 27.8%).
The spectral data of product is same as above.
Embodiment 8
Using 2- phenyl cyclohexanone as raw material
2- phenyl cyclohexanone (34.8mg, 0.2mmol), ammonium ceric nitrate are sequentially added in dry 15mL tube sealing (330.0mg, 0.6mmol) and Cu (OAc)25.0mL DMF is then added, with lid in (64mg, 0.40mmol) under argon atmosphere Son sealing, reacts 14 hours in 100 DEG C of oil baths.After consumption of raw materials is complete, system is cooled to room temperature, is then added The dilution of 5.0mL petroleum ether, directly progress column chromatography (petrol ether/ethyl acetate=40:1).Finally obtain light yellow solid (14.5mg, yield 33.0%).
The spectral data of product is same as above.
Embodiment 9
Using 2- phenyl cyclohexanone as raw material
2- phenyl cyclohexanone (34.8mg, 0.2mmol), ammonium ceric nitrate are sequentially added in dry 15mL tube sealing (495.0mg, 0.9mmol) and Cu (OAc)24.0mL CH is then added in (30mg, 0.20mmol) under argon atmosphere3CN is used Lid sealing, reacts 17 hours in 85 DEG C of oil baths.After consumption of raw materials is complete, system is cooled to room temperature, is then added The dilution of 5.0mL petroleum ether, directly progress column chromatography (petrol ether/ethyl acetate=40:1).Finally obtain light yellow solid (25.8mg, yield 51.0%).
The spectral data of product is same as above.
Embodiment 10
Using 2- phenyl cyclohexanone as raw material
It is sequentially added in dry 100mL tube sealing 2- phenyl cyclohexanone (1.00g), ammonium ceric nitrate (8.0g) and Cu (OAc)2(500mg) 30.0mL DCE is then added under argon atmosphere, is sealed with lid, and it is small that 24 are reacted in 90 DEG C of oil baths When.After consumption of raw materials is complete, system is cooled to room temperature, the dilution of 5.0mL petroleum ether, directly progress column chromatography is then added (petrol ether/ethyl acetate=40:1).Finally obtain light yellow solid (662mg, yield 52.5%).The spectral data of product is same On.
Embodiment 11
Using 2- (4-Br- phenyl) cyclohexanone as raw material
2- (4-Br- phenyl) cyclohexanone (50.4mg, 0.2mmol), cerous nitrate are sequentially added in dry 15mL tube sealing Ammonium (330.0mg, 0.6mmol) and Cu (OAc)24.0mLDCE is then added in (48mg, 0.30mmol) under argon atmosphere, uses Lid sealing, reacts 12 hours in 85 DEG C of oil baths.After consumption of raw materials is complete, system is cooled to room temperature, is then added The dilution of 5.0mL petroleum ether, directly progress column chromatography (petrol ether/ethyl acetate=40:1).Finally obtain light yellow solid (25.8mg, yield 51.0%).
Product detection data are as follows:
1H NMR(400MHz,CDCl3): δ 7.59 (d, J=8.7Hz, 2H), 7.22 (d, J=8.7Hz, 2H), 3.12- 3.06(m,1H),2.81-2.74(m,1H),2.71-2.65(m,1H),2.57-2.50(m,1H),2.01-1.76(m,3H), 1.81-1.73(m,1H)；13C NMR(100MHz,CDCl3):δ199.9,132.4,131.2,130.0,124.8,100.3, 40.1,35.3,27.1,22.0.
Embodiment 12
Using 2- (3- methoxyl group-phenyl) cyclohexanone as raw material
It is sequentially added in dry 15mL tube sealing with 2- (3- methoxyl group-phenyl) cyclohexanone (40.8mg, 0.2mmol), Ammonium ceric nitrate (110.0mg, 0.2mmol) and Cu (OAc)2Then 4.0mL is added under argon atmosphere in (48mg, 0.30mmol) DCE is sealed with lid, is reacted 12 hours in 85 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 (22.9mg, yield 46.0%).
Product detection data are as follows:
1H NMR(400MHz,CDCl3): δ 7.38 (t, J=8.1Hz 1H), 6.98 (dd, J=2.4Hz, J=2.0Hz, 1H),6.94-9.92(m,1H),6.87-6.86(m,1H),3.81(s,3H),3.07-3.00(m,1H),2.90-2.85(m, 1H),2.70-2.65(m,1H),2.61-2.53(m,1H),1.96-1.87(m,3H),1.80-1.72(m,1H)；13C NMR (100MHz,CDCl3):δ200.5,160.2,133.5,130.2,120.6,115.1,114.8,100.9,55.5,40.2, 35.4,27.2,22.1.
Embodiment 13
Using 2- phenyl cyclopentanone as raw material
It is sequentially added in dry 15mL tube sealing with 2-- phenyl cyclopentanone (32.0mg, 0.2mmol), ammonium ceric nitrate (450.0mg, 0.75mmol) and Cu (OAc)2(16mg, 0.10mmol) 4.0mL DCE is then added under argon atmosphere, uses Lid sealing, reacts 12 hours in 100 DEG C of oil baths.After consumption of raw materials is complete, system is cooled to room temperature, is then added The dilution of 5.0mL petroleum ether, directly progress column chromatography (petrol ether/ethyl acetate=40:1).Finally obtain light yellow solid (21.7mg, yield 51.0%).
Product detection data are as follows:
1H NMR(400MHz,CDCl3):δ7.53-7.51(m,2H),7.47-7.45(m,3H),3.23-3.16(m,1H), 2.95-2.88(m,1H),2.70-2.64(m,1H),2.52-2.43(m,1H),2.22-2.15(m,1H),1.99-1.93(m, 1H)；13C NMR(100MHz,CDCl3):δ205.0,131.2,130.3,129.2,128.1,97.7,36.4,35.4,18.4.
Embodiment 14
Using 2- (4- nitrobenzophenone) cycloheptanone as raw material
2- (4- nitrobenzophenone) cycloheptanone (46.6mg, 0.2mmol), cerous nitrate are sequentially added in dry 15mL tube sealing Ammonium (330.0mg, 0.6mmol) and Cu (OAc)2(16mg, 0.10mmol) 4.0mL DCE is then added under argon atmosphere, uses Lid sealing, reacts 12 hours in 85 DEG C of oil baths.After consumption of raw materials is complete, system is cooled to room temperature, is then added The dilution of 5.0mL petroleum ether, directly progress column chromatography (petrol ether/ethyl acetate=40:1).Finally obtain light yellow solid (31.5mg, yield 56.6%).
Product detection data are as follows:
1H NMR(400MHz,CDCl3): δ 8.31 (d, J=8.8Hz, 2H), 7.52 (d, J=8.8Hz, 2H), 3.20- 3.14(m,1H),2.80-2.75(m,1H),2.58-2.45(m,2H),2.09-2.04(m,1H),1.96-1.88(m,3H), 1.81-1.71(m,1H),1.55-1.46(m,1H)；13C NMR(100MHz,CDCl3):δ200.9,148.6,141.0, 129.3,124.2,101.9,41.8,34.6,30.1,26.9,25.4.
Embodiment 15
Using isoflavanone as raw material
Isoflavanone (44.8mg, 0.2mmol), ammonium ceric nitrate are sequentially added in dry 15mL tube sealing (660.0mg, 1.2mmol) and Cu (OAc)24.0mL DCE is then added, with lid in (16mg, 0.10mmol) under argon atmosphere Son sealing, reacts 12 hours in 85 DEG C of oil baths.After consumption of raw materials is complete, system is cooled to room temperature, 5.0mL is then added Petroleum ether dilution, directly progress column chromatography (petrol ether/ethyl acetate=40:1).Finally obtaining light yellow solid, (28.5mg is produced Rate 53.0%).
Product detection data are as follows:
1H NMR(400MHz,CDCl3): δ 8.02 (dd, J=1.4Hz, J=1.4Hz, 1H), 7.55-7.51 (m, 1H), 7.46-7.40 (m, 5H), 7.13-7.10 (m, 1H), 6.97 (d, J=8.4Hz, 1H), 5.38 (d, J=12.4Hz, 1H), 5.19 (d, J=12.4Hz, 1H)；13C NMR(100MHz,CDCl3):δ182.6,160.4,137.3,130.7,129.2,128.9, 128.7,128.0,122.9,119.4,118.1,93.4,70.9.
Embodiment 16
Using 1- methyl -2- tetralone as raw material
1- methyl -2- tetralone (32.0mg, 0.2mmol), ammonium ceric nitrate are sequentially added in dry 15mL tube sealing (220.0mg, 0.4mmol) and Cu (OAc)24.0mL DCE is then added, with lid in (16mg, 0.10mmol) under argon atmosphere Son sealing, reacts 12 hours in 85 DEG C of oil baths.After consumption of raw materials is complete, system is cooled to room temperature, 5.0mL is then added Petroleum ether dilution, directly progress column chromatography (petrol ether/ethyl acetate=40:1).Finally obtaining light yellow solid, (24.3mg is produced Rate 59.2%).
Product detection data are as follows:
1H NMR(400MHz,CDCl3): δ 7.44-7.34 (m, 3H), 7.29 (d, J=7.6Hz, 1H), 3.33-3.25 (m, 1H),3.03-3.00(m,2H),2.78-2.70(m,1H),2.05(s,3H)；13C NMR(100MHz,CDCl3):δ201.1, 137.3,133.7,130.3,128.9,128.0,127.0,92.9,36.6,27.8,22.4.
Embodiment 17
Using 2- naphthalene cyclohexanone as raw material
2- naphthalene cyclohexanone (44.8mg, 0.2mmol), ammonium ceric nitrate are sequentially added in dry 15mL tube sealing (825.0mg, 1.5mmol) and Cu (OAc)24.0mL DCE is then added, with lid in (32mg, 0.20mmol) under argon atmosphere Son sealing, reacts 12 hours in 105 DEG C of oil baths.After consumption of raw materials is complete, system is cooled to room temperature, is then added The dilution of 5.0mL petroleum ether, directly progress column chromatography (petrol ether/ethyl acetate=40:1).Finally obtain light yellow solid (26.9mg, yield 50.0%).
Product detection data are as follows:
1H NMR(400MHz,CDCl3): δ 7.91 (d, J=8.7Hz, 1H), 7.87-7.83 (m, 3H), 7.58-7.52 (m, 2H), 7.41 (dd, J=2.0Hz, 2.0Hz, 1H), 3.189-3.12 (m, 1H), 3.06-3.01 (m, 1H), 2.74-2.68 (m, 1H),2.62-2.54(m,1H),1.96-1.92(m,3H),1.85-1.78(m,1H)；13C NMR(100MHz,CDCl3):δ 200.7,133.8,133.1,129.5,129.1,128.7,128.5,127.79,127.78,127.0,125.1,101.2, 40.3,35.4,27.3,22.2.
Embodiment 18
Using 2- biphenyl pentylcyclohexanone as raw material
2- biphenyl pentylcyclohexanone (50.0mg, 0.2mmol), ammonium ceric nitrate are sequentially added in dry 15mL tube sealing (990.0mg, 1.8mmol) and Cu (OAc)24.0mL DCE is then added, with lid in (16mg, 0.10mmol) under argon atmosphere Son sealing, reacts 12 hours in 95 DEG C of oil baths.After consumption of raw materials is complete, system is cooled to room temperature, 5.0mL is then added Petroleum ether dilution, directly progress column chromatography (petrol ether/ethyl acetate=40:1).Finally obtaining light yellow solid, (36.0mg is produced Rate 61.0%).
Product detection data are as follows:
1H NMR(400MHz,CDCl3): δ 7.68 (d, J=8.4Hz, 2H), 7.60 (d, J=7.4Hz, 2H), 7.48- 7.39(m,5H),3.15-3.08(m,1H),2.96-2.91(m,1H),2.73-2.67(m,1H),2.64-2.56(m,1H), 2.00-1.91(m,3H),1.87-1.76(m,1H)；13C NMR(100MHz,CDCl3):δ200.6,143.1,139.9, 130.9,129.1,128.8,128.1,127.9,127.3,100.9,40.2,35.3,27.3,22.1.
Embodiment 19
Using 1- benzyl -3- methyl carbonyl indoles as raw material
1- benzyl -3- methyl carbonyl indoles (47.4mg, 0.2mmol), nitric acid are sequentially added in dry 15mL tube sealing Cerium ammonium (495.0mg, 0.9mmol) and Cu (OAc)2Then 4.0mLDCE is added under argon atmosphere in (16mg, 0.10mmol), It is sealed with lid, is reacted 12 hours in 75 DEG C of oil baths.After consumption of raw materials is complete, system is cooled to room temperature, is then added The dilution of 5.0mL petroleum ether, directly progress column chromatography (petrol ether/ethyl acetate=40:1).Finally obtain light yellow solid (33.6mg, yield 59.5%).
Product detection data are as follows:
1H NMR(400MHz,CDCl3):δ7.38-7.31(m,5H),7.31-7.28(m,2H),7.11-7.07(m,1H), 6.76 (d, J=7.9Hz, 1H), 5.13 (d, J=15.8Hz, 1H), 4.82 (d, J=15.8Hz, 1H), 2.07 (s, 3H)；13C NMR(100MHz,CDCl3):δ169.8,143.2,134.6,131.7,129.1,128.1,127.2,126.3,123.8, 123.5,110.5,89.0,44.3,20.3.
Embodiment 20
Using 6- methoxyl group -2- (4- nitrobenzophenone) -1- tetrahydro, how ketone is raw material
Sequentially added in dry 15mL tube sealing 6- methoxyl group -2- (4- nitrobenzophenone) -1- tetrahydro how ketone (59.4mg, 0.2mmol), ammonium ceric nitrate (330.0mg, 0.6mmol) and Cu (OAc)2(16mg, 0.10mmol), then under argon atmosphere 4.0mL DCE is added, is sealed with lid, is reacted 12 hours in 85 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 (36.3mg, yield 53.0%).
Product detection data are as follows:
1H NMR(400MHz,CDCl3): δ 8.30-8.26 (m, 2H), 7.62 (d, J=2.2Hz, 1H), 7.56-7.53 (m, 2H),7.17-7.12(m,2H),3.88(s,3H),3.50-3.43(m,1H),3.13-3.06(m,2H),2.79-2.71(m, 1H)；13C NMR(100MHz,CDCl3):δ187.5,159.2,148.7,138.2,134.5,131.4,130.4,129.5, 124.13,124.11,110.4,97.4,55.8,33.3,25.3。
Embodiment 21
Using 2- phenyl cyclohexanone as raw material
2- phenyl cyclohexanone (34.8mg, 0.2mmol), copper nitrate are sequentially added in dry 15mL tube sealing (564.0mg, 0.30mmol) and Cu (OAc)2(32mg, 0.20mmol) 3.0mL DCE is then added under argon atmosphere, uses Lid sealing, reacts 16 hours in 80 DEG C of oil baths.After consumption of raw materials is complete, system is cooled to room temperature, is then added The dilution of 5.0mL petroleum ether, directly progress column chromatography (petrol ether/ethyl acetate=40:1).Finally obtain light yellow solid (20.6mg, yield 44.8%).
The spectral data of product is the same as embodiment 1.
Embodiment 22
Using 2- phenyl cyclohexanone as raw material
2- phenyl cyclohexanone (34.8mg, 0.2mmol), fuming nitric aicd are sequentially added in dry 15mL tube sealing (0.3mL) and Cu (OAc)2(48mg, 0.3mmol) 4.0mL DCE is then added under argon atmosphere, is sealed with lid, in It is reacted 16 hours in 100 DEG C of oil baths.After consumption of raw materials is complete, system is cooled to room temperature, it is dilute that 5.0mL petroleum ether is then added It releases, directly progress column chromatography (petrol ether/ethyl acetate=40:1).Finally obtain light yellow solid (20.1mg, yield 44.5%).
The spectral data of product is the same.
Embodiment 23
Using 2- phenyl cyclohexanone as raw material
2- phenyl cyclohexanone (34.8mg, 0.2mmol), nitrite tert-butyl are sequentially added in dry 15mL pipe (316mg) and Cu (OAc)23.0mL DCE is then added in (48mg, 0.3mmol) under oxygen atmosphere, anti-in 100 DEG C of oil baths It answers 16 hours.After consumption of raw materials is complete, system is cooled to room temperature, the dilution of 5.0mL petroleum ether, directly progress column is then added It chromatographs (petrol ether/ethyl acetate=40:1).Finally obtain light yellow solid (23.6mg, yield 52.8%).
The spectral data of product is the same.
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 (7)

1. a kind of α-nitro cyclanone synthetic method, the α-nitro cyclanone structural formula are as follows:A For 5~10 member rings, R is alkyl, substituted-phenyl, benzyl or aryl, and R ' is hydrogen, alkyl or aryl, and synthesis step includes: copper-based Or under the catalysis of ferrum-based catalyst,It reacts to obtain the α-nitro cyclanone with nitrating agent；
The copper-based catalysts are copper acetate, copper sulphate, copper oxide, cupric iodide, copper bromide, acetylacetone copper or copper chloride；
The ferrum-based catalyst is ferric trichloride；
The nitrating agent be nitric acid, copper nitrate, ferric nitrate, magnesium nitrate, bismuth nitrate, nitrite tert-butyl, isoamyl nitrite or Ammonium ceric nitrate；
The synthetic method carries out in organic solvent, the organic solvent be 1,2- dichloroethanes, methylene chloride, n-hexane, One or more of hexamethylene, n -nonane, acetonitrile, normal heptane, dimethyl sulfoxide, dimethylformamide.
2. synthetic method according to claim 1, it is characterised in that: describedWith nitrating agent, catalyst Molar ratio is 1:(2-20): (0.05-0.3).
3. synthetic method according to claim 1, it is characterised in that: the A be include 0~3 O, S, N heteroatomic 5 ~10 member rings.
4. synthetic method according to claim 1, it is characterised in that: the alkyl is C1-C8 alkyl, and the aryl is benzene Base, naphthalene.
5. synthetic method according to claim 1, it is characterised in that: the substituted-phenyl be halogenophenyl, nitrobenzophenone, Methoxyphenyl, xenyl.
6. synthetic method according to claim 1, it is characterised in that: the α-nitro cyclanone has
7. synthetic method according to claim 1, it is characterised in that: the organic solvent is 1,2- dichloroethanes or second Nitrile.
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