CN112811991A - Synthesis method of p-methoxystyrene - Google Patents
Synthesis method of p-methoxystyrene Download PDFInfo
- Publication number
- CN112811991A CN112811991A CN202110137511.8A CN202110137511A CN112811991A CN 112811991 A CN112811991 A CN 112811991A CN 202110137511 A CN202110137511 A CN 202110137511A CN 112811991 A CN112811991 A CN 112811991A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- methoxystyrene
- halogenated
- acids
- ethanol
- 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.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/26—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesizing p-methoxystyrene, which comprises the steps of using p-methoxyacetophenone as a raw material, firstly carrying out hydrogenation reduction to generate 1- (4-methoxyphenyl) ethanol, then carrying out dehydration elimination reaction to obtain a crude product, and finally rectifying to obtain the p-methoxystyrene. The invention adopts a catalytic hydrogenation method to obtain the intermediate 1- (4-methoxyphenyl) ethanol, the reaction selectivity of the step is excellent and can reach 98-99%, and meanwhile, hydrogen is used as a cleaning gas, so that the environmental pollution is avoided, and the industrial production is facilitated.
Description
Technical Field
The invention relates to the field of organic synthesis, in particular to a method for synthesizing p-methoxystyrene.
Background
Para-methoxystyrene is an important chemical raw material, can replace styrene compounds, and is widely applied to various fields such as a light polymerization inhibitor, a material, a medical intermediate, a pesticide, an adhesive, a coating, a sun-screening agent and the like. Besides, the p-methoxystyrene can be used as a polymerization monomer to synthesize polymers with different structures, and the synthesized polymer contains a protecting group which is easily subjected to acidolysis by light, so that the p-methoxystyrene can be used as an excellent corrosion-resistant material to be applied to the electronic information industry.
The current methods for synthesizing p-methoxystyrene mainly comprise:
patent US5489731A discloses that p-methoxy styrene is prepared by taking p-methoxy benzyl alcohol as a raw material and reacting with triphenylphosphine, formaldehyde and hydrobromic acid through Wittig reaction. In the method, the Wittig reagent is complex to prepare and has high use requirement, and gaseous monobromomethane is used in the reaction, so that special reaction equipment is needed, and the expanded production is not facilitated.
In patent CN1660743A, p-methoxyacetophenone is used as a raw material, reduced to 1- (4-methoxyphenyl) ethanol by potassium borohydride, esterified with excessive potassium bisulfate in cyclohexane to generate sulfonic acid-1- (4-methoxyphenyl) ethyl ester, and finally subjected to elimination reaction to obtain p-methoxystyrene. The method has long synthesis route, needs a large amount of potassium bisulfate and cyclohexane solvent, and is easy to cause chemical pollution. And the method has the advantages of difficult reaction in the last step, extremely low yield, poor purity of crude products and unsuitability for industrial production.
In patent CN101747162A, p-methoxyacetophenone is used as a raw material, is reduced by potassium borohydride to generate p-methoxy-alpha-methylbenzyl alcohol, is subjected to esterification reaction with potassium hydrogen sulfate, and is subjected to elimination reaction in a high-temperature cracking tube to obtain p-methoxystyrene. The method has the advantages of extremely low conversion rate during elimination reaction, easy polymerization of products in a pyrolysis tube, poor yield, and large amount of unreacted raw materials and etherification byproducts in a crude product.
In patent CN104447230A, p-methoxyacetophenone is used as a raw material, reduced by potassium borohydride to obtain 1- (4-methoxyphenyl) ethanol, then subjected to dehydration reaction under the action of potassium hydrogen sulfate to obtain a crude product, and finally rectified to obtain p-methoxystyrene. In the method, potassium borohydride is used for reduction, the post-treatment steps are complicated, a plurality of raw and auxiliary materials are needed, and the method is not suitable for industrial expanded production.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for synthesizing p-methoxystyrene, which comprises the steps of using p-methoxyacetophenone as a raw material, firstly carrying out hydrogenation reduction to generate 1- (4-methoxyphenyl) ethanol, then carrying out dehydration elimination reaction to obtain a crude product, and finally carrying out rectification to obtain the p-methoxystyrene. The synthesis method adopts a catalytic hydrogenation method to obtain the intermediate 1- (4-methoxyphenyl) ethanol, has excellent selectivity which can reach 98-99%, and simultaneously, hydrogen is used as a clean gas, so that the environmental pollution is avoided, and the industrial production is facilitated.
The invention achieves the above object through the following technical scheme.
A method for synthesizing p-methoxystyrene comprises the following steps:
(1) in an organic solvent, introducing hydrogen into methoxyacetophenone under the action of a first catalyst to perform hydrogenation to obtain 1- (4-methoxyphenyl) ethanol;
(2) in the presence of an organic solvent, 1- (4-methoxyphenyl) ethanol is subjected to elimination reaction under the action of a second catalyst to obtain the p-methoxystyrene.
The reaction formula is as follows:
the first catalyst in the step (1) is a Raney type catalyst and/or a transition metal supported catalyst. The Raney type catalyst is preferably one or the combination of Raney nickel, Raney cobalt, Raney palladium and Raney copper; the transition metal supported catalyst is preferably one or more of palladium/carbon, platinum/carbon, ruthenium/carbon, nickel/alumina, platinum/alumina, palladium/ferroferric oxide, nickel-copper/alumina, rhodium/silica, and platinum-rhodium/alumina.
The organic solvent in the hydrogenation reaction is an alcohol solvent, such as methanol, ethanol, n-propanol, isopropanol, and the like.
The mass of the catalyst is 1-50% of that of the p-methoxyacetophenone, and preferably 5-10%.
The reaction temperature is 50-150 ℃, and the hydrogen pressure is 1-10 MPa.
The second catalyst in the step (2) is at least one selected from acetic acid, halogenated acetic acid, phosphoric acid, hydrochloric acid, sulfuric acid and alkyl sulfonic acid with 1-20 carbon atoms, aryl sulfonic acid, alkyl aryl sulfonic acid, halogenated aryl sulfonic acid, alkyl carboxylic acid, aryl carboxylic acid, halogenated alkyl carboxylic acid, halogenated aryl carboxylic acid and alkyl halogenated aryl carboxylic acid.
The molar ratio of the dosage of the catalyst to the 1- (4-methoxyphenyl) ethanol is (0.001-0.2): 1, the preferable molar ratio is (0.05-0.1): 1.
the organic solvent is at least one of alkane, cycloalkane, aromatic hydrocarbon, alkyl aromatic hydrocarbon, halogenated alkane, halogenated cycloalkane, halogenated aromatic hydrocarbon and alkyl halogenated aromatic hydrocarbon with 1-20 carbon atoms.
The temperature of the elimination reaction is 50-200 ℃, preferably 120-150 ℃.
The method also comprises the step of rectifying the crude p-methoxystyrene obtained in the step (2) to obtain the p-methoxystyrene.
The rectification pressure is preferably 10-50 mmHg, and the rectification temperature is preferably 25-35 mmHg.
Compared with the prior art, the invention has the advantages that:
(1) the invention adopts a catalytic hydrogenation method to obtain an intermediate 1- (4-methoxyphenyl) ethanol, and has good reaction selectivity and high yield which reaches 98-99 percent, thereby improving the yield of the whole reaction;
(2) the invention uses clean gas hydrogen as a reducing agent, avoids using a borohydride compound reagent, greatly reduces chemical pollution and conforms to the concept of environmental protection;
(3) the post-treatment step of the catalytic hydrogenation reaction is simple, and a complicated operation process is not needed, so that the method is favorable for industrial production.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of p-methoxystyrene
Detailed Description
Example 1
Adding p-methoxyacetophenone (75.1g, 0.5mol), ruthenium/carbon catalyst (3.7g, 5 wt%) and 500mL of cyclohexane into a 1L high-pressure kettle, introducing nitrogen for three times, sealing the high-pressure kettle, introducing hydrogen to 5Mpa, starting stirring after ensuring that the reaction kettle is airtight, heating to 50 ℃, maintaining the hydrogen pressure at 5MPa, reacting for 10h, terminating the reaction, cooling, evacuating hydrogen, pumping out reaction liquid in the kettle, filtering to remove the catalyst, and carrying out reduced pressure distillation and concentration to obtain 1- (4-methoxyphenyl) ethanol, wherein the yield is 98%;
p-toluenesulfonic acid (8.6g, 0.05mol) and 500mL of toluene were charged into a 1L three-necked flask, stirred to be sufficiently dissolved, placed in an oil bath, and heated at 110 ℃. 1- (4-methoxyphenyl) ethanol (152g, 1mol) was added in advance to the dropping funnel, and after the oil bath temperature reached 110 ℃, the Dean-Stark trap and the dropping funnel were assembled. Then 1- (4-methoxyphenyl) ethanol was added to the flask through a dropping funnel to form a reflux state, the dropping rate was kept constant, and dropping was completed within 1h, followed by stopping heating and cooling the reaction to room temperature. Adding anhydrous sodium sulfate, drying and filtering to obtain a crude product of the p-methoxystyrene.
And transferring the crude p-methoxystyrene into a three-neck flask, adding a rectifying column, controlling the liquid temperature at 75 ℃, rectifying, and after 8 hours, completing distillation to obtain 127.4g of colorless and transparent p-methoxystyrene with the yield of 95%.
Example 2:
adding p-methoxyacetophenone (75.1g, 0.5mol), a palladium/carbon catalyst (6.0g, 8 wt%) and 500mL of isopropanol into a 1L high-pressure kettle, then introducing nitrogen for three times, sealing the high-pressure kettle, introducing hydrogen to 6Mpa, ensuring that the reaction kettle is airtight, starting stirring, heating to 70 ℃, maintaining the hydrogen pressure at 6MPa, reacting for 5 hours, stopping the reaction, cooling, evacuating the hydrogen, pumping out a reaction solution in the kettle, filtering to remove the catalyst, carrying out reduced pressure distillation and concentration to obtain 1- (4-methoxyphenyl) ethanol, wherein the yield is 98%);
benzenesulfonic acid (12.6g, 0.08mol) and 500mL of xylene were charged in a 1L three-necked flask, stirred to be sufficiently dissolved, placed in an oil bath, and the heating temperature was set at 130 ℃. 1- (4-methoxyphenyl) ethanol (152g, 1mol) was added in advance to the dropping funnel, and after the oil bath temperature reached 130 ℃, the Dean-Stark trap and the dropping funnel were assembled. Then 1- (4-methoxyphenyl) ethanol was added to the flask through a dropping funnel to form a reflux state, the dropping rate was kept constant, and the dropping was completed within 0.5h, followed by stopping heating and cooling the reaction to room temperature. Adding anhydrous sodium sulfate, drying and filtering to obtain a crude product of the p-methoxystyrene.
And transferring the crude p-methoxystyrene into a three-neck flask, adding a rectifying column, controlling the liquid temperature at 75 ℃, rectifying, and after 8 hours, completing distillation to obtain 127.9g of colorless and transparent p-methoxystyrene with the yield of 95%.
Example 3:
adding p-methoxyacetophenone (75.1g, 0.5mol), Raney nickel catalyst (7.5g, 10 wt%) and 500mL of toluene into a 1L autoclave, introducing nitrogen for three times, sealing the autoclave, introducing hydrogen to 8Mpa, ensuring that the autoclave is airtight, starting stirring, heating to 100 ℃, maintaining the hydrogen pressure at 8MPa, reacting for 3h, stopping the reaction, cooling, evacuating the hydrogen, pumping out the reaction solution in the autoclave, filtering to remove the catalyst, and carrying out reduced pressure distillation and concentration to obtain 1- (4-methoxyphenyl) ethanol, wherein the yield is 92%;
hydrochloric acid (3.6g, 0.1mol) and 500mL of tetrahydrofuran were charged into a 1L three-necked flask, stirred to be sufficiently dissolved, placed in an oil bath, and set at a heating temperature of 60 ℃. 1- (4-methoxyphenyl) ethanol (152g, 1mol) was added in advance to the dropping funnel, and after the oil bath temperature reached 60 ℃, the Dean-Stark trap and the dropping funnel were assembled. Then 1- (4-methoxyphenyl) ethanol was added to the flask through a dropping funnel to form a reflux state, the dropping rate was kept constant, and the dropping was completed within 1.5h, followed by stopping heating and cooling the reaction to room temperature. Adding anhydrous sodium sulfate, drying and filtering to obtain a crude product of the p-methoxystyrene.
And transferring the crude p-methoxystyrene into a three-neck flask, adding a rectifying column, controlling the liquid temperature at 75 ℃, rectifying, and after 8 hours, completing distillation to obtain 126.5g of colorless and transparent p-methoxystyrene with the yield of 94%.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the invention is not limited to the embodiments described above, which are described in the specification only to illustrate the principles of the invention. The invention also includes various insubstantial changes and modifications within the spirit of the invention, as claimed by those skilled in the art.
Claims (10)
1. A method for synthesizing p-methoxystyrene comprises the following steps:
(1) in an organic solvent, introducing hydrogen into methoxyacetophenone under the action of a first catalyst to perform hydrogenation to obtain 1- (4-methoxyphenyl) ethanol;
(2) in the presence of an organic solvent, 1- (4-methoxyphenyl) ethanol is subjected to elimination reaction under the action of a second catalyst to obtain the p-methoxystyrene.
2. The process according to claim 1, characterized in that the first catalyst is a raney-type catalyst and/or a transition metal supported catalyst; the Raney type catalyst is preferably one or the combination of Raney nickel, Raney cobalt, Raney palladium and Raney copper; the transition metal supported catalyst is preferably one or more of palladium/carbon, platinum/carbon, ruthenium/carbon, nickel/alumina, platinum/alumina, palladium/ferroferric oxide, nickel-copper/alumina, rhodium/silica, and platinum-rhodium/alumina.
3. The method according to claim 1, characterized in that the organic solvent is an alcoholic solvent, preferably methanol, ethanol, n-propanol or isopropanol.
4. The process according to claim 1 or 2, characterized in that the mass of the first catalyst is 1 to 50%, preferably 5 to 10% of the mass of p-methoxyacetophenone.
5. The process according to claim 1 to 4, wherein the reaction temperature is 50 to 150 ℃ and the hydrogen pressure is 1 to 10 MPa.
6. The method according to claim 1, wherein the second catalyst in the step (2) is at least one selected from the group consisting of acetic acid, halogenated acetic acid, phosphoric acid, hydrochloric acid, sulfuric acid and alkylsulfonic acids having 1 to 20 carbon atoms, arylsulfonic acids, alkylarylsulfonic acids, halogenated arylsulfonic acids, alkylhalogenated arylsulfonic acids, alkylcarboxylic acids, arylcarboxylic acids, halogenated alkylcarboxylic acids, halogenated arylcarboxylic acids and alkylhalogenated arylcarboxylic acids.
7. The process according to claim 1 or 6, characterized in that the molar ratio of the second catalyst used to 1- (4-methoxyphenyl) ethanol is (0.001 to 0.2): 1, the preferable molar ratio is (0.05-0.1): 1.
8. the method according to claim 1, wherein the organic solvent is at least one selected from the group consisting of alkanes, cycloalkanes, aromatics, alkylaromatics, halogenated alkanes, halogenated cycloalkanes, halogenated aromatics and alkylhalogenated aromatics having 1 to 20 carbon atoms.
9. The process according to claim 1, characterized in that the temperature of the elimination reaction is between 50 and 200 ℃, preferably between 120 and 150 ℃.
10. The method according to claim 1, further comprising the step of rectifying the crude p-methoxystyrene obtained in the step (2) to obtain p-methoxystyrene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110137511.8A CN112811991A (en) | 2021-02-01 | 2021-02-01 | Synthesis method of p-methoxystyrene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110137511.8A CN112811991A (en) | 2021-02-01 | 2021-02-01 | Synthesis method of p-methoxystyrene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112811991A true CN112811991A (en) | 2021-05-18 |
Family
ID=75861120
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110137511.8A Pending CN112811991A (en) | 2021-02-01 | 2021-02-01 | Synthesis method of p-methoxystyrene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112811991A (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02121944A (en) * | 1988-10-28 | 1990-05-09 | Mitsui Petrochem Ind Ltd | Method for producing ketones |
| HU9701335D0 (en) * | 1997-07-31 | 1997-09-29 | Chinoin Gyogyszer Es Vegyeszet | Process for producing 1-(3,4-dimethoxy-phenol)-ethanol |
| JP2002179621A (en) * | 2000-12-08 | 2002-06-26 | Adchemco Corp | Method for producing 4-acetoxystyrene |
| JP2002179622A (en) * | 2000-12-08 | 2002-06-26 | Adchemco Corp | Method for producing 4-acetoxystyrene |
| US6608232B1 (en) * | 1999-01-08 | 2003-08-19 | Rhodia Chimie | Method for preparing a benzylic-type ether |
| DE10236918A1 (en) * | 2002-08-12 | 2004-02-26 | Symrise Gmbh & Co. Kg | Production of alkyl phenyl carbinol for use in perfumery involves hydrogenation of alkyl phenyl ketone in presence of a nickel catalyst and a basic additive |
| CN1660743A (en) * | 2004-12-15 | 2005-08-31 | 上海大学 | The synthetic method of 4-methoxystyrene |
| CN101747162A (en) * | 2009-12-25 | 2010-06-23 | 南京工业大学 | Synthetic process of p-methoxystyrene |
| JP2011231048A (en) * | 2010-04-27 | 2011-11-17 | National Institute Of Advanced Industrial Science & Technology | Method of hydrogenating alkyl aryl ketone |
| CN104447230A (en) * | 2014-12-20 | 2015-03-25 | 华诺森（武汉）生物医药技术有限公司 | Method for preparing 4-methoxystyrene |
-
2021
- 2021-02-01 CN CN202110137511.8A patent/CN112811991A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02121944A (en) * | 1988-10-28 | 1990-05-09 | Mitsui Petrochem Ind Ltd | Method for producing ketones |
| HU9701335D0 (en) * | 1997-07-31 | 1997-09-29 | Chinoin Gyogyszer Es Vegyeszet | Process for producing 1-(3,4-dimethoxy-phenol)-ethanol |
| CN1286674A (en) * | 1997-07-31 | 2001-03-07 | 农业化学杀虫剂制造贸易和销售有限公司 | Process for preparation of 1-(3,4-dimethoxyphenyl) ethanol |
| US6608232B1 (en) * | 1999-01-08 | 2003-08-19 | Rhodia Chimie | Method for preparing a benzylic-type ether |
| JP2002179621A (en) * | 2000-12-08 | 2002-06-26 | Adchemco Corp | Method for producing 4-acetoxystyrene |
| JP2002179622A (en) * | 2000-12-08 | 2002-06-26 | Adchemco Corp | Method for producing 4-acetoxystyrene |
| DE10236918A1 (en) * | 2002-08-12 | 2004-02-26 | Symrise Gmbh & Co. Kg | Production of alkyl phenyl carbinol for use in perfumery involves hydrogenation of alkyl phenyl ketone in presence of a nickel catalyst and a basic additive |
| CN1660743A (en) * | 2004-12-15 | 2005-08-31 | 上海大学 | The synthetic method of 4-methoxystyrene |
| CN101747162A (en) * | 2009-12-25 | 2010-06-23 | 南京工业大学 | Synthetic process of p-methoxystyrene |
| JP2011231048A (en) * | 2010-04-27 | 2011-11-17 | National Institute Of Advanced Industrial Science & Technology | Method of hydrogenating alkyl aryl ketone |
| CN104447230A (en) * | 2014-12-20 | 2015-03-25 | 华诺森（武汉）生物医药技术有限公司 | Method for preparing 4-methoxystyrene |
Non-Patent Citations (2)
| Title |
|---|
| WEINSTOCK, JOSEPH等: "Synthesis and renal vasodilator activity of some dopamine agonist 1-aryl-2,3,4,5-tetrahydro-1H-3-benzazepine-7,8-diols: halogen and methyl analogs of fenoldopam", 《JOURNAL OF MEDICINAL CHEMISTRY》 * |
| 吴永贵: "对甲氧基苯乙烯的合成工艺", 《化工进展》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111187153B (en) | Preparation method of 1, 3-cyclohexanedione | |
| CN114702402B (en) | Synthetic method of fluoro-phenyl amino acid hydrochloride | |
| CN113773182B (en) | Method for synthesizing 6, 8-dichloro octanoate | |
| CN111620884B (en) | Synthetic method of triethylene diamine | |
| CN112811991A (en) | Synthesis method of p-methoxystyrene | |
| CN102167657B (en) | Hdrogenation synthesis method for preparing 2-methyl allyl alcohol by using recyclable catalyst | |
| CN101781222A (en) | Method for preparing enamine ketone compound | |
| CN101781199B (en) | Chemical synthesis method of O-acylcalix[4]arene | |
| CN110903181B (en) | Method for preparing p-benzoquinone compound by double-catalytic system | |
| CN114516796B (en) | A kind of method for preparing 5-oxohexanoic acid ester | |
| CN114797988B (en) | Synthesis of composite catalyst and method for preparing beta-isophorone | |
| CN112961030B (en) | Method for catalytic synthesis of 4- (trans-4-alkyl cyclohexyl) cyclohexanone | |
| US6689913B2 (en) | Process for preparing terbinafine and HCI salt thereof | |
| CN101397247B (en) | Indan-1-carboxylic acid synthesis method of bulk drug for clidanic acid | |
| CN112939715A (en) | Synthesis method of 4-alkyl biphenyl acetylene | |
| CN115819232B (en) | Synthesis method of cycloalkyl acrylate compound | |
| WO2008083708A1 (en) | Improved process for the preparation of phenethylamine derivatives | |
| CN111116312B (en) | A kind of method for preparing 1,2,4-butanetriol by catalytic hydrogenation | |
| CN110357782A (en) | A kind of preparation method of middle long-chain fatty alcohol and its ester | |
| CN116396331A (en) | Synthesis method of chiral 2, 5-diphenyl phosphoric acid | |
| CN106883111A (en) | A kind of preparation method of the ketone of 2 cyclohexene 1 | |
| CN119569534A (en) | A kind of synthetic method of cyclopropyl alcohol | |
| CN112778108A (en) | Synthesis method of 4-substituted cyclohexanone | |
| CN118388325A (en) | Preparation method of 1-naphthol compound | |
| CN116217413A (en) | A kind of synthetic method of key intermediate N-methyl-3-hydroxyamphetamine |
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 |