CN112125830A - Polyamide compound and preparation method thereof - Google Patents
Polyamide compound and preparation method thereof Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 20
- 229920002647 polyamide Polymers 0.000 title claims abstract description 7
- 238000002360 preparation method Methods 0.000 title description 7
- 239000004952 Polyamide Substances 0.000 title description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000000047 product Substances 0.000 claims abstract description 46
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 32
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 31
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 18
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000003949 imides Chemical class 0.000 claims abstract description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910010084 LiAlH4 Inorganic materials 0.000 claims abstract description 10
- 239000012280 lithium aluminium hydride Substances 0.000 claims abstract description 10
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 9
- 239000012467 final product Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 125000002252 acyl group Chemical group 0.000 claims abstract description 7
- 238000007112 amidation reaction Methods 0.000 claims abstract description 7
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 7
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 7
- 238000003379 elimination reaction Methods 0.000 claims abstract description 7
- 230000000269 nucleophilic effect Effects 0.000 claims abstract description 7
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 4
- ZJFOZWUVVZAYGJ-UHFFFAOYSA-N C(=O)OC=O.C1CC=C1 Chemical compound C(=O)OC=O.C1CC=C1 ZJFOZWUVVZAYGJ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 14
- HAUDLKKUHAFHRO-UHFFFAOYSA-N 2-oxaspiro[3.3]hept-6-ene-1,3-dione Chemical compound O=C1OC(=O)C11C=CC1 HAUDLKKUHAFHRO-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 235000010265 sodium sulphite Nutrition 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 6
- 229910010082 LiAlH Inorganic materials 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 238000006722 reduction reaction Methods 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000011541 reaction mixture Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 49
- 238000001035 drying Methods 0.000 abstract description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 abstract description 12
- 239000000243 solution Substances 0.000 abstract description 11
- 239000012295 chemical reaction liquid Substances 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 39
- 239000000203 mixture Substances 0.000 description 19
- 238000001914 filtration Methods 0.000 description 17
- 238000001816 cooling Methods 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000012043 crude product Substances 0.000 description 12
- 239000000706 filtrate Substances 0.000 description 12
- 238000004809 thin layer chromatography Methods 0.000 description 12
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- -1 amide compounds Chemical class 0.000 description 6
- 230000006872 improvement Effects 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 150000001263 acyl chlorides Chemical class 0.000 description 2
- 150000001408 amides Chemical group 0.000 description 2
- 230000004071 biological effect Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000002155 anti-virotic effect Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920000962 poly(amidoamine) Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 238000009333 weeding Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D207/10—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D207/16—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Indole Compounds (AREA)
Abstract
The invention discloses a polyamide-based compound, which is prepared by the following steps: 1) 1, 3-diaminopropane and cyclobut-3-ene diformic anhydride are added into a three-neck flask, and nucleophilic addition-elimination reaction is carried out to generate imide; followed by LiAlH4Reducing the carbonyl group as a reducing agent. 2) Adding potassium permanganate, heating to perform oxidation reaction to generate carboxyl. 3) Dissolving the product in oxalyl chloride, dropwise adding DMF (dimethyl formamide), heating for acyl chlorination reaction, drying after the reaction is finished, dissolving the dried product in tetrahydrofuran, adding the solution into an aqueous solution of monohydrate ammonia for amidation reaction, concentrating under reduced pressure after the reaction is finished, extracting the product with DCM (dichloromethane), and distilling the reaction liquid under reduced pressure to obtain the final product.
Description
Technical Field
The invention belongs to the field of amide compounds, and particularly relates to a multi-amide compound and a preparation method thereof.
Background
The amide compound is a compound produced by substituting hydrogen on a nitrogen atom of ammonia or amine with an acyl group, and can be also regarded as a compound produced by substituting a hydroxyl group in a carboxylic acid molecule with an amino group or an aminophenyl group. The amide compound has biological activities such as bacteriostasis, disinsection, weeding and antivirus, and attracts wide attention, and different groups are introduced into an amide structure through structural modification to synthesize a compound with broad-spectrum biological activity, so that the compound plays an important role in the creation of novel efficient pesticides. Meanwhile, the compound can be used for producing vitamins, hormones, antibacterial agents and the like in the medical industry and can be used as an important intermediate for organic synthesis in organic reaction. The amido compound has important promoting effect on the development of industries such as medicine, agriculture and the like.
Disclosure of Invention
In order to enrich the types of amide-based compounds, the invention designs and prepares a polyamide-based compound and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a polyamido compound having the structural formula:
a method for preparing a polyamido compound, comprising the steps of:
mixing 1, 3-diaminopropane and cyclobut-3-ene diformic anhydride, introducing nitrogen, and performing nucleophilic addition-elimination reaction at 150-200 ℃ to generate imide; followed by LiAlH4Reducing carbonyl for a reducing agent at 0-35 ℃;
adding potassium permanganate into the reduced carbonyl, and heating to 90-100 ℃ to perform oxidation reaction to generate carboxyl;
and dissolving the carboxyl product in oxalyl chloride, dropwise adding DMF (dimethyl formamide), heating to 20-25 ℃ for acyl chlorination reaction, dissolving the product with tetrahydrofuran, and adding the product into an aqueous solution of monohydrate ammonia for amidation reaction to obtain the final product.
As a further improvement of the present invention, the molar ratio of 1, 3-diaminopropane to cyclobut-3-enedicarboxylic anhydride in the nucleophilic addition-elimination reaction is 1: 4.
As a further improvement of the invention, in the reduction reaction, LiAlH4The molar ratio of the 1, 3-diaminopropane to the water is 2-2.4: 1.
As a further improvement of the invention, in the oxidation reaction, the excess potassium permanganate is removed with sodium sulfite.
As a further improvement of the invention, in the oxidation reaction, the amount of the potassium permanganate substance is 2-4 times of the amount of the 1, 3-diaminopropane substance.
As a further improvement of the invention, in the acyl chlorination reaction, the amount of oxalyl chloride is 4-6 times of that of 1, 3-diaminopropane, and one drop of DMF is added dropwise as a catalyst.
As a further improvement of the invention, in the amidation reaction, the amount of the substance of ammonia monohydrate is 4 to 6 times the amount of the substance of 1, 3-diaminopropane.
The preparation method comprises the steps of mixing 1, 3-diaminopropane and cyclobut-3-ene dicarboxylic anhydride, and carrying out nucleophilic addition-elimination reaction to generate imide; subsequently reducing the carbonyl group; carrying out oxidation reaction to generate carboxyl; carrying out acyl chlorination reaction and amidation reaction to obtain the final product. The method is simple, raw materials are easy to obtain, the cost is low, continuous production can be carried out, and the prepared amide compound has an important promoting effect on the development of industries such as medicine, agriculture and the like.
Drawings
FIG. 1 is a scheme for synthesizing a polyamidoamine compound obtained in example 4.
Detailed Description
The reaction equation of the preparation process of the polyamide-based compound is as follows:
according to the reaction mechanism, the invention adopts the following technical scheme:
a polyamido compound having a structural formula:
the preparation method of the polyamide-based compound comprises the following steps:
1) 1, 3-diaminopropane and cyclobut-3-ene dicarboxylic anhydride are added into a three-neck flask, nitrogen is introduced, and the mixture is stirred at the temperature of 1Reacting for 2-5 h at 50-200 ℃, and performing nucleophilic addition-elimination reaction to generate imide; followed by LiAlH4Reducing carbonyl by a reducing agent at 0-35 ℃ for 4-6 h. Wherein the molar ratio of the 1, 3-diaminopropane to the cyclobut-3-enedicarboxylic anhydride is 1:4, LiAlH4The molar ratio of the 1, 3-diaminopropane to the water is 2-2.4: 1.
2) Diluting the product, slowly adding potassium permanganate at 0 ℃, heating to perform oxidation reaction to generate carboxyl, and reacting at 90-100 ℃ for 10-12 h; wherein the amount of potassium permanganate is 2-4 times of that of 1, 3-diaminopropane, sodium sulfite is added to remove excessive potassium permanganate after the reaction is finished, diatomite is adopted for filtration, ethyl acetate is adopted for extracting impurities, an aqueous phase is collected, the pH value is adjusted to 2-4, a product is separated out, and the product is obtained after filtration and drying to constant weight.
3) Dissolving the product in oxalyl chloride, dropwise adding DMF (N, N-dimethylformamide) at 0 ℃, heating for acyl chlorination reaction, and reacting for 1-2 h at 20-25 ℃. The mass of acyl chloride is 4-6 times of that of 1, 3-diaminopropane, one drop of DMF (dimethyl formamide) is used as a catalyst and is dripped, after the reaction is finished, the product is dried in a spinning mode, tetrahydrofuran is used for dissolving the product after the drying in the spinning mode, the product is slowly dripped into a monohydrate ammonia water solution at the temperature of 0 ℃ for amidation reaction, the mass of the acyl chloride is 4-6 times of that of 1, 3-diaminopropane, one drop of DMF is used as a catalyst and is dripped, after the reaction is finished, the product is concentrated under reduced pressure, DCM (dichloromethane) is used for extracting the product, and the reaction liquid is distilled under reduced pressure to obtain the.
The technical solution in the embodiments of the present invention will be clearly and completely described below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) 1, 3-diaminopropane (7.4g, 0.1mol) and cyclobutane-3-enedicarboxylic anhydride (49.6g, 0.4mol) were added dropwise in this order to a 250mL three-necked flask equipped with a reflux condenser, nitrogen was introduced 3 times, and then the mixture was heated to 180 ℃ for reaction for 3 hours, and the completion of the reaction was monitored by TLC (Thin Layer Chromatography). After the reaction is finished, cooling to room temperature, adding 50mL of distilled water, extracting for 3 times by adopting 80mL of ethyl acetate, drying by anhydrous magnesium sulfate, filtering, concentrating under reduced pressure to obtain a crude product, and finally separating by a column to obtain colorless oily imide.
(2) 80mL of tetrahydrofuran dried with sodium metal were charged into a 250mL three-necked flask, cooled to 0 ℃ using a cold salt bath, and 7.6g of LiAlH were slowly added in portions4After stirring for 3min, slowly dropwise adding the imide dissolved in tetrahydrofuran into a three-neck flask, and raising the temperature to 25 ℃ after the addition is finished to react for 4 h. The completion of the reaction was monitored by TLC (Thin Layer Chromatography). After the reaction is finished, cooling to 0 ℃, and sequentially adding 7.6mLH under ice salt bath2O, 7.6mL 15% aqueous NaOH and 22.8mLH2O quenching excess LiAlH4Filtering, fully washing a filter cake by using ethyl acetate, drying the filtrate by using anhydrous magnesium sulfate, concentrating under reduced pressure to obtain a crude product, and finally separating by using a column to obtain a product.
(3) Adding the product and 80mL of distilled water into a 250mL three-neck flask, placing the three-neck flask in an ice salt bath, cooling to 0 ℃, and slowly adding potassium permanganate KMnO4(40g, the adding time is 40min), after all the components are added, slowly raising the temperature to 90 ℃ for reaction for 12 h. Excess KMnO was quenched by adding 80mL of saturated aqueous sodium sulfite solution to a three-necked flask4(ii) a After the purple color is faded, slowly cooling and filtering MnO generated in the reaction by diatomite while the MnO is hot2Obtaining clear filtrate; then extracting the filtrate for 3 times by using ethyl acetate to remove impurities, collecting a water phase, adjusting the pH value of the water phase to 2 by using dilute hydrochloric acid to precipitate a solid, and filtering and drying to obtain a pure product.
(4) The product and 50.4g of oxalyl chloride are added into a three-neck flask, after the mixture is cooled to 0 ℃, one drop of DMF is added dropwise, and after the mixture is stirred uniformly, the mixture is heated to 20 ℃ for reaction for 1 hour. The completion of the reaction was monitored by TLC (Thin Layer Chromatography). And after the reaction is finished, dissolving the obtained product by using 40mL of dried tetrahydrofuran, slowly dropwise adding the dissolved product into a monohydrate ammonia water solution at 0 ℃, after the reaction is finished, concentrating under reduced pressure, extracting the obtained crude product by using 40mL of LPCM, and distilling under reduced pressure to obtain a final product.
The product obtained in example 1 was obtained in 53% yield.
Example 2
(1) 1, 3-diaminopropane (7.4g, 0.1mol) and cyclobutane-3-enedicarboxylic anhydride (49.6g, 0.4mol) were added dropwise in this order to a 250mL three-necked flask equipped with a reflux condenser, nitrogen was introduced 3 times, and then the mixture was heated to 150 ℃ for 2 hours, and the completion of the reaction was monitored by TLC (Thin Layer Chromatography). After the reaction is finished, cooling to room temperature, adding 50mL of distilled water, extracting for 3 times by adopting 80mL of ethyl acetate, drying by anhydrous magnesium sulfate, filtering, concentrating under reduced pressure to obtain a crude product, and finally separating by a column to obtain colorless oily imide.
(2) 90mL of tetrahydrofuran dried with sodium metal were charged into a 250mL three-necked flask, cooled to 0 ℃ using a cold salt bath, and 8.36g of LiAlH were slowly added in portions4After stirring for 3min, slowly dropwise adding the imide dissolved in tetrahydrofuran into a three-neck flask, and raising the temperature to 30 ℃ after the addition for reaction for 5 h. The completion of the reaction was monitored by TLC (Thin Layer Chromatography). After the reaction is finished, cooling to 0 ℃, and sequentially adding 8.4mLH into the mixture under ice salt bath2O, 8.4mL 15% aqueous NaOH and 25.2mLH2O quenching excess LiAlH4Filtering, fully washing a filter cake by using ethyl acetate, drying the filtrate by using anhydrous magnesium sulfate, concentrating under reduced pressure to obtain a crude product, and finally separating by using a column to obtain a product.
(3) Adding the product and 80mL of distilled water into a 250mL three-neck flask, placing the three-neck flask in an ice salt bath, cooling to 0 ℃, and slowly adding potassium permanganate KMnO4(31.6g, the addition time is 40min), and after the addition is finished, the temperature is slowly raised to 100 ℃ for reaction for 10 h. Excess KMnO was quenched by adding 80mL of saturated aqueous sodium sulfite solution to a three-necked flask4(ii) a After the purple color is faded, slowly cooling and filtering MnO generated in the reaction by diatomite while the MnO is hot2Obtaining clear filtrate; then extracting the filtrate for 3 times by using ethyl acetate to remove impurities, collecting a water phase, adjusting the pH value of the water phase to 3 by using dilute hydrochloric acid to precipitate a solid, and filtering and drying to obtain a pure product.
(4) The product and 63.5g of oxalyl chloride are added into a three-neck flask, after the mixture is cooled to 0 ℃, one drop of DMF is added dropwise, and after the mixture is stirred uniformly, the mixture is heated to 20 ℃ for reaction for 1 hour. The completion of the reaction was monitored by TLC (Thin Layer Chromatography). And after the reaction is finished, dissolving the obtained product by using 40mL of dried tetrahydrofuran, slowly dropwise adding the dissolved product into a monohydrate ammonia water solution at 0 ℃, after the reaction is finished, concentrating under reduced pressure, extracting the obtained crude product by using 40mL of LPCM, and distilling under reduced pressure to obtain a final product.
The product obtained in example 2 was obtained in 58% yield.
Example 3
(1) 1, 3-diaminopropane (7.4g, 0.1mol) and cyclobutane-3-enedicarboxylic anhydride (49.6g, 0.4mol) were added dropwise in this order to a 250mL three-necked flask equipped with a reflux condenser, nitrogen was introduced 3 times, and then the mixture was heated to 200 ℃ for 5 hours, and the completion of the reaction was monitored by TLC (Thin Layer Chromatography). After the reaction is finished, cooling to room temperature, adding 50mL of distilled water, extracting for 3 times by adopting 80mL of ethyl acetate, drying by anhydrous magnesium sulfate, filtering, concentrating under reduced pressure to obtain a crude product, and finally separating by a column to obtain colorless oily imine.
(2) 100mL of tetrahydrofuran dried with sodium metal was charged into a 250mL three-necked flask, cooled to 0 ℃ using a cold salt bath, and 9.12g of LiAlH was slowly added in portions4After stirring for 3min, slowly dropwise adding the imide dissolved in tetrahydrofuran into a three-neck flask, and raising the temperature to 35 ℃ after the addition for reacting for 6 h. The completion of the reaction was monitored by TLC (Thin Layer Chromatography). After the reaction is finished, cooling to 0 ℃, and sequentially adding 9.2mLH under ice salt bath2O, 9.2mL 15% aqueous NaOH and 27.6mLH2O quenching excess LiAlH4Filtering, fully washing a filter cake by using ethyl acetate, drying the filtrate by using anhydrous magnesium sulfate, concentrating under reduced pressure to obtain a crude product, and finally separating by using a column to obtain a product.
(3) Adding the product and 80mL of distilled water into a 250mL three-neck flask, placing the three-neck flask in an ice salt bath, cooling to 0 ℃, and slowly adding potassium permanganate KMnO4(50g, the adding time is 40min), and after the adding is finished, slowly raising the temperature to 90 ℃ for reaction for 12 h. Excess KMnO was quenched by adding 80mL of saturated aqueous sodium sulfite solution to a three-necked flask4(ii) a After the purple color is faded, slowly cooling and using silicon while it is hotFiltering MnO generated in the reaction by using diatomite2Obtaining clear filtrate; then extracting the filtrate for 3 times by using ethyl acetate to remove impurities, collecting a water phase, adjusting the pH value of the water phase to 4 by using dilute hydrochloric acid to precipitate a solid, and filtering and drying to obtain a pure product.
(4) The product and 57.2g of oxalyl chloride are added into a three-neck flask, after the mixture is cooled to 0 ℃, one drop of DMF is added dropwise, and after the mixture is stirred uniformly, the mixture is heated to 20 ℃ for reaction for 1 hour. The completion of the reaction was monitored by TLC (Thin Layer Chromatography). And after the reaction is finished, dissolving the obtained product by using 40mL of dried tetrahydrofuran, slowly dropwise adding the dissolved product into a monohydrate ammonia water solution at 0 ℃, after the reaction is finished, concentrating under reduced pressure, extracting the obtained crude product by using 40mL of LPCM, and distilling under reduced pressure to obtain a final product.
The product obtained in example 3 is obtained in 62% yield.
Example 4
(1) 1, 3-diaminopropane (7.4g, 0.1mol) and cyclobutane-3-enedicarboxylic anhydride (49.6g, 0.4mol) were added dropwise in this order to a 250mL three-necked flask equipped with a reflux condenser, nitrogen was introduced 3 times, and then the mixture was heated to 190 ℃ for 5 hours, and the completion of the reaction was monitored by TLC (Thin Layer Chromatography). After the reaction is finished, cooling to room temperature, adding 50mL of distilled water, extracting for 3 times by adopting 80mL of ethyl acetate, drying by anhydrous magnesium sulfate, filtering, concentrating under reduced pressure to obtain a crude product, and finally separating by a column to obtain colorless oily imide.
(2) 80mL of tetrahydrofuran dried with sodium metal were charged into a 250mL three-necked flask, cooled to 0 ℃ using a cold salt bath, and 9.5g of LiAlH were slowly added in portions4After stirring for 3min, slowly dropwise adding the imide dissolved in tetrahydrofuran into a three-neck flask, and raising the temperature to 25 ℃ after the addition is finished to react for 6 h. The completion of the reaction was monitored by TLC (Thin Layer Chromatography). After the reaction is finished, cooling to 0 ℃, and sequentially adding 9.5mLH into the mixture under ice salt bath2O, 9.5mL 15% aqueous NaOH and 28.5mLH2O quenching excess LiAlH4Filtering, fully washing a filter cake by using ethyl acetate, drying the filtrate by using anhydrous magnesium sulfate, concentrating under reduced pressure to obtain a crude product, and finally separating by using a column to obtain a product.
(3) Will be at the topAdding the product and 80mL of distilled water into a 250mL three-neck flask, placing the three-neck flask in an ice salt bath, cooling to 0 ℃, and slowly adding potassium permanganate KMnO4(63.2g, the addition time is 40min), after the addition is finished, the temperature is slowly raised to 100 ℃ for reaction for 10 h. Excess KMnO was quenched by adding 80mL of saturated aqueous sodium sulfite solution to a three-necked flask4(ii) a After the purple color is faded, slowly cooling and filtering MnO generated in the reaction by diatomite while the MnO is hot2Obtaining clear filtrate; then extracting the filtrate for 3 times by using ethyl acetate to remove impurities, collecting a water phase, adjusting the pH value of the water phase to 2 by using dilute hydrochloric acid to precipitate a solid, and filtering and drying to obtain a pure product.
(4) The product and 76.2g of oxalyl chloride are added into a three-neck flask, after the mixture is cooled to 0 ℃, one drop of DMF is added dropwise, and after the mixture is stirred uniformly, the mixture is heated to 20 ℃ for reaction for 1 hour. The completion of the reaction was monitored by TLC (Thin Layer Chromatography). And after the reaction is finished, dissolving the obtained product by using 40mL of dried tetrahydrofuran, slowly dropwise adding the dissolved product into a monohydrate ammonia water solution at 0 ℃, after the reaction is finished, concentrating under reduced pressure, extracting the obtained crude product by using 40mL of LPCM, and distilling under reduced pressure to obtain a final product.
The yield of the product obtained in example 4 was 66%.
In order to characterize the structural characteristics of a polyamido compound, the polyamido compound synthesized in example 4 was subjected to nuclear magnetic hydrogen spectroscopy, and the results are shown below:
1H NMR(300MHz,DMSO):7.21(s,8H),2.83-2.46(m,12H),2.43(m,4H),1.56(m,2H)ppm。
the foregoing is a more detailed description of the invention and it is not intended that the invention be limited to the specific embodiments described herein, but that various modifications, alterations, and substitutions may be made by those skilled in the art without departing from the spirit of the invention, which should be construed to fall within the scope of the invention as defined by the appended claims.
Claims (8)
1. A polyamido compound having the structural formula:
2. a method for preparing a polyamide-based compound, comprising the steps of:
mixing 1, 3-diaminopropane and cyclobut-3-ene diformic anhydride, introducing nitrogen, and performing nucleophilic addition-elimination reaction at 150-200 ℃ to generate imide; followed by LiAlH4Reducing carbonyl for a reducing agent at 0-35 ℃;
adding potassium permanganate into the reduced carbonyl, and heating to 90-100 ℃ to perform oxidation reaction to generate carboxyl;
and dissolving the carboxyl product in oxalyl chloride, dropwise adding DMF (dimethyl formamide), heating to 20-25 ℃ for acyl chlorination reaction, dissolving the product with tetrahydrofuran, and adding the product into an aqueous solution of monohydrate ammonia for amidation reaction to obtain the final product.
3. The production method according to claim 2, wherein the molar ratio of 1, 3-diaminopropane to cyclobut-3-enedicarboxylic anhydride in the nucleophilic addition-elimination reaction is 1: 4.
4. The method according to claim 2, wherein LiAlH is added to the reaction mixture in the reduction reaction4The molar ratio of the 1, 3-diaminopropane to the water is 2-2.4: 1.
5. The method of claim 2, wherein in the oxidation reaction, excess potassium permanganate is removed using sodium sulfite.
6. The method according to claim 2, wherein the amount of potassium permanganate is 2 to 4 times the amount of 1, 3-diaminopropane in the oxidation reaction.
7. The method according to claim 2, wherein the amount of oxalyl chloride is 4 to 6 times that of 1, 3-diaminopropane in the acid chlorination reaction, and DMF is added dropwise as a catalyst.
8. The method according to claim 2, wherein the amount of the substance of ammonia monohydrate is 4 to 6 times the amount of the substance of 1, 3-diaminopropane in the amidation reaction.
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