阅读说明：本技术 一种2[(n-4-氯苯基)-1h-吡唑-3-基氧甲基]硝基苯的合成 (Synthesis of 2[ (N-4-chlorphenyl) -1H-pyrazol-3-yloxymethyl ] nitrobenzene ) 是由 王进 廖道华 祁康旭 徐瑶 潘光飞 曾挺 于 2021-06-16 设计创作，主要内容包括：本发明公开了一种2[(N-4-氯苯基)-1H-吡唑-3-基氧甲基]硝基苯的合成,由邻硝基甲苯在稀盐酸体系中跟碘化钾、双氧水合成得到邻硝基苄基碘,然后跟1-(4-氯苯基)-3-吡唑醇反应得到2[(N-4-氯苯基)-1H-吡唑-3-基氧甲基]硝基苯。本发明2[(N-4-氯苯基)-1H-吡唑-3-基氧甲基]硝基苯的合成方法几乎没有副产物,二碘代物不易生成,邻硝基甲苯的转化率高,可达99％以上。(The invention discloses a synthesis method of 2[ (N-4-chlorphenyl) -1H-pyrazol-3-yloxymethyl ] nitrobenzene, which comprises the steps of synthesizing o-nitrobenzyl iodide with potassium iodide and hydrogen peroxide in a dilute hydrochloric acid system, and then reacting with 1- (4-chlorphenyl) -3-pyrazol alcohol to obtain the 2[ (N-4-chlorphenyl) -1H-pyrazol-3-yloxymethyl ] nitrobenzene. The synthetic method of the 2[ (N-4-chlorphenyl) -1H-pyrazol-3-yloxymethyl ] nitrobenzene has almost no by-product, diiodo is not easy to generate, and the conversion rate of o-nitrotoluene is high and can reach more than 99%.)

1. The synthesis of 2[ (N-4-chlorphenyl) -1H-pyrazol-3-yloxymethyl ] nitrobenzene is characterized by comprising the following steps:

step S10, putting ortho-nitrotoluene into a reactor, adding water, hydrochloric acid, potassium iodide and dichloroethane, heating to 70-85 ℃, dropwise adding hydrogen peroxide, and keeping the temperature at 70-85 ℃ for 2 hours after dropwise adding;

step S20, controlling the content of o-nitrobenzyl to be below 1%, cooling to 45 ℃, standing for layering, performing desolventizing treatment on the lower layer, and removing dichloroethane to obtain o-nitrobenzyl iodide;

step S30, adding 1- (4-chlorphenyl) -3-pyrazole alcohol, water and potassium hydroxide into the o-nitrobenzyl iodide obtained by desolvation in step S20, heating to 60-70 ℃, and preserving heat for 3-5 hours;

and step S40, cooling to 25 ℃, centrifuging, and obtaining a solid material which is 2[ (N-4-chlorphenyl) -1H-pyrazol-3-yloxymethyl ] nitrobenzene after centrifuging.

2. The synthesis method according to claim 1, wherein in step S10, the concentration of hydrogen peroxide is 20-40%.

3. The synthesis method according to claim 1, wherein in step S10, the molar ratio of o-nitrotoluene to potassium iodide is 1: 1-1.15.

4. The synthesis method according to claim 1, wherein in step S10, the molar ratio of o-nitrotoluene to hydrogen peroxide is 1: 1.10-1.32.

5. The method according to claim 1, wherein the concentration of hydrochloric acid in step S10 is 20% to 40%.

6. The method according to claim 1, wherein in step S30, the molar ratio of o-nitrobenzyl iodide to 1- (4-chlorophenyl) -3-pyrazolol is 1:1 to 1.22.

7. The method of claim 1, wherein the purity of the sodium hydroxide in step S30 is 90%.

8. The method of claim 1, wherein in step S40, the mother solution obtained by centrifugation is concentrated, and the concentrated aqueous solution of potassium iodide is used.

Technical Field

The invention relates to the technical field of synthesis of organic compounds, in particular to synthesis of 2[ (N-4-chlorphenyl) -1H-pyrazol-3-yloxymethyl ] nitrobenzene.

Background

The traditional synthesis process of 2[ (N-4-chlorphenyl) -1H-pyrazol-3-yloxymethyl ] nitrobenzene is to brominate o-nitrotoluene in a reaction kettle to obtain o-nitrobenzyl bromide, and then to react with 1- (4-chlorphenyl) -3-pyrazol alcohol to obtain the product. However, 2-bromo is easily generated in the preparation process of o-nitrobenzyl bromide, and more than 30% of o-nitrotoluene can not react. The reaction formula is as follows:

bromination side reaction:

the dibromo compound content is generally more than 8 percent, and the o-nitrotoluene is not reacted for more than 30 percent, so that the produced 2[ (N-4-chlorphenyl) -1H-pyrazol-3-yloxymethyl ] nitrobenzene has low content and needs to be refined for many times.

Disclosure of Invention

Aiming at the problems, the invention provides a method for synthesizing 2[ (N-4-chlorphenyl) -1H-pyrazol-3-yloxymethyl ] nitrobenzene, which comprises the steps of synthesizing o-nitrobenzyl iodide with potassium iodide and hydrogen peroxide in a dilute hydrochloric acid system, and then reacting with 1- (4-chlorphenyl) -3-pyrazol alcohol to obtain the 2[ (N-4-chlorphenyl-1H-pyrazol-3-yloxymethyl ] nitrobenzene.

The technical scheme adopted by the invention for solving the problems is as follows: the synthesis of 2[ (N-4-chlorphenyl) -1H-pyrazol-3-yloxymethyl ] nitrobenzene includes the following steps:

step S10, putting ortho-nitrotoluene into a reactor, adding water, hydrochloric acid, potassium iodide and dichloroethane, heating to 70-85 ℃, dropwise adding hydrogen peroxide, and preserving heat for 2 hours at 70-85 ℃ after dropwise adding;

step S20, controlling the content of o-nitrobenzyl to be below 1%, cooling to 45 ℃, standing for layering, performing desolventizing treatment on the lower layer, and removing dichloroethane to obtain o-nitrobenzyl iodide;

step S30, adding 1- (4-chlorphenyl) -3-pyrazole alcohol, water and potassium hydroxide into the o-nitrobenzyl iodide obtained by desolvation in the step S20, heating to 60-70 ℃, and preserving heat for 3-5 hours;

and step S40, cooling to 25 ℃, centrifuging, and obtaining a solid material which is 2[ (N-4-chlorphenyl) -1H-pyrazol-3-yloxymethyl ] nitrobenzene after centrifuging.

Further, in step S10, the concentration of the hydrogen peroxide is 20 to 40%.

Further, in step S10, the molar ratio of o-nitrotoluene to potassium iodide is 1:1 to 1.15.

In step S10, the molar ratio of the o-nitrotoluene to the hydrogen peroxide is 1:1.10 to 1.32.

Further, in step S10, the concentration of hydrochloric acid is 20-40%.

Further, in step S30, the molar ratio of the o-nitrobenzyl iodide to the 1- (4-chlorophenyl) -3-pyrazolol is 1:1 to 1.22.

Further, in step S30, the purity of the sodium hydroxide is 90%.

Further, in step S40, the mother liquor obtained by the centrifugation is concentrated, and the concentrated potassium iodide aqueous solution is used.

The synthetic reaction formula of the 2[ (N-4-chlorphenyl) -1H-pyrazol-3-yloxymethyl ] nitrobenzene is as follows:

the invention has the advantages that:

(1) the synthetic method of the 2[ (N-4-chlorphenyl) -1H-pyrazol-3-yloxymethyl ] nitrobenzene almost has no by-product, diiodo is not easy to generate, and the conversion rate of o-nitrotoluene is high and can reach more than 99%;

(2) according to the synthetic method of the 2[ (N-4-chlorphenyl) -1H-pyrazol-3-yloxymethyl ] nitrobenzene, the content of the synthesized 2[ (N-4-chlorphenyl) -1H-pyrazol-3-yloxymethyl ] nitrobenzene is high and can reach more than 98%, and the potassium iodide can be recycled, so that the production cost is greatly reduced.

In addition to the objects, features and advantages described above, other objects, features and advantages of the present invention are also provided. The present invention will be described in further detail below.

Drawings

FIG. 1 is a flow chart of the synthesis of 2[ (N-4-chlorophenyl) -1H-pyrazol-3-yloxymethyl ] nitrobenzene according to the invention.

Detailed Description

The following detailed description of embodiments of the invention, but the invention can be practiced in many different ways, as defined and covered by the claims.

Example 1

The synthesis of 2[ (N-4-chlorphenyl) -1H-pyrazol-3-yloxymethyl ] nitrobenzene includes the following steps:

step S10, putting 140g of o-nitrotoluene with the purity of 99% into a reactor, adding 200g of water, 125g of hydrochloric acid with the concentration of 30%, 176g of potassium iodide with the purity of 99% and 260g of dichloroethane, heating to 75-80 ℃, dropwise adding 136g of hydrogen peroxide with the concentration of 30%, and after dropwise adding, keeping the temperature at 75-80 ℃ for 2 hours;

step S20, controlling the content of o-nitrobenzyl to be below 1%, cooling to 45 ℃, standing for layering, performing desolventizing treatment on the lower layer, and removing dichloroethane to obtain 259g of 98.5% o-nitrobenzyl iodide;

step S30, adding 195g of 99% pure 1- (4-chlorophenyl) -3-pyrazole alcohol, 360g of water and 68g of 90% pure potassium hydroxide into the o-nitrobenzyl iodide obtained by the desolvation in the step S20, heating to 65 ℃, and keeping the temperature for 4 hours;

and step S40, cooling to 25 ℃, centrifuging to obtain mother liquor, concentrating, mechanically using concentrated potassium iodide aqueous solution, and centrifuging to obtain a solid material 2[ (N-4-chlorphenyl-1H-pyrazol-3-yloxymethyl ] nitrobenzene.

Example 2

The synthesis of 2[ (N-4-chlorphenyl) -1H-pyrazol-3-yloxymethyl ] nitrobenzene includes the following steps:

step S10, putting 140g of o-nitrotoluene with the purity of 99% into a reactor, adding 220g of water, 195g of hydrochloric acid with the concentration of 20%, 180g of potassium iodide with the purity of 99% and 260g of dichloroethane, heating to 75-80 ℃, dropwise adding 210g of hydrogen peroxide with the concentration of 20%, after dropwise adding, keeping the temperature at 75-80 ℃ for 2 hours;

step S20, controlling the content of o-nitrobenzyl to be below 1%, cooling to 45 ℃, standing for layering, performing desolventizing treatment on the lower layer, and removing dichloroethane to obtain 259.4g of 98.7% o-nitrobenzyl iodide;

step S30, adding 195g of 99% pure 1- (4-chlorophenyl) -3-pyrazole alcohol, 380g of water and 70g of 90% pure potassium hydroxide into the o-nitrobenzyl iodide obtained by the desolvation in the step S20, heating to 60 ℃, and keeping the temperature for 3 hours;

and step S40, cooling to 25 ℃, centrifuging to obtain mother liquor, concentrating, mechanically using concentrated potassium iodide aqueous solution, centrifuging to obtain a solid material 2[ (N-4-chlorphenyl-1H-pyrazol-3-yloxymethyl ] nitrobenzene, wherein the weight of the solid material is 319.8 g.

Example 3

The synthesis of 2[ (N-4-chlorphenyl) -1H-pyrazol-3-yloxymethyl ] nitrobenzene includes the following steps:

step S10, adding 140g of o-nitrotoluene with the purity of 99% into a reactor, adding 250g of water, 99.75g of hydrochloric acid with the concentration of 40%, 182g of potassium iodide with the purity of 99% and 280g of dichloroethane, heating to 75-80 ℃, dropwise adding 94.875g of hydrogen peroxide with the concentration of 40%, after dropwise adding, keeping the temperature at 75-80 ℃ for 2 hours;

step S20, controlling the content of o-nitrobenzyl to be below 1%, cooling to 45 ℃, standing for layering, carrying out desolventizing treatment on the lower layer, and removing dichloroethane to obtain 258.2g of o-nitrobenzyl iodide with the content of 98.1%;

step S30, adding 195g of 99% pure 1- (4-chlorophenyl) -3-pyrazole alcohol, 380g of water and 75g of 90% pure potassium hydroxide into the o-nitrobenzyl iodide obtained by the desolvation in the step S20, heating to 70 ℃, and keeping the temperature for 5 hours;

and step S40, cooling to 25 ℃, centrifuging to obtain mother liquor, concentrating, mechanically using concentrated potassium iodide aqueous solution, centrifuging to obtain solid material 2[ (N-4-chlorphenyl) -1H-pyrazol-3-yloxymethyl ] nitrobenzene, wherein the weight is 316.8 g.

Example 4

The synthesis of 2[ (N-4-chlorphenyl) -1H-pyrazol-3-yloxymethyl ] nitrobenzene includes the following steps:

step S10, adding 140g of o-nitrotoluene with the purity of 99% into a reactor, adding 280g of water, 142g of hydrochloric acid with the concentration of 30%, 195g of potassium iodide with the purity of 99% and 300g of dichloroethane, heating to 75-80 ℃, dropwise adding 132g of hydrogen peroxide with the concentration of 30%, after dropwise adding, keeping the temperature at 75-80 ℃ for 2 hours;

step S20, controlling the content of o-nitrobenzyl to be below 1%, cooling to 45 ℃, standing for layering, performing desolventizing treatment on the lower layer, and removing dichloroethane to obtain 259.5g of o-nitrobenzyl iodide with the content of 99.2%;

step S30, adding 239g of 1- (4-chlorophenyl) -3-pyrazole alcohol with the purity of 99%, 350g of water and 65g of potassium hydroxide with the purity of 90% into the o-nitrobenzyl iodide obtained by the desolvation in the step S20, heating to 620 ℃, and preserving heat for 3.5 hours;

and step S40, cooling to 25 ℃, centrifuging to obtain mother liquor, concentrating, mechanically using concentrated potassium iodide aqueous solution, centrifuging to obtain a solid material 2[ (N-4-chlorphenyl) -1H-pyrazol-3-yloxymethyl ] nitrobenzene, wherein the weight of the solid material is 323.2 g.

Example 5

The synthesis of 2[ (N-4-chlorphenyl) -1H-pyrazol-3-yloxymethyl ] nitrobenzene includes the following steps:

step S10, adding 140g of o-nitrotoluene with the purity of 99% into a reactor, adding 240g of water, 134g of hydrochloric acid with the concentration of 30%, 170g of potassium iodide with the purity of 99% and 260g of dichloroethane, heating to 75-80 ℃, dropwise adding 151.5g of hydrogen peroxide with the concentration of 30%, after dropwise adding, keeping the temperature at 75-80 ℃ for 2 hours;

step S20, controlling the content of o-nitrobenzyl to be below 1%, cooling to 45 ℃, standing for layering, performing desolventizing treatment on the lower layer, and removing dichloroethane to obtain 259.3g of 98.4% o-nitrobenzyl iodide;

step S30, adding 198g of 99% pure 1- (4-chlorophenyl) -3-pyrazole alcohol, 360g of water and 69g of 90% pure potassium hydroxide into the o-nitrobenzyl iodide obtained by the desolvation in the step S20, heating to 68 ℃, and keeping the temperature for 4.5 hours;

and step S40, cooling to 25 ℃, centrifuging to obtain mother liquor, concentrating, mechanically using concentrated potassium iodide aqueous solution, centrifuging to obtain a solid material 2[ (N-4-chlorphenyl) -1H-pyrazol-3-yloxymethyl ] nitrobenzene, wherein the weight of the solid material is 317.4 g.

The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.