CN106187816A - A kind of method that fracture based on C N key carrys out synthesizing oxime ether compounds - Google Patents
A kind of method that fracture based on C N key carrys out synthesizing oxime ether compounds Download PDFInfo
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- CN106187816A CN106187816A CN201610548682.9A CN201610548682A CN106187816A CN 106187816 A CN106187816 A CN 106187816A CN 201610548682 A CN201610548682 A CN 201610548682A CN 106187816 A CN106187816 A CN 106187816A
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- compound
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- ether compound
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- QXDXFTABXLXDTI-JXMROGBWSA-N C/C(/c(cc1)ccc1[N+]([O-])=O)=N\OC Chemical compound C/C(/c(cc1)ccc1[N+]([O-])=O)=N\OC QXDXFTABXLXDTI-JXMROGBWSA-N 0.000 description 1
- LBQDMHWTGODORW-NBVRZTHBSA-N CCOc(cc1)ccc1/C(/C)=N/OCc1ccccc1 Chemical compound CCOc(cc1)ccc1/C(/C)=N/OCc1ccccc1 LBQDMHWTGODORW-NBVRZTHBSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
Abstract
The present invention relates to a kind of method that fracture based on C N key carrys out synthesizing oxime ether compounds, the method includes reacting the compound of the compound of reaction equation (1) Yu reaction equation (2) under the conditions of peroxide, organic solvent, preparing formula (3) oximido ether compound, its reaction expression is as follows:The synthetic route of the inventive method is short, initiation material is simple, reaction condition is gentle, peroxide is inexpensive pollution-free, and substrate spectrum is wide, and product is easily separated, and when expanding the reaction of gram level to when, our reaction also can obtain the good suitability.
Description
Technical field
The invention belongs to pharmaceutical-chemical intermediate and related chemistry technical field, be specifically related to multiple oximido ether compound
Green synthesis method.
Background technology
Oximido ether compound is widely used in chemical field, and the framing structure of its compound is often found in medicine, natural work
Property product, in agricultural chemicals equimolecular structure, it is seen that the skeleton of oximido ether compound has wide scientific research value and market
Prospect.
Common oximido ether compound has traditional synthetic method, substantially can be divided into two kinds: a kind of method is to utilize
Compound containing carbonyl or aldehyde functions directly primary amine hydrochlorate substituted with alkoxyl reacts, and can directly generate
Oximido ether compound.Another kind of method is to utilize the compound containing carbonyl or aldehyde functions directly to react with azanol,
Then utilize halogenated compound to react therewith, after taking off hydrogen halides, obtain corresponding oximido ether compound.Traditional synthesis
Although method is used till today always, but use at many substrates and also can there is many limitation.Therefore, how by simpler
Initiation material, less reactions steps, gentle reaction condition, and use cheap free of contamination catalyst or oxidant
The research work preparing oximido ether compound is the most necessary.
Summary of the invention
The problem to be solved in the present invention is to provide the synthetic method of a kind of efficient multiple oximido ether compound.
For solving above-mentioned technical problem, the technical solution used in the present invention is:
The synthetic method of a kind of oximido ether compound, the method includes the compound of reaction equation (1) and reaction equation (2)
Compound reacts under the conditions of peroxide, organic solvent, prepares formula (3) oximido ether compound, and its reaction expression is as follows:
Wherein R1For C1-C6 alkyl (preferably methyl, ethyl) or benzyl；R2For hydrogen, isobutyl group, cyclohexyl, phenyl, two
Methyl substituents, methoxyl group, ethyoxyl, benzyloxy, dimethoxy substituent group, methylene-dioxy, nitro, halogen or methylsulfonyl；
R3For hydrogen, C1-C6 alkyl (preferably methyl, propyl group), replace C1-C6 alkyl, acetonitrile-base, benzyl or phenyl.
Preferably, described peroxide is in ammonium persulfate-sodium bisulfate, potassium peroxydisulfate, sodium peroxydisulfate or Ammonium persulfate.
One；It is highly preferred that described peroxide is potassium peroxydisulfate.
Preferably, described organic solvent is ethanol, methanol, ethylene glycol, glycol dimethyl ether or Isosorbide-5-Nitrae-dioxane
A kind of；It is highly preferred that described organic solvent is ethanol or methanol；Most preferably, described organic solvent is methanol.
Preferably, the mol ratio of described formula (1) compound and formula (2) compound is 1:1～1.5.
Preferably, the mol ratio of described formula (1) compound and peroxide is 1:0.4～2.4.
Preferably, the addition of described organic solvent is 20 times of formula (1) compound by weight.
Preferably, described reaction temperature is 50～90 DEG C, and the response time is 12～25 hours, it is highly preferred that described reaction
Temperature is 80 DEG C；Response time is 20 hours.
The present invention has the advantage that with good effect: the synthetic route of the inventive method is short, initiation material simple, reaction
Mild condition, peroxide are inexpensive pollution-free, and substrate spectrum is wide, and product is easily separated, and when expand to gram level reaction time
Waiting, our reaction also can obtain the good suitability.
Accompanying drawing explanation
Fig. 1 is embodiment 1-6 compound 1a1H nuclear-magnetism,13C nuclear magnetic spectrogram.
Fig. 2 is embodiment 7 compound 2a1H nuclear-magnetism,13C nuclear magnetic spectrogram.
Fig. 3 is embodiment 8 compound 3a1H nuclear-magnetism,13C nuclear magnetic spectrogram.
Fig. 4 is embodiment 9 compound 4a1H nuclear-magnetism,13C nuclear magnetic spectrogram.
Fig. 5 is embodiment 10 compound 5a1H nuclear-magnetism,13C nuclear magnetic spectrogram.
Fig. 6 is embodiment 11 compound 6a1H nuclear-magnetism,13C nuclear magnetic spectrogram.
Fig. 7 is embodiment 12 compound 7a1H nuclear-magnetism,13C nuclear magnetic spectrogram.
Fig. 8 is embodiment 13 compound 8a1H nuclear-magnetism,13C nuclear magnetic spectrogram.
Fig. 9 is embodiment 14 compound 9a1H nuclear-magnetism,13C nuclear magnetic spectrogram.
Figure 10 is embodiment 15 compound 10a1H nuclear-magnetism,13C nuclear magnetic spectrogram.
Figure 11 is embodiment 16 compound 11a1H nuclear-magnetism,13C nuclear magnetic spectrogram.
Figure 12 is embodiment 17 compound 12a1H nuclear-magnetism,13C nuclear magnetic spectrogram.
Figure 13 is embodiment 18 compound 13a1H nuclear-magnetism,13C nuclear magnetic spectrogram.
Figure 14 is embodiment 19 compound 14a1H nuclear-magnetism,13C nuclear magnetic spectrogram.
Figure 15 is embodiment 20 compound 15a1H nuclear-magnetism,13C nuclear magnetic spectrogram.
Figure 16 is embodiment 21 compound 16a1H nuclear-magnetism,13C nuclear magnetic spectrogram.
Detailed description of the invention
Further illustrate below in conjunction with specific embodiment, but protection scope of the present invention is not limited to embodiment and represents
Scope.
Originally screening reaction is to carry out, when we are by raw material under conditions of the 0.5mmol that N methoxy benzamide is thrown
The amount that N methoxy benzamide is thrown expands g level to when reacting, and finds also to achieve the highest productivity.I.e. at round-bottomed flask
Middle addition paraethoxyacetophenone (10.5mmol, 1.8g), N methoxy benzamide (7.0mmol, 1.1g), potassium peroxydisulfate
(14.0mmol, 3.8g), absolute methanol 30mL, sealing, stirring reaction 20 hours under 80 degree.Being cooled to room temperature, decompression removes
After solvent, obtain 1-(4-by column chromatographic isolation and purification (eluant is petrol ether/ethyl acetate=600:1)
Ethoxyphenyl) ethanone O-methyl oxime 1.3g, productivity 94%.
The synthesis of embodiment 1:1-(4-ethoxyphenyl) ethanone O-methyl oxime (1a)
Add paraethoxyacetophenone (0.75mmol, 127mg), N-methoxy benzamide in the reactor
(0.5mmol, 78.2mg), potassium peroxydisulfate (1.0mmol, 270.3mg), absolute methanol 2mL, sealing, stirring reaction at 80 DEG C
20 hours.Be cooled to room temperature, after removal of solvent under reduced pressure, by column chromatographic isolation and purification (eluant be petrol ether/ethyl acetate=
600:1) obtain 1-(4-ethoxyphenyl) ethanone O-methyl oxime (1a) 90.8mg, productivity 94%.
1H NMR(400MHz,CDCl3): δ 7.58 (d, J=8.5Hz, 2H), 6.87 (d, J=8.5Hz, 2H), 4.04 (q, J
=7.0Hz, 2H), 3.97 (s, 3H), 2.19 (s, 3H), 1.41 (t, J=7.0Hz, 3H)；13C NMR(100MHz,CDCl3):δ
159.8,154.3,129.0,127.3,114.3,63.5,61.8,14.8,12.5.
The synthesis of embodiment 2:1-(4-ethoxyphenyl) ethanone O-methyl oxime (1a)
Add paraethoxyacetophenone (0.75mmol, 127mg), N-methoxy benzamide in the reactor
(0.5mmol, 78.2mg), sodium peroxydisulfate (1.0mmol, 238.1mg), absolute methanol 2mL, sealing, stirring reaction at 80 DEG C
20 hours.Be cooled to room temperature, after removal of solvent under reduced pressure, by column chromatographic isolation and purification (eluant be petrol ether/ethyl acetate=
600:1) obtain 1-(4-ethoxyphenyl) ethanone O-methyl oxime (1a) 45.1mg, productivity 47%.
The synthesis of embodiment 3:1-(4-ethoxyphenyl) ethanone O-methyl oxime (1a)
Add paraethoxyacetophenone (0.75mmol, 127mg), N-methoxy benzamide in the reactor
(0.5mmol, 78.2mg), potassium peroxydisulfate (1.0mmol, 270.3mg), dehydrated alcohol 2mL, sealing, stirring reaction at 80 DEG C
20 hours.Be cooled to room temperature, after removal of solvent under reduced pressure, by column chromatographic isolation and purification (eluant be petrol ether/ethyl acetate=
600:1) obtain 1-(4-ethoxyphenyl) ethanone O-methyl oxime (1a) 26.1mg, productivity 27%.
The synthesis of embodiment 4:1-(4-ethoxyphenyl) ethanone O-methyl oxime (1a)
Add paraethoxyacetophenone (0.75mmol, 127mg), N-methoxy benzamide in the reactor
(0.5mmol, 78.2mg), potassium peroxydisulfate (1.0mmol, 270.3mg), absolute methanol 2mL, sealing, stirring reaction at 60 DEG C
20 hours.Be cooled to room temperature, after removal of solvent under reduced pressure, by column chromatographic isolation and purification (eluant be petrol ether/ethyl acetate=
600:1) obtain 1-(4-ethoxyphenyl) ethanone O-methyl oxime (1a) 38.6mg, productivity 40%.
The synthesis of embodiment 5:1-(4-ethoxyphenyl) ethanone O-methyl oxime (1a)
Add paraethoxyacetophenone (0.75mmol, 127mg), N-methoxy benzamide in the reactor
(0.5mmol, 78.2mg), potassium peroxydisulfate (1.0mmol, 270.3mg), absolute methanol 2mL, sealing, stirring reaction at 80 DEG C
12 hours.Be cooled to room temperature, after removal of solvent under reduced pressure, by column chromatographic isolation and purification (eluant be petrol ether/ethyl acetate=
600:1) obtain 1-(4-ethoxyphenyl) ethanone O-methyl oxime (1a) 59.9mg, productivity 62%.
The synthesis of embodiment 6:1-(4-ethoxyphenyl) ethanone O-methyl oxime (1a)
Add in the reactor paraethoxyacetophenone (0.5mmol, 85mg), N-methoxy benzamide (0.5mmol,
78.2mg), potassium peroxydisulfate (1.0mmol, 270.3mg), absolute methanol 2mL, sealing, at 80 DEG C stirring reaction 20 hours.Cold
But, to room temperature, after removal of solvent under reduced pressure, obtained by column chromatographic isolation and purification (eluant is petrol ether/ethyl acetate=600:1)
To 1-(4-ethoxyphenyl) ethanone O-methyl oxime (1a) 83.1mg, productivity 86%.
The synthesis of embodiment 7:1-(4-nitrophenyl) ethanone O-methyl oxime (2a)
Add in the reactor p-nitroacetophenone (0.75mmol, 128mg), N methoxy benzamide (0.5mmol,
78.2mg), potassium peroxydisulfate (1.0mmol, 270.3mg), absolute methanol 2mL, sealing, at 80 DEG C stirring reaction 20 hours.Cold
But, to room temperature, after removal of solvent under reduced pressure, obtained by column chromatographic isolation and purification (eluant is petrol ether/ethyl acetate=600:1)
To 1-(4-nitrophenyl) ethanone O-methyl oxime (2a) 83.5mg, productivity 86%.
1H NMR(400MHz,CDCl3): δ 8.22 (d, J=8.9Hz, 2H), 7.83 (d, J=8.9Hz, 2H), 4.05 (s,
3H),2.26(s,3H).13C NMR(100MHz,CDCl3):δ152.5,148.0,142.6,126.7,123.6,62.5,12.3.
The synthesis of embodiment 8:1-(4-(methylsulfonyl) phenyl) ethanone O-methyl oxime (3a)
Add in the reactor to methylsulfonyl 1-Phenylethanone. (0.75mmol, 152mg), N methoxy benzamide (0.5mmol,
78.2mg), potassium peroxydisulfate (1.0mmol, 270.3mg), absolute methanol 2mL, sealing, at 80 DEG C stirring reaction 20 hours.Cold
But, to room temperature, after removal of solvent under reduced pressure, obtained by column chromatographic isolation and purification (eluant is petrol ether/ethyl acetate=5:1)
1-(4-(methylsulfonyl) phenyl) ethanone O-methyl oxime (3a) 86.3mg, productivity 76%.
1H NMR(400MHz,CDCl3): δ 7.93 (d, J=8.3Hz, 2H), 7.85 (d, J=8.3Hz, 2H), 4.04 (s,
3H),3.06(s,3H),2.25(s,3H).13C NMR(100MHz,CDCl3):δ152.8,141.8,140.5,127.5,
126.8,62.4,44.5,12.4.
The synthesis of embodiment 9:1-(3,4-dimethoxyphenyl) ethanone O-methyl oxime (4a)
Add 3,4-dimethoxy-acetophenone (0.75mmol, 139mg), N methoxy benzamide in the reactor
(0.5mmol, 78.2mg), potassium peroxydisulfate (1.0mmol, 270.3mg), absolute methanol 2mL, sealing, stirring reaction at 80 DEG C
20 hours.Be cooled to room temperature, after removal of solvent under reduced pressure, by column chromatographic isolation and purification (eluant be petrol ether/ethyl acetate=
10:1) obtain 1-(3,4-dimethoxyphenyl) ethanone O-methyl oxime (4a) 101.3mg, productivity 97%.
1H NMR(400MHz,CDCl3): δ 7.30 (d, J=2.1Hz, 1H), 7.14 (dd, J=8.3,2.1Hz, 1H),
6.84 (d, J=8.4Hz, 1H), 3.99 (s, 3H), 3.91 (d, J=13.2Hz, 6H), 2.21 (s, 3H).13C NMR(100MHz,
CDCl3):δ154.2,150.1,148.9,129.4,119.1,110.6,108.6,61.8,55.9,12.5.
The synthesis of embodiment 10:4-methylbenzaldehyde O-methyl oxime (5a)
Add in the reactor p-tolyl aldehyde (0.75mmol, 92uL), N methoxy benzamide (0.5mmol,
78.2mg), potassium peroxydisulfate (1.0mmol, 270.3mg), absolute methanol 2mL, sealing, at 80 DEG C stirring reaction 20 hours.Cold
But, to room temperature, after removal of solvent under reduced pressure, 4-is obtained by column chromatographic isolation and purification (eluant is petroleum ether)
Methylbenzaldehyde O-methyl oxime (4a) 55.1mg, productivity 74%.
1H NMR(400MHz,CDCl3): δ 8.03 (s, 1H), 7.47 (d, J=8.1Hz, 2H), 7.17 (d, J=7.9Hz,
2H),3.96(s,3H),2.35(s,3H).13C NMR(100MHz,CDCl3):δ148.6,140.0,129.4,127.0,61.9,
21.5.
The synthesis of embodiment 11:4-chlorobenzaldehyde O-methyl oxime (6a)
Add in the reactor 4-chloro-benzaldehyde (0.75mmol, 109mg), N methoxy benzamide (0.5mmol,
78.2mg), potassium peroxydisulfate (1.0mmol, 270.3mg), absolute methanol 2mL, sealing, at 80 DEG C stirring reaction 20 hours.Cold
But, to room temperature, after removal of solvent under reduced pressure, 4-is obtained by column chromatographic isolation and purification (eluant is petroleum ether)
Chlorobenzaldehyde O-methyl oxime (6a) 57.2mg, productivity 68%.
1H NMR(400MHz,CDCl3): δ 8.01 (s, 1H), 7.51 (d, J=8.5Hz, 2H), 7.34 (d, J=8.5Hz,
2H),3.97(s,3H).13C NMR(100MHz,CDCl3):δ147.4,135.7,130.7,129.0,128.2,62.2.
The synthesis of embodiment 12:3,4-dimethylbenzaldehyde O-methyl oxime (7a)
Add 3,4-dimethylbenzaldehyde (0.75mmol, 102uL), N methoxy benzamide in the reactor
(0.5mmol, 78.2mg), potassium peroxydisulfate (1.0mmol, 270.3mg), absolute methanol 2mL, sealing, stirring reaction at 80 DEG C
20 hours.Be cooled to room temperature, after removal of solvent under reduced pressure, by column chromatographic isolation and purification (eluant be petrol ether/ethyl acetate=
800:1) obtain 3,4-dimethylbenzaldehyde O-methyl oxime (7a) 64.3mg, productivity 79%.
1H NMR(400MHz,CDCl3): δ 8.01 (s, 1H), 7.38 (s, 1H), 7.28 (d, J=7.7Hz, 1H), 7.12
(d, J=7.7Hz, 1H), 3.96 (s, 3H), 2.26 (s, 6H).13C NMR(100MHz,CDCl3):δ148.9,138.8,
137.0,130.0,129.7,127.9,124.9,61.9,19.8,19.7.
The synthesis of embodiment 13:4-(benzyloxy) benzaldehyde O-methyl oxime (8a)
Add in the reactor P-benzyloxybenzaldehyde (0.75mmol, 163mg), N methoxy benzamide (0.5mmol,
78.2mg), potassium peroxydisulfate (1.0mmol, 270.3mg), absolute methanol 2mL, sealing, at 80 DEG C stirring reaction 20 hours.Cold
But, to room temperature, after removal of solvent under reduced pressure, obtained by column chromatographic isolation and purification (eluant is petrol ether/ethyl acetate=600:1)
To 4-(benzyloxy) benzaldehyde O-methyl oxime (8a) 107.4mg, productivity 89%.
1H NMR(400MHz,CDCl3): δ 8.01 (s, 1H), 7.51 (d, J=8.7Hz, 2H), 7.44 7.32 (m, 5H),
6.96 (d, J=8.7Hz, 2H), 5.07 (s, 2H), 3.94 (s, 3H).13C NMR(100MHz,CDCl3):δ160.1,148.2,
136.6,128.7,128.5,128.1,127.5,125.1,115.1,70.1,61.9.
The synthesis of embodiment 14:3-(methoxyimino)-3-phenylpropanenitrile (9a)
Add in the reactor benzoyl acetonitrile (0.75mmol, 111mg), N methoxy benzamide (0.5mmol,
78.2mg), potassium peroxydisulfate (1.0mmol, 270.3mg), absolute methanol 2mL, sealing, at 80 DEG C stirring reaction 20 hours.Cold
But, to room temperature, after removal of solvent under reduced pressure, obtained by column chromatographic isolation and purification (eluant is petrol ether/ethyl acetate=400:1)
To 3-(methoxyimino)-3-phenylpropanenitrile (9a) 67.3mg, productivity 77%.
1H NMR(400MHz,CDCl3):δ7.64(s,2H),7.42(s,3H),4.08(s,3H),3.77(s,2H).13C
NMR(100MHz,CDCl3):δ146.3,133.2,130.2,128.9,126.2,115.0,62.8,15.1.
The synthesis of embodiment 15:1,2-diphenylethanone O-methyl oxime (10a)
Add in the reactor benzyl phenyl ketone (0.75mmol, 152mg), N methoxy benzamide (0.5mmol,
78.2mg), potassium peroxydisulfate (1.0mmol, 270.3mg), absolute methanol 2mL, sealing, at 80 DEG C stirring reaction 20 hours.Cold
But, to room temperature, after removal of solvent under reduced pressure, 1,2-is obtained by column chromatographic isolation and purification (eluant is petroleum ether)
Diphenylethanone O-methyl oxime (10a) 58.3mg, productivity 52%.
1H NMR(400MHz,CDCl3):δ7.66–7.60(m,2H),7.32–7.30(m,3H),7.27–7.14(m,5H),
4.14(s,2H),4.02(s,3H).13C NMR(100MHz,CDCl3):δ156.1,136.7,135.7,129.1,128.6,
128.5,128.5,126.5,126.3,62.1,32.7.
The synthesis of embodiment 16:1-phenylbutan-1-one O-methyl oxime (11a)
Add in the reactor butyrophenone (0.75mmol, 110uL), N methoxy benzamide (0.5mmol, 78.2mg),
Potassium peroxydisulfate (1.0mmol, 270.3mg), absolute methanol 2mL, sealing, stirring reaction 20 hours at 80 DEG C.It is cooled to room temperature,
After removal of solvent under reduced pressure, obtain 1-by column chromatographic isolation and purification (eluant is petrol ether/ethyl acetate=1000:1)
Phenylbutan-1-one O-methyl oxime (11a) 54.9mg, productivity 62%.
1H NMR(400MHz,CDCl3):δ7.65–7.59(m,2H),7.39–7.30(m,3H),3.97(s,3H),2.75–
2.68 (m, 2H), 1.60 1.51 (m, 2H), 0.95 (t, J=7.4Hz, 3H).13C NMR(100MHz,CDCl3):δ158.7,
136.0,129.0,128.4,126.3,61.8,28.6,20.0,14.3.
The synthesis of embodiment 17:2-bromo-1-phenylethanone O-methyl oxime (12a)
Add 2 in the reactor ,-bromoacetophenone (0.75mmol, 151mg), N methoxy benzamide (0.5mmol,
78.2mg), potassium peroxydisulfate (1.0mmol, 270.3mg), absolute methanol 2mL, sealing, at 80 DEG C stirring reaction 20 hours.Cold
But, to room temperature, after removal of solvent under reduced pressure, 2-bromo-1-is obtained by column chromatographic isolation and purification (eluant is petroleum ether)
Phenylethanone O-methyl oxime (12a) 56.3mg, productivity 98%.
NMR(400MHz,CDCl3):δ7.72–7.69(m,2H),7.43–7.37(m,3H),4.35(s,2H),4.09(s,
3H).13C NMR(100MHz,CDCl3):δ152.6,133.5,129.7,128.7,126.0,62.8,18.1.
The synthesis of embodiment 18:1-(4-ethoxyphenyl) ethanone O-ethyl oxime (13a)
Add in the reactor paraethoxyacetophenone (0.75mmol, 127mg), N ethoxy benzamide (0.5mmol,
85.2mg), potassium peroxydisulfate (1.0mmol, 270.3mg), absolute methanol 2mL, sealing, at 80 DEG C stirring reaction 20 hours.Cold
But, to room temperature, after removal of solvent under reduced pressure, obtained by column chromatographic isolation and purification (eluant is petrol ether/ethyl acetate=600:1)
To 1-(4-ethoxyphenyl) ethanone O-ethyl oxime (13a) 100.4mg, productivity 97%.
1H NMR(400MHz,CDCl3): δ 7.58 (d, J=8.9Hz, 2H), 6.87 (d, J=8.9Hz, 2H), 4.22 (q, J
=7.0Hz, 2H), 4.04 (q, J=7.0Hz, 2H), 2.20 (s, 3H), 1.41 (t, J=7.0Hz, 3H), 1.32 (t, J=
7.0Hz,3H).13C NMR(100MHz,CDCl3):δ159.7,153.9,129.3,127.3,114.3,69.5,63.5,14.8,
12.7.
The synthesis of embodiment 19:1-(4-nitrophenyl) ethanone O-ethyl oxime (14a)
Add in the reactor p-nitroacetophenone (0.75mmol, 128mg), N ethoxy benzamide (0.5mmol,
85.2mg), potassium peroxydisulfate (1.0mmol, 270.3mg), absolute methanol 2mL, sealing, at 80 DEG C stirring reaction 20 hours.Cold
But, to room temperature, after removal of solvent under reduced pressure, obtained by column chromatographic isolation and purification (eluant is petrol ether/ethyl acetate=600:1)
To 1-(4-nitrophenyl) ethanone O-ethyl oxime (14a) 95.1mg, productivity 91%.
1H NMR(400MHz,CDCl3): δ 8.21 (d, J=9.0Hz, 2H), 7.83 (d, J=9.0Hz, 2H), 4.30 (q, J
=7.1Hz, 2H), 2.26 (s, 3H), 1.35 (t, J=7.1Hz, 3H).13C NMR(100MHz,CDCl3):δ152.1,147.9,
142.9,123.6,70.4,14.8,12.4.
The synthesis of embodiment 20:1-(4-ethoxyphenyl) ethanone O-benzyl oxime (15a)
Add in the reactor paraethoxyacetophenone (0.75mmol, 127mg), N benzyloxy Benzoylamide (0.5mmol,
117.2mg), potassium peroxydisulfate (1.0mmol, 270.3mg), absolute methanol 2mL, sealing, at 80 DEG C stirring reaction 20 hours.Cold
But, to room temperature, after removal of solvent under reduced pressure, obtained by column chromatographic isolation and purification (eluant is petrol ether/ethyl acetate=600:1)
To 1-(4-ethoxyphenyl) ethanone O-benzyl oxime (15a) 115.4mg, productivity 86%.
1H NMR(400MHz,CDCl3): δ 7.57 (d, J=8.8Hz, 2H), 7.41 (d, J=7.3Hz, 2H), 7.35 (t, J
=7.4Hz, 2H), 7.31-7.27 (m, 1H), 6.86 (d, J=8.8Hz, 2H), 5.22 (s, 2H), 4.02 (q, J=7.0Hz,
2H), 2.23 (s, 3H), 1.40 (t, J=7.0Hz, 3H).13C NMR(100MHz,CDCl3):δ159.8,154.6,138.3,
129.0,128.4,128.2,127.7,127.4,114.3,76.1,63.5,14.8,12.8.
The synthesis of embodiment 21:4-(benzyloxy) benzaldehyde O-benzyl oxime (16a)
Add in the reactor P-benzyloxybenzaldehyde (0.75mmol, 163mg), N benzyloxy Benzoylamide (0.5mmol,
117.2mg), potassium peroxydisulfate (1.0mmol, 270.3mg), absolute methanol 2mL, sealing, at 80 DEG C stirring reaction 20 hours.Cold
But, to room temperature, after removal of solvent under reduced pressure, obtained by column chromatographic isolation and purification (eluant is petrol ether/ethyl acetate=500:1)
To 4-(benzyloxy) benzaldehyde O-benzyl oxime (16a) 140.7mg, productivity 89%.
1H NMR(400MHz,CDCl3): δ 8.08 (s, 1H), 7.51 (d, J=8.7Hz, 2H), 7.43-7.30 (m, 10H),
6.95 (d, J=8.7Hz, 2H), 5.18 (s, 2H), 5.07 (s, 2H).13C NMR(100MHz,CDCl3):δ160.1,148.7,
137.7,136.6,128.7,128.6,128.4,128.4,128.1,127.9,127.5,125.1,115.1,76.3,70.1.
Above the embodiment of the invention is described in detail, but described content has been only the preferable of the invention
Embodiment, it is impossible to be considered the practical range for limiting the present invention.All impartial changes made according to the invention scope with
Improve, within all should still belonging to this patent covering scope.
Claims (10)
1. the synthetic method of an oximido ether compound, it is characterised in that: the method includes the compound of reaction equation (1) with anti-
The compound answering formula (2) reacts under the conditions of peroxide, organic solvent, prepares formula (3) oximido ether compound, its reaction expression
As follows:
Wherein R1For C1-C6 alkyl or benzyl；R2For hydrogen, isobutyl group, cyclohexyl, phenyl, dimethyl substituents, methoxyl group, second
Epoxide, benzyloxy, dimethoxy substituent group, methylene-dioxy, nitro, halogen or methylsulfonyl；R3For hydrogen, C1-C6 alkyl, replacement
C1-C6 alkyl, acetonitrile-base, benzyl or phenyl.
A kind of synthetic method of oximido ether compound, it is characterised in that: wherein R1For methyl, ethyl
Or benzyl；R2For hydrogen, isobutyl group, cyclohexyl, phenyl, dimethyl substituents, methoxyl group, ethyoxyl, benzyloxy, dimethoxy
Substituent group, methylene-dioxy, nitro, halogen or methylsulfonyl；R3For hydrogen, methyl, propyl group, replacement C1-C6 alkyl, acetonitrile-base, benzyl
Base or phenyl.
The synthetic method of a kind of oximido ether compound the most according to claim 1, it is characterised in that: described peroxide
For the one in ammonium persulfate-sodium bisulfate, potassium peroxydisulfate, sodium peroxydisulfate or Ammonium persulfate..
The synthetic method of a kind of oximido ether compound the most according to claim 3, it is characterised in that: described peroxide
For potassium peroxydisulfate.
5. according to the synthetic method of a kind of oximido ether compound described in claim 1 or 3, it is characterised in that: described is organic
Solvent is ethanol, methanol, ethylene glycol, glycol dimethyl ether or the one of Isosorbide-5-Nitrae-dioxane.
The synthetic method of a kind of oximido ether compound the most according to claim 5, it is characterised in that: described organic solvent is
Ethanol or methanol.
The synthetic method of a kind of oximido ether compound the most according to claim 6, it is characterised in that: described organic solvent is
Methanol.
The synthetic method of a kind of oximido ether compound the most according to claim 1 and 2, it is characterised in that: described formula (1) is changed
The mol ratio of compound and formula (2) compound is 1:1～1.5.
The synthetic method of a kind of oximido ether compound the most according to claim 1 and 2, it is characterised in that: described formula (1) is changed
The mol ratio of compound and peroxide is 1:0.4～2.4.
The synthetic method of a kind of oximido ether compound the most according to claim 1 and 2, it is characterised in that: described organic molten
The addition of agent is 20 times of formula (1) compound by weight.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1182423A (en) * | 1995-02-24 | 1998-05-20 | 纳幕尔杜邦公司 | Fungicidal cyclic amides |
| CN103172613A (en) * | 2013-01-05 | 2013-06-26 | 南开大学 | O-formylamino benzamide derivative containing N-cyano sulfone(sulfur) imine and preparation method and use thereof |
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2016
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1182423A (en) * | 1995-02-24 | 1998-05-20 | 纳幕尔杜邦公司 | Fungicidal cyclic amides |
| CN103172613A (en) * | 2013-01-05 | 2013-06-26 | 南开大学 | O-formylamino benzamide derivative containing N-cyano sulfone(sulfur) imine and preparation method and use thereof |
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| Title |
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| HUNG-YAT THU ET AL.: "Intermolecular Amidation of Unactivated sp2 and sp3 C−H Bonds via Palladium-Catalyzed Cascade C−H Activation Nitrene Insertion", 《J. AM. CHEM. SOC.》 * |
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