CN113527116A - Preparation method of aminophenol containing methylene - Google Patents
Preparation method of aminophenol containing methylene Download PDFInfo
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- CN113527116A CN113527116A CN202110824133.0A CN202110824133A CN113527116A CN 113527116 A CN113527116 A CN 113527116A CN 202110824133 A CN202110824133 A CN 202110824133A CN 113527116 A CN113527116 A CN 113527116A
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- methylene
- hydroxymethylphenol
- aminophenol
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- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 title claims abstract 6
- CQRYARSYNCAZFO-UHFFFAOYSA-N salicyl alcohol Chemical compound OCC1=CC=CC=C1O CQRYARSYNCAZFO-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 18
- MMCPOSDMTGQNKG-UHFFFAOYSA-N anilinium chloride Chemical compound Cl.NC1=CC=CC=C1 MMCPOSDMTGQNKG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 238000000746 purification Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 4
- 238000006396 nitration reaction Methods 0.000 abstract description 4
- 238000007336 electrophilic substitution reaction Methods 0.000 abstract description 3
- 125000002091 cationic group Chemical group 0.000 abstract 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 31
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 24
- HNIQGEAPSBAOEJ-UHFFFAOYSA-N 4-[(4-aminophenyl)methylidene]cyclohexa-1,5-dien-1-ol Chemical group NC1=CC=C(C=C1)C=C1CC=C(C=C1)O HNIQGEAPSBAOEJ-UHFFFAOYSA-N 0.000 description 10
- 239000013078 crystal Substances 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- BVJSUAQZOZWCKN-UHFFFAOYSA-N p-hydroxybenzyl alcohol Chemical compound OCC1=CC=C(O)C=C1 BVJSUAQZOZWCKN-UHFFFAOYSA-N 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000001256 steam distillation Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 238000006683 Mannich reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- -1 benzene ring hydrogen Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Images
Classifications
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- 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
- C07C213/02—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 involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
-
- 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
- C07C213/10—Separation; Purification; Stabilisation; Use of additives
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of organic synthesis, and discloses a preparation method of aminophenol containing methylene. The reaction raw materials in the preparation method comprise acid, hydroxymethyl phenol or derivatives of hydroxymethyl phenol; the acid is aniline hydrochloride or aniline hydrochloride derivative. According to the invention, the amino phenol containing methylene is obtained through a specific reaction raw material and a cationic electrophilic substitution reaction, so that the nitration and hydrogenation reaction processes with high risk are avoided, and the yield of the amino phenol containing methylene is over 78 percent, even over 80 percent.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a preparation method of aminophenol containing methylene.
Background
The molecular structure of the aminophenol contains a phenol group and an amino group, a high molecular material can be constructed through esterification and amidation, and the aminophenol can also be used as different monomers to obtain the benzoxazine resin with large molecular weight through Mannich reaction (Mannich reaction). However, the common p-aminophenol has poor stability and is easy to blacken under illumination and heating, which leads to high requirements on storage, transportation and feeding of the common p-aminophenol and is not beneficial to industrial production. Therefore, it is necessary to produce aminophenols having good stability.
In the prior art, 4 steps of reaction are usually needed for producing the methylene-containing aminophenol with good stability, so that the yield of the methylene-containing aminophenol is very low, even if the yield of each step of reaction is 90%, the yield of the finally prepared methylene-containing aminophenol is hardly more than 65% through the 4 steps of reaction. In addition, in the prior art, the aminophenol containing methylene is generally obtained by nitration and hydrogenation reactions, and the reaction risk is high.
Therefore, it is desirable to provide a novel process for the preparation of methylene group-containing aminophenols which produces methylene group-containing aminophenols in high yields and in which the reaction is relatively safe.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. To this end, the invention proposes a process for the preparation of aminophenols containing methylene groups, which produces aminophenols containing methylene groups in yields exceeding 78%, even exceeding 80%. The solubility of the methylene group-containing aminophenol is higher than that of the methylene group-free aminophenol.
The invention conception of the invention is as follows: the invention obtains the aminophenol containing methylene through cation electrophilic substitution reaction by specific reaction raw materials (the reaction raw materials comprise acid, hydroxymethyl phenol or derivatives of hydroxymethyl phenol), thereby avoiding the nitration and hydrogenation processes with high risk, and the yield of the aminophenol containing methylene is more than 78 percent, even more than 80 percent.
In a first aspect of the invention, a process for the preparation of a methylene group-containing aminophenol is provided.
Specifically, the preparation method of the aminophenol containing the methylene comprises the steps of preparing a reaction raw material, wherein the reaction raw material comprises acid, hydroxymethyl phenol or derivatives of the hydroxymethyl phenol.
Preferably, the acid is aniline hydrochloride or a derivative of aniline hydrochloride.
Preferably, the structural formula of the hydroxymethylphenol or the derivative of the hydroxymethylphenol is shown as the formula (1):
wherein R2 represents H or alkyl.
More preferably, the alkyl group is an alkyl group having 1 to 6 carbon atoms.
More preferably, the hydroxymethylphenol is p-hydroxymethylphenol.
Preferably, the reaction raw materials further comprise a substance represented by the structural formula (2):
wherein R1 represents H or alkyl.
More preferably, the alkyl group is an alkyl group having 1 to 6 carbon atoms.
More preferably, R1 is H, namely the substance shown in the formula (2) is aniline.
Preferably, the molar ratio of the acid (e.g. aniline hydrochloride or aniline hydrochloride derivative), hydroxymethylphenol or hydroxymethylphenol derivative is 0.2: (0.05-0.3); further preferably, the molar ratio of the acid, the hydroxymethylphenol or the derivative of the hydroxymethylphenol is 0.2: (0.08-0.15); more preferably, the molar ratio of the acid, the hydroxymethylphenol or the derivative of hydroxymethylphenol is 0.2: 0.1.
preferably, the substance represented by the formula (2) (for example, aniline) is used in an excess amount, and the molar ratio of the hydroxymethylphenol or a derivative of the hydroxymethylphenol to the substance represented by the formula (2) (for example, aniline) is 0.1: (0.1-1); more preferably, the molar ratio of the hydroxymethylphenol or the derivative of hydroxymethylphenol to the substance represented by the formula (2) (for example, aniline) is 0.1: (0.2-0.6).
Preferably, the preparation method of the aminophenol containing methylene comprises the following steps:
mixing aniline hydrochloride or aniline hydrochloride derivatives, hydroxymethyl phenol or hydroxymethyl phenol derivatives and substances shown in a formula (2) under an inert gas atmosphere, and heating to react to obtain the aminophenol containing methylene.
Preferably, the inert gas includes at least one of nitrogen and a rare gas.
Preferably, the temperature of the heating reaction is 100-130 ℃; further preferably, the temperature of the heating reaction is 115-125 ℃.
Preferably, the heating reaction time is 0.8-1.5 hours; further preferably, the heating reaction time is 1 to 1.5 hours.
Preferably, after the heating reaction is finished, a separation and purification process is further included.
Further preferably, the separation and purification process specifically comprises: and pouring the mixture obtained after the heating reaction into water, adding alkali and ester for extraction separation, drying an organic layer, distilling the solvent under reduced pressure, performing steam distillation on the residual oily substance to remove excessive aniline, and recrystallizing with saturated NaCl water/ethanol to obtain white crystals. The white crystal is aminophenol containing methylene with the purity of not less than 99 percent.
In order to avoid the attack of cations on p-hydroxymethylphenol itself, an excess of aniline is used. The combination of residual aniline in the crude product after the reaction and the aminophenol containing methylene is not beneficial to the recrystallization purification of the aminophenol containing methylene, so that the redundant aniline is separated and recovered through steam distillation, and the purification of the aminophenol containing methylene through recrystallization is facilitated (the purity can be improved to 99.3%).
Preferably, the base and ester are NaHCO3And ethyl acetate.
Preferably, the structural formula of the amino phenol containing methylene is shown as the formula (3):
wherein R1 and R2 each independently represent H or an alkyl group.
More preferably, the alkyl group is an alkyl group having 1 to 6 carbon atoms.
More preferably, the name of the aminophenol containing methylene is 4- ((4-aminophenyl) -methylene) phenol, and the specific structural formula is shown as a formula (4).
The substance has no discoloration under air, light and heating conditions, and has good stability and can not be oxidized after being stored in air for one year.
The process for synthesizing the methylene group-containing aminophenol represented by the formula (4) is represented by the following formula:
the interpretation of equation (5) is: HCl liberated from aniline hydrochloride forms active cations with p-hydroxymethyl phenol at the reaction temperature, and can attack electron-rich aniline, and finally the amino phenol containing methylene shown in the formula (4) is prepared.
The second aspect of the present invention provides the use of the above-mentioned process for the preparation of methylene group-containing aminophenols in the field of organic synthesis.
Preferably, the polymer material is further prepared by the above-mentioned preparation method.
Compared with the prior art, the invention has the following beneficial effects:
the invention obtains the aminophenol containing methylene through cation electrophilic substitution reaction by specific reaction raw materials (the reaction raw materials comprise acid, hydroxymethyl phenol or derivatives of hydroxymethyl phenol), thereby avoiding the nitration and hydrogenation reaction processes with high risk, and the yield of the aminophenol containing methylene is more than 78 percent, even more than 80 percent.
Drawings
FIG. 1 is an IR spectrum of a white crystal obtained in example 1 of the present invention;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of a white crystal obtained in example 1 of the present invention.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples are given for illustration. It should be noted that the following examples are not intended to limit the scope of the claimed invention.
The starting materials, reagents or apparatuses used in the following examples are conventionally commercially available or can be obtained by conventionally known methods, unless otherwise specified.
In the Nuclear Magnetic Resonance hydrogen spectrogram testing process, a Bruk Nuclear Magnetic Resonance spectrometer (Nuclear Magnetic Resonance Spectroscopy) and deuterated dimethyl sulfoxide (DMSO-d6) are used as solvents, TMS tetramethylsilane is used as an internal standard, and the working frequency is 500 MHz.
The procedure for measuring the IR spectrum uses an IR Prestage-21 Fourier Infrared Spectrometer (Fourier Transform Infrared Spectrometer) to measure the IR spectrum, and uses potassium bromide to perform tabletting, the wave number measuring range is 4000--1The sample was scanned 22 times.
Example 1: preparation of 4- ((4-aminophenyl) -methylene) phenol
The specific structural formula of the 4- ((4-aminophenyl) -methylene) phenol is shown as a formula (4).
The synthesis of 4- ((4-aminophenyl) -methylene) phenol of formula (4) is shown as follows:
specifically, the preparation method of the 4- ((4-aminophenyl) -methylene) phenol shown in the formula (4) comprises the following steps:
mixing aniline hydrochloride (26.0g, 0.2mol), p-hydroxymethyl phenol (12.4g, 0.1mol) and aniline (24mL, 0.2mol) in a three-neck flask under nitrogen atmosphere, heating to react at 120 deg.C for 1.5 hrIn this case, the mixture obtained after the reaction under heating is poured into water, NaHCO is added3After neutralization to neutrality, ethyl acetate was added for extraction separation, the organic layer was dried and the solvent was distilled under reduced pressure, and the remaining oil was subjected to steam distillation to remove excess aniline and then recrystallized from saturated NaCl water/ethanol to give white crystals (16.1g) of 4- ((4-aminophenyl) -methylene) phenol in a yield of 80.9% of 4- ((4-aminophenyl) -methylene) phenol.
FIG. 1 is an IR spectrum of a white crystal obtained in example 1 of the present invention; as can be seen from FIG. 1 (the abscissa "Wavenumber" of FIG. 1 represents the wave number and the ordinate "Transparency" represents the Transparency), at 3400cm-1Has an absorption peak of-OH and 3286cm-1And 3350cm-1Is represented by-NH2The typical absorption peak of (2) and the C-H absorption peak of another methylene group is 2966cm-1To (3).
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of a white crystal obtained in example 1 of the present invention ("f 1" in FIG. 2 indicates a chemical shift). As can be seen from FIG. 2, the single peak at a chemical shift of 9.20ppm is a peak of-OH, the four doublet peaks at 6.50-6.95ppm are resonance peaks of benzene ring hydrogen, and the doublet peak at 4.86ppm is NH2The doublet at 3.63ppm is-CH2Peak of (2).
As can be seen from the characterization results of FIGS. 1-2, the structural formula of the white crystal obtained in example 1 is shown in formula (4).
Example 2
The only difference in example 2 compared to example 1 was that the heating reaction temperature in example 2 was 130 ℃ and the reaction time was 1 hour, and the yield of 4- ((4-aminophenyl) -methylene) phenol produced was 81.0%.
Example 3
Example 3 differs from example 1 only in that aniline was used in an amount of 0.15mol in example 3, and the yield of 4- ((4-aminophenyl) -methylene) phenol was 79.1%.
Example 4
Example 4 differs from example 1 only in that aniline hydrochloride was used in an amount of 0.15mol in example 4, and the yield of 4- ((4-aminophenyl) -methylene) phenol was 78.3%.
It should be further noted that, within the technical solutions of the present invention, for example, by changing the amount of the raw materials, the reaction temperature and the reaction time, the technical problems to be solved by the present invention can be solved, and the yield of the amino phenol containing methylene group is more than 78%, even more than 80%.
Claims (10)
1. The preparation method of the aminophenol containing the methylene is characterized in that reaction raw materials in the preparation method comprise acid, hydroxymethyl phenol or derivatives of the hydroxymethyl phenol.
2. The method according to claim 1, wherein the acid is aniline hydrochloride or an aniline hydrochloride derivative.
3. The method according to claim 1, wherein the hydroxymethylphenol or a hydroxymethylphenol derivative has a structural formula represented by the formula (1):
wherein R2 represents H or alkyl.
4. The method of claim 2, wherein the reaction raw material further comprises a substance represented by the formula (2):
wherein R1 represents H or alkyl.
5. The process according to claim 2, wherein the molar ratio of the acid, hydroxymethylphenol or derivative of hydroxymethylphenol is 0.2: (0.05-0.3).
6. The method according to claim 4, wherein the molar ratio of the hydroxymethylphenol or the derivative of hydroxymethylphenol to the substance represented by the formula (2) is 0.1: (0.1-1).
7. The method for preparing according to claim 4 or 6, characterized by comprising the steps of:
mixing aniline hydrochloride or aniline hydrochloride derivatives, hydroxymethyl phenol or hydroxymethyl phenol derivatives and substances with a structural formula shown in a formula (2) in an inert gas atmosphere, and heating to react to obtain the methylene-containing aminophenol.
8. The method as claimed in claim 7, wherein the temperature of the heating reaction is 100-130 ℃.
9. The method according to claim 7, further comprising a separation and purification process after the heating reaction is completed.
10. Use of the preparation process according to any one of claims 1 to 9 in the field of organic synthesis.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101855266A (en) * | 2007-08-23 | 2010-10-06 | 亨茨曼国际有限公司 | Process for preparing polyaromatic polyisocyanate compositions |
| WO2013057069A1 (en) * | 2011-10-21 | 2013-04-25 | Bayer Intellectual Property Gmbh | Polycyclic aromatic polyamines and methods for production thereof |
| CN103483161A (en) * | 2013-09-06 | 2014-01-01 | 中科院广州化学有限公司 | Ultrasonic assisted method for synthesizing sodium 4,4'-methylenebis(2,6-dihydroxymethyl phenate) |
| CN111233633A (en) * | 2020-04-01 | 2020-06-05 | 山东莱芜润达新材料有限公司 | Preparation method of high para bisphenol F |
-
2021
- 2021-07-21 CN CN202110824133.0A patent/CN113527116A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101855266A (en) * | 2007-08-23 | 2010-10-06 | 亨茨曼国际有限公司 | Process for preparing polyaromatic polyisocyanate compositions |
| WO2013057069A1 (en) * | 2011-10-21 | 2013-04-25 | Bayer Intellectual Property Gmbh | Polycyclic aromatic polyamines and methods for production thereof |
| CN103483161A (en) * | 2013-09-06 | 2014-01-01 | 中科院广州化学有限公司 | Ultrasonic assisted method for synthesizing sodium 4,4'-methylenebis(2,6-dihydroxymethyl phenate) |
| CN111233633A (en) * | 2020-04-01 | 2020-06-05 | 山东莱芜润达新材料有限公司 | Preparation method of high para bisphenol F |
Non-Patent Citations (1)
| Title |
|---|
| VANGALA ET AL.: "Correspondence between Molecular Functionality and Crystal Structures. Supramolecular Chemistry of a Family of Homologated Aminophenols", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》, vol. 125, no. 47, pages 14495 - 14509 * |
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Application publication date: 20211022 |