CN112538007B - Preparation method of 2, 5-disubstituted-1, 4-terephthalaldehyde - Google Patents

Preparation method of 2, 5-disubstituted-1, 4-terephthalaldehyde Download PDF

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CN112538007B
CN112538007B CN202011308711.7A CN202011308711A CN112538007B CN 112538007 B CN112538007 B CN 112538007B CN 202011308711 A CN202011308711 A CN 202011308711A CN 112538007 B CN112538007 B CN 112538007B
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terephthalaldehyde
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陈艳君
史海波
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    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
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    • C07—ORGANIC CHEMISTRY
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    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
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    • C07C47/544—Diformyl benzenes; Alkylated derivatives thereof
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Abstract

The invention belongs to the technical field of organic synthesis, and particularly relates to a preparation method of 2, 5-disubstituted-1, 4-terephthalaldehyde. The 2, 5-disubstituted-1, 4-p-phenylenediamine is prepared by the oxidation reaction of 2, 5-disubstituted-1, 4-dibromobenzene and DMF under the catalysis of hexamethylphosphoric triamide (HMPA) and tert-butyl lithium. The reaction activity is greatly improved by adding tert-butyl lithium into the reaction system, and the existing form of the carbocation ions is stabilized by virtue of trace HMPA, so that the reaction yield is greatly improved under the combined action of tert-butyl lithium and HMPA, and is both 78% or more, and the product quantification efficiency is greatly improved.

Description

Preparation method of 2, 5-disubstituted-1, 4-terephthalaldehyde
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a preparation method of 2, 5-disubstituted-1, 4-terephthalaldehyde.
Background
2, 5-disubstituted-1, 4-p-phthalaldehyde is widely applied as a photoelectric material, and in the prior art, 2, 5-disubstituted-1, 4-dibromobenzene is mostly adopted as a raw material and synthesized into 2, 5-disubstituted-1, 4-dialdehyde by extracting halogen at low temperature through n-butyl lithium. However, the existing synthesis method has the disadvantages of difficult product obtaining, complicated post-treatment and low yield. The literature reports Miao Z, Liu G, Cui Y, equivalent. novel Stratability for Construction of the useful Organic Frameworks Transformed from Nonporous equivalent Organic Polymers [ J ]. Angewandte Chemie, 2019, 131(15):4960-4964 with 4 equivalents of n-butyllithium, a yield of only 13%; the literature reports that P, Wessig, M, et al, molecular Rods Based on Oligo-dibromo-thioketals [ J ]. The Journal of Organic Chemistry, 2016, 81(3): 1125-one 1136 oxidizes different alkyl-substituted dibromobenzenes with a small equivalent of n-butyllithium, again in yields of only 15% to 32%. Therefore, on the basis of the prior art, a new synthesis method is needed to be searched for and optimized and improved.
Disclosure of Invention
The present invention has been made keeping in mind the above problems occurring in the prior art, and an object of the present invention is to provide a process for producing 2, 5-disubstituted-1, 4-terephthalaldehyde which is capable of greatly improving the yield of the product.
The above object of the present invention can be achieved by the following technical solutions: the preparation method of the 2, 5-disubstituted-1, 4-terephthalaldehyde comprises the step of carrying out oxidation reaction on the 2, 5-disubstituted-1, 4-dibromobenzene and DMF (dimethyl formamide) under the catalysis of hexamethylphosphoric triamide (HMPA) and tert-butyl lithium to prepare the 2, 5-disubstituted-1, 4-terephthalaldehyde.
Preferably, the preparation method of the 2, 5-disubstituted-1, 4-terephthalaldehyde specifically comprises the following steps:
s1, weighing 2, 5-disubstituted-1, 4-dibromobenzene, hexamethylphosphoric triamide (HMPA), tert-butyl lithium and DMF in proportion for later use;
s2, putting the 2, 5-disubstituted-1, 4-dibromobenzene and hexamethylphosphoric triamide into a three-neck flask, putting the three-neck flask into a dry ice ethanol bath for cooling, then dropwise adding tert-butyl lithium, heating to room temperature after dropwise adding, and stirring;
s3, resetting the reaction system in the S2 in a dry ice ethanol bath for cooling, dropwise adding DMF into the system, removing the dry ice ethanol bath after dropwise adding, and stirring at room temperature;
and S4, after the reaction is finished, carrying out post-treatment in an ice bath to obtain a white solid product.
Preferably, the 2, 5-disubstituted-1, 4-dibromobenzene has the following structure:
Figure BDA0002789088760000021
any one of the above.
Preferably, the molar ratio of the 2, 5-disubstituted-1, 4-dibromobenzene to the hexamethylphosphoric triamide (HMPA) to the tert-butyl lithium is 1: (0.02-0.05): (2.1-2.5). The addition of the above substances in proportion can ensure maximum bromine extraction, increase the stability of carbonium ions, inhibit excessive side reactions and increase the conversion rate of the reaction to the maximum extent.
Preferably, the temperature of the dry ice ethanol bath is reduced to- (75-80 ℃) in the steps S2 and S3.
Preferably, in the step S2, the mixture is stirred for 20-40min after being warmed to room temperature.
Preferably, in step S3, the amount of DMF added is 10 to 20 equivalents based on the mole number of 2, 5-disubstituted-1, 4-dibromobenzene.
Preferably, the stirring time at room temperature in the step S3 is 50-70 min.
Preferably, the post-processing of step S4 is specifically: under ice bath, 40-60mL of saturated ammonium chloride aqueous solution is dripped into a reaction system and quenched; extracting with ethyl acetate for 2-4 times, washing the organic phase with saturated saline solution for 2-4 times, drying the organic phase, concentrating under reduced pressure, evaporating to dryness, subjecting the crude product to column chromatography, and purifying to obtain white solid.
The reaction route of the invention comprises the following steps:
1、
Figure BDA0002789088760000031
the nuclear magnetic resonance hydrogen spectrum of the product is as follows:1HNMR(CDCl3，500MHz)，δ(ppm):10.33(s，2H，-CHO)；7.70(s，2H，ArH)；2.70(s，6H，CH3)；
2、
Figure BDA0002789088760000032
the nuclear magnetic resonance hydrogen spectrum of the product is as follows:1HNMR(CDCl3，300MHz)，δ(ppm):10.35(s，2H，-CHO)；7.70(s，2H，ArH)；3.08(q，4H，CH2)；1.25(t，6H，CH3)；
3、
Figure BDA0002789088760000033
the nuclear magnetic resonance hydrogen spectrum of the product is as follows:1HNMR(CDCl3，300MHz)，δ(ppm):10.52(2H，s，-CHO)，7.43(s，2H，ArH)，4.18(4H，q，J＝7.2，-OCH2CH3)，1.48(6H，t，J＝7.2，-OCH2CH3)。
compared with the prior art, the invention has the following beneficial effects:
the invention adopts tert-butyl lithium, greatly improves the reaction activity, stabilizes the existing form of carbon cations by virtue of trace HMPA, greatly improves the reaction yield by the combined action of tert-butyl lithium and HMPA, and greatly improves the efficiency of product quantification by 78 percent or more.
Detailed Description
The following are specific examples of the present invention and illustrate the technical solutions of the present invention for further description, but the present invention is not limited to these examples. The raw materials used in the examples of the present invention are those commonly used in the art, and the methods used in the examples are those conventional in the art, unless otherwise specified.
In the column chromatography purification process of the embodiment of the invention, the eluent is prepared by mixing petroleum ether and ethyl acetate according to the volume ratio of 10: 1.
Example 1
Designing a reaction route:
Figure BDA0002789088760000041
5g of the starting material (19mmol) and 0.17g, 0.95mmol of hexamethylphosphoric triamide (HMPA) were weighed into a 500mL three-necked flask, placed in a thermometer, and subjected to vacuum ventilation for 3 times, then placed in a dry ice ethanol bath, the temperature was controlled at-78 ℃, and 2.1equiv of tert-butyllithium (39.9mmol, 30.69mL, 1.3M/L) was added dropwise over 1 hour. Slowly warmed to room temperature and stirred at room temperature for 20 min. Then the reaction system is placed in a dry ice ethanol bath again, the temperature is kept at-78 ℃, 13.89g of DMF is slowly dripped into the system, after the dripping is finished, the dry ice ethanol bath is removed, and the stirring is carried out for 50min at the room temperature. Under ice bath, 40mL of saturated ammonium chloride aqueous solution is dropwise added into a reaction system and quenched; extracting with ethyl acetate for 2 times, washing the organic phase with saturated saline solution for 2 times, drying the organic phase, concentrating under reduced pressure, evaporating to dryness, and purifying the crude product by column chromatography to obtain white solid 2.54g with yield of 82%. White solid NMR spectrum of1HNMR(CDCl3，500MHz)，δ(ppm):10.33(s，2H，-CHO)；7.70(s，2H，ArH)；2.70(s，6H，CH3) And determining the target product.
Example 2
The reaction route is designed as follows:
Figure BDA0002789088760000051
5.5g of the starting material (19mmol) and 0.17g, 0.95mmol of hexamethylphosphoric triamide (HMPA) were weighed into a 500mL three-necked flask, placed in a thermometer, and subjected to vacuum ventilation for 3 times, then placed in a dry ice ethanol bath, the temperature was controlled at-79 ℃, and 2.1equiv of tert-butyllithium (39.9mmol, 30.69mL, 1.3M/L) was added dropwise over 1 hour. Slowly warmed to room temperature and stirred at room temperature for 30 min. Then the reaction system is placed in a dry ice ethanol bath again, the temperature is kept at-79 ℃, 13.89g of DMF is slowly dripped into the system, after the dripping is finished, the dry ice ethanol bath is removed, and the stirring is carried out for 60min at the room temperature. Under ice bath, 50mL of saturated ammonium chloride aqueous solution is dropwise added to the reaction system and quenched; extracting with ethyl acetate for 3 times, washing the organic phase with saturated saline solution for 3 times, drying the organic phase, concentrating under reduced pressure, evaporating to dryness, and purifying the crude product by column chromatography to obtain white solid 2.96g with yield of 82%. White solid NMR spectrum of1HNMR(CDCl3，300MHz)，δ(ppm):10.35(s，2H，-CHO)；7.70(s，2H，ArH)；3.08(q，4H，CH2)；1.25(t，6H，CH3) And determining the target product.
Example 3
Designing a reaction route:
Figure BDA0002789088760000052
6.15g of the starting material (19mmol) and 0.068g, 0.38mmol of hexamethylphosphoric triamide (HMPA) were weighed into a 500mL three-necked flask, a thermometer was placed inside, and after 3 times of vacuum ventilation, the flask was placed in a dry ice ethanol bath, the temperature was controlled at-80 ℃ and 2.1equiv of tert-butyllithium (39.9mmol, 30.69mL, 1.3M/L) was added dropwise over 1 hour. Slowly warmed to room temperature and stirred at room temperature for another 40 min. Then the reaction system is placed in a dry ice ethanol bath again, the temperature is kept at minus 80 ℃, 16.64g of DMF is slowly dripped into the system, after the dripping is finished, the dry ice ethanol bath is removed, and the stirring is carried out for 70min at the room temperature. Under ice bath, 60mL of saturated ammonium chloride aqueous solution is dropwise added to the reaction system and quenched; extracting with ethyl acetate for 4 times, washing the organic phase with saturated saline solution for 4 times, drying the organic phase, concentrating under reduced pressure, evaporating to dryness, and purifying the crude product by column chromatography to obtain white solid 3.29g with yield of 78%. White solid nuclear magnetic resonance hydrogen spectrum of1HNMR(CDCl3，300MHz)，δ(ppm):10.52(2H，s，-CHO)，7.43(s，2H，ArH)，4.18(4H，q，J＝7.2，-OCH2CH3)，1.48(6H，t，J＝7.2，-OCH2CH3) And determining the target product.
Example 4
Designing a reaction route:
Figure BDA0002789088760000061
5g of the starting material (19mmol) and 0.17g, 0.95mmol of hexamethylphosphoric triamide (HMPA) were weighed into a 500mL three-necked flask, placed in a thermometer, and subjected to vacuum ventilation for 3 times, then placed in a dry ice ethanol bath, the temperature was controlled at-78 ℃, and 2.3equiv of tert-butyllithium (43.7mmol, 33.61mL, 1.3M/L) was added dropwise over 1 hour. Slowly warmed to room temperature and stirred at room temperature for 20 min. Then the reaction system is placed in a dry ice ethanol bath again, the temperature is kept at-78 ℃, 13.89g of DMF is slowly dripped into the system, after the dripping is finished, the dry ice ethanol bath is removed, and the stirring is carried out for 50min at the room temperature. Under ice bath, 40mL of saturated ammonium chloride aqueous solution is dropwise added to the reaction system and quenched; extracting with ethyl acetate for 2 times, washing the organic phase with saturated saline solution for 2 times, drying the organic phase, concentrating under reduced pressure, evaporating to dryness, and purifying the crude product by column chromatography to obtain white solid 2.46g with yield of 80%. White solid nuclear magnetic resonance hydrogen spectrum of1HNMR(CDCl3，500MHz)，δ(ppm):10.33(s，2H，-CHO)；7.70(s，2H，ArH)；2.70(s，6H，CH3) And determining the target product.
Example 5
Designing a reaction route:
Figure BDA0002789088760000071
5g of the starting material (19mmol) and 0.17g, 0.95mmol of hexamethylphosphoric triamide (HMPA) were weighed into a 500mL three-necked flask, placed in a thermometer, and subjected to vacuum ventilation for 3 times, then placed in a dry ice ethanol bath, the temperature was controlled at-78 ℃, and 2.5equiv of tert-butyllithium (47.5mmol, 29.69mL, 1.6M/L) was added dropwise over 1 hour. Slowly warmed to room temperature and stirred at room temperature for 20 min. Then the reaction body is putThe system is replaced in a dry ice ethanol bath, the temperature is kept at minus 78 ℃, 13.89g of DMF is slowly dripped into the system, after the dripping is finished, the dry ice ethanol bath is removed, and the stirring is carried out for 50min at the room temperature. Under ice bath, 40mL of saturated ammonium chloride aqueous solution is dropwise added to the reaction system and quenched; extracting with ethyl acetate for 2 times, washing the organic phase with saturated saline solution for 2 times, drying the organic phase, concentrating under reduced pressure, evaporating to dryness, and purifying the crude product by column chromatography to obtain white solid 2.52g with yield of 81.3%. White solid nuclear magnetic resonance hydrogen spectrum of1HNMR(CDCl3，500MHz)，δ(ppm):10.33(s，2H，-CHO)；7.70(s，2H，ArH)；2.70(s，6H，CH3) And determining the target product.
Comparative example 1
The only difference from example 1 was that the same amount of n-butyllithium as that of t-butyllithium was used in place of t-butyllithium in the reaction to give 1.035g of a white solid with a yield of 33.6%; the nuclear magnetic data were as in example 1.
Comparative example 2
The only difference from example 1 is that HMPA was not added to the reaction system, giving 1.386g of a white solid with a yield of 45%; the nuclear magnetic data were as in example 1.
Comparative example 3
The only difference from example 1 was that the amount of t-butyllithium added to the reaction system was 2.6equiv, and 2.157g of a white solid was obtained in a yield of 70%; the nuclear magnetic data were as in example 1.
Comparative example 4
The only difference from example 1 was that the amount of t-butyllithium added to the reaction system was 2.0equiv, giving 2.194g of a white solid in a yield of 71.2%; the nuclear magnetic data were as in example 1.
As can be seen from the yields of the above examples 1 to 5 and comparative examples 1 to 4, the product yields obtained by the technical scheme of the invention are both 78% and above. When the same amount of n-butyl lithium is adopted to replace tert-butyl lithium to participate in the reaction system, the product yield only reaches 33.6 percent; when HMPA is not added into the reaction system, the stability of the carbocation in the system is not stable enough, which easily affects the stability of the reaction process, and further affects the reaction conversion rate, and the product yield is only 45%. In addition, although a proper amount of tert-butyl lithium can greatly improve the activity of a reaction system, the improvement of the activity of the system is limited due to a small amount of tert-butyl lithium, the reaction period is long, side reactions are easily caused, the yield of products is reduced, the addition amount is large, the activity of the system is overlarge, the reaction process is unstable, and the conversion rate and the final yield of target products are also influenced.
The technical scope of the invention claimed by the embodiments herein is not exhaustive and new solutions formed by equivalent replacement of single or multiple technical features in the embodiments are also within the scope of the invention, and all parameters involved in the solutions of the invention do not have mutually exclusive combinations if not specifically stated.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

Claims (8)

1. A preparation method of 2, 5-disubstituted-1, 4-terephthalaldehyde is characterized in that the 2, 5-disubstituted-1, 4-terephthalaldehyde is prepared by oxidation reaction of 2, 5-disubstituted-1, 4-dibromobenzene and DMF under the catalysis of hexamethylphosphoric triamide (HMPA) and tert-butyl lithium;
the preparation method comprises the following steps:
s1, weighing 2, 5-disubstituted-1, 4-dibromobenzene, hexamethylphosphoric triamide (HMPA), tert-butyl lithium and DMF in proportion for later use;
s2, putting the 2, 5-disubstituted-1, 4-dibromobenzene and hexamethylphosphoric triamide into a three-neck flask, putting the three-neck flask into a dry ice ethanol bath for cooling, then dropwise adding tert-butyl lithium, heating to room temperature after dropwise adding, and stirring;
s3, resetting the reaction system in the S2 in a dry ice ethanol bath for cooling, dropwise adding DMF into the system, removing the dry ice ethanol bath after dropwise adding, and stirring at room temperature;
and S4, after the reaction is finished, carrying out post-treatment in an ice bath to obtain a white solid product.
2. 2,5 according to claim 1The preparation method of the-disubstituted-1, 4-terephthalaldehyde is characterized in that the 2, 5-disubstituted-1, 4-dibromobenzene comprises the following structure:
Figure FDA0003449597240000011
any one of the above.
3. The method for preparing 2, 5-disubstituted-1, 4-terephthalaldehyde according to claim 1, wherein the molar ratio of the 2, 5-disubstituted-1, 4-dibromobenzene, hexamethylphosphoric triamide (HMPA) and tert-butyl lithium is 1: (0.02-0.05): (2.1-2.5).
4. The process for producing 2, 5-disubstituted-1, 4-terephthalaldehyde according to claim 1, wherein the temperature of the dry ice-ethanol bath is lowered to- (75 to 80 ℃) in steps S2 and S3.
5. The process for producing 2, 5-disubstituted-1, 4-terephthalaldehyde according to claim 1, wherein the reaction solution is stirred for 20 to 40min after being warmed to room temperature in step S2.
6. The method for preparing 2, 5-disubstituted-1, 4-terephthalaldehyde according to claim 1, wherein the amount of DMF added in step S3 is 10 to 20 equivalents based on the molar number of 2, 5-disubstituted-1, 4-dibromobenzene.
7. The process for preparing 2, 5-disubstituted-1, 4-terephthalaldehyde according to claim 1, wherein the stirring time at room temperature in step S3 is 50 to 70 min.
8. The method for preparing 2, 5-disubstituted-1, 4-terephthalaldehyde according to claim 1, wherein the post-treatment of step S4 specifically comprises: under ice bath, 40-60mL of saturated ammonium chloride aqueous solution is dripped into a reaction system and quenched; extracting with ethyl acetate for 2-4 times, washing the organic phase with saturated saline solution for 2-4 times, drying the organic phase, concentrating under reduced pressure, evaporating to dryness, and purifying the crude product by column chromatography to obtain a white solid.
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Citations (1)

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Publication number Priority date Publication date Assignee Title
CN1270165A (en) * 1999-02-04 2000-10-18 Ss制药株式会社 Preparation of difluorobenzoethylketone derivatives

Patent Citations (1)

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Publication number Priority date Publication date Assignee Title
CN1270165A (en) * 1999-02-04 2000-10-18 Ss制药株式会社 Preparation of difluorobenzoethylketone derivatives

Non-Patent Citations (3)

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Molecular Rods Based on Oligo-spiro-thioketals;P. Wessig et al.;《J. Org. Chem.》;20160112;第81卷;第1125-1136页 *
Nature-inspired design of tetraindoles: Optimization of the core structure and evaluation of structure–activity relationship;Hajjaj H. M. et al.;《Bioorg. Med. Chem. Lett.》;20160729;第26卷;第4497-4503页 *
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