CN116903476A - Large-steric-hindrance polybasic aniline/phenol and preparation method thereof - Google Patents

Large-steric-hindrance polybasic aniline/phenol and preparation method thereof Download PDF

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CN116903476A
CN116903476A CN202310854986.8A CN202310854986A CN116903476A CN 116903476 A CN116903476 A CN 116903476A CN 202310854986 A CN202310854986 A CN 202310854986A CN 116903476 A CN116903476 A CN 116903476A
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phenol
aniline
hindrance
polyaniline
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刘恒
王孝华
张春雨
张学全
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Qingdao University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
    • C07C211/49—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring having at least two amino groups bound to the carbon skeleton
    • C07C211/50—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring having at least two amino groups bound to the carbon skeleton with at least two amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/78—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
    • C07C217/82—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring
    • C07C217/84—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring the oxygen atom of at least one of the etherified hydroxy groups being further bound to an acyclic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
    • C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
    • C07C39/15—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings with all hydroxy groups on non-condensed rings, e.g. phenylphenol
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
    • C07C39/24—Halogenated derivatives
    • C07C39/367—Halogenated derivatives polycyclic non-condensed, containing only six-membered aromatic rings as cyclic parts, e.g. halogenated poly-hydroxyphenylalkanes

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Abstract

A large steric hindrance polybasic aniline/phenol and a preparation method thereof are provided, wherein the polybasic aniline/phenol is one of the structural general formulas (I), (II), (III) and (IV): x, Y substituent R 1 ‑R 9 The structures shown are described in the specification and claims. The preparation method is that aniline/phenol and ortho-substituted raw material 1, 2-di ((substituted phenyl) hydroxymethyl) benzene or meta-substituted raw material 1, 3-di ((substituted phenyl) are used as raw materials) Hydroxymethyl) benzene or para-substituted 1, 4-di ((substituted phenyl) hydroxymethyl) benzene is used as a raw material, and the Fock reaction is carried out under the catalysis of a mixture of 1-100 times of concentrated hydrochloric acid and 0.5-50 times of strong Lewis acid, so as to obtain the product. The preparation method is a brand new type of high-steric-hindrance polyamine/phenol compound and has the advantages of high yield and simple operation.

Description

Large-steric-hindrance polybasic aniline/phenol and preparation method thereof
Technical Field
The invention belongs to the field of organic compounds, and particularly relates to a high-steric-hindrance polyaniline/phenol and a preparation method thereof.
Background
The aniline/phenol is an important intermediate for synthesizing chemical products such as medicines, pesticides, dyes, fragrances and the like, and has very wide application. Aniline/phenol can be classified into monoaniline/phenol, dianiline/phenol, trianiline/phenol, quaternionic aniline/phenol, etc. according to the number of amino groups or hydroxyl groups in the compound, wherein the two or more aniline/phenol compounds can be collectively referred to as polyanilines/phenols.
The large steric hindrance aniline/phenol refers to aniline/phenol derivatives containing super steric hindrance substituent groups on the aromatic ring. One of the more common classes of phenotypic groups is the diphenylmethyl substituent. The compounds are prepared by the Fuke reaction of common aniline/phenol raw materials and benzhydrol derivatives in the presence of strong Lewis acid (US 4436936). In addition to their use as chemical intermediates, anilines/phenols containing such highly sterically hindered substituents have made significant progress in the field of catalysts in recent years. The alpha-diimine nickel/palladium complex prepared by the reaction of the large steric hindrance aniline and the diketone can obviously improve the heat resistance of the catalyst and obtain ultra-high molecular weight polyethylene (J.Am.chem.Soc., 2013,135 (44), 16316; angew.chem.int.ed.,2016,55 (42), 13281-13285); the single-metallocene titanium catalyst containing the large hindered phenol has high catalytic activity (Polymer, 2016,100,188-193) for catalyzing the copolymerization of ethylene and alpha-olefin monomers. However, the large sterically hindered anilines/phenols reported so far are predominantly monoanilides/phenols. In view of this, the present invention provides a highly sterically hindered polyanilines/phenols and a process for their preparation. The method can greatly expand the variety and range of the large-steric-hindrance polybasic aniline/phenol.
Disclosure of Invention
In order to enrich the variety and range of the large-steric-hindrance polybasic aniline/phenol, the invention provides the large-steric-hindrance polybasic aniline/phenol and a preparation method thereof.
The large steric hindrance polybasic aniline/phenol provided by the invention has a structural general formula (I-IV), and the specific structural general formula is as follows:
in the general structural formulas (I, II, III and IV), X represents NH 2 Or OH, Y represents an alkyl or aryl group of H, C to C20, a substituent R 1 -R 9 Each independently represents one of hydrogen, C1-C40 alkyl or aryl, C1-C40 alkoxy and halogen; the halogen is one of fluorine, chlorine and bromine; the space and electronic effect can be regulated and controlled, and the benzene ring bridged in the middle can be in an ortho-position, an meta-position and a para-position substitution structure.
More preferably, the highly sterically hindered polybasic aniline/phenol is preferably one of the following structures:
the synthetic route and the preparation method of the large-steric-hindrance polybasic aniline/phenol are as follows according to the structural general formula:
for the large steric hindrance polybasic aniline/phenol is large steric hindrance dibasic aniline/phenol, namely the large steric hindrance polybasic aniline/phenol with the structural general formula (I) or the structural general formula (II), the synthetic route is as follows:
for the large steric hindrance polybasic aniline/phenol with the structural general formula (I), the synthetic route is as follows:
for the large steric hindrance polybasic aniline/phenol of the general structural formula (II), the synthetic route is as follows:
the preparation method of the large steric hindrance polybasic aniline/phenol with the general structural formula (I) or the general structural formula (II) comprises the following steps:
mixing 2-5 times of substituted aniline/phenol with 1 times of ortho-substituted raw material 1, 2-di ((substituted phenyl) hydroxymethyl) benzene or meta-substituted raw material 1, 3-di ((substituted phenyl) hydroxymethyl) benzene or para-substituted raw material 1, 4-di ((substituted phenyl) hydroxymethyl) benzene at 130-200 ℃ uniformly, and then slowly adding a mixture of 1-100 times of concentrated hydrochloric acid and 0.5-50 times of strong Lewis acid. Then the reaction is continued for 0.1 to 10 hours at this temperature and then cooled to room temperature. After post-treatment, the large steric hindrance polybasic aniline/phenol with the general structural formula (I) or the general structural formula (II) of the target product is obtained. Preferably, the amount of substituted aniline/phenol is 2 times the amount and the reaction temperature is 160 ℃. Preferably, the strong lewis acid is zinc chloride, preferably in an amount of 2 to 10 times. Preferably, the reaction time is from 0.5 to 2 hours.
When the large steric hindrance polybasic aniline/phenol is a large steric hindrance ternary amine/phenol compound, the synthetic route is as follows:
for the large steric hindrance polybasic aniline/phenol of the general structural formula (III), the synthetic route is as follows:
for the large steric hindrance polybasic aniline/phenol of the general structural formula (IV), the synthetic route is as follows:
the preparation method of the large steric hindrance polybasic aniline/phenol with the structural formula (III) or (IV) comprises the following steps:
mixing 3-100 times of substituted aniline/phenol and 1 time of 1,3, 5-tri ((substituted phenyl) hydroxymethyl) benzene at 130-200deg.C, and slowly adding 1-100 times of concentrated hydrochloric acid and 0.5-100 times of strong Lewis acid. Then the reaction is continued for 0.1 to 10 hours at this temperature and then cooled to room temperature. After post-treatment, the large steric hindrance polybasic aniline/phenol with the general structural formula (III) or the general structural formula (IV) of the target product is obtained. More preferably, the usage amount of the substituted aniline/phenol is 3 times, the reaction temperature is 160 ℃, the strong Lewis acid is zinc chloride, the usage amount is 3-30 times, and the reaction time is 0.5-2 hours.
The beneficial effects of the polyanilines/phenols disclosed by the invention are mainly shown as follows: a novel high-steric-hindrance polyaniline/phenol compound is prepared, and a high-efficiency synthesis method is provided.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of a large-steric-hindrance diphenylamine I-1 prepared in an embodiment of the present invention.
FIG. 2 is a nuclear magnetic hydrogen spectrum of the large-steric-hindrance diphenylamine I-2 prepared in the embodiment of the present invention.
FIG. 3 is a nuclear magnetic hydrogen spectrum of the large-steric-hindrance ternary aniline III-1 prepared in the embodiment of the invention.
Detailed Description
The present invention will be described in further detail with reference to examples.
Examples 1
Synthesis of highly hindered diphenylamine I-1: 2, 4-dimethylaniline (10.0 mmol,2.0 equiv.) and 1, 3-di ((phenyl) hydroxymethyl) benzene (5.0 mmol,1.0 equiv.) were added to a 200 ml thick-walled pressure-resistant bottle and heated to 160 ℃. A concentrated hydrochloric acid solution (50.0 equiv.) of zinc chloride (10.0 mmol,2.0 equiv.) was slowly added and the reaction was strongly exothermic. After continuing the reaction at this temperature for 2 hours, the reaction was allowed to cool to room temperature. Dissolved in 500 ml of dichloromethane, washed three times with 200 ml of water and dried over anhydrous magnesium sulfate. Filtering, filteringAfter concentration, column chromatography was performed with 30:1 (petroleum ether: ethyl acetate) eluent to give a light brown solid powder. The yield thereof was found to be 85%. The nuclear magnetic hydrogen spectrum of the obtained light brown solid powder is shown in figure 1, 1 H NMR(400MHz,Chloroform-d)δ7.27-7.18(m,9H,ArH),7.07(d,4H,ArH),6.95(d,3H,ArH),6.78(s,2H,ArH),6.28(s,2H,ArH),5.38(s,2H,CH),3.28(s,4H,-NH 2 ),2.10(t,12H,CH 3 ).
examples 2
Synthesis of highly hindered diphenylamine I-1: the other reaction conditions were the same as in example (I) except that 5.0 times of 2, 4-dimethylaniline was used. The yield thereof was found to be 95%.
Example (III)
Synthesis of highly hindered diphenylamine I-1: the reaction temperature was 130℃and the other reaction conditions were the same as in example (I). The yield thereof was found to be 72%.
Example (IV)
Synthesis of highly hindered diphenylamine I-1: the reaction temperature was 200℃and the other reaction conditions were the same as in example (I). The yield thereof was found to be 98%.
Example (five)
Synthesis of highly hindered diphenylamine I-1: the reaction conditions were the same as in example (I) except that 0.5 times of zinc chloride was used. The yield thereof was found to be 82%.
Example (six)
Synthesis of highly hindered diphenylamine I-1: the reaction conditions were the same as in example (I) except that 50 times of zinc chloride was used. The yield thereof was found to be 98%.
Example (six)
Synthesis of highly hindered diphenylamine I-1: the reaction time was 10 hours, and the other reaction conditions were the same as in example (I). The yield thereof was found to be 92%.
Example (seven)
Synthesis of highly hindered diphenylamine I-2: 1, 3-Di ((methylphenyl) hydroxymethyl) benzene was used as a starting material, and the other reaction conditions were the same as in example (I). Yield: 90%. Nuclear magnetic hydrogen spectrum of large steric hindrance diphenylamine I-2As can be seen in figure 2 of the drawings, 1 H NMR(400MHz,Chloroform-d)δ7.19-7.10(m,6H,ArH),7.00(d,4H,ArH),6.70(s,4H,ArH),6.65(s,1H,ArH),6.21(s,2H,ArH),5.27(s,2H,CH),3.20(s,4H,-NH 2 ),2.14(s,3H,CH 3 ),2.03(d,12H,CH 3 ).
example (eight)
Synthesis of highly hindered diphenylamine I-3: 1, 3-bis ((t-butylphenyl) hydroxymethyl) benzene was used as a starting material, and the other reaction conditions were the same as in example (I). Yield: 86%. 1 H NMR(400MHz,Chloroform-d)δ7.25-7.16(m,6H,ArH),7.07-7.01(m,6H,ArH),6.77(s,2H,ArH),6.62(d,1H,ArH),6.26(s,2H,ArH),5.36(s,2H,CH),3.27(s,4H,-NH 2 ),2.09(t,12H,CH 3 ),1.17(d,9H,CH 3 ).
Example nine
Synthesis of highly hindered diphenylamine I-4: 2, 4-Dimethoxyaniline was used as a starting material, and the other reaction conditions were the same as in example (I). Yield: 86%. 1 H NMR(400MHz,Chloroform-d)δ7.25–7.15(m,7H,ArH),7.06–6.97(m,6H,ArH),6.85(dd,J＝7.8,1.8Hz,2H,ArH),6.64(d,J＝1.9Hz,1H,ArH),6.43(s,2H,ArH),5.67(s,2H,CH),3.88(s,6H,OMe),3.63(s,6H,OMe).
Examples (ten)
Synthesis of highly hindered diphenylamine I-5: the 2-phenyl-4-methylaniline was used as the starting material, and the other reaction conditions were the same as in example (I). Yield: 66%. 1 H NMR(400MHz,Chloroform-d)δ7.47–7.22(m,16H,ArH),7.22–7.09(m,4H,ArH),7.05(d,J＝2.7Hz,4H,ArH),6.88(m,J＝4.3,2.1Hz,2H,ArH),6.44(m,J＝6.8,2.1Hz,2H,ArH),5.49(s,2H,CH),3.40(s,4H,-NH 2 ),2.17(s,3H,CH 3 ),2.16(s,3H,CH 3 ).
Example (eleven)
Synthesis of highly hindered dihydric phenol I-6: 2, 4-dimethylphenol was used as a starting material, and the other reaction conditions were the same as in example (I). Yield: 76%. 1 H NMR(400MHz,Chloroform-d)δ7.38–7.24(m,8H,ArH),7.14(dd,J＝7.5,1.6Hz,4H,ArH),7.04(d,J＝1.8Hz,2H,ArH),6.88(d,J＝1.9Hz,2H,ArH),6.42(d,J＝2.5Hz,2H,ArH),5.65(s,2H,CH),4.44(s,2H,-OH),2.25–2.14(m,12H,CH 3 ).
Example (twelve)
Synthesis of highly hindered dihydric phenol I-7: 2-bromo-4-methylphenol was used as starting material, and the other reaction conditions were the same as in example (I). Yield: 56%. 1 H NMR(400MHz,CDCl 3 )δ7.38–7.33(m,4H,ArH),7.33–7.22(m,4H,ArH),7.13–7.07(m,4H,ArH),7.05–7.00(m,2H,ArH),6.96(s,2H,ArH),6.80(d,J＝2.2Hz,2H,ArH),5.86(s,2H,CH),5.47–5.42(m,2H,-OH),1.21–1.11(m,6H,CH 3 ).
Example (thirteen)
Synthesis of highly hindered dihydric phenol I-8: 2-bromo-4-tert-butylphenol was used as the starting material, and the other reaction conditions were the same as in example (I). Yield: 81%. 1 H NMR(400MHz,CDCl 3 )δ7.38–7.33(m,7H,ArH),7.33–7.22(m,2H,ArH),7.13–7.07(m,4H,ArH),7.05–7.00(m,2H,ArH),6.96(s,1H,ArH),6.80(d,J＝2.2Hz,2H,ArH),5.86(s,2H,CH),5.47–5.42(m,2H,-OH),1.21–1.11(m,18H,tBu).
Examples (fourteen)
Synthesis of highly hindered diphenylamine I-9: 2, 4-dimethylaniline and 1, 4-di ((phenyl) hydroxymethyl) benzene were used as starting materials, and the other reaction conditions were the same as in example (I). Yield: 95%. 1 H NMR(200MHz,Chloroform-d)δ7.48–7.08(m,14H,ArH),6.91(d,J＝2.1Hz,2H,ArH),6.47(d,J＝2.1Hz,2H,ArH),5.57(s,2H,CH),3.43(s,4H,-NH 2 ),2.23(s,6H,CH 3 ),2.21(s,6H,CH 3 ).
Example (fifteen)
Synthesis of highly hindered dihydric phenol I-10: 2, 4-dimethylphenol and 1, 4-di ((phenyl) hydroxymethyl) benzene were used as starting materials, and the other reaction conditions were the same as in example (one). Yield: 65%. 1 H NMR(400MHz,CDCl 3 )δ7.32(d,J＝7.8Hz,6H,ArH),7.19(d,J＝1.8Hz,4H,ArH),7.10(s,4H,ArH),6.87(d,J＝2.3Hz,2H,ArH),6.47(t,J＝2.9Hz,2H,ArH),5.67(d,J＝8.1Hz,2H,CH),4.48–4.43(m,2H,-OH),2.19(d,J＝12.0Hz,12H,CH 3 ).
Example (sixteen)
Synthesis of highly hindered diphenylamine II-1: 2, 6-dimethylaniline and 1, 4-di ((phenyl) hydroxymethyl) benzene were used as the starting materials, and the other reaction conditions were the same as in example (I). Yield: 92%.
Example (sixteen)
Synthesis of highly hindered diphenylamine II-2: 2, 6-dimethylphenol and 1, 4-di ((phenyl) hydroxymethyl) benzene were used as starting materials, and the other reaction conditions were the same as in example (one). Yield: 90%.
Example (seventeen)
Synthesis of highly hindered triphenylamine III-1: 2, 4-dimethylaniline and 1,3, 5-tris ((substituted phenyl) hydroxymethyl) benzene were used as starting materials, and the other reaction conditions were the same as in example (one). Yield: 90%. The nuclear magnetic hydrogen spectrum of the prepared large-steric-hindrance ternary aniline III-1 is shown in figure 3, 1 H NMR(400MHz,Chloroform-d)δ7.26–7.16(m,9H,ArH),7.12–6.97(m,6H,ArH),6.85–6.60(m,6H,ArH),6.33–6.10(m,3H,ArH),5.31(s,3H,CH),3.24(s,6H,-NH 2 ),2.12(s,9H,CH 3 ),2.11(s,9H,CH 3 ).
example (eighteen)
Synthesis of highly hindered triphenylamine III-1: 2, 4-dimethylphenol and 1,3, 5-tris ((substituted phenyl) hydroxymethyl) benzene were used as starting materials, and the other reaction conditions were the same as in example (one). Yield: 95%.
Example (nineteen)
Synthesis of highly hindered triphenylamine IV-1: 2, 6-dimethylaniline and 1,3, 5-tris ((substituted phenyl) hydroxymethyl) benzene were used as starting materials, and the other reaction conditions were the same as in example (one). Yield: 96%.
Example (twenty)
Synthesis of highly hindered triphenylamine IV-2: the other reaction conditions were the same as in example (I) except that 2, 6-dimethylphenol and 1,3, 5-tris ((substituted phenyl) hydroxymethyl) benzene were used as starting materials. Yield: 98%.

Claims (10)

1. The large steric hindrance polybasic aniline/phenol is one of the following structural general formulas (I-IV):
in the general structural formulas (I, II, III and IV), X represents NH 2 Or OH, Y represents an alkyl or aryl group of H, C to C20, a substituent R 1 -R 9 Each independently represents one of hydrogen, C1-C40 alkyl or aryl, C1-C40 alkoxy and halogen.
2. The high steric hindrance polyaniline/phenol according to claim 1, wherein the halogen is one of fluorine, chlorine and bromine.
3. The high-steric-hindrance polyaniline/phenol according to claim 1, wherein the benzene ring bridged in the middle in the general structural formulae (I-IV) is selected from the group consisting of ortho-, meta-, and para-substituted structures.
4. The high steric-polynary aniline/phenol according to claim 1 wherein the high steric-polynary aniline/phenol is specifically one of the following structures:
5. the process for preparing a highly sterically hindered polyaniline/phenol as described in claim 1, wherein the synthetic route for the highly sterically hindered polyaniline/phenol of the general structural formula (I) is:
for the large steric hindrance polybasic aniline/phenol of the general structural formula (II), the synthetic route is as follows:
6. the method for preparing a large sterically hindered polyaniline/phenol according to claim 5, comprising the steps of:
mixing 2-5 times of substituted aniline/phenol with 1 time of ortho-substituted raw material 1, 2-di ((substituted phenyl) hydroxymethyl) benzene or meta-substituted raw material 1, 3-di ((substituted phenyl) hydroxymethyl) benzene or para-substituted raw material 1, 4-di ((substituted phenyl) hydroxymethyl) benzene uniformly according to a molar ratio at 130-200 ℃, and then adding a mixture of 1-100 times of concentrated hydrochloric acid and 0.5-50 times of strong Lewis acid; then continuously reacting for 0.1-10 hours at the temperature, and cooling to room temperature; after post-treatment, the large steric hindrance polybasic aniline/phenol with the general structural formula (I) or the general structural formula (II) of the target product is obtained.
7. The method for preparing a large-steric-hindrance polyaniline/phenol according to claim 6, wherein the strong lewis acid is zinc chloride in an amount of 2 to 10 times.
8. The process for preparing a highly sterically hindered polyaniline/phenol as described in claim 1, wherein the synthetic route for the highly sterically hindered polyaniline/phenol of the general structural formula (III) is:
for the large steric hindrance polybasic aniline/phenol of the general structural formula (IV), the synthetic route is as follows:
9. the method for preparing a large sterically hindered polyaniline/phenol according to claim 8, comprising the steps of:
mixing 3-100 times of substituted aniline/phenol and 1 time of 1,3, 5-tri ((substituted phenyl) hydroxymethyl) benzene at 130-200 ℃, and adding 1-100 times of concentrated hydrochloric acid and 0.5-100 times of strong Lewis acid; continuing to react for 0.1-10 hours at the temperature, and cooling to room temperature; after post-treatment, the large steric hindrance polybasic aniline/phenol with the general structural formula (III) or the general structural formula (IV) of the target product is obtained.
10. The method for preparing a large-steric-hindrance polyaniline/phenol according to claim 9, wherein the strong lewis acid is zinc chloride in an amount of 3 to 30 times and the reaction time is 0.5 to 2 hours.
CN202310854986.8A 2023-07-13 2023-07-13 Large-steric-hindrance polybasic aniline/phenol and preparation method thereof Pending CN116903476A (en)

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