CN107011211B - A kind of preparation method of para-Phthalonitrile - Google Patents
A kind of preparation method of para-Phthalonitrile Download PDFInfo
- Publication number
- CN107011211B CN107011211B CN201610057612.3A CN201610057612A CN107011211B CN 107011211 B CN107011211 B CN 107011211B CN 201610057612 A CN201610057612 A CN 201610057612A CN 107011211 B CN107011211 B CN 107011211B
- Authority
- CN
- China
- Prior art keywords
- phthalonitrile
- para
- preparation
- ethylmethylimidazolium
- ionic liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920006391 phthalonitrile polymer Polymers 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000002608 ionic liquid Substances 0.000 claims abstract description 22
- UINDRJHZBAGQFD-UHFFFAOYSA-O 2-ethyl-3-methyl-1h-imidazol-3-ium Chemical compound CCC1=[NH+]C=CN1C UINDRJHZBAGQFD-UHFFFAOYSA-O 0.000 claims abstract description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims abstract description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000746 purification Methods 0.000 claims abstract description 6
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 5
- 239000012043 crude product Substances 0.000 claims abstract description 5
- 238000007333 cyanation reaction Methods 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical class CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- LJSQFQKUNVCTIA-UHFFFAOYSA-N diethyl sulfide Chemical compound CCSCC LJSQFQKUNVCTIA-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 150000002825 nitriles Chemical class 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- ZJXZSIYSNXKHEA-UHFFFAOYSA-N ethyl dihydrogen phosphate Chemical compound CCOP(O)(O)=O ZJXZSIYSNXKHEA-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- RUDVWHPOZIYHRF-UHFFFAOYSA-N C(C)O.P(=O)(OCC)(O)O Chemical compound C(C)O.P(=O)(OCC)(O)O RUDVWHPOZIYHRF-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical class CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- FZENGILVLUJGJX-NSCUHMNNSA-N (E)-acetaldehyde oxime Chemical compound C\C=N\O FZENGILVLUJGJX-NSCUHMNNSA-N 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- -1 Ethyl imidazol Chemical compound 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- YOTHLDKOPCDROR-UHFFFAOYSA-N P(=O)(OCC)(O)O.N1C=NC=C1 Chemical compound P(=O)(OCC)(O)O.N1C=NC=C1 YOTHLDKOPCDROR-UHFFFAOYSA-N 0.000 description 1
- 238000000297 Sandmeyer reaction Methods 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- OVYTZAASVAZITK-UHFFFAOYSA-M sodium;ethanol;hydroxide Chemical compound [OH-].[Na+].CCO OVYTZAASVAZITK-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/22—Preparation of carboxylic acid nitriles by reaction of ammonia with carboxylic acids with replacement of carboxyl groups by cyano groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to a kind of preparation methods of para-Phthalonitrile, and terephthalic acid (TPA) is added in cyanation device, and ethylmethylimidazolium biphosphate ionic liquid is added, and dosage is the 15~50% of terephthalic acid (TPA) volume；Logical ammonia, is then reacted；After completion of the reaction, para-Phthalonitrile crude product carry out rectification and purification to get.During the method for the present invention prepares para-Phthalonitrile as solvent and catalyst using ethylmethylimidazolium biphosphate ionic liquid for terephthalic acid (TPA) nitrilation, compared with the prior art, raw material is easy to get, easy to operate, catalyst preparation is simple, and reaction temperature reduces.
Description
Technical field
The invention belongs to organic synthesis fields, and in particular to a kind of preparation method of para-Phthalonitrile.
Background technology
Aromatic dicarboxylic nitrile is that the fine-chemical intermediate for having extensive use can using the chemical activity of its cyano
A series of pesticide, medicine, dyestuff, fragrance etc. are synthesized, the every field of national economy is widely used in.
The traditional preparation method of aromatic dicarboxylic nitrile include sandmeyer reactions, halogenated hydrocarbons and the direct cyaniding of cyanide and
Aromatic aldehyde is dehydrated through aldoxime or gas phase catalysis ammonification etc., these method General reactions routes are longer, complex process, difficult separation are pure
Change, is seriously polluted, especially raw material is more difficult to get or need to use reagent costly, thus production cost is higher, is not suitable for work
Industry metaplasia is produced.
At this stage, the main method that the production of aromatic dicarboxylic nitrile uses is aromatic hydrocarbon ammoxidation technology, ammonia oxidation and biography
System method is compared, although having the advantages such as raw material is cheap and easy to get, reaction route is short, product is disposable, still remains reaction
Temperature is higher (410 DEG C or more), and the problems such as very high is required to catalyst preparation.
Invention content
It is an object of the invention to solve the problems, such as aromatic dicarboxylic nitrile production in the prior art, a kind of terephthaldehyde is provided
The preparation method of nitrile, the raw materials technology is cheap and easy to get, reaction route is short, product is disposable, and catalyst preparation is simple, reaction
Temperature is low.
Technical solution
There are ionic liquid many excellent properties, many ionic liquids to have the dual function of solvent and catalyst, tool
There is a high thermal stability, acidic ion liquid, especially bronsted acid ionic liquid are due to green non-pollution, to nothing
The dissolubility that machine and organic compound have all had, acidic site difference is uniform, the features such as being easy to be detached with product.This hair
A person of good sense uses ethylmethylimidazolium biphosphate ionic liquid while being used as catalysts and solvents, is used for terephthalic acid (TPA) nitrilation
During preparing para-Phthalonitrile.It is specific as follows：
A kind of preparation method of para-Phthalonitrile, includes the following steps：
(1) terephthalic acid (TPA) is added in cyanation device, and ethylmethylimidazolium dihydric phosphate ionic liquid is added
Body, dosage are 15~50%, preferably the 20~40% of terephthalic acid (TPA) volume；
(2) lead to ammonia, then reacted；
(3) after completion of the reaction, by para-Phthalonitrile crude product carry out rectification and purification to get.
In step (1), the preparation method of ethylmethylimidazolium biphosphate ionic liquid：In ice bath and it is stirred continuously
Under the conditions of, by diethyl sulfide acid esters be slowly dropped into etc. amount of substance 1- methylimidazoles in, continue after being added dropwise stirring wait for it is anti-
It should carry out completely, obtaining ethylmethylimidazolium base sulfate ion liquid；Obtained ionic liquid is slowly added dropwise to containing NaOH
Ethanol solution in, after complete reaction, colorless cleared solution is obtained by filtration；Then phosphoric acid is added into colorless cleared solution,
Colourless transparent solution, evaporation are obtained after filtering, vacuum drying obtains ethylmethylimidazolium biphosphate ionic liquid.
In step (2), reaction temperature is 320~340 DEG C, and the reaction time is 50~90min.
In step (3), when rectification and purification, rectifying column kettle temperature is 250~300 DEG C, and tower top temperature is 230~280 DEG C, vacuum
Degree is 0.005~0.001MPa.
Advantageous effect：The technological operation is simple, raw material is cheap and easy to get, reaction route is short, product is disposable, and catalyst
It prepares simply, reaction temperature is low.
Specific implementation mode
Below by embodiment, the invention will be further described, but it is necessary to note that following embodiment is served only for invention
The further explanation of content, does not constitute limiting the scope of the invention.
Embodiment 1
Prepare ethylmethylimidazolium biphosphate ionic liquid：0.1mol 1- methylimidazoles are added in there-necked flask,
0.1mol diethyl phosphates are added dropwise, continues to stir 2h after adding, water white transparency ionic liquid 1- methyl -3- second is obtained by the reaction
Base imidazole ethyl phosphate；The NaOH of twice 1- methyl -3- ethyl imidazol(e) ethyl phosphate molal quantitys is taken to be dissolved in ethyl alcohol, by
It is added dropwise in 1- methyl -3- ethyl imidazol(e) ethyl phosphate ethanol solutions, generates white precipitate, water white transparency liquid is obtained by filtration
Equimolar phosphoric acid solution is added in body in the liquid, has a small amount of solid to generate, liquid is obtained by filtration again；By aforesaid liquid
Evaporation removes water and alcohol, then product ethylmethylimidazolium biphosphate ionic liquid, yield 97% are obtained after being dried in vacuo；
50g terephthalic acid (TPA)s are added in cyanation device, and ethylmethylimidazolium dihydric phosphate ionic liquid is added
Body 10mL leads to ammonia, is warming up to 320 DEG C, insulation reaction 50min, and after completion of the reaction, para-Phthalonitrile crude product carries out rectification and purification,
Rectifying column kettle temperature is 260 DEG C, and tower top temperature is 240 DEG C (vacuum degree 0.002MPa), yield 64%.
Embodiment 2
Prepare ethylmethylimidazolium biphosphate ionic liquid：0.5mol 1- methylimidazoles are added in there-necked flask,
0.5mol diethyl phosphates are added dropwise, continues to stir 1.5h after adding, water white transparency ionic liquid 1- methyl -3- is obtained by the reaction
Ethyl imidazol(e) ethyl phosphate；The NaOH of twice 1- methyl -3- ethyl imidazol(e) ethyl phosphate molal quantitys is taken to be dissolved in ethyl alcohol,
It is added dropwise in 1- methyl -3- ethyl imidazol(e) ethyl phosphate ethanol solutions, generates white precipitate, water white transparency is obtained by filtration
Equimolar phosphoric acid solution is added in liquid in the liquid, has a small amount of solid to generate, liquid is obtained by filtration again；By above-mentioned liquid
Evacuator body removes water and alcohol, then product ethylmethylimidazolium biphosphate ionic liquid, yield 98% are obtained after being dried in vacuo；
100g terephthalic acid (TPA)s are added in cyanation device, and ethylmethylimidazolium dihydric phosphate ionic liquid is added
Body 20mL is warming up to 340 DEG C, insulation reaction 100min, and after completion of the reaction, para-Phthalonitrile crude product carries out rectification and purification, rectifying
Tower reactor temperature is 260 DEG C, and tower top temperature is 240 DEG C (vacuum degree 0.002MPa), yield 60%.
Claims (4)
1. a kind of preparation method of para-Phthalonitrile, which is characterized in that include the following steps：
(1) terephthalic acid (TPA) is added in cyanation device, and ethylmethylimidazolium biphosphate ionic liquid is added,
Dosage is the 15~50% of terephthalic acid (TPA) volume；
(2) lead to ammonia, then reacted；
(3) after completion of the reaction, by para-Phthalonitrile crude product carry out rectification and purification to get；
In step (2), reaction temperature is 320~340 DEG C, and the reaction time is 50~90min.
2. the preparation method of para-Phthalonitrile as described in claim 1, which is characterized in that in step (1), ethylmethylimidazolium
The preparation method of biphosphate ionic liquid is：In ice bath and under conditions of be stirred continuously, diethyl sulfide acid esters is slowly dripped
Enter to etc. amount of substance 1- methylimidazoles in, continue to stir that wait for that reaction carries out complete after being added dropwise, obtain ethylmethylimidazolium
Base sulfate ion liquid；Obtained ionic liquid is slowly added dropwise in the ethanol solution containing NaOH, after complete reaction, mistake
Filter obtains colorless cleared solution；Then phosphoric acid is added into colorless cleared solution, colourless transparent solution is obtained after filtering, evaporates, very
Sky is dried to obtain ethylmethylimidazolium dihydric phosphate.
3. the preparation method of para-Phthalonitrile as described in claim 1, which is characterized in that in step (1), ethylmethylimidazolium
The dosage of biphosphate ionic liquid is the 20~40% of terephthalic acid (TPA) volume.
4. the preparation method of the para-Phthalonitrile as described in claims 1 or 2 or 3, which is characterized in that in step (3), rectifying carries
When pure, rectifying column kettle temperature is 250~300 DEG C, and tower top temperature is 230~280 DEG C, and vacuum degree is 0.005~0.001MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610057612.3A CN107011211B (en) | 2016-01-27 | 2016-01-27 | A kind of preparation method of para-Phthalonitrile |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610057612.3A CN107011211B (en) | 2016-01-27 | 2016-01-27 | A kind of preparation method of para-Phthalonitrile |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107011211A CN107011211A (en) | 2017-08-04 |
| CN107011211B true CN107011211B (en) | 2018-10-02 |
Family
ID=59439196
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610057612.3A Active CN107011211B (en) | 2016-01-27 | 2016-01-27 | A kind of preparation method of para-Phthalonitrile |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107011211B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2802715C1 (en) * | 2020-10-30 | 2023-08-31 | Корея Кумхо Петрохемикал Ко., Лтд. | System for producing a phthalonitrile-based compound and method for producing a phthalonitrile-based compound with its use |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102594141B1 (en) * | 2020-10-30 | 2023-10-26 | 금호석유화학 주식회사 | System for producing phthalonitrile-based compound and method for producing phthalonitrile-based compound using the same |
| TWI818294B (en) * | 2021-07-23 | 2023-10-11 | 韓商錦湖石油化學股份有限公司 | A method for preparing phthalonitrile-based compound |
| CN113666872A (en) * | 2021-09-28 | 2021-11-19 | 烟台大学 | Preparation method of halogen-free hydroxyl imidazolium |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006058710A1 (en) * | 2004-12-01 | 2006-06-08 | Degussa Gmbh | Method for producing amino- or hydroxybenzonitriles |
| CN105016942A (en) * | 2014-04-16 | 2015-11-04 | 中国石化扬子石油化工有限公司 | Preparation methods of nitrile and corresponding amine |
-
2016
- 2016-01-27 CN CN201610057612.3A patent/CN107011211B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006058710A1 (en) * | 2004-12-01 | 2006-06-08 | Degussa Gmbh | Method for producing amino- or hydroxybenzonitriles |
| CN105016942A (en) * | 2014-04-16 | 2015-11-04 | 中国石化扬子石油化工有限公司 | Preparation methods of nitrile and corresponding amine |
Non-Patent Citations (1)
| Title |
|---|
| "锌、铝氧化物催化合成十二烷二腈";兴可等;《化工生产与技术》;20051231;第22卷(第2期);10-11,37 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2802715C1 (en) * | 2020-10-30 | 2023-08-31 | Корея Кумхо Петрохемикал Ко., Лтд. | System for producing a phthalonitrile-based compound and method for producing a phthalonitrile-based compound with its use |
| RU2804352C1 (en) * | 2021-09-10 | 2023-09-28 | Корея Кумхо Петрохемикал Ко., Лтд. | Method for preparing phthalonitrile-based compound |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107011211A (en) | 2017-08-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Boucher‐Jacobs et al. | Catalytic deoxydehydration of glycols with alcohol reductants. | |
| Qiao et al. | Polyoxometalate-based protic alkylimidazolium salts as reaction-induced phase-separation catalysts for olefin epoxidation | |
| Yadav et al. | An eco-friendly approach for the synthesis of α-aminophosphonates using ionic liquids | |
| CN109761851A (en) | A kind of preparation method of isophthalodinitrile | |
| CN105949129B (en) | A kind of imidazolium bromide ionic liquid with amino group and preparation method and application thereof | |
| CN108794400A (en) | A kind of ionic liquid and its preparation method and application containing amino acid of the cation with amino | |
| CN103570493A (en) | Method for synthesizing 1,2-orthodiol through immobilized type heteropolyacid phase-transfer catalytic oxidation | |
| CN101704824A (en) | Catalytic preparation method of dicyclopentadiene dioxide by quaternary ammonium heteropoly phosphato tungstate | |
| CN107011211B (en) | A kind of preparation method of para-Phthalonitrile | |
| CN105061185A (en) | Method for catalytic synthesis of benzoic acid by use of anthraquinone under lighting condition | |
| CN107188849B (en) | Mesoporous ionic liquid heteropoly acid salt catalyst for benzene hydroxylation reaction, preparation method and application thereof | |
| CN103143381B (en) | Carbon-nitrogen material immobilized heteropoly acid catalyst and olefin epoxidation synthesis method | |
| CN105521825A (en) | Catalyst for preparing phenol by oxidation of benzene, preparation method and application thereof | |
| CN101838198A (en) | Method for preparing carboxylic ester | |
| CN103787835A (en) | Process for preparing terpilenol | |
| CN102786436B (en) | A kind of method of synthesizing cyanoacetate | |
| CN115181081B (en) | A method for synthesizing β-phenyl-γ-butyrolactone | |
| CN106892807B (en) | A kind of preparation method of the isophorone using organic imidazoles system quaternary ammonium strong base catalyst | |
| CN103554060A (en) | Catalyst used for synthesizing glycidol from glycerol and dimethyl carbonate by employing one-step method | |
| CN103951565B (en) | The synthesis of three core quaternary ammonium salt. template agent and the preparation and application of molecular sieve solid acid | |
| CN104610064B (en) | One-pot method using carbonate as a catalyst for the preparation of dimethyl carbonate | |
| CN108047001A (en) | A kind of method for synthesizing 2,5- xylenols | |
| CN107814691A (en) | A kind of method for synthesizing guaethol | |
| CN109824491B (en) | Production method of 2,3,4, 4' -tetrahydroxybenzophenone | |
| CN109761850A (en) | A kind of preparation method of benzonitrile |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |