CN104262166A - Method for preparing o-phenylenediamine and derivative of o-phenylenediamine - Google Patents
Method for preparing o-phenylenediamine and derivative of o-phenylenediamine Download PDFInfo
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Abstract
The invention relates to a method for synthesizing organic compounds, and provides a method for preparing o-phenylenediamine and a derivative of o-phenylenediamine, for solving the problems that the process route is complex, a great amount of byproducts can be generated and are hard to purify, the reaction condition is rigorous, the environment pollution is severe and the like in a conventional method for synthesizing o-phenylenediamine derivatives. The method disclosed by the invention comprises the following steps: by taking azobenzene and a derivative of the azobenzene as raw materials, synthesizing the o-nitro azobenzene and the derivative of the o-nitro azobenzene under the coactions of a catalyst, an oxidant and a nitrating agent, and further reducing by using a reducing agent, thereby obtaining the o-phenylenediamine and the derivative of the o-phenylenediamine. The method provided by the invention has the advantages that the raw materials are cheap and easy to obtain, the operation is simple, convenient and safe, the synthesis steps are short, the purification is simple, no great waste acid pollution is caused, and the like.
Description
Technical field
The present invention is specifically related to the synthetic method of organic compound, and particularly a kind of take nitrogen benzide as the raw material first nitrated O-Phenylene Diamine preparation method restored.
Background technology
O-phenylene diamine derivatives is the important organic synthesis of a class and fine-chemical intermediate, mainly for the production of benzimidazole germicide, as can prevent and treat multiple kinds of crops, forest and the Micobial Disease of fruits and vegetables and the fresh-keeping of fruits and vegetables with store the derosal that synthesizes and, thiophanate_methyl etc., in addition, O-phenylene diamine derivatives is as dyestuff intermediate, for the preparation of vat dyes and cationic dyestuff, produce the yellowish-brown M of fur, cationic dyestuff, vat scarlet GG, reductive bright orange GR.Also for the manufacture of polymeric amide, urethane and levelling agent etc.
The industrialized route of current domestic production O-Phenylene Diamine mainly contains 3 kinds of methods such as sodium sulfide reducing and catalytic hydrogenating reduction: (1) sodium sulfide reducing reacts in pressure 98 ~ 196kPa, temperature of reaction 105 ~ 110 DEG C of situations with o-Nitraniline and sodium sulfide solution, also can carry out under temperature of reaction 120 ~ 130 DEG C and normal pressure, reaction times 3 ~ 4h, obtains O-Phenylene Diamine; (2) iron powder reducing under reduced iron powder effect, obtains O-Phenylene Diamine with o-Nitraniline.Although these two kinds of method production technique are simple, product yield is low, high expensive, and a large amount of waste water and dregs especially produced are difficult to process, and environmental pollution is quite serious.(3) technique of Preparation of O-Phenylenediamine by Catalytic Hydrogenation, as Chinese patent CN102633653A, which disclose a kind of method that o-Nitraniline shortening produces O-Phenylene Diamine, although the advantage such as have that good product quality, yield are high, " three wastes " few, but usually need to operate under elevated pressure conditions, to equipment and security requirement higher.In addition; the raw material o-Nitraniline that above method uses is all that after acetylize is protected, mixed acid nitrification and then hydrolysis obtain again by aniline; step is very complicated too; for the O-Phenylene Diamine of synthesis containing different substituents; owing to restricting by substituting group locating rule; denitrification step in Material synthesis there will be multiple isomer, is difficult to be separated.
Therefore, develop a kind of novel, general, the short O-Phenylene Diamine synthetic method of step easy and simple to handle is very necessary.
Summary of the invention
For solve at present synthesis O-Phenylene Diamine and derivative thereof method in complicated, the by product of operational path be difficult to purify more, severe reaction conditions and the problem such as environmental pollution is serious, the present invention proposes the preparation method of a kind of O-Phenylene Diamine and derivative thereof, synthetic method of the present invention has that raw material is cheap and easy to get, easy to operate and safe, synthesis step is short, purifying is simple, without advantages such as a large amount of spent acid pollutions.
The present invention is achieved by the following technical solutions: the preparation method of a kind of O-Phenylene Diamine and derivative thereof is take azobenzene and its derivatives as raw material, adjacent nitro-azo benzene and its derivative is synthesized through catalyzer, oxygenant, nitrating agent acting in conjunction, be reduced to O-Phenylene Diamine and derivative thereof by going back original reagent again, reaction structure formula is as follows:
，
R in reaction structure formula is selected from the one in H, methyl, ethyl, methoxyl group, sec.-propyl, the tertiary butyl, phenyl, itrile group, nitro or halogen.
Concrete steps are: azobenzene and its derivatives, catalyzer, oxygenant, nitrating agent are joined in the pressure-resistant seal pipe of organic solvent and reacted; After having reacted, cross and filter filter residue, and use washed with dichloromethane filter residue, collect filtrate drying; Then be spin-dried for by the solvent in filtrate, carry out purifying with silicagel column, eluent obtains adjacent nitro-azo benzene and its derivative; Again by adjacent for gained nitro-azo benzene derivative with go back original reagent, in an inert atmosphere, room temperature reduction reaction 10 ~ 30 hours, obtains end product O-Phenylene Diamine and derivative thereof.
Described catalyzer is selected from palladium, Palladous chloride, triphenylphosphine palladium chloride, tetrakis triphenylphosphine palladium, diacetonitrile palladium chloride a kind of, and the mol ratio of catalyzer and azobenzene and its derivatives is 1:5 ~ 10, and preferred molar ratio is 1:10.
Described oxygenant is selected from the one in Potassium Persulphate, iodobenzene diacetate, ceric ammonium nitrate (CAN), and the mol ratio of oxygenant and azobenzene and its derivatives is 1 ~ 3:1, and preferred molar ratio is 2:1.
Described nitrating agent is selected from Sodium Nitrite, potassium nitrite, the one in silver nitrite, is 1 ~ 3:1 with the mol ratio of azobenzene and its derivatives, preferred 2:1.
The organic solvent of described reaction is low polar organic solvent, and be preferably 1,2-ethylene dichloride (DEC), consumption is the amount making dissolution with solvents.
Described temperature of reaction is 80 ~ 130 DEG C, and the reaction times is 24 ~ 72 hours, and reaction is preferably 110 DEG C, 24 hours.
Described eluent is the mixing solutions of ethyl acetate and sherwood oil, and wherein the volume ratio of ethyl acetate and sherwood oil is 1:6.
Described original reagent of going back is zinc powder, the formic acid mix reagent in methanol solvate.The concentration of adjacent nitroazobenzene in formic acid is 0.1 ~ 0.2N, and the mol ratio of zinc powder and adjacent nitro-azo benzene and its derivative is 1 ~ 1.5: 1,
As preferably, the reduction reaction time is 24 hours.Rare gas element is preferably nitrogen or argon gas, and room temperature is 20 ~ 25 degrees Celsius.
Compared with prior art, the invention has the beneficial effects as follows:
(1) raw material nitrogen benzide is directly from aniline synthesis, and restore to Acetanilide is nitrated again the complex steps finally obtaining o-Nitraniline by aniline without the need to passing through, route is simple;
(2) the denitrification step isomer-free of nitrogen benzide produces, and avoids complicated isomer separation step;
(3) nitrogen benzide denitrification step is raw without excessive nitration product, avoids spent acid and pollutes;
(4) be reduced to O-Phenylene Diamine by adjacent nitroazobenzene and only need single step reaction, equipment requirements is not high.
Embodiment
Below by embodiment, the present invention is described in further detail.
Embodiment 1:
54.6 mg(0.3 mmol are added in an airtight reaction vessel) nitrogen benzide, 6.7 mg(0.03 mmol) palladium, 92.3 mg(0.6 mmol) silver nitrite, 162.2 mg(0.6 mmol) Potassium Persulphate, 3.5 mL DCE, reaction mixture stirring reaction 72 hours under 110 DEG C of conditions.After reaction stops, being cooled to room temperature, adding 10 mL methylene dichloride, slough solvent after decompress filter in reaction solution, residue is through column chromatography [GF254 silica gel (100-200 order); Eluent is V (sherwood oil)/V (ethyl acetate)=6/1] separating-purifying, obtain red brown solid 2-nitroazobenzene, yield is 95%.By 2-nitroazobenzene (0.3 mmol), zinc powder (0.36 mmol), formic acid (2 mL) mixing, in methanol solvate under condition of nitrogen gas room temperature reaction 24 hours, obtain the O-Phenylene Diamine that yield is 88%.
mp?102-104?oC;?IR?(neat):?n?=?3352?(NH2)?cm
-1;?1H?NMR?(CDCl3,?500?MHz):?δ?6.76-6.72?(m,?4H),?3.38?(s,?4H);?13C?NMR?(CDCl3,?125?MHz):?δ?134.76,?120.28,?116.76;?GC-MS?(EI,?70?eV):?m/z?=?108?[M+].
Embodiment 2:
54.6 mg(0.3 mmol are added in an airtight reaction vessel) nitrogen benzide, 0.03 mmol Palladous chloride, 0.6 mmol potassium nitrite, 0.6 mmol ceric ammonium nitrate, 3.5 mL DCE, reaction mixture stirring reaction 48 hours under 110 DEG C of conditions.After reaction stops, being cooled to room temperature, adding 10 mL methylene dichloride, slough solvent after decompress filter in reaction solution, residue is through column chromatography [GF254 silica gel (100-200 order); Eluent is V (sherwood oil)/V (ethyl acetate)=6/1] separating-purifying, obtain red brown solid 2-nitroazobenzene, productive rate is 70%.By 2-nitroazobenzene (0.3 mmol), zinc powder (0.45mol), formic acid (3 mL) mixing, in methanol solvate under condition of nitrogen gas room temperature reaction 24 hours, obtain the O-Phenylene Diamine that yield is 80%.
mp?102-104?oC;?IR?(neat):?n?=?3352?(NH2)?cm
-1;?1H?NMR?(CDCl3,?500?MHz):?δ?6.76-6.72?(m,?4H),?3.38?(s,?4H);?13C?NMR?(CDCl3,?125?MHz):?δ?134.76,?120.28,?116.76;?GC-MS?(EI,?70?eV):?m/z?=?108?[M+].
Embodiment 3:
0.3 mmol nitrogen benzide is added, 0.03 mmol diacetonitrile palladium chloride, 0.6 mmol Sodium Nitrite, 0.6 mmol Potassium Persulphate, 3.5 mL DCE, reaction mixture stirring reaction 72 hours under 110 DEG C of conditions in an airtight reaction vessel.After reaction stops, being cooled to room temperature, adding 10 mL methylene dichloride, slough solvent after decompress filter in reaction solution, residue is through column chromatography [GF254 silica gel (100-200 order); Eluent is V (sherwood oil)/V (ethyl acetate)=6/1] separating-purifying, obtain red brown solid 2-nitroazobenzene, productive rate is 56%.By 2-nitroazobenzene (0.3 mmol), zinc powder (0.36mol), formic acid (2 mL) mixing, in methanol solvate under condition of nitrogen gas room temperature reaction 24 hours, obtain the O-Phenylene Diamine that yield is 88%.
mp?102-104?oC;?IR?(neat):?n?=?3352?(NH2)?cm
-1;?1H?NMR?(CDCl3,?500?MHz):?δ?6.76-6.72?(m,?4H),?3.38?(s,?4H);?13C?NMR?(CDCl3,?125?MHz):?δ?134.76,?120.28,?116.76;?GC-MS?(EI,?70?eV):?m/z?=?108?[M+].
Embodiment 4
0.3 mmol nitrogen benzide is added, 0.06 mmol palladium, 0.6 mmol silver nitrite, 0.6 mmol Potassium Persulphate, 3.5 mL DCE, reaction mixture stirring reaction 48 hours under 90 DEG C of conditions in an airtight reaction vessel.After reaction stops, being cooled to room temperature, adding 10 mL methylene dichloride, slough solvent after decompress filter in reaction solution, residue is through column chromatography [GF254 silica gel (100-200 order); Eluent is V (sherwood oil)/V (ethyl acetate)=6/1] separating-purifying, obtain red brown solid 2-nitroazobenzene, productive rate is 85%.By 2-nitroazobenzene (0.3 mmol), zinc powder (0.36mol), formic acid (1.5 mL) mixing, in methanol solvate under argon gas condition room temperature reaction 24 hours, obtain the O-Phenylene Diamine that yield is 80%.
mp?102-104?oC;?IR?(neat):?n?=?3352?(NH2)?cm
-1;?1H?NMR?(CDCl3,?500?MHz):?δ?6.76-6.72?(m,?4H),?3.38?(s,?4H);?13C?NMR?(CDCl3,?125?MHz):?δ?134.76,?120.28,?116.76;?GC-MS?(EI,?70?eV):?m/z?=?108?[M+].
Embodiment 5
0.3 mmol nitrogen benzide is added, 0.08mmol Palladous chloride, 0.3 mmol silver nitrite, 0.3 mmol ceric ammonium nitrate, 3.5 mL DCE, reaction mixture stirring reaction 72 hours under 80 DEG C of conditions in an airtight reaction vessel.After reaction stops, being cooled to room temperature, adding 10 mL methylene dichloride, slough solvent after decompress filter in reaction solution, residue is through column chromatography [GF254 silica gel (100-200 order); Eluent is V (sherwood oil)/V (ethyl acetate)=6/1] separating-purifying, obtain red brown solid 2-nitroazobenzene, yield is 54%.By 2-nitroazobenzene (0.3 mmol), zinc powder (0.45mol), formic acid (2 mL) mixing, in methanol solvate under condition of nitrogen gas room temperature reaction 30 hours, obtain the O-Phenylene Diamine that yield is 85%.
mp?102-104?oC;?IR?(neat):?n?=?3352?(NH2)?cm
-1;?1H?NMR?(CDCl3,?500?MHz):?δ?6.76-6.72?(m,?4H),?3.38?(s,?4H);?13C?NMR?(CDCl3,?125?MHz):?δ?134.76,?120.28,?116.76;?GC-MS?(EI,?70?eV):?m/z?=?108?[M+].
Embodiment 6:
0.3 mmol 4 is added, 4 '-dimethyl nitrogen benzide, 0.03 mmol triphenylphosphine palladium chloride, 0.9mmol potassium nitrite, 0.9 mmol Potassium Persulphate, 3.5 mL DCE, reaction mixture stirring reaction 36 hours under 130 DEG C of conditions in an airtight reaction vessel.After reaction stops, being cooled to room temperature, adding 10 mL methylene dichloride, slough solvent after decompress filter in reaction solution, residue is through column chromatography [GF254 silica gel (100-200 order); Eluent is V (sherwood oil)/V (ethyl acetate)=6/1] separating-purifying, obtain red brown solid 2-nitro-4,4 '-dimethyl nitrogen benzide, yield is 65%.By 2-nitro-4,4 '-dimethyl nitrogen benzide (0.3 mmol), zinc powder (0.45mol), formic acid (3 mL) mix, in methanol solvate under condition of nitrogen gas room temperature reaction 10 hours, obtain the 4-methyl isophthalic acid of yield 76%, 2-phenylenediamine yellow solid.
mp?87-89?oC;?IR?(neat):?(?=?3422?(NH
2)?cm
-1;?
1H?NMR?(CDCl
3,?500?MHz):?δ?6.63?(d,?
J?=?10?Hz,?1H),?6.54?(t,?
J?=?5?Hz,?2H),?3.30?(s,?4H),?2.23?(s,?3H);?
13C?NMR?(CDCl
3,?125?MHz):?δ?134.99,?131.82,?129.97,?117.40,?117.05,?20.66;?GC-MS?(EI,?70?eV):?
m/z?=?122?[M
+].
Embodiment 7:
0.3 mmol 2 is added, 2 '-dimethyl nitrogen benzide, 0.03 mmol palladium, 0.9 mmol Sodium Nitrite, 0.9mmol iodobenzene diacetate, 3.5 mL DCE, reaction mixture stirring reaction 72 hours under 110 DEG C of conditions in an airtight reaction vessel.After reaction stops, being cooled to room temperature, adding 10 mL methylene dichloride, slough solvent after decompress filter in reaction solution, residue is through column chromatography [GF254 silica gel (100-200 order); Eluent is V (sherwood oil)/V (ethyl acetate)=6/1] separating-purifying, obtain brown liquid 2-nitro-6,6 '-dimethyl nitrogen benzide, yield is 69%.By 2-nitro-6,6 '-dimethyl nitrogen benzide (0.3 mmol), zinc powder (0.36mol), formic acid (2 mL) mix, in methanol solvate under condition of nitrogen gas room temperature reaction 20 hours, obtain the 2-methyl isophthalic acid that yield is 89%, 2-phenylenediamine yellow solid.
mp?71-72?oC;?IR?(neat):?(?=?3413?(NH
2)?cm
-1;?
1H?NMR?(CDCl
3,?500?MHz):?δ6.58?(d,?
J?=?10?Hz,?1H),?6.52?(t,?
J?=?5?Hz,?2H),?3.41?(s,?4H),?2.26?(s,?3H);?
13C?NMR?(CDCl
3,?125?MHz):?δ?135.11,?132.82,?129.13,?116.40,?116.05,?19.74;?GC-MS?(EI,?70?eV):?
m/z?=?122?[M
+].
Embodiment 8:
0.3 mmol 3 is added, 3 '-dimethyl nitrogen benzide, 0.05mmol tetrakis triphenylphosphine palladium, 0.6 mmol silver nitrite, 0.6mmol ceric ammonium nitrate, 3.5 mL DCE, reaction mixture stirring reaction 60 hours under 90 DEG C of conditions in an airtight reaction vessel.After reaction stops, being cooled to room temperature, adding 10 mL methylene dichloride, slough solvent after decompress filter in reaction solution, residue is through column chromatography [GF254 silica gel (100-200 order); Eluent is V (sherwood oil)/V (ethyl acetate)=6/1] separating-purifying, obtain brown liquid 2-nitro-5,5 '-dimethyl nitrogen benzide, yield is 90%.By 2-nitro-5,5 '-dimethyl nitrogen benzide (0.3 mmol), zinc powder (0.45mol), formic acid (1.5 mL) mix, in methanol solvate under condition of nitrogen gas room temperature reaction 24 hours, obtain the 4-methyl isophthalic acid that yield is 90%, 2-phenylenediamine yellow solid.
mp?87-89?oC;?IR?(neat):?(?=?3422?(NH
2)?cm
-1;?
1H?NMR?(CDCl
3,?500?MHz):?δ?6.63?(d,?
J?=?10?Hz,?1H),?6.54?(t,?
J?=?5?Hz,?2H),?3.30?(s,?4H),?2.23?(s,?3H);?
13C?NMR?(CDCl
3,?125?MHz):?δ?134.99,?131.82,?129.97,?117.40,?117.05,?20.66;?GC-MS?(EI,?70?eV):?
m/z?=?122?[M
+].
Embodiment 9:
0.3 mmol 3,3 ', 5 is added, 5 '-tetramethyl-nitrogen benzide, 0.06 mmol palladium, 0.5 mmol potassium nitrite, 0.5mmol Potassium Persulphate, 3.5 mL DCE, reaction mixture stirring reaction 50 hours under 100 DEG C of conditions in an airtight reaction vessel.After reaction stops, being cooled to room temperature, adding 10 mL methylene dichloride, slough solvent after decompress filter in reaction solution, residue is through column chromatography [GF254 silica gel (100-200 order); Eluent is V (sherwood oil)/V (ethyl acetate)=6/1] separating-purifying, obtain brown liquid 2-nitro-3,3 ', 5,5 '-tetramethyl-nitrogen benzide, yield is 63%.By 2-nitro 3,3 ', 5,5 '-tetramethyl-nitrogen benzide (0.3 mmol), zinc powder (0.36mol), formic acid (3 mL) mix, in methanol solvate under condition of nitrogen gas room temperature reaction 24 hours, obtain 3,5-dimethyl 1, the 2-phenylenediamine yellow solids that yield is 75%.
mp?127-128?oC;?IR?(neat):?(?=?3456?(NH
2)?cm
-1;?
1H?NMR?(CDCl
3,?500?MHz):?δ?6.53?(s,?1H),?6.48?(d,?
J?=?10?Hz,?1H),?3.06?(s,?4H),?2.20?(t,?
J?=?10?Hz,?3H),?2.14?(s,?3H);?
13C?NMR?(CDCl
3,?125?MHz):?δ?134.22,?132.31,?130.55,?128.71,?122.54,?118.57,?20.57,?18.85;?GC-MS?(EI,?70?eV):?
m/z?=?136?[M
+].
Embodiment 10:
0.3 mmol 3,3 ', 4 is added in an airtight reaction vessel, 4 '-tetramethyl-nitrogen benzide, 0.03 mmol tetrakis triphenylphosphine palladium, 0.6 mmol Sodium Nitrite, 0.6 mmol iodobenzene diacetate, 3.5 mL DCE, reaction mixture stirring reaction 40 hours under 110 DEG C of conditions.After reaction stops, being cooled to room temperature, adding 10 mL methylene dichloride, slough solvent after decompress filter in reaction solution, residue is through column chromatography [GF254 silica gel (100-200 order); Eluent is V (sherwood oil)/V (ethyl acetate)=6/1] separating-purifying, obtain brown liquid 2-nitro-3,3 ' 4,4 '-tetramethyl-nitrogen benzide, yield is 74%.By 2-nitro-3,3 ', 4,4 '-tetramethyl-nitrogen benzide (0.3 mmol), zinc powder (0.36mol), formic acid (2 mL) mix, in methanol solvate under condition of nitrogen gas room temperature reaction 24 hours, obtain 4,5-dimethyl-1, the 2-phenylenediamine yellow solids that yield is 78%.
mp?126-128?oC;?IR?(neat):?(?=?3451?(NH
2)?cm
-1;?
1H?NMR?(CDCl
3,?500?MHz):?δ?6.48?(d,?
J?=?10?Hz,?2H),?3.21?(s,?4H),?2.20?(d,?
J?=?10?Hz,?6H);?
13C?NMR?(CDCl
3,?125?MHz):?δ?134.24,?130.56,?128.70,?123.58,?122.53,?115.61,?20.57,?17.39;?GC-MS?(EI,?70?eV):?
m/z?=?136?[M
+].
Claims (10)
1. the preparation method of an O-Phenylene Diamine and derivative thereof, it is characterized in that, described preparation method is take azobenzene and its derivatives as raw material, adjacent nitro-azo benzene and its derivative is synthesized through catalyzer, oxygenant, nitrating agent acting in conjunction, be reduced to O-Phenylene Diamine and derivative thereof by going back original reagent again, reaction structure formula is as follows:
。
2. the preparation method of a kind of O-Phenylene Diamine according to claim 1 and derivative thereof, is characterized in that, the R in reaction structure formula is selected from the one in H, methyl, ethyl, methoxyl group, sec.-propyl, the tertiary butyl, phenyl, itrile group, nitro or halogen.
3. the preparation method of a kind of O-Phenylene Diamine according to claim 1 and derivative thereof, is characterized in that, described concrete steps are: azobenzene and its derivatives, catalyzer, oxygenant, nitrating agent are joined in the pressure-resistant seal pipe of organic solvent and reacted; After having reacted, cross and filter filter residue, and use washed with dichloromethane filter residue, collect filtrate drying; Then be spin-dried for by the solvent in filtrate, carry out purifying with silicagel column, eluent obtains adjacent nitro-azo benzene and its derivative; Again by adjacent for gained nitro-azo benzene derivative with go back original reagent, in an inert atmosphere, room temperature reduction reaction 10 ~ 30 hours, obtains end product O-Phenylene Diamine and derivative thereof.
4. a kind of O-Phenylene Diamine according to claim 1 or 3 and the preparation method of derivative thereof, it is characterized in that, described catalyzer is selected from palladium, Palladous chloride, triphenylphosphine palladium chloride, tetrakis triphenylphosphine palladium, diacetonitrile palladium chloride a kind of, mol ratio 1:5 ~ 10 of catalyzer and azobenzene and its derivatives.
5. a kind of O-Phenylene Diamine according to claim 1 or 3 and the preparation method of derivative thereof, it is characterized in that, described oxygenant is selected from the one in Potassium Persulphate, iodobenzene diacetate, ceric ammonium nitrate, and the mol ratio of oxygenant and azobenzene and its derivatives is 1 ~ 3:1.
6. a kind of O-Phenylene Diamine according to claim 1 or 3 and the preparation method of derivative thereof, it is characterized in that, described nitrating agent is selected from Sodium Nitrite, potassium nitrite, the one in silver nitrite, is 1 ~ 3:1 with the mol ratio of azobenzene and its derivatives.
7. the preparation method of a kind of O-Phenylene Diamine according to claim 3 and derivative thereof, is characterized in that: the organic solvent of described reaction is low polar organic solvent.
8. a kind of O-Phenylene Diamine according to claim 1 or 3 and the preparation method of derivative thereof, is characterized in that: described original reagent of going back is zinc powder, the formic acid mix reagent in methanol solvate.
9. the preparation method of a kind of O-Phenylene Diamine according to claim 8 and derivative thereof, is characterized in that, the concentration of adjacent nitroazobenzene in formic acid is 0.1 ~ 0.2N, and the mol ratio of zinc powder and adjacent nitro-azo benzene and its derivative is 1 ~ 1.5: 1.
10. the preparation method of a kind of O-Phenylene Diamine according to claim 1 and derivative thereof, is characterized in that, described temperature of reaction is 80 ~ 130 DEG C, and the reaction times is 24 ~ 72 hours.
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| CN109970701A (en) * | 2019-04-02 | 2019-07-05 | 常州大学 | It is a kind of to use I2O5/NaNO2The method for nitrifying Electron rich aromatic compounds of group |
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| CN106349082A (en) * | 2016-08-29 | 2017-01-25 | 安阳师范学院 | Preparation method of m-alkylaniline |
| CN106518734A (en) * | 2016-10-21 | 2017-03-22 | 丽水学院 | Method for preparation of sulfinic acid ester from thiophenol or thiol |
| CN109970701A (en) * | 2019-04-02 | 2019-07-05 | 常州大学 | It is a kind of to use I2O5/NaNO2The method for nitrifying Electron rich aromatic compounds of group |
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