CN119192233A

CN119192233A - A toluenesulfonyldiazodiphenylphosphine compound and its preparation method and application

Info

Publication number: CN119192233A
Application number: CN202411319247.XA
Authority: CN
Inventors: 赵青海; 陈炽; 刘林; 于卫华
Original assignee: Guangzhou Chenhong Technology Co ltd
Current assignee: Guangzhou Chenhong Technology Co ltd
Priority date: 2024-03-19
Filing date: 2024-09-22
Publication date: 2024-12-27
Anticipated expiration: 2044-09-22
Also published as: CN119192233B; CN117924357A

Abstract

The invention belongs to the technical field of organic synthesis, and discloses a tosyl diazo diphenyl phosphorus compound, a preparation method and application thereof. The structural formula of the tosyl diazo diphenyl phosphorus compound is shown as formula I. The preparation method comprises the following steps of adding p-toluenesulfonyl hydrazine into an organic solvent, stirring and dissolving uniformly, cooling to 5-10 ℃, dropwise adding diphenyl phosphorus chloride, stirring and reacting at room temperature, heating to 40-50 ℃ after the reaction is finished, dropwise adding hydrogen peroxide, heating to reflux temperature, carrying out reflux reaction, standing and layering after the reaction is finished, removing an aqueous phase layer, concentrating and crystallizing an organic phase, and obtaining the toluenesulfonyl diazodiphenyl phosphorus compound. The tosyl diazo diphenyl phosphorus compound of the invention can be used as a photoinitiator. And the synthesis method is simple, the reaction condition is mild, the raw material sources are wide, the production cost is low, and the method is easy to apply in industrialization.

Description

Tosyl diazo diphenyl phosphorus compound and preparation method and application thereof

Technical Field

The invention belongs to the technical field of organic synthesis, and particularly relates to a tosyl diazo diphenyl phosphorus compound, a preparation method and application thereof.

Background

Diphenylphosphine compounds are widely used in flame retardants and light stabilizers and in the fields of dyes, pigments, medicine, and the like. The tosyl has stronger electrophilicity and good stability, so that the tosyl has wide application in organic synthesis. First, tosyl can react with nucleophiles as electrophiles to form new compounds. For example, tosyl groups can be reacted with amines to form sulfonamide compounds, or alcohols to form sulfonate compounds. These reactions find wide application in pharmaceutical synthesis and in the synthesis of natural products. Meanwhile, the sulfonate also has wide application in the fields of flame retardants, dispersants and the like. However, at present, new structural compounds obtained by combining a diphenylphosphine compound with a tosyl group have been rarely reported as application of photoinitiators.

Disclosure of Invention

In view of the above-mentioned shortcomings and drawbacks of the prior art, a primary object of the present invention is to provide a tosyl diazo diphenyl phosphorus compound (SPN).

It is another object of the present invention to provide a process for producing the above tosyl diazo diphenyl phosphorus compound.

It is a further object of the present invention to provide the use of the above tosyl diazo diphenyl phosphorus compound as an ultraviolet light initiator.

The invention aims at realizing the following technical scheme:

a tosyl diazo diphenyl phosphorus compound has a structural formula shown in the following formula I:

the preparation method of the tosyl diazo diphenyl phosphorus compound comprises the following preparation steps:

(1) Adding p-toluenesulfonyl hydrazine into an organic solvent, stirring and dissolving uniformly, cooling to 5-10 ℃, then dropwise adding diphenyl phosphorus chloride, and stirring and reacting at room temperature after the dropwise adding is finished;

(2) Heating to 40-50 ℃ after the reaction in the step (1), dropwise adding hydrogen peroxide, heating to a reflux temperature for reflux reaction, standing and layering after the reaction is finished to remove a water phase layer, and concentrating and crystallizing an organic phase to obtain the tosyl diazo diphenyl phosphorus compound.

Further, in the step (1), the organic solvent is dichloroethane.

Further, the temperature of the reaction system is controlled below 25 ℃ in the process of dropwise adding the diphenyl phosphorus chloride in the step (1).

Further, in the step (1), the stirring reaction time is 3-5 hours.

Further, in the step (1), the molar ratio of the p-toluenesulfonyl hydrazine to the diphenyl phosphorus chloride is 0.9-1.1:1.

Further, the molar ratio of the hydrogen peroxide added in the step (2) to the p-toluenesulfonyl hydrazide is 2-3:1 based on the hydrogen peroxide content.

Further, the time of the reflux reaction in the step (2) is 2-3 hours.

Further, the temperature of crystallization in the step (2) is 5 to-5 ℃.

The synthetic route for the above reaction is shown below:

the application of the tosyl diazo diphenyl phosphorus compound as an ultraviolet initiator. Can be applied to ultraviolet light curing of white ink systems for plastics and PCBs. Has the advantages of strong adhesive force, light resistance, yellowing resistance, high temperature resistance, high hardness and the like.

Compared with the prior art, the invention has the beneficial effects that:

(1) The tosyl diazo diphenyl phosphorus compound provided by the invention contains a diphenyl phosphorus compound structure and a benzenesulfonyl structure, and a diazo connecting group is further introduced, so that the application performance of the two compounds can be combined or improved, and the application range of the compound is widened.

(2) The synthesis method provided by the invention is simple, mild in reaction condition, wide in raw material source, high in purity and yield of the obtained product, low in production cost and easy to industrialize.

(3) The tosyl diazo diphenyl phosphorus compound provided by the invention has obvious ultraviolet absorption and initiation characteristics, can be applied to ultraviolet curing of white ink systems for plastics and PCBs, and has the advantages of strong adhesive force, light resistance, yellowing resistance, high temperature resistance, high hardness and the like.

Drawings

FIG. 1 is an infrared spectrum of a tosyl diazo diphenyl phosphorus compound obtained in example;

FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of the tosyl diazo diphenyl phosphorus compound obtained in the example;

FIG. 3 is an external appearance pattern of the tosyl diazo diphenyl phosphorus compound obtained in the example;

FIG. 4 is a chart showing the ultraviolet scanning spectrum of the tosyl diazo diphenyl phosphorus compound obtained in example.

Detailed Description

The present invention will be described in further detail with reference to examples and drawings, but embodiments of the present invention are not limited thereto.

Example 1

A preparation method of a tosyl diazo diphenyl phosphorus compound comprises the following preparation steps:

(1) Into a 3L flask, p-toluenesulfonyl hydrazine (186 g) and 500ml of dichloroethane were added and mixed, and stirred and dissolved uniformly, and the temperature was lowered to 5 ℃. To the flask was added dropwise diphenyl phosphorus chloride (220 g), the temperature was controlled to 25℃or lower, and after the completion of the addition, the reaction was allowed to proceed at room temperature for 4 hours.

(2) And (3) heating to 40-50 ℃ after the reaction in the step (1), dropwise adding hydrogen peroxide (250 g, 30 wt%) into the flask, slowly heating to reflux after the dropwise adding is finished, refluxing for 2.5 hours, separating out water after the reaction is finished, evaporating 300 ml of dichloroethane of the product, cooling to about 0 ℃, and generating a large amount of white crystalline solid, namely the tosyl diazo diphenyl phosphorus compound (SPN) of the product.

The tosyl diazo diphenyl phosphorus compound obtained in this example was detected to have a purity of 96.1% and a yield of 96.4%.

The infrared spectrum and the nuclear magnetic resonance hydrogen spectrum of the tosyl diazo diphenyl phosphorus compound obtained in this example are shown in fig. 1 and fig. 2, respectively. The target product is obtained through the identification spectrogram.

The tosyl diazo diphenyl phosphorus compound obtained in this example was in the form of white crystals, and the external appearance thereof was as shown in FIG. 3.

The ultraviolet scanning spectrum of the tosyl diazo diphenyl phosphorus compound obtained in this example is shown in FIG. 4. As can be seen from FIG. 4, the tosyl diazo diphenyl phosphorus compound obtained by the invention has obvious ultraviolet absorption and excitation characteristics.

The tosyl diazo diphenyl phosphorus compound obtained in the embodiment is applied to UV curing of protective adhesive ink for plastics such as PVC buckle plates, floor tiles, PET, PC and the like:

The ink comprises 46.25% of prepolymer (aliphatic acrylic polyurethane), 30% of UV monomer (TMPTA, ethoxylated trimethylolpropane triacrylate), 20% of titanium pigment, 3% of initiator SPN, 0.5% of flatting agent (polydimethylsiloxane), 0.2% of defoamer (polyether silicone oil) and 0.05% of polymerization inhibitor HQ.

The obtained ink is cured by irradiation of a UV lamp for 15s to be completely cured. The obtained protective adhesive has the advantages of strong adhesive force, light resistance, yellowing resistance, high temperature resistance, high hardness and the like.

Example 2

(1) Into a 3L flask, p-toluenesulfonyl hydrazine (170 g) and 500 ml of dichloroethane were added and mixed, and stirred and dissolved uniformly, and the temperature was lowered to 10 ℃. To the flask was added dropwise diphenyl phosphorus chloride (220 g), the temperature was controlled to 25℃or lower, and after the completion of the addition, the reaction was allowed to proceed at room temperature for 3 hours.

(2) And (3) heating to 40-50 ℃ after the reaction in the step (1), dropwise adding hydrogen peroxide (250 g, 30 wt%) into the flask, slowly heating to reflux after the dropwise adding is finished, refluxing for 2 hours, separating out water after the reaction is finished, evaporating 350 ml of dichloroethane of the product, cooling to about 0 ℃, and generating a large amount of white crystalline solid, namely the tosyl diazodiphenyl phosphorus compound (SPN) of the product.

The tosyl diazo diphenyl phosphorus compound obtained in this example was detected to have a purity of 95.7% and a yield of 96.3%.

Example 3

(1) Into a 3L flask, p-toluenesulfonyl hydrazine (200 g) and 500 ml of dichloroethane were added and mixed, and stirred and dissolved uniformly, and the temperature was lowered to 10 ℃. To the flask was added dropwise diphenyl phosphorus chloride (220 g), the temperature was controlled to 25℃or lower, and after the completion of the addition, the reaction was allowed to proceed at room temperature for 5 hours.

(2) And (3) heating to 40-50 ℃ after the reaction in the step (1), dropwise adding hydrogen peroxide (250 g, 30 wt%) into the flask, slowly heating to reflux after the dropwise adding is finished, refluxing for 3 hours, separating out water after the reaction is finished, evaporating 350 ml of dichloroethane of the product, cooling to about 0 ℃, and generating a large amount of white crystalline solid, namely the tosyl diazodiphenyl phosphorus compound (SPN) of the product.

The tosyl diazo diphenyl phosphorus compound obtained in this example was detected to have a purity of 95.6% and a yield of 96.2%.

The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.

Claims

1. A toluenesulfonyldiazodiphenylphosphine compound, characterized in that the structural formula of the toluenesulfonyldiazodiphenylphosphine compound is shown in the following formula I:

2. The method for preparing a tosyldiazodiphenylphosphine compound according to claim 1, characterized in that it comprises the following preparation steps:

(1) adding p-toluenesulfonyl hydrazide to an organic solvent, stirring and dissolving it uniformly, cooling it to 5-10° C., then adding diphenylphosphine chloride dropwise, and stirring and reacting at room temperature after the addition is complete;

(2) After the reaction in step (1) is completed, the temperature is raised to 40-50° C., hydrogen peroxide is added dropwise, and the temperature is raised to reflux temperature for reflux reaction. After the reaction is completed, the aqueous phase is removed by standing and the organic phase is concentrated and crystallized to obtain a tosyldiazodiphenylphosphine compound.

3. The method for preparing a toluenesulfonyldiazodiphenylphosphine compound according to claim 2, wherein the organic solvent in step (1) is ethylene dichloride.

4. The method for preparing a tosyldiazodiphenylphosphine compound according to claim 2, characterized in that the temperature of the reaction system is controlled to be below 25°C during the process of dropwise adding diphenylphosphine chloride in step (1).

5. The method for preparing a toluenesulfonyldiazodiphenylphosphine compound according to claim 2, characterized in that the stirring reaction time in step (1) is 3 to 5 hours.

6. The method for preparing a toluenesulfonyldiazodiphenylphosphine compound according to claim 2, characterized in that the molar ratio of p-toluenesulfonylhydrazine to diphenylphosphine chloride added in step (1) is 0.9-1.1:1.

7. The method for preparing a toluenesulfonyldiazodiphenylphosphine compound according to claim 2, characterized in that the molar ratio of the amount of hydrogen peroxide added in step (2) to p-toluenesulfonylhydrazine is 2 to 3:1 based on the hydrogen peroxide content.

8. The method for preparing a toluenesulfonyldiazodiphenylphosphine compound according to claim 2, characterized in that the reflux reaction time in step (2) is 2 to 3 hours.

9. The method for preparing a toluenesulfonyldiazodiphenylphosphine compound according to claim 2, characterized in that the temperature of the crystallization in step (2) is 5 to -5°C.

10. Use of the toluenesulfonyldiazodiphenylphosphine compound according to claim 1 as an ultraviolet light initiator.