CN111484412A - Method for synthesizing compound containing indan structure - Google Patents
Method for synthesizing compound containing indan structure Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
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- C07C2602/00—Systems containing two condensed rings
- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/04—One of the condensed rings being a six-membered aromatic ring
- C07C2602/08—One of the condensed rings being a six-membered aromatic ring the other ring being five-membered, e.g. indane
Abstract
The invention provides a method for synthesizing a compound containing an indane structure, which comprises the following steps: 1) carrying out nitration reaction on indan compounds of the compounds shown in the general formula (I) in the presence of a solid acid catalyst to obtain compounds shown in the general formulas (II) and (III); 2) in the presence of a reducing agent, the compounds represented by the general formula (II) and the general formula (III) are subjected to a reduction reaction to obtain compounds represented by the general formula (IV) and the general formula (V), wherein R in the general formula (I), (II), (III), (IV) and (V)1、R2、R3And R4Independently of one another is hydrogen, C1‑4Alkyl radical, C1‑4Alkoxy, halogen, hydroxy or carboxy.
Description
Technical Field
The invention belongs to the field of organic chemistry, and particularly relates to a method for synthesizing a compound containing an indane structure.
Background
The 5(6) -amino-1- (4-aminophenyl) -1,3, 3-trimethyl indane (DAPI) with the structure shown in the specification is diamine containing an indane structure, and is mainly used as an excellent epoxy curing agent or a synthetic monomer of special polyimide.
The structure of the compound contains a cyclic indane structure, so that the compound has good thermal stability, oxidation resistance and electrical property, and the methyl in the structure enables a benzene ring to generate an induced dipole, so that the compound has good compatibility with a plurality of high polymer materials. Therefore, the polyimide resin is used as a curing agent in various epoxy resins, and simultaneously, the polyimide formed by the polyimide resin has good heat resistance and flexibility.
At present, the preparation method of the compound containing the indane structure mainly starts from 1-phenyl-1, 3, 3-trimethylindane as a raw material, and the 5(6) -amino-1- (4-aminophenyl) -1,3, 3-trimethylindane (DAPI) is prepared by nitration by a nitro-sulfur method and catalytic reduction. The preparation method is a homogeneous reaction, and the conversion rate is relatively high. However, the method involves the use of mixed acid, and the concentrated sulfuric acid is gradually changed into dilute sulfuric acid due to moisture generated in the reaction process, so that not only is equipment corrosion caused and the maintenance cost of the equipment is increased, but also a large amount of mixed acid in the later period causes the pollution problem of the later period environment and the increase of the production cost.
For example, the synthesis and curing performance of 5(6) -amino-1- (4-aminophenyl) -1,3, 3-trimethylindane are described in the related literature (Jiqinglin et al, "study on synthesis and curing properties of 5(6) -amino-1- (4-aminophenyl) -1,3, 3-trimethylindane", glass fiber reinforced plastic/composite material, 2011, No. 4). The synthesis method is carried out by adopting a traditional selectivity-free nitro-sulfur method, and describes the complicated links of obtaining a nitration product 5(6) -nitro-1- (4-aminophenyl) -1,3, 3-trimethylindan (DNPI), such as extraction, waste acid washing and the like.
Moreover, the conventional nitrosulfur method is not selective in preparing DNPI, and the proportions of 5-nitro-1- (4-nitrophenyl) -1,3, 3-trimethylindan (5 '-DNPI) and 6-nitro-1- (4-nitrophenyl) -1,3, 3-trimethylindan (6' -DNPI) in the obtained nitrated product are generally kept at about 45% and 55%.
Therefore, there is a need in the art to provide a low-cost, efficient, environmentally friendly, and selective method for synthesizing compounds containing indane structures (e.g., 5(6) -amino-1- (4-aminophenyl) -1,3, 3-trimethylindane). The indane-containing structural compound synthesized by the method can overcome the defects of synthesis and purification of the existing products, and the indane-containing structural compound with better quality and lower price is prepared, so that the application requirements of the material in epoxy curing and polyimide preparation in the market are met.
Disclosure of Invention
The invention provides a method for synthesizing a compound containing an indane structure, which comprises the following steps:
1) in the presence of a solid acid catalyst, carrying out nitration reaction on the indane compound shown in the general formula (I) to obtain compounds shown in the general formulas (II) and (III);
2) in the presence of a reducing agent, carrying out reduction reaction on the compounds shown in the general formula (II) and the general formula (III) to obtain products shown in the general formula (IV) and the general formula (V),
in the general formulae (I), (II), (III), (IV), (V), R1、R2、R3And R4Independently of one another is hydrogen, C1-4Alkyl or C1-4Alkoxy, halogen, hydroxy or carboxy.
In a preferred embodiment, in the general formulae (I), (II), (III), (IV), (V), R1、R2、R3And R4Are all hydrogen.
In a preferred embodiment, the solid acid catalyst in step 1) is selected from one or more of super strong solid acid, sulfonic acid resin, and mesoporous molecular sieve.
In a preferred embodiment, the super-strong solid acid is selected from the group consisting of: SO (SO)4 2-/TiO2-ZrO2、SO4 2-/TiO2、SO4 2-/ZrO2、SO4 2-/WO3-ZrO2、SO4 2-/SnO2-Al2O3、SO4 2-/TiO2-La3+One or more of; the sulfonic acid resin type catalyst is selected from one or more of perfluorinated sulfonic acid resin and perfluoroalkyl sulfimide salt; the mesoporous molecular sieve type catalyst is selected from one or more of MCM-48, MCM-41 and MCM-22.
In a preferred embodiment, the amount of the solid acid catalyst added in step 1) is in the range of 1 to 20% by weight, preferably in the range of 3 to 15% by weight, most preferably in the range of 5 to 10% by weight, based on the compound of formula (I).
In a preferred embodiment, the reaction temperature in step 1) is from 40 ℃ to 110 ℃, preferably from 60 ℃ to 90 ℃, most preferably from 70 ℃ to 80 ℃.
In a preferred embodiment, the reducing agent in step 2) comprises a palladium on carbon catalyst.
In a preferred embodiment, the palladium on carbon catalyst is used in an amount of 1 to 20 wt%, preferably 2 to 15 wt%, most preferably 3 to 10 wt% of the compounds of formula (II) and formula (III).
In a preferred embodiment, step 2) is carried out under a hydrogen atmosphere at a hydrogen pressure in the range of from 1.0MPa to 3.0MPa, preferably in the range of from 1.2MPa to 2.5MPa, most preferably in the range of from 1.4MPa to 2.2 MPa.
In a preferred embodiment, the reaction temperature in step 2) is from 40 ℃ to 120 ℃, preferably from 60 ℃ to 90 ℃, most preferably from 70 ℃ to 85 ℃.
In a preferred embodiment, the weight ratio of the compound of formula (IV) to the compound of formula (V) in the product is less than 45: 55.
Drawings
The invention is further described below with reference to the accompanying drawings. In the drawings, there is shown in the drawings,
FIG. 1 is a hydrogen spectrum of compound 5(6) -nitro-1- (4-nitrophenyl) -1,3, 3-trimethylindan (DNPI) prepared in example 1.
FIG. 2 is a carbon spectrum of compound 5(6) -nitro-1- (4-nitrophenyl) -1,3, 3-trimethylindan (DNPI) prepared in example 1.
FIG. 3 is a hydrogen spectrum of 5(6) -amino-1- (4-aminophenyl) -1,3, 3-trimethylindan (DAPI) prepared in example 1.
FIG. 4 is a carbon spectrum of 5(6) -amino-1- (4-aminophenyl) -1,3, 3-trimethylindan (DAPI) prepared in example 1.
FIG. 5 is a liquid phase diagram of the product of example 1 after nitration.
FIG. 6 is a liquid phase diagram of the product of the reduction reaction of example 1.
FIG. 7 is a comparison of glass transition temperatures of DAPI in application example 1 after curing with DDM and MMS.
Detailed Description
In the present specification, the technical features of the respective preferred technical aspects and the more preferred technical aspects may be combined with each other to form a new technical aspect, unless otherwise specified. For the sake of brevity, the applicant omits specific descriptions of these combinations in the specification, however, all technical solutions which combine these technical features should be considered to be written in this specification in an explicit manner.
Percentages are by weight unless otherwise indicated. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In addition, any methods and materials similar or equivalent to those described herein can be used in the practice of the present invention. The preferred embodiments and materials described herein are intended to be exemplary only.
The invention aims to provide an economical, convenient, green and environment-friendly method for industrially synthesizing a compound containing an indane structure.
The method for synthesizing the compound containing the indane structure comprises the following steps of:
1) carrying out nitration reaction on indan compounds of the compounds shown in the general formula (I) in the presence of a solid acid catalyst to obtain compounds shown in the general formulas (II) and (III);
2) in the presence of a reducing agent, the compounds shown in the general formula (II) and the general formula (III) are subjected to reduction reaction to obtain compounds shown in the general formula (IV) and the general formula (V),
preferably, in the general formulae (I), (II), (III), (IV), (V), R1、R2、R3And R4Independently of one another is hydrogen, C1-4Alkyl or C1-4Alkoxy, halogen, hydroxy or carboxy. More preferably, in the general formulae (I), (II), (III), (IV), (V), R1、R2、R3And R4Independently hydrogen, methyl, ethyl, propyl, methoxy, ethoxy, propoxy, chloro, hydroxy or carboxy.
Preferably, the nitration reaction comprises one or more of the following steps:
(a) adding a solid acid catalyst and a nitric acid solution into a reaction kettle for mixing, and heating a solid-liquid mixture at 40-110 ℃;
(b) heating the compound of formula (I) to a molten state (e.g., at a temperature of 60 ℃ to 110 ℃);
(c) dropwise adding the molten compound of the general formula (I) into the reaction kettle in the step (a) by using a dropwise adding device, and keeping the reaction temperature at 40-110 ℃ for reaction;
(d) after the reaction is finished, adding an organic solvent to dissolve the obtained crude product, separating liquid to remove a mixture of lower-layer nitric acid and solid acid, and filtering and recovering the mixture to obtain a solid acid catalyst and low-concentration nitric acid;
(e) adding a weak base solution into the upper layer liquid to adjust the pH value to be close to neutral, and then separating liquid to remove a washing layer;
(f) drying the separated organic solvent layer to remove water, and removing the solvent by rotary evaporation to obtain a viscous liquid product;
(g) taking an alcohol solvent, heating to a reflux temperature to dissolve the liquid product to prepare a supersaturated solution, reducing the temperature of the system, and gradually separating out the product to obtain the white powder products of the general formula (II) and the general formula (III). The yield is about 85 percent, and the purity is more than 99.5 percent.
Preferably, the nitric acid solution used in step (a) may be a nitric acid solution of any concentration range.
In some embodiments, the nitric acid solution used in step (a) is a nitric acid solution having a concentration of 50 to 70 weight percent. For example, the nitric acid solution used in step (a) is a nitric acid solution having a concentration of 69% by weight.
In some embodiments, the nitric acid solution used in step (a) may be a nitric acid solution having a concentration of 86 to 98 weight percent.
Preferably, the solid acid catalyst used in step (a) is selected from: one or more of super-strong solid acid, sulfonic acid resin, mesoporous molecular sieve and the like. Preferably, the solid acid catalyst is a super strong solid acid.
Preferably, the amount of the solid acid catalyst added in step (a) is generally 1 to 20% by weight, preferably 3 to 15% by weight, most preferably 5 to 10% by weight of the compound of formula (I).
Preferably, the mixture of solid acid catalyst and nitric acid solution mentioned in step (a) is heated to a temperature in the range of 40 ℃ to 110 ℃, preferably in the range of 60 ℃ to 100 ℃, most preferably in the range of 60 ℃ to 80 ℃.
Preferably, the compound of formula (I) mentioned in step (c) is added dropwise at a rate in the range of from 5g/min to 20g/min, preferably in the range of from 8g/min to 16g/min, most preferably in the range of from 10g/min to 15 g/min.
Preferably, the reaction temperature mentioned in step (c) is controlled in the range of 40 ℃ to 110 ℃, preferably in the range of 60 ℃ to 90 ℃, most preferably in the range of 70 ℃ to 80 ℃.
Preferably, the reaction time mentioned in step (c) is in the range of 2 to 16 hours, preferably in the range of 4 to 12 hours, most preferably in the range of 6 to 8 hours.
Preferably, the organic solvent in step (d) which dissolves the crude product is selected from: methanol, ethanol, isopropanol, dichloromethane, chloroform, carbon tetrachloride, 1, 2-dichloromethane, or mixtures thereof.
Preferably, the weak base for adjusting the pH in step (e) comprises NaHCO3. In some preferred embodiments, the weak base for adjusting the pH in step (e) is 2-10 wt.% NaHCO3. In one embodiment, the weak base used to adjust the pH in step (e) is 5 wt.% NaHCO3。
Preferably, the alcoholic solvent of the dissolution product in step (g) is selected from: methanol, ethanol, isopropanol, n-butanol, or mixtures thereof.
Preferably, the precipitation temperature mentioned in step (g) is controlled between 0 ℃ and 15 ℃, preferably in the range of 0 ℃ to 10 ℃, most preferably in the range of 5 ℃ to 10 ℃.
Preferably, the reduction reaction comprises one or more of the following steps:
(h) adding the purified products of the general formula (II) and the general formula (III) and a reducing agent into a high-pressure reaction kettle, replacing the products by high-purity nitrogen, and adding the alcohol solvent into the reaction kettle under negative pressure;
(i) filling hydrogen into the reaction kettle, maintaining the pressure of the hydrogen at 1.0-3.0 MPa, and reacting at the temperature of 40-120 ℃;
(j) after the reaction is finished, filtering the reaction solution under the protection of nitrogen to remove the reducing agent, and performing rotary evaporation on the filtrate to obtain crude products of the general formula (IV) and the general formula (V);
(k) the crude products of the general formula (IV) and the general formula (V) are treated by an organic solvent and are pulverized to obtain white solid powder, the yield is about 80%, and the purity is about 99%.
Preferably, the reducing agent mentioned in step (h) comprises a palladium on carbon catalyst. Preferably, the amount of the palladium-carbon catalyst is 1 to 20 wt%, preferably 2 to 15 wt%, and most preferably 3 to 10 wt% of the products of the general formula (II) and the general formula (III) obtained by the nitration reaction.
Preferably, the alcoholic solvent mentioned in step (h) is methanol, ethanol, isopropanol, n-butanol, or a mixture thereof.
Preferably, the hydrogen maintenance pressure mentioned in step (i) is in the range of 1.0MPa to 3.0MPa, preferably in the range of 1.2MPa to 2.5MPa, most preferably in the range of 1.4MPa to 2.2 MPa.
Preferably, the reaction temperature referred to in step (i) is in the range of from 40 ℃ to 120 ℃, preferably in the range of from 60 ℃ to 90 ℃, most preferably in the range of from 70 ℃ to 85 ℃.
Preferably, the reaction time mentioned in step (i) is in the range of 2 to 24 hours, preferably in the range of 4 to 12 hours, most preferably in the range of 4 to 6 hours.
Preferably, the organic solvent mentioned in step (k) is selected from: n-hexane, n-heptane, petroleum ether, pentane, octane, isooctane, methanol, ethanol, isopropanol, ethyl acetate, toluene, xylene, or mixtures thereof.
The method for synthesizing the compound containing the indane structure can be used for obtaining the compounds with the general formula (IV) and the general formula (V) with the purity of 99%.
In a preferred embodiment, the weight ratio of the compound of formula (IV) to the compound of formula (V) in the product obtained by the synthesis method of the invention is less than 45: 55. In a more preferred embodiment, the weight ratio of compound of formula (IV) to compound of formula (V) in the product obtained by the synthesis method of the invention is less than 35: 75.
The indane structure-containing compound prepared by the synthesis method is particularly suitable to be used as a curing agent of epoxy resin and/or used for synthesizing polyimide.
The method for synthesizing the compound containing the indane structure adopts the solid acid catalyst to realize nitration, and the mesoporous channel of the solid acid limits the free rotation of the compound of the raw material general formula (I), so that certain nitration selectivity is shown. The method for synthesizing the compound containing the indane structure has the following characteristics: (1) solid acid is used for replacing sulfuric acid, waste acid after catalytic digestion is simply filtered, and waste acid solution is pure dilute nitric acid solution and can be used as a nitrating agent again after being thickened; (2) the solid acid obtained by filtering can be repeatedly utilized after being cleaned, dried and simply activated; (3) the special catalytic mechanism of the solid acid is beneficial to the position selection of the nitro group, and the compound finally has certain nitration selectivity. In addition, the catalytic reduction process adopts a palladium-carbon catalytic hydrogenation mode, and the products of the general formula (IV) and the general formula (V) in a white solid powder state are finally obtained through filtering and pulverization under the protection of nitrogen.
Compared with the traditional preparation method, the synthesis method disclosed by the invention has the advantages that solid acid is used as a catalyst to replace sulfuric acid in the existing nitric-sulfur process, a novel nitration system is formed, the nitration efficiency is higher, the post-treatment mode is more environment-friendly, the link of extracting products from mixed acid is avoided, a large amount of acidic waste liquid generated in the mixed acid treatment process is avoided, the conversion rate of intermediate nitration products obtained after the digestion process is more than 95%, the yield is about 85%, and the solid acid catalyst still has higher conversion efficiency when being reused for 3 times. In addition, palladium carbon is used as a catalyst in the catalytic reduction process, the reduction conversion rate is about 97%, and the yield reaches about 80%.
The present invention is described in further detail below with reference to specific embodiments, and the experimental methods in the following examples, which do not indicate specific conditions, are generally performed under conventional conditions or conditions recommended by the manufacturers. Unless otherwise indicated, percentages are typically expressed as weight percentages. The scope of the present invention includes, but is not limited to, the following examples, and any modifications in the details and form of the technical solution of the present invention may be made without departing from the meaning and scope of the present application.
The following examples help to further illustrate the invention but do not limit it in any way.
The indane raw material adopted in the following examples is 1-phenyl-1, 3, 3-trimethylindane; DNPI is 5(6) -nitro-1- (4-aminophenyl) -1,3, 3-trimethylindane, i.e., a mixture of 5-nitro-1- (4-nitrophenyl) -1,3, 3-trimethylindane (5 '-DNPI) and 6-nitro-1- (4-nitrophenyl) -1,3, 3-trimethylindane (6' -DNPI); DAPI is 5(6) -amino-1- (4-aminophenyl) -1,3, 3-trimethylindane, i.e., a mixture of 5-amino-1- (4-aminophenyl) -1,3, 3-trimethylindane (5 '-DAPI) and 6-amino-1- (4-aminophenyl) -1,3, 3-trimethylindane (6' -DAPI).
Example 1
37.94g of TiCl are added4Dissolving in 0.2 mol/L HCl solution, and mixing 64.45g ZrOCl2·8H2Dissolving O in distilled water to obtain 0.2 mol/L solution, and preparing TiCl according to the atom ratio of zirconium to titanium (1:1)4And ZrOCl2·8H2Dropwise adding the mixed solution of O into 1 mol/L ammonia water under rapid stirring to adjust the pH value of the system to 9.0-10.0, precipitating, aging for 24h, filtering, repeatedly washing and suction filtering until no Cl exists in the solution-Drying the obtained precipitate at 110 ℃ for 8-9H, cooling, grinding into powder with the particle size of less than 0.149mm, and adding 1 mol/L H2SO4Soaking the powder in a proportion of 15m L/g for 15min, filtering, drying at 110 ℃ for 8-9 h, and roasting at 500 ℃ for 1h to obtain SO4 2-/ZrO2-TiO2Solid super acidic catalyst.
1.1kg (about 12.3mol) of 69 wt% nitric acid was charged into a 5L glass jacketed reaction kettle, followed by the super strong SO prepared above4 2-/TiO2-ZrO217.7g of super-strong solid acid catalyst, stirring and fully mixing, heating to the reaction temperature of 60 ℃, then gradually dripping 354g (1.5mol) of previously melted indane raw material 1-phenyl-1, 3, 3-trimethyl indane into a three-neck flask at the rotating speed of 300rpm according to the dripping speed of 10g/min, reacting for 6 hours, adding 1.5L dichloroethane to dissolve an organic layer after the reaction is finished, placing the reaction liquid into a separating funnel for standing and layering, separating out the organic layer, extracting the nitric acid layer by using 1L dichloroethane, collecting the obtained organic layer and the previous organic layer together, and utilizing 500m L5% NaHCO 5% to collect the organic layer together3The organic layer was washed to neutrality with anhydrous MgSO4And (5) drying. Finally, the obtained organic phase was subjected to solvent removal by a rotary evaporator to obtain 13.5g of a viscous yellow liquid. Adding 200ml of 97% industrial ethanol into the viscous liquid, heating until the industrial ethanol is fully dissolved, stirring, cooling the system to 10 ℃, cooling, and standing to precipitate milky solid powder. Filtering and drying to obtain a DNPI product. The yield was 88.7% and the purity of the final product was 99.0%. 5 '-DNPI and 6' -DNPI account for 31% and 69%, respectively.
The results of nuclear magnetic analysis were as follows: 1H-NMR (500MHz, CDCl3) (ppm)8.19(dd, J ═ 18.7,9.5Hz, H1,1H,),8.13(d, J ═ 9.0Hz,2H, H6),8.02(d, J ═ 50.5Hz,1H, H3),7.42-7.18(m,3H, H2/H5),2.55-2.12(m,2H, H4),1.78(s,3H, H9),1.40(s,2H, H8),1.09(s,2H, H7); 13C NMR (CDCl3) (ppm)159.64,156.95,149.19,147.86,146.29,127.37,123.79,123.68,120.25,58.85,51.10,43.44,30.43,30.24, 30.07.
Adding 65.2g of DNPI and a Pd/C catalyst with the DNPI mass fraction of 10% into a 1L pressure reaction kettle, installing the reaction kettle, adding high-purity nitrogen to 2.0MPa from a gas phase valve after the installation, performing leak detection operation, maintaining the pressure for 40min, and emptying N after the airtightness is good2Punching and evacuating twice, replacing air in the kettle, adding ethanol 600m L under negative pressure, opening a high-purity hydrogen valve, filling hydrogen and maintaining 1.6MPa, connecting a kettle body magnetic coupling stirring data line and an external heating device, starting to heat and stir, reacting for 8 hours after the temperature reaches 70 ℃, filtering a Pd/C catalyst after the reaction is finished, adding 500m L n-hexane after the filtrate is steamed in a rotary manner, stirring and cooling, filtering, and drying in vacuum to obtain white powder, wherein the yield is 84%, and the purity is about 98% by Waters 2695 type high performance liquid chromatography, using acetonitrile as the liquidity and using a C18 column as a stationary phase.
The results of nuclear magnetic analysis were as follows: 1H-NMR (500MHz, CDCl)3)(ppm)6.99(d,J＝9.0Hz,2H,H5),7.01-6.87(m,1H,H2),6.63(dd,J＝8.0,2.3Hz,1H,H1),6.64-6.54(m,2H,H6),6.47(dd,J＝54.1,2.2Hz,1H,H3),3.65(s,4H,H10),2.21(dd,J＝95.8,12.9Hz,2H,H4),1.61(s,3H,H9),1.29(s,3H,H8),1.03(s,3H,H7)；13C NMR(CDCl3)(ppm)153.60,150.79,145.24,143.88,142.88,127.72,114.69,111.55,109.22,59.84,50.06,42.73,30.77,30.57,30.31。
Example 2
Adding 1.1kg (about 12.3mol) of 69 wt% nitric acid into a 5L glass jacket reaction kettle, then adding 21.2g of MCM-41 mesoporous molecular sieve type catalyst (Tianjin Minghua catalyst Co., Ltd.), stirring and mixing thoroughly, heating to the reaction temperature of 80 ℃, then gradually adding 354g (1.5mol) of pre-melted indane raw material dropwise into the reaction kettle at the rotating speed of 300rpm according to the dropwise adding speed of 8g/minReacting in a flask for 12 hours, adding 1.5L trichloromethane to dissolve an organic layer after the reaction is finished, placing the reaction solution in a separating funnel for standing and layering, separating the organic layer, extracting the nitric acid layer with 1L trichloromethane, collecting the obtained organic layer and the previous organic layer together, and utilizing 500m L3% NaHCO to dissolve the organic layer3The organic layer was washed to neutrality with anhydrous MgSO4And (5) drying. And finally, removing the solvent from the obtained organic phase by a rotary evaporator to obtain viscous yellow liquid, adding 400ml of 97% industrial ethanol into the viscous yellow liquid, heating until the viscous yellow liquid is fully dissolved, stirring to cool the system to 10 ℃, cooling, and standing to precipitate milky solid powder. Filtering and drying to obtain a DNPI product. The yield was 80.2% and the purity of the final product was 94.3%. The 5 '-DNPI and 6' -DNPI account for 28% and 72%, respectively.
The results of nuclear magnetic analysis were as follows: 1H-NMR (500MHz, CDCl3) (ppm)8.19(dd, J ═ 18.7,9.5Hz, H1,1H,),8.13(d, J ═ 9.0Hz,2H, H6),8.02(d, J ═ 50.5Hz,1H, H3),7.42-7.18(m,3H, H2/H5),2.55-2.12(m,2H, H4),1.78(s,3H, H9),1.40(s,2H, H8),1.09(s,2H, H7); 13C NMR (CDCl3) (ppm)159.64,156.95,149.19,147.86,146.29,127.37,123.79,123.68,120.25,58.85,51.10,43.44,30.43,30.24, 30.07.
Adding 65.2g of DNPI and a Pd/C catalyst with the DNPI mass fraction of 12% into a 1L pressure reaction kettle, installing the reaction kettle, adding high-purity nitrogen to 2.0MPa from a gas phase valve after the installation, performing leak detection operation, maintaining the pressure for 40min, and emptying N after the airtightness is good2And then stamping and evacuating twice, replacing the air in the kettle, adding ethanol 600m L under negative pressure, opening a high-purity hydrogen valve after the above operation is completed, filling hydrogen and maintaining 1.8MPa, connecting a kettle body magnetic coupling stirring data line and external heating equipment, starting heating and stirring, reacting for 4 hours after the temperature reaches 90 ℃, filtering a Pd/C catalyst after the reaction is finished, adding 500m L n-hexane after the filtrate is steamed in a rotary manner, stirring and cooling, filtering, and drying in vacuum to obtain white powder, wherein the yield is 85%, and the purity is about 89.5%.
The results of nuclear magnetic analysis were as follows: 1H-NMR (500MHz, CDCl)3)(ppm)6.99(d,J＝9.0Hz,2H,H5),7.01-6.87(m,1H,H2),6.63(dd,J＝8.0,2.3Hz,1H,H1),6.64-6.54(m,2H,H6),6.47(dd,J＝54.1,2.2Hz,1H,H3),3.65(s,4H,H10),2.21(dd,J＝95.8,12.9Hz,2H,H4),1.61(s,3H,H9),1.29(s,3H,H8),1.03(s,3H,H7)；13C NMR(CDCl3)(ppm)153.60,150.79,145.24,143.88,142.88,127.72,114.69,111.55,109.22,59.84,50.06,42.73,30.77,30.57,30.31。
Example 3
Adding 1.1kg (about 12.3mol) of 69 wt% nitric acid into a 5L glass jacketed reaction kettle, adding 28.3g of C102 macroporous cation resin type catalyst (catalyst factory of southern Kaiki university), stirring, heating to 60 deg.C, gradually adding 354g (1.5mol) of the pre-melted indane raw material, dropping into a three-neck flask at 300rpm according to 15g/min dropping speed, reacting for 6 hr, adding 1L monochloromethane to dissolve the organic layer after the reaction is finished, placing the reaction solution into a separating funnel, standing for layering, separating the organic layer, extracting the nitric acid layer with 1L monochloromethane, collecting the obtained organic layer and the previous organic layer together, and utilizing 500m L6% NaHCO 6%3The organic layer was washed to neutrality with anhydrous MgSO4And (5) drying. Finally, removing the solvent from the obtained organic phase by a rotary evaporator to obtain viscous yellow liquid, adding 400ml of 97% industrial ethanol into the viscous yellow liquid, heating until the viscous yellow liquid is fully dissolved, stirring to cool the system to 10 ℃, cooling, and standing to precipitate milky solid powder. Filtering and drying to obtain a DNPI product. The yield was 88.7% and the purity of the final product was 98.3%. The 5 '-DNPI and 6' -DNPI account for 44% and 56%, respectively.
The results of nuclear magnetic analysis were as follows: 1H-NMR (500MHz, CDCl3) (ppm)8.19(dd, J ═ 18.7,9.5Hz, H1,1H,),8.13(d, J ═ 9.0Hz,2H, H6),8.02(d, J ═ 50.5Hz,1H, H3),7.42-7.18(m,3H, H2/H5),2.55-2.12(m,2H, H4),1.78(s,3H, H9),1.40(s,2H, H8),1.09(s,2H, H7); 13C NMR (CDCl3) (ppm)159.64,156.95,149.19,147.86,146.29,127.37,123.79,123.68,120.25,58.85,51.10,43.44,30.43,30.24, 30.07.
Adding 65.2g of DNPI and 5% of Pd/C catalyst by mass percent of DNPI into a 1L pressure reaction kettle, installing the reaction kettle, adding high-purity nitrogen to 2.0MPa from a gas phase valve after the installation, performing leak detection operation, maintaining the pressure for 40min, and emptying N after the airtightness is good2And then stamping and evacuating twice, replacing the air in the kettle, adding ethanol 600m L under negative pressure, opening a high-purity hydrogen valve after the above operation is completed, filling hydrogen and maintaining 1.8MPa, connecting a kettle body magnetic coupling stirring data line and external heating equipment, starting heating and stirring, reacting for 10h after the temperature reaches 60 ℃, filtering a Pd/C catalyst after the reaction is finished, adding 500m L n-hexane after the filtrate is steamed in a rotary manner, stirring and cooling, filtering, and drying in vacuum to obtain white powder with the yield of 92% and the purity of about 95%.
The results of nuclear magnetic analysis were as follows: 1H-NMR (500MHz, CDCl)3)(ppm)6.99(d,J＝9.0Hz,2H,H5),7.01-6.87(m,1H,H2),6.63(dd,J＝8.0,2.3Hz,1H,H1),6.64-6.54(m,2H,H6),6.47(dd,J＝54.1,2.2Hz,1H,H3),3.65(s,4H,H10),2.21(dd,J＝95.8,12.9Hz,2H,H4),1.61(s,3H,H9),1.29(s,3H,H8),1.03(s,3H,H7)；13C NMR(CDCl3)(ppm)153.60,150.79,145.24,143.88,142.88,127.72,114.69,111.55,109.22,59.84,50.06,42.73,30.77,30.57,30.31。
Example 4
Adding 1.1kg (about 12.3mol) of 69 wt% nitric acid into a 5L glass jacketed reaction kettle, adding 35.4g MCM-41 mesoporous molecular sieve catalyst (Tianjin Minghua catalyst Co., Ltd.), stirring and mixing thoroughly, heating to reaction temperature of 90 deg.C, gradually adding 354g (1.5mol) of the pre-melted indane raw material, dropping the indane raw material into a three-neck flask at 300rpm according to dropping speed of 12g/min, reacting for 8 hours, adding 1L monochloromethane to dissolve an organic layer after the reaction is finished, placing the reaction liquid into a separating funnel for static layering, separating the organic layer, extracting the nitric acid layer with 1L monochloromethane, collecting the obtained organic layer with the previous organic layer, and collecting 500m L3% NaHCO with L3The organic layer was washed to neutrality with anhydrous MgSO4And (5) drying. And finally, removing the solvent from the obtained organic phase by a rotary evaporator to obtain viscous yellow liquid, adding 300ml of 97% industrial ethanol into the viscous yellow liquid, heating until the viscous yellow liquid is fully dissolved, stirring to cool the system to 5 ℃, cooling, and standing to precipitate milky solid powder. Filtering and drying to obtain a DNPI product. The yield was 90.3% and the purity of the final product was 99.2%.
The results of nuclear magnetic analysis were as follows: 1H-NMR (500MHz, CDCl3) (ppm)8.19(dd, J ═ 18.7,9.5Hz, H1,1H,),8.13(d, J ═ 9.0Hz,2H, H6),8.02(d, J ═ 50.5Hz,1H, H3),7.42-7.18(m,3H, H2/H5),2.55-2.12(m,2H, H4),1.78(s,3H, H9),1.40(s,2H, H8),1.09(s,2H, H7); 13C NMR (CDCl3) (ppm)159.64,156.95,149.19,147.86,146.29,127.37,123.79,123.68,120.25,58.85,51.10,43.44,30.43,30.24, 30.07.
Adding 65.2g of DNPI and 5% of Pd/C catalyst by mass percent of DNPI into a 1L pressure reaction kettle, installing the reaction kettle, adding high-purity nitrogen to 2.0MPa from a gas phase valve after the installation, performing leak detection operation, maintaining the pressure for 40min, and emptying N after the airtightness is good2And then stamping and evacuating twice, replacing the air in the kettle, adding ethanol 600m L under negative pressure, opening a high-purity hydrogen valve after the above operation is completed, filling hydrogen and maintaining 2.2MPa, connecting a kettle body magnetic coupling stirring data line and external heating equipment, starting heating and stirring, reacting for 6 hours after the temperature reaches 70 ℃, filtering a Pd/C catalyst after the reaction is finished, adding 500m L n-hexane after the filtrate is steamed in a rotary manner, stirring and cooling, filtering, and drying in vacuum to obtain white powder, wherein the yield is 90%, the purity is about 98.4%, and the content of 5 '-DNPI and 6' -DNPI is respectively 22% and 78%.
The results of nuclear magnetic analysis were as follows: 1H-NMR (500MHz, CDCl)3)(ppm)6.99(d,J＝9.0Hz,2H,H5),7.01-6.87(m,1H,H2),6.63(dd,J＝8.0,2.3Hz,1H,H1),6.64-6.54(m,2H,H6),6.47(dd,J＝54.1,2.2Hz,1H,H3),3.65(s,4H,H10),2.21(dd,J＝95.8,12.9Hz,2H,H4),1.61(s,3H,H9),1.29(s,3H,H8),1.03(s,3H,H7)；13C NMR(CDCl3)(ppm)153.60,150.79,145.24,143.88,142.88,127.72,114.69,111.55,109.22,59.84,50.06,42.73,30.77,30.57,30.31。
Example 5
1.1kg (about 12.3mol) of 69% by weight nitric acid was charged into a 5L glass-jacketed reaction vessel, and then SO was added to each vessel4 2-/WO3-ZrO224.8g of super-strong solid acid catalyst (HND-32, south China general chemical Co., Ltd.) is stirred and mixed fully, the temperature is raised to 65 ℃, then 354g (1.5mol) of indane raw material which is melted in advance is gradually added at the rotating speed of 300rpm according to the ratio of 8g/minDropping the mixture into a three-neck flask at a dropping speed, reacting for 7 hours, adding 1.5L 1, 2-dichloroethane to dissolve an organic layer after the reaction is finished, placing the reaction solution into a separating funnel for standing and layering, separating the organic layer, extracting a nitric acid layer by using 1L 1, 2-dichloroethane, collecting the obtained organic layer and the previous organic layer together, and utilizing 500m L3 percent NaHCO to extract the nitric acid layer3The organic layer was washed to neutrality with anhydrous MgSO4And (5) drying. And finally, removing the solvent from the obtained organic phase by a rotary evaporator to obtain viscous yellow liquid, adding 300ml of 97% industrial ethanol into the viscous yellow liquid, heating until the viscous yellow liquid is fully dissolved, stirring to cool the system to 5 ℃, cooling, and standing to precipitate milky solid powder. Filtering and drying to obtain a DNPI product. The yield was 90.3% and the purity of the final product was 99.2%. 5 '-DNPI and 6' -DNPI account for 35% and 65%, respectively.
The results of nuclear magnetic analysis were as follows: 1H-NMR (500MHz, CDCl3) (ppm)8.19(dd, J ═ 18.7,9.5Hz, H1,1H,),8.13(d, J ═ 9.0Hz,2H, H6),8.02(d, J ═ 50.5Hz,1H, H3),7.42-7.18(m,3H, H2/H5),2.55-2.12(m,2H, H4),1.78(s,3H, H9),1.40(s,2H, H8),1.09(s,2H, H7); 13C NMR (CDCl3) (ppm)159.64,156.95,149.19,147.86,146.29,127.37,123.79,123.68,120.25,58.85,51.10,43.44,30.43,30.24, 30.07.
Adding 65.2g of DNPI and 5% of Pd/C catalyst by mass percent of DNPI into a 1L pressure reaction kettle, installing the reaction kettle, adding high-purity nitrogen to 2.0MPa from a gas phase valve after the installation, performing leak detection operation, maintaining the pressure for 40min, and emptying N after the airtightness is good2And then stamping and evacuating twice, replacing the air in the kettle, adding ethanol 600m L under negative pressure, opening a high-purity hydrogen valve after the above operation is completed, filling hydrogen and maintaining 2.2MPa, connecting a kettle body magnetic coupling stirring data line and external heating equipment, starting heating and stirring, reacting for 6h after the temperature reaches 70 ℃, filtering a Pd/C catalyst after the reaction is finished, adding 500m L n-hexane after the filtrate is steamed in a rotary manner, stirring and cooling, filtering, and drying in vacuum to obtain white powder with the yield of 90% and the purity of about 98.4%.
The results of nuclear magnetic analysis were as follows: 1H-NMR (500MHz, CDCl)3)(ppm)6.99(d,J＝9.0Hz,2H,H5),7.01-6.87(m,1H,H2),6.63(dd,J＝8.0,2.3Hz,1H,H1),6.64-6.54(m,2H,H6),6.47(dd,J＝54.1,2.2Hz,1H,H3),3.65(s,4H,H10),2.21(dd,J＝95.8,12.9Hz,2H,H4),1.61(s,3H,H9),1.29(s,3H,H8),1.03(s,3H,H7)；13C NMR(CDCl3)(ppm)153.60,150.79,145.24,143.88,142.88,127.72,114.69,111.55,109.22,59.84,50.06,42.73,30.77,30.57,30.31。
Example 6
1.1kg (about 12.3mol) of 69% by weight nitric acid was charged into a 5L glass-jacketed reaction vessel, and then SO was added to each vessel4 2-/ZrO231.9g of type catalyst (HND-8, south China general chemical Co., Ltd., Jiangyin City) is stirred and mixed sufficiently, the temperature is raised to 70 ℃, then 354g (1.5mol) of the indane raw material which is melted in advance is gradually dripped into a three-neck flask at the rotating speed of 300rpm according to the dripping speed of 10g/min, the reaction is carried out for 5 hours, 1L dichloromethane is added to dissolve an organic layer after the reaction is finished, the reaction liquid is placed into a separating funnel for standing and layering, the organic layer is separated, the nitric acid layer is extracted by 1L dichloromethane, the obtained organic layer and the previous organic layer are collected together, and 500m L5 percent NaHCO is utilized to extract the nitric acid layer3The organic layer was washed to neutrality with anhydrous MgSO4And (5) drying. And finally, removing the solvent from the obtained organic phase by a rotary evaporator to obtain viscous yellow liquid, adding 300ml of 97% industrial ethanol into the viscous yellow liquid, heating until the viscous yellow liquid is fully dissolved, stirring to cool the system to 8 ℃, cooling, and standing to precipitate milky solid powder. Filtering and drying to obtain a DNPI product. The yield was 87.6% and the purity of the final product was 88.6%. 5 '-DNPI and 6' -DNPI account for 29% and 71%, respectively.
The results of nuclear magnetic analysis were as follows: 1H-NMR (500MHz, CDCl3) (ppm)8.19(dd, J ═ 18.7,9.5Hz, H1,1H,),8.13(d, J ═ 9.0Hz,2H, H6),8.02(d, J ═ 50.5Hz,1H, H3),7.42-7.18(m,3H, H2/H5),2.55-2.12(m,2H, H4),1.78(s,3H, H9),1.40(s,2H, H8),1.09(s,2H, H7); 13C NMR (CDCl3) (ppm)159.64,156.95,149.19,147.86,146.29,127.37,123.79,123.68,120.25,58.85,51.10,43.44,30.43,30.24, 30.07.
Adding 65.2g of DNPI and 5 mass percent of DNPI Pd/C catalyst into a 1L pressure reaction kettle, installing the reaction kettle, and adding high-purity nitrogen to 2.0M through a gas phase valve after the reaction kettle is installedPa, performing leak detection operation, maintaining the pressure for 40min, and emptying N if the airtightness is good2And then stamping and evacuating twice, replacing air in the kettle, then adding 500m L ethanol under negative pressure, after the above operations are completed, opening a high-purity hydrogen valve, filling hydrogen and maintaining 2.0MPa, connecting a kettle body magnetic coupling stirring data line and external heating equipment, starting up to heat up and stir, reacting for 10h after the temperature reaches 80 ℃, filtering a Pd/C catalyst after the reaction is finished, adding 500m L n-hexane after the filtrate is steamed in a rotary manner, stirring and cooling, filtering, and drying in vacuum to obtain white powder, wherein the yield is 89.6%, and the purity is about 98.8%.
The results of nuclear magnetic analysis were as follows: 1H-NMR (500MHz, CDCl)3)(ppm)6.99(d,J＝9.0Hz,2H,H5),7.01-6.87(m,1H,H2),6.63(dd,J＝8.0,2.3Hz,1H,H1),6.64-6.54(m,2H,H6),6.47(dd,J＝54.1,2.2Hz,1H,H3),3.65(s,4H,H10),2.21(dd,J＝95.8,12.9Hz,2H,H4),1.61(s,3H,H9),1.29(s,3H,H8),1.03(s,3H,H7)；13C NMR(CDCl3)(ppm)153.60,150.79,145.24,143.88,142.88,127.72,114.69,111.55,109.22,59.84,50.06,42.73,30.77,30.57,30.31。
Example 7
Adding 1.1kg (about 12.3mol) of 69 wt% nitric acid into a 5L glass jacket reaction kettle, adding 7.1g MCM-22 mesoporous molecular sieve type catalyst (Tianjin Minghua catalyst Co., Ltd.) respectively, stirring and mixing fully, heating to the reaction temperature of 50 ℃, then gradually dripping 354g (1.5mol) of pre-melted indane raw material into a three-neck flask at the rotating speed of 300rpm according to the dripping speed of 8g/min, reacting for 5 hours, adding 1.5L carbon tetrachloride to dissolve an organic layer after the reaction is finished, placing the reaction liquid into a separating funnel for standing and layering, separating the organic layer, extracting the nitric acid layer by using 1L carbon tetrachloride, collecting the obtained organic layer and the previous organic layer together, and utilizing 800m L2% NaHCO 23The organic layer was washed to neutrality with anhydrous MgSO4And (5) drying. Finally, the obtained organic phase is subjected to solvent removal through a rotary evaporator to obtain viscous yellow liquid, 400ml of 97% industrial ethanol is added into the viscous yellow liquid to be heated until the viscous yellow liquid is fully dissolved, the system is cooled to 8 ℃ through stirring, and light yellow solid powder is precipitated through standing. Filtering and drying to obtainDNPI products. The yield was 65.4% and the purity of the final product was 84.1%. 5 '-DNPI and 6' -DNPI account for 37% and 63%, respectively.
The results of nuclear magnetic analysis were as follows: 1H-NMR (500MHz, CDCl3) (ppm)8.19(dd, J ═ 18.7,9.5Hz, H1,1H,),8.13(d, J ═ 9.0Hz,2H, H6),8.02(d, J ═ 50.5Hz,1H, H3),7.42-7.18(m,3H, H2/H5),2.55-2.12(m,2H, H4),1.78(s,3H, H9),1.40(s,2H, H8),1.09(s,2H, H7); 13C NMR (CDCl3) (ppm)159.64,156.95,149.19,147.86,146.29,127.37,123.79,123.68,120.25,58.85,51.10,43.44,30.43,30.24, 30.07.
Adding 65.2g of DNPI and 5% of Pd/C catalyst by mass percent of DNPI into a 1L pressure reaction kettle, installing the reaction kettle, adding high-purity nitrogen to 2.0MPa from a gas phase valve after the installation, performing leak detection operation, maintaining the pressure for 40min, and emptying N after the airtightness is good2And then stamping and evacuating twice, replacing air in the kettle, adding ethanol 400m L under negative pressure, opening a high-purity hydrogen valve after the above operation is completed, filling hydrogen and maintaining 1.6MPa, connecting a kettle body magnetic coupling stirring data line and external heating equipment, starting heating and stirring, reacting for 12h after the temperature reaches 70 ℃, filtering a Pd/C catalyst after the reaction is finished, adding 500m L n-hexane after the filtrate is steamed in a rotary manner, stirring and cooling, filtering, and drying in vacuum to obtain white powder, wherein the yield is 72.6%, and the purity is about 92.5%.
The results of nuclear magnetic analysis were as follows: 1H-NMR (500MHz, CDCl)3)(ppm)6.99(d,J＝9.0Hz,2H,H5),7.01-6.87(m,1H,H2),6.63(dd,J＝8.0,2.3Hz,1H,H1),6.64-6.54(m,2H,H6),6.47(dd,J＝54.1,2.2Hz,1H,H3),3.65(s,4H,H10),2.21(dd,J＝95.8,12.9Hz,2H,H4),1.61(s,3H,H9),1.29(s,3H,H8),1.03(s,3H,H7)；13C NMR(CDCl3)(ppm)153.60,150.79,145.24,143.88,142.88,127.72,114.69,111.55,109.22,59.84,50.06,42.73,30.77,30.57,30.31。
Example 8
Adding 1.1kg (about 12.3mol) of 69 wt% nitric acid into a 5L glass jacketed reaction kettle, adding 15.1g Nafion perfluorosulfonic acid resin type catalyst (south America chemical Co., Ltd., Jiangyun city), stirring, mixing, heating to reaction temperature of 70 deg.C, and gradually adding 354g (1.5mol) of previously melted indane raw material at 300rpmQuickly dropping the mixture into a three-neck flask at a dropping speed of 15g/min, reacting for 8 hours, adding 1.5L carbon tetrachloride to dissolve an organic layer after the reaction is finished, placing the reaction solution into a separating funnel for standing and layering, separating the organic layer, extracting a nitric acid layer by using 1L carbon tetrachloride, collecting the obtained organic layer and the previous organic layer together, and utilizing 500m L5 percent NaHCO 5 percent3The organic layer was washed to neutrality with anhydrous MgSO4And (5) drying. Finally, the obtained organic phase is subjected to solvent removal through a rotary evaporator to obtain viscous yellow liquid, 300ml of 97% industrial ethanol is added into the viscous yellow liquid to be heated until the viscous yellow liquid is fully dissolved, the system is cooled to 10 ℃ through stirring, and light yellow solid powder is precipitated through standing. Filtering and drying to obtain a DNPI product. The yield was 88.3% and the purity of the final product was 92.2%. 5 '-DNPI and 6' -DNPI account for 41% and 59%, respectively.
The results of nuclear magnetic analysis were as follows: 1H-NMR (500MHz, CDCl3) (ppm)8.19(dd, J ═ 18.7,9.5Hz, H1,1H,),8.13(d, J ═ 9.0Hz,2H, H6),8.02(d, J ═ 50.5Hz,1H, H3),7.42-7.18(m,3H, H2/H5),2.55-2.12(m,2H, H4),1.78(s,3H, H9),1.40(s,2H, H8),1.09(s,2H, H7); 13C NMR (CDCl3) (ppm)159.64,156.95,149.19,147.86,146.29,127.37,123.79,123.68,120.25,58.85,51.10,43.44,30.43,30.24, 30.07.
Adding 65.2g of DNPI and 5% of Pd/C catalyst by mass percent of DNPI into a 1L pressure reaction kettle, installing the reaction kettle, adding high-purity nitrogen to 2.0MPa from a gas phase valve after the installation, performing leak detection operation, maintaining the pressure for 40min, and emptying N after the airtightness is good2And then stamping and evacuating twice, replacing the air in the kettle, then adding ethanol 600m L through negative pressure, after the operations are completed, opening a high-purity hydrogen valve, filling hydrogen and maintaining 1.8MPa, connecting a kettle body magnetic coupling stirring data line and external heating equipment, starting up to heat and stir, reacting for 8 hours after the temperature reaches 90 ℃, filtering a Pd/C catalyst after the reaction is finished, adding 500m L n-hexane into filtrate after rotary evaporation, stirring and cooling, filtering, and performing vacuum drying to obtain white powder, wherein the yield is 89.4%, and the purity is about 96.5%.
The results of nuclear magnetic analysis were as follows: 1H-NMR (500MHz, CDCl)3)(ppm)6.99(d,J＝9.0Hz,2H,H5),7.01-6.87(m,1H,H2),6.63(dd,J＝8.0,2.3Hz,1H,H1),6.64-6.54(m,2H,H6),6.47(dd,J＝54.1,2.2Hz,1H,H3),3.65(s,4H,H10),2.21(dd,J＝95.8,12.9Hz,2H,H4),1.61(s,3H,H9),1.29(s,3H,H8),1.03(s,3H,H7)；13C NMR(CDCl3)(ppm)153.60,150.79,145.24,143.88,142.88,127.72,114.69,111.55,109.22,59.84,50.06,42.73,30.77,30.57,30.31。
Application example 1
Weighing 20.31g of DAPI, placing the DAPI into a 100ml plastic cup with a cover, weighing 59.72g E51 epoxy resin, covering the cover tightly, placing the DAPI into a rotation and revolution stirrer, stirring for 10min, placing the stirred mixture on a three-roll grinder, grinding until the particle size is about 5 μm, and repeating the operation for 3 times to obtain the epoxy adhesive. In the same ratio, DDM (4,4' -diaminodiphenylmethane, Shanghai medicine reagent) and DDS (diaminodiphenyl sulfone, Shanghai medicine reagent) are adopted to prepare the corresponding epoxy glue composition. The formulated epoxy gel was introduced into a mold, a sample was taken for gel time measurement, and the resulting cured sample was subjected to TGA analysis. The comparative results are shown in the following table.
Table 1: gel time of epoxy resins with different curing agents
Table 2: heat resistance of epoxy resin cured product containing different curing agents
Application example 2
The DAPI series Polyimide (PI) is prepared by a chemical imidization method, and is prepared by homopolymerization of DAPI with commercial dianhydride 6FDA (hexafluoro dianhydride), ODPA (4,4' -oxydiphthalic anhydride), BPDA (biphenyl tetracarboxylic dianhydride), BTDA (3,3 ', 4,4' - -benzophenone tetracarboxylic dianhydride) and PMDA (pyromellitic dianhydride).
The preparation process of the PI is illustrated by taking DAPI-6FDA as an example, a diamine monomer DAPI (6.7172g, 0.025mol) and DMF (101.28g) are added into a 250m L three-neck flask, stirred and dissolved, then 6FDA (11.1558g, 0.025mol) is added at one time to form a solution with the weight fraction of 15 wt%, the solution is reacted for 24 hours at 40 ℃ under the protection of nitrogen to obtain polyamic acid (PAA) solution, then triethylamine and acetic anhydride with the molar ratio of DAPI to triethylamine to acetic anhydride of 1:10:10 are added, the reaction is continued for 24 hours at 40 ℃ to carry out chemical imidization, a large amount of deionized water is used for dilution after the reaction is finished, white filiform solid is separated out by rapid stirring, the filtration is stored in a vacuum drying oven at 50 ℃ overnight, then the drying is carried out at 80 ℃ and 150 ℃ for one hour respectively, the cooling is carried out to obtain polyimide DAPI-6FDA containing an indane structure, and the other preparations are prepared according to the method.
The solubility of the polyimide materials prepared were compared as shown in Table 3.
Table 3: comparison of solubility of different polyimides in solvents
+: soluble at room temperature; -: insoluble at room temperature
The optical properties of the comparative polyimide materials are shown in Table 4.
Table 4: comparison of optical Properties of different polyimides
Claims (9)
1. A process for the synthesis of a compound containing an indane structure, said process comprising the steps of:
1) carrying out nitration reaction on the indane compound shown in the general formula (I) in the presence of a solid acid catalyst to obtain compounds shown in the general formulas (II) and (III);
2) in the presence of a reducing agent, carrying out reduction reaction on the compounds shown in the general formula (II) and the general formula (III) to obtain products shown in the general formula (IV) and the general formula (V),
in the general formulae (I), (II), (III), (IV), (V), R1、R2、R3And R4Independently of one another is hydrogen, C1-4Alkyl radical, C1-4Alkoxy, halogen, hydroxy or carboxy; preferably, in the general formulae (I), (II), (III), (IV), (V), R1、R2、R3And R4Are all hydrogen.
2. The method of claim 1, wherein the solid acid catalyst in step 1) is selected from one or more of super strong solid acid, sulfonic acid resin, and mesoporous molecular sieve.
3. The method of claim 2, wherein the super strong solid acid is selected from the group consisting of: SO (SO)4 2-/TiO2-ZrO2、SO4 2-/TiO2、SO4 2-/ZrO2、SO4 2-/WO3-ZrO2、SO4 2-/SnO2-Al2O3、SO4 2-/TiO2-La3+One or more of; the sulfonic acid resin type catalyst is selected from one or more of perfluorinated sulfonic acid resin and perfluoroalkyl sulfimide salt; the mesoporous molecular sieve type catalyst is selected from one or more of MCM-48, MCM-41 and MCM-22.
4. The process according to any one of claims 1 to 3, wherein the solid acid catalyst is added in step 1) in an amount of 1 to 20% by weight, preferably in the range of 3 to 15% by weight, most preferably in the range of 5 to 10% by weight, based on the compound of formula (I).
5. The process according to any one of claims 1 to 3, wherein the reaction temperature in step 1) is from 40 ℃ to 110 ℃, preferably from 60 ℃ to 90 ℃, most preferably from 70 ℃ to 80 ℃.
6. The method of any one of claims 1-3, wherein the reducing agent in step 2) comprises a palladium on carbon catalyst.
7. The process according to claim 6, wherein the palladium on carbon catalyst is used in an amount of 1 to 20 wt%, preferably 2 to 15 wt%, most preferably 3 to 10 wt% of the compounds of formula (II) and formula (III).
8. The process according to any of claims 1 to 3, wherein the reaction temperature in step 2) is from 40 ℃ to 120 ℃, preferably from 60 ℃ to 90 ℃, most preferably from 70 ℃ to 85 ℃.
9. The process of any one of claims 1 to 3, wherein the weight ratio of the compound of formula (IV) to the compound of formula (V) in the product is less than 45: 55.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117466754A (en) * | 2023-12-27 | 2024-01-30 | 中节能万润股份有限公司 | Indane structural compound crystallization method for epoxy resin curing agent |
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| US3856752A (en) * | 1973-10-01 | 1974-12-24 | Ciba Geigy Corp | Soluble polyimides derived from phenylindane diamines and dianhydrides |
| RU2559356C1 (en) * | 2014-01-09 | 2015-08-10 | Федеральное государственное бюджетное учреждение науки Институт нефтехимии и катализа Российской академии наук | Method of producing 5(6)-nitro-1-(4-nitrophenyl)-1,3,3-trimethylindanes |
| CN106748963A (en) * | 2016-12-01 | 2017-05-31 | 北京航空航天大学 | Polyamidoimide containing indane structural and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3856752A (en) * | 1973-10-01 | 1974-12-24 | Ciba Geigy Corp | Soluble polyimides derived from phenylindane diamines and dianhydrides |
| RU2559356C1 (en) * | 2014-01-09 | 2015-08-10 | Федеральное государственное бюджетное учреждение науки Институт нефтехимии и катализа Российской академии наук | Method of producing 5(6)-nitro-1-(4-nitrophenyl)-1,3,3-trimethylindanes |
| CN106748963A (en) * | 2016-12-01 | 2017-05-31 | 北京航空航天大学 | Polyamidoimide containing indane structural and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117466754A (en) * | 2023-12-27 | 2024-01-30 | 中节能万润股份有限公司 | Indane structural compound crystallization method for epoxy resin curing agent |
| CN117466754B (en) * | 2023-12-27 | 2024-03-12 | 中节能万润股份有限公司 | Indane structural compound crystallization method for epoxy resin curing agent |
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