A kind of preparation method of o-phenylenediamine and its derivatives

Abstract

The present invention specifically relates to a method for synthesizing organic compounds. In order to solve the problems in the current method for synthesizing o-phenylenediamine derivatives, such as complex process routes, many by-products that are difficult to purify, harsh reaction conditions, and serious environmental pollution, the present invention proposes an ortho-phenylenediamine derivative. The preparation method of phenylenediamine and its derivatives uses azobenzene and its derivatives as raw materials, synthesizes o-nitroazobenzene and its derivatives through the joint action of catalysts, oxidants, and nitrating agents, and then reduces them to o-nitroazobenzene and its derivatives by reducing reagents. The synthesis method of the phenylenediamine and its derivatives has the advantages of cheap and easy-to-obtain raw materials, simple and safe operation, short synthesis steps, simple purification, and no large amount of waste acid pollution.

Description

technical field

[0001] The invention specifically relates to a method for synthesizing organic compounds, in particular to a method for preparing o-phenylenediamine using azobenzene as a raw material, which is first nitrated and then reduced. Background technique

[0002] O-phenylenediamine derivatives are an important class of organic synthesis and fine chemical intermediates, mainly used in the production of benzimidazole fungicides, such as the prevention and treatment of bacterial diseases of various crops, trees, fruits and vegetables, as well as the preservation and storage of fruits and vegetables Carbendazim and thiophanate-methyl, etc. In addition, o-phenylenediamine derivatives are used as dye intermediates for the preparation of vat dyes and cationic dyes, and the production of fur yellow brown M, cationic dyes, vat red GG, vat brilliant Orange Gr. It is also used in the manufacture of polyamide, polyurethane and leveling agent.

[0003] At present, the domestic...

Examples

Embodiment 1

[0025] Add 54.6 mg (0.3 mmol) azobenzene, 6.7 mg (0.03 mmol) palladium acetate, 92.3 mg (0.6 mmol) silver nitrite, 162.2 mg (0.6 mmol) potassium persulfate, 3.5 mL DCE into a closed reaction vessel , the reaction mixture was stirred and reacted at 110° C. for 72 hours. After the reaction stopped, cool to room temperature, add 10 mL of dichloromethane to the reaction solution, remove the solvent after suction filtration under reduced pressure, and the residue was subjected to column chromatography [GF254 silica gel (100-200 mesh); eluent was V (petroleum ether) / V(ethyl acetate)=6 / 1] separation and purification to obtain reddish-brown solid 2-nitroazobenzene with a yield of 95%. 2-Nitroazobenzene (0.3 mmol), zinc powder (0.36 mmol), and formic acid (2 mL) were mixed and reacted in methanol solvent under nitrogen atmosphere for 24 hours at room temperature to obtain o-benzene with a yield of 88%. diamine.

[0026]

[0027] mp 102-104 ºC; IR (neat): n = 3352 (NH2) cm -1 ; 1H...

Embodiment 2

[0029] Add 54.6 mg (0.3 mmol) of azobenzene, 0.03 mmol of palladium chloride, 0.6 mmol of potassium nitrite, 0.6 mmol of ceric ammonium nitrate, 3.5 mL of DCE into a closed reaction vessel, and stir the reaction mixture at 110°C for 48 Hour. After the reaction stopped, cool to room temperature, add 10 mL of dichloromethane to the reaction solution, remove the solvent after suction filtration under reduced pressure, and the residue was subjected to column chromatography [GF254 silica gel (100-200 mesh); eluent was V (petroleum ether) / V(ethyl acetate)=6 / 1] separation and purification to obtain reddish-brown solid 2-nitroazobenzene with a yield of 70%. 2-Nitroazobenzene (0.3 mmol), zinc powder (0.45 mol), and formic acid (3 mL) were mixed and reacted in a methanol solvent under nitrogen at room temperature for 24 hours to obtain o-benzene with a yield of 80%. diamine.

[0030]

[0031] mp 102-104 ºC; IR (neat): n = 3352 (NH2) cm -1 ; 1H NMR (CDCl3, 500MHz): δ 6.76-6.72 (m, ...

Embodiment 3

[0033] Add 0.3 mmol of azobenzene, 0.03 mmol of diacetonitrile palladium dichloride, 0.6 mmol of sodium nitrite, 0.6 mmol of potassium persulfate, 3.5 mL of DCE into a closed reaction vessel, and stir the reaction mixture at 110°C for 72 hours . After the reaction stopped, cool to room temperature, add 10 mL of dichloromethane to the reaction solution, remove the solvent after suction filtration under reduced pressure, and the residue was subjected to column chromatography [GF254 silica gel (100-200 mesh); eluent was V (petroleum ether) / V(ethyl acetate)=6 / 1] separation and purification to obtain reddish-brown solid 2-nitroazobenzene with a yield of 56%. 2-Nitroazobenzene (0.3 mmol), zinc powder (0.36 mol), and formic acid (2 mL) were mixed and reacted in methanol solvent under nitrogen at room temperature for 24 hours to obtain o-benzene with a yield of 88%. diamine.

[0034]

[0035] mp 102-104 ºC; IR (neat): n = 3352 (NH2) cm -1 ; 1H NMR (CDCl3, 500MHz): δ 6.76-6.72 (m...

technical field

[0001] The invention specifically relates to a method for synthesizing organic compounds, in particular to a method for preparing o-phenylenediamine using azobenzene as a raw material, which is first nitrated and then reduced. Background technique

[0002] O-phenylenediamine derivatives are an important class of organic synthesis and fine chemical intermediates, mainly used in the production of benzimidazole fungicides, such as the prevention and treatment of bacterial diseases of various crops, trees, fruits and vegetables, as well as the preservation and storage of fruits and vegetables Carbendazim and thiophanate-methyl, etc. In addition, o-phenylenediamine derivatives are used as dye intermediates for the preparation of vat dyes and cationic dyes, and the production of fur yellow brown M, cationic dyes, vat red GG, vat brilliant Orange Gr. It is also used in the manufacture of polyamide, polyurethane and leveling agent.

[0003] At present, the domestic...

Examples

Embodiment 1

[0025] Add 54.6 mg (0.3 mmol) azobenzene, 6.7 mg (0.03 mmol) palladium acetate, 92.3 mg (0.6 mmol) silver nitrite, 162.2 mg (0.6 mmol) potassium persulfate, 3.5 mL DCE into a closed reaction vessel , the reaction mixture was stirred and reacted at 110° C. for 72 hours. After the reaction stopped, cool to room temperature, add 10 mL of dichloromethane to the reaction solution, remove the solvent after suction filtration under reduced pressure, and the residue was subjected to column chromatography [GF254 silica gel (100-200 mesh); eluent was V (petroleum ether) / V(ethyl acetate)=6 / 1] separation and purification to obtain reddish-brown solid 2-nitroazobenzene with a yield of 95%. 2-Nitroazobenzene (0.3 mmol), zinc powder (0.36 mmol), and formic acid (2 mL) were mixed and reacted in methanol solvent under nitrogen atmosphere for 24 hours at room temperature to obtain o-benzene with a yield of 88%. diamine.

[0026]

[0027] mp 102-104 ºC; IR (neat): n = 3352 (NH2) cm -1 ; 1H...

Embodiment 2

[0029] Add 54.6 mg (0.3 mmol) of azobenzene, 0.03 mmol of palladium chloride, 0.6 mmol of potassium nitrite, 0.6 mmol of ceric ammonium nitrate, 3.5 mL of DCE into a closed reaction vessel, and stir the reaction mixture at 110°C for 48 Hour. After the reaction stopped, cool to room temperature, add 10 mL of dichloromethane to the reaction solution, remove the solvent after suction filtration under reduced pressure, and the residue was subjected to column chromatography [GF254 silica gel (100-200 mesh); eluent was V (petroleum ether) / V(ethyl acetate)=6 / 1] separation and purification to obtain reddish-brown solid 2-nitroazobenzene with a yield of 70%. 2-Nitroazobenzene (0.3 mmol), zinc powder (0.45 mol), and formic acid (3 mL) were mixed and reacted in a methanol solvent under nitrogen at room temperature for 24 hours to obtain o-benzene with a yield of 80%. diamine.

[0030]

[0031] mp 102-104 ºC; IR (neat): n = 3352 (NH2) cm -1 ; 1H NMR (CDCl3, 500MHz): δ 6.76-6.72 (m, ...

Embodiment 3

[0033] Add 0.3 mmol of azobenzene, 0.03 mmol of diacetonitrile palladium dichloride, 0.6 mmol of sodium nitrite, 0.6 mmol of potassium persulfate, 3.5 mL of DCE into a closed reaction vessel, and stir the reaction mixture at 110°C for 72 hours . After the reaction stopped, cool to room temperature, add 10 mL of dichloromethane to the reaction solution, remove the solvent after suction filtration under reduced pressure, and the residue was subjected to column chromatography [GF254 silica gel (100-200 mesh); eluent was V (petroleum ether) / V(ethyl acetate)=6 / 1] separation and purification to obtain reddish-brown solid 2-nitroazobenzene with a yield of 56%. 2-Nitroazobenzene (0.3 mmol), zinc powder (0.36 mol), and formic acid (2 mL) were mixed and reacted in methanol solvent under nitrogen at room temperature for 24 hours to obtain o-benzene with a yield of 88%. diamine.

[0034]

[0035] mp 102-104 ºC; IR (neat): n = 3352 (NH2) cm -1 ; 1H NMR (CDCl3, 500MHz): δ 6.76-6.72 (m...

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