CN103709024A - Method for preparing 4,6-diacetylresorcinol by acetylating resorcinol - Google Patents
Method for preparing 4,6-diacetylresorcinol by acetylating resorcinol Download PDFInfo
- Publication number
- CN103709024A CN103709024A CN201310735713.8A CN201310735713A CN103709024A CN 103709024 A CN103709024 A CN 103709024A CN 201310735713 A CN201310735713 A CN 201310735713A CN 103709024 A CN103709024 A CN 103709024A
- Authority
- CN
- China
- Prior art keywords
- resorcinol
- diacetyl
- cooled
- temperature
- room temperature
- 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.)
- Granted
Links
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 title claims abstract description 259
- GEYCQLIOGQPPFM-UHFFFAOYSA-N 1-(5-acetyl-2,4-dihydroxyphenyl)ethanone Chemical compound CC(=O)C1=CC(C(C)=O)=C(O)C=C1O GEYCQLIOGQPPFM-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 22
- 230000000397 acetylating effect Effects 0.000 title abstract 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 135
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims abstract description 73
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 99
- 238000006243 chemical reaction Methods 0.000 claims description 43
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 33
- 230000004044 response Effects 0.000 claims description 33
- 238000005070 sampling Methods 0.000 claims description 33
- 238000000967 suction filtration Methods 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 150000005207 1,3-dihydroxybenzenes Chemical class 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 6
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 6
- 238000005917 acylation reaction Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 2
- 229940098779 methanesulfonic acid Drugs 0.000 abstract 3
- 230000010933 acylation Effects 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 229960001755 resorcinol Drugs 0.000 description 134
- 238000003756 stirring Methods 0.000 description 62
- 230000009466 transformation Effects 0.000 description 31
- 238000013019 agitation Methods 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- -1 Resorcinol 4,6-diacetyl Resorcinol Chemical compound 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 2
- 239000012346 acetyl chloride Substances 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- GAKFXHZPQGSWHQ-UHFFFAOYSA-N 4,6-diaminobenzene-1,3-diol;hydrochloride Chemical compound Cl.NC1=CC(N)=C(O)C=C1O GAKFXHZPQGSWHQ-UHFFFAOYSA-N 0.000 description 1
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000006389 diacetylation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229920006253 high performance fiber Polymers 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/455—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation with carboxylic acids or their derivatives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing 4,6-diacetylresorcinol by acetylating resorcinol under the action of methanesulfonic acid. The method mainly comprises the following step: by using methanesulfonic acid as a catalyst and acetic anhydride or acetic acid as an acylation reagent, reacting at 90-150 DEG C to convert resorcinol into the 4,6-diacetylresorcinol, wherein the methanesulfonic acid/acetic anhydride or acetic acid/resorcinol mole ratio is (0.5-5)/(1-5)/1. Compared with the prior art, the method disclosed by the invention reduces the dependence on precursor chemicals, is more efficient, convenient and environment-friendly, and has the advantage of low cost.
Description
Technical field
The present invention relates to the preparation of 4,6-diacetyl Resorcinol, mainly relate under environmental friendliness condition, adopt the method for the efficient preparation of Resorcinol 4,6-diacetyl Resorcinol, belong to organic chemical synthesis technical field.
Background technology
Fu Ke acidylate (Friedel-Crafts acylation; FC) be widely used in medicine and the field of chemical synthesis; Resorcinol acetylize, oximate method synthetic 4; 6-diamino resorcin (4; 6-diaminoresorcinol; abbreviation DAR) intermediate 4, the main method of 6-diacetyl Resorcinol.DAR is the crucial monomer of synthesized high-performance fiber polyparaphenylene benzo-dioxazole (PBO), and the purity of DAR monomer has directly affected the quality of PBO polymkeric substance and final pbo fiber.Resorcinol acetylize, oximate method are made raw material with Resorcinol; by 4; the technique that the diacetylation of 6, oximate, Beckmann reset, are hydrolyzed; see Fig. 1 (Zhang Chunyan etc.; a kind of preparation method of new 4,6-diaminoresorcinol hydrochloride and with the condensation polymerization [J] of terephthalic acid, SCI; 2004
25, 556-559; Kawachi J etc., Process for Producing 4,6-Diaminoresorcinols[P], 1999, US5892118).The method is compared following advantage with traditional synthetic method: avoided the intermediate product nitro substituted compound deposits yields that carinogenicity is very high; Owing to having avoided catalytic hydrogenation process, the strong corrosion effect that the HC1 that has avoided again producing in catalytic hydrogenation process causes, thus needn't use expensive catalyst P d/C and catalytic hydrogenation reaction equipment, reduced reaction cost; The selectivity of this reaction is very high, has avoided a large amount of purifying techniques, and product purity can reach polymerization-grade.But by Resorcinol, by Fu Ke acylation reaction, prepare 4 at present, a 6-diacetyl Resorcinol (Yin Quan, the discovery history [J] of Friedel-Crafts reaction, chemistry circular, 2000,59-62) also there are problems, as used the metallic compounds such as zinc chloride, aluminum chloride as catalytic reagent, this class catalyzer is difficult to process, and environmental pollution is serious; Usage quantity is large, and cost is also relatively high; Use a large amount of catalyzer to make reaction soln thickness, stirring is difficult and inhomogeneous etc.
Fu Ke acetylization reaction adopts Acetyl Chloride 98Min., diacetyl oxide or acetic acid etc. as acylating reagent conventionally, and at present Resorcinol acetylize mainly adopts diacetyl oxide as acylating reagent, and diacetyl oxide is easy toxogen material processed, and its use is subject to strict restriction and management and control; Acetyl Chloride 98Min. acidylate ability is the strongest, but acylation reaction is not easy control, and Odor stimulation, and toxicity is larger; Acetic acid due to a little less than acidylate ability, side reaction is many, so the application of its acidylate aspect is restricted, acetic acid acidylate ability is the most weak, but is easy to get most.Also there is at present correlative study (GADGIL; V.; Ramachandra Process for the Preparation of a Cosmetic Active[P]. 2004. WO2004080939) with acetic acid, replace diacetyl oxide to carry out acylation reaction to Resorcinol; but it is high that temperature of reaction requires; time is long, and productive rate is lower.Therefore, need a kind of environmental friendliness of exploitation, with low cost and technique badly simple 4, the preparation technology of 6-diacetyl Resorcinol.
Summary of the invention
For current Resorcinol acetylize, prepare 4; the problems such as the environmental pollution of 6-diacetyl Resorcinol seriously, cost is higher, operation easier is large; the present invention proposes a kind of efficient, easy, environmental protection, the method for 4,6-diacetyl Resorcinol is prepared in Resorcinol acetylize with low cost.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
In reactor, add methylsulfonic acid as catalyzer, diacetyl oxide (AN) or acetic acid (AA) are as acetylizing agent, mix and blend, then in mixture, to add Resorcinol (Resorcinol), mol ratio be methylsulfonic acid/diacetyl oxide or acetic acid/Resorcinol=(0.5 ~ 5)/(1 ~ 5)/1; Then stir and heat, temperature range is 90 ~ 150 ℃; HPLC observing response is done in per sampling half an hour, after completion of the reaction, is cooled to room temperature, adds water and methyl alcohol, again carries out heated and stirred, is finally cooled to room temperature, and product is separated out, and suction filtration obtains 4,6-diacetyl Resorcinol.
Further improve catalyzer, in methylsulfonic acid, add P
2o
5, form P
2o
5catalyst system with methylsulfonic acid.In reaction vessel, add Resorcinol, P
2o
5, acetic acid or diacetyl oxide and methylsulfonic acid stir, P
2o
5molar weight be less than or equal to 1.5 times of Resorcinol molar weight, mol ratio is: P
2o
5/ methylsulfonic acid/acetic acid or diacetyl oxide/Resorcinol=(0 ~ 1.5)/(0.5 ~ 5)/(1 ~ 5)/1.
The present invention, by using methylsulfonic acid to replace the conventional zinc chloride of prior art as catalyzer, has reduced the use of metal catalyst, has reduced chemical pollution, improved reaction efficiency, and reaction soln viscosity is less, stirs.In addition catalyst system has been done to further improvement, adopted methylsulfonic acid+P
2o
5as catalyst system, preferably acetic acid, as acetylation reagent, has reduced the dependence of commute system poison pharmaceutical chemicals, makes that present method is efficient, easy, environmental protection and with low cost.
Accompanying drawing explanation
Fig. 1 Resorcinol is under methylsulfonic acid effect, and in diacetyl oxide or acetic acid, acidylate is prepared 4,6-diacetyl resorcin reaction schematic diagram, and wherein in reaction formula, R represents acylating reagent: diacetyl oxide or acetic acid
Fig. 24,6-diacetyl Resorcinol
1h NMR spectrogram.
Embodiment
Embodiment 1
Temperature
90 ℃mSA/AN/Resorcinol(mol ratio) under=2.2/2.2/1 condition; Resorcinol acetylize prepares 4; 6-diacetyl Resorcinol: measure methylsulfonic acid 7mL, diacetyl oxide 11mL in 100mL there-necked flask; toward wherein adding 5.5g Resorcinol, stirring and dissolving, is then increased to temperature after 90 ℃; HPLC is in per sampling half an hour; observing response, after completion of the reaction, is cooled to room temperature; add water 15mL and methyl alcohol 10mL; be heated to 80 ℃ and stir after half an hour, be cooled to room temperature in air, suction filtration obtains 4; 6-diacetyl Resorcinol, transformation efficiency is 77.8%.
110 ℃ of temperature, MSA/AN/Resorcinol(mol ratio)=2.2/2.2/1, Resorcinol acetylize prepares 4, 6-diacetyl Resorcinol: measure methylsulfonic acid 7mL, diacetyl oxide 11mL is in 100mL there-necked flask, under agitation condition, toward wherein adding 5.5g Resorcinol, stirring and dissolving, temperature is increased to 110 ℃, HPLC is in per sampling half an hour, observing response, after completion of the reaction, be cooled to room temperature, add water 15mL and methyl alcohol 10mL, being heated to 80 ℃ stirred after half an hour, in air, be cooled to room temperature, suction filtration obtains 4, 6-diacetyl Resorcinol, transformation efficiency is 84.6%.
Embodiment 3
130 ℃ of temperature, MSA/AN/Resorcinol(mol ratio)=2.2/2.2/1, Resorcinol acetylize prepares 4, 6-diacetyl Resorcinol: measure methylsulfonic acid 7mL, diacetyl oxide 11mL is in 100mL there-necked flask, under agitation condition, toward wherein adding 5.5g Resorcinol, stirring and dissolving, temperature is increased to 130 ℃, HPLC is in per sampling half an hour, observing response, after completion of the reaction, be cooled to room temperature, add water 15mL and methyl alcohol 10mL, being heated to 80 ℃ stirred after half an hour, in air, be cooled to room temperature, suction filtration obtains 4, 6-diacetyl Resorcinol, transformation efficiency is 90.5%.
150 ℃ of temperature, MSA/AN/Resorcinol(mol ratio)=2.2/2.2/1, Resorcinol acetylize prepares 4, 6-diacetyl Resorcinol: measure methylsulfonic acid 7mL, diacetyl oxide 11mL is in 100mL there-necked flask, under agitation condition, toward wherein adding 5.5g Resorcinol, stirring and dissolving, temperature is increased to 150 ℃, HPLC is in per sampling half an hour, observing response, after completion of the reaction, be cooled to room temperature, add water 15mL and methyl alcohol 10mL, being heated to 80 ℃ stirred after half an hour, in air, be cooled to room temperature, suction filtration obtains 4, 6-diacetyl Resorcinol, transformation efficiency is 89.6%.
Embodiment 5
130 ℃ of temperature, MSA/AN/Resorcinol(mol ratio)=5.0/2.2/1, Resorcinol acetylize prepares 4, 6-diacetyl Resorcinol: measure methylsulfonic acid 16.2mL, diacetyl oxide 11mL is in 100mL there-necked flask, under agitation condition, toward wherein adding 5.5g Resorcinol, stirring and dissolving, temperature is increased to 130 ℃, HPLC is in per sampling half an hour, observing response, after completion of the reaction, be cooled to room temperature, add water 15mL and methyl alcohol 10mL, being heated to 80 ℃ stirred after half an hour, in air, be cooled to room temperature, suction filtration obtains 4, 6-diacetyl Resorcinol, transformation efficiency is 87.0%.
temperature130 ℃,
mSA/ AN/Resorcinol(mol ratio)=
1.1/ 2.2/1; Resorcinol acetylize prepares 4; 6-diacetyl Resorcinol: measure methylsulfonic acid 3.6mL, diacetyl oxide 11mL in 100mL there-necked flask; under agitation condition; toward wherein adding 5.5g Resorcinol, stirring and dissolving, is increased to 130 ℃ by temperature; HPLC is in per sampling half an hour; observing response, after completion of the reaction, is cooled to room temperature; add water 15mL and methyl alcohol 10mL; be heated to 80 ℃ and stir after half an hour, be cooled to room temperature in air, suction filtration obtains 4; 6-diacetyl Resorcinol, transformation efficiency is 86.1%.
Embodiment 7
temperature130 ℃,
mSA/ AN/Resorcinol(mol ratio)=
0.5/ 2.2/1; Resorcinol acetylize prepares 4; 6-diacetyl Resorcinol: measure methylsulfonic acid 1.8mL, diacetyl oxide 11mL in 100mL there-necked flask; under agitation condition; toward wherein adding 5.5g Resorcinol; stirring and dissolving, is increased to 130 ℃ of per samplings half an hour by temperature and is HPLC, observing response; after completion of the reaction; be cooled to room temperature, add water 15mL and methyl alcohol 10mL, be heated to 80 ℃ and stir after half an hour; in air, be cooled to room temperature; suction filtration obtains 4,6-diacetyl Resorcinol, and transformation efficiency is 76.8%.
temperature130 ℃, MSA/
aN/ Resorcinol(mol ratio)=2.2/
5/ 1,4,6-diacetyl Resorcinol is prepared in Resorcinol acetylize: measure methylsulfonic acid 7.4mL, diacetyl oxide 24m
lin 100mL there-necked flask, under agitation condition, toward wherein adding 5.5g Resorcinol; stirring and dissolving, is increased to 130 ℃ by temperature, and HPLC is in per sampling half an hour; observing response, after completion of the reaction, is cooled to room temperature; add water 15mL and methyl alcohol 10mL; be heated to 80 ℃ and stir after half an hour, be cooled to room temperature in air, suction filtration obtains 4; 6-diacetyl Resorcinol, transformation efficiency is 85.0%.
Embodiment 9
temperature130 ℃, MSA/
aN/ Resorcinol(mol ratio)=2.2/
1/ 1; Resorcinol acetylize prepares 4; 6-diacetyl Resorcinol: measure methylsulfonic acid 7.4mL, diacetyl oxide 5.0mL in 100mL there-necked flask; under agitation condition; toward wherein adding 5.5g Resorcinol, stirring and dissolving, is increased to 130 ℃ by temperature; HPLC is in per sampling half an hour; observing response, after completion of the reaction, is cooled to room temperature; add water 15mL and methyl alcohol 10mL; be heated to 80 ℃ and stir after half an hour, be cooled to room temperature in air, suction filtration obtains 4; 6-diacetyl Resorcinol, transformation efficiency is 62.0%.
temperature130 ℃, P
2o
5/ MSA/
aN/ Resorcinol(mol ratio)=
1.5/ 2.2/
2.2/ 1,4,6-diacetyl Resorcinol is prepared in Resorcinol acetylize: the P that measures methylsulfonic acid 7.4mL, diacetyl oxide 11mL, 10.0g
2o
5in 100mL there-necked flask, under agitation condition, toward wherein adding 5.5g Resorcinol; stirring and dissolving, is increased to 130 ℃ by temperature, and HPLC is in per sampling half an hour; observing response, after completion of the reaction, is cooled to room temperature; add water 15mL and methyl alcohol 10mL; be heated to 80 ℃ and stir after half an hour, be cooled to room temperature in air, suction filtration obtains 4; 6-diacetyl Resorcinol, transformation efficiency is 87.2%.
Embodiment 11
temperature 90℃, P
2o
5/ MSA/
aN/ Resorcinol(mol ratio)=0.74/0.5/1/1,4,6-diacetyl Resorcinol is prepared in Resorcinol acetylize: the P that measures methylsulfonic acid 1.8mL mL, diacetyl oxide 5.0mL, 5.2g
2o
5in 100mL there-necked flask, under agitation condition, toward wherein adding 5.5g Resorcinol; stirring and dissolving, is increased to 90 ℃ by temperature, and HPLC is in per sampling half an hour; observing response, after completion of the reaction, is cooled to room temperature; add water 15mL and methyl alcohol 10mL; be heated to 80 ℃ and stir after half an hour, be cooled to room temperature in air, suction filtration obtains 4; 6-diacetyl Resorcinol, transformation efficiency is 45.0%.
temperature150 ℃, P
2o
5/ MSA/
aN/ Resorcinol(mol ratio)=0.1/5/5/1,4,6-diacetyl Resorcinol is prepared in Resorcinol acetylize: measure methylsulfonic acid 16.2mL, diacetyl oxide 24m
l, 0.71g P
2o
5in 100mL there-necked flask, under agitation condition, toward wherein adding 5.5g Resorcinol; stirring and dissolving, is increased to 150 ℃ by temperature, and HPLC is in per sampling half an hour; observing response, after completion of the reaction, is cooled to room temperature; add water 15mL and methyl alcohol 10mL; be heated to 80 ℃ and stir after half an hour, be cooled to room temperature in air, suction filtration obtains 4; 6-diacetyl Resorcinol, transformation efficiency is 84.6%.
Embodiment 13
130 ℃ of temperature, MSA/
aA/ Resorcinol(mol ratio)=2.2/
1/ 1,4,6-diacetyl Resorcinol is prepared in Resorcinol acetylize: measure methylsulfonic acid 7mL, acetic acid 3.0mL in 250mL there-necked flask; under agitation condition, toward wherein adding 5.5g Resorcinol, stirring and dissolving; temperature is increased to 130 ℃, and HPLC, observing response are in per sampling half an hour; after completion of the reaction, be cooled to room temperature, add water 15mL and methyl alcohol 10mL; be heated to 80 ℃ and stir after half an hour, be cooled to room temperature in air, suction filtration obtains 4; 6-diacetyl Resorcinol, transformation efficiency is 5.0%.
130 ℃ of temperature, MSA/
aA/ Resorcinol(mol ratio)=2.2/
2/ 1,4,6-diacetyl Resorcinol is prepared in Resorcinol acetylize: measure methylsulfonic acid 7mL, acetic acid 6.3mL in 250mL there-necked flask; under agitation condition, toward wherein adding 5.5g Resorcinol, stirring and dissolving; temperature is increased to 130 ℃, and HPLC, observing response are in per sampling half an hour; after completion of the reaction, be cooled to room temperature, add water 15mL and methyl alcohol 10mL; be heated to 80 ℃ and stir after half an hour, be cooled to room temperature in air, suction filtration obtains 4; 6-diacetyl Resorcinol, transformation efficiency is 8.6%.
Embodiment 15
130 ℃ of temperature, MSA/
aA/ Resorcinol(mol ratio)=2.2/
5/ 1,4,6-diacetyl Resorcinol is prepared in Resorcinol acetylize: measure methylsulfonic acid 7mL, acetic acid 14mL in 250mL there-necked flask; under agitation condition, toward wherein adding 5.5g Resorcinol, stirring and dissolving; temperature is increased to 130 ℃, and HPLC, observing response are in per sampling half an hour; after completion of the reaction, be cooled to room temperature, add water 15mL and methyl alcohol 10mL; be heated to 80 ℃ and stir after half an hour, be cooled to room temperature in air, suction filtration obtains 4; 6-diacetyl Resorcinol, transformation efficiency is 17.8%.
Embodiment 16
90 ℃ of temperature, MSA/
aA/ Resorcinol(mol ratio)=0.5/3/1; Resorcinol acetylize prepares 4; 6-diacetyl Resorcinol: measure methylsulfonic acid 1.8 mL, acetic acid 9.3mL in 250mL there-necked flask; under agitation condition; toward wherein adding 5.5g Resorcinol, stirring and dissolving, is increased to 90 ℃ by temperature; HPLC is in per sampling half an hour; observing response, after completion of the reaction, is cooled to room temperature; add water 15mL and methyl alcohol 10mL; be heated to 80 ℃ and stir after half an hour, be cooled to room temperature in air, suction filtration obtains 4; 6-diacetyl Resorcinol, transformation efficiency is 11.2%.
Embodiment 17
150 ℃ of temperature, MSA/
aA/ Resorcinol(mol ratio)=5/5/1; Resorcinol acetylize prepares 4; 6-diacetyl Resorcinol: measure methylsulfonic acid 16.2mL, acetic acid 14mL in 250mL there-necked flask; under agitation condition; toward wherein adding 5.5g Resorcinol, stirring and dissolving, is increased to 150 ℃ by temperature; HPLC is in per sampling half an hour; observing response, after completion of the reaction, is cooled to room temperature; add water 15mL and methyl alcohol 10mL; be heated to 80 ℃ and stir after half an hour, be cooled to room temperature in air, suction filtration obtains 4; 6-diacetyl Resorcinol, transformation efficiency is 15.1%.
Embodiment 18
130 ℃ of temperature,
p 2 o 5 / MSA/AA/Resorcinol(mol ratio)=
0.10/ 2.2/5/1,4,6-diacetyl Resorcinol is prepared in Resorcinol acetylize: take the Resorcinol of 5.5g, the P of 0.71g
2o
5in the there-necked flask of 100 mL, measure acetic acid 14 mL in above-mentioned there-necked flask, and add the methylsulfonic acid of 7 mL.Stirring and dissolving, and the temperature to 130 ℃ that raises.HPLC is in per sampling half an hour, and observing response, after completion of the reaction, is cooled to room temperature, adds water 15mL and methyl alcohol 10mL, is heated to 80 ℃ and stirs after half an hour, is cooled to room temperature in air, and suction filtration obtains 4,6-diacetyl Resorcinol, and transformation efficiency is 17.6%.
Embodiment 19
130 ℃ of temperature,
p 2 o 5 / MSA/AA/Resorcinol(mol ratio)=
0.37/ 2.2/5/1,4,6-diacetyl Resorcinol is prepared in Resorcinol acetylize: take the Resorcinol of 5.5g, the P of 2.6g
2o
5in the there-necked flask of 100 mL, measure acetic acid 14 mL in above-mentioned there-necked flask, and add the methylsulfonic acid of 7 mL.Stirring and dissolving, and the temperature to 130 ℃ that raises.HPLC is in per sampling half an hour, and observing response, after completion of the reaction, is cooled to room temperature, adds water 15mL and methyl alcohol 10mL, is heated to 80 ℃ and stirs after half an hour, is cooled to room temperature in air, and suction filtration obtains 4,6-diacetyl Resorcinol, and transformation efficiency is 50.8%.
Embodiment 20
130 ℃ of temperature,
p 2 o 5 / MSA/AA/Resorcinol(mol ratio)=
0.74/ 2.2/5/1,4,6-diacetyl Resorcinol is prepared in Resorcinol acetylize: take the Resorcinol of 5.5g, the P of 5.2g
2o
5in the there-necked flask of 100 mL, measure acetic acid 14 mL in above-mentioned there-necked flask, and add the methylsulfonic acid of 7 mL.Stirring and dissolving, and the temperature to 130 ℃ that raises.HPLC is in per sampling half an hour, and observing response, after completion of the reaction, is cooled to room temperature, adds water 15mL and methyl alcohol 10mL, is heated to 80 ℃ and stirs after half an hour, is cooled to room temperature in air, and suction filtration obtains 4,6-diacetyl Resorcinol, and transformation efficiency is 90.6%.
Embodiment 21
130 ℃ of temperature,
p 2 o 5 / MSA/AA/Resorcinol(mol ratio)=
1.5/ 2.2/5/1,4,6-diacetyl Resorcinol is prepared in Resorcinol acetylize: take the Resorcinol of 5.5g, the P of 10.0g
2o
5in the there-necked flask of 100 mL, measure acetic acid 14 mL in above-mentioned there-necked flask, and add the methylsulfonic acid of 7 mL.Stirring and dissolving, and the temperature to 130 ℃ that raises.HPLC is in per sampling half an hour, and observing response, after completion of the reaction, is cooled to room temperature, adds water 15mL and methyl alcohol 10mL, is heated to 80 ℃ and stirs after half an hour, is cooled to room temperature in air, and suction filtration obtains 4,6-diacetyl Resorcinol, and transformation efficiency is 88.9%.
Embodiment 22
90 ℃ of temperature, P
2o
5/ MSA/AA/Resorcinol(mol ratio)=0.74/2.2/5/1,4,6-diacetyl Resorcinol is prepared in Resorcinol acetylize: the P that takes 5.5g Resorcinol, 5.2g
2o
5in the there-necked flask of 100 mL, measure acetic acid 14 mL in above-mentioned there-necked flask, and add 7 mL methylsulfonic acids.Stirring and dissolving, and the temperature to 90 ℃ that raises.HPLC is in per sampling half an hour, and observing response, after completion of the reaction, is cooled to room temperature, adds water 15mL and methyl alcohol 10mL, is heated to 80 ℃ and stirs after half an hour, is cooled to room temperature in air, and suction filtration obtains 4,6-diacetyl Resorcinol, and transformation efficiency is 76.2%.
Embodiment 23
110 ℃ of temperature, P
2o
5/ MSA/AA/Resorcinol(mol ratio)=0.74/2.2/5/1,4,6-diacetyl Resorcinol is prepared in Resorcinol acetylize: take the Resorcinol of 5.5g, the P of 5.2g
2o
5in the there-necked flask of 100 mL, measure acetic acid 14 mL in above-mentioned there-necked flask, and add the methylsulfonic acid of 7 mL.Stirring and dissolving, and the temperature to 110 ℃ that raises.HPLC is in per sampling half an hour, and observing response, after completion of the reaction, is cooled to room temperature, adds water 15mL and methyl alcohol 10mL, is heated to 80 ℃ and stirs after half an hour, is cooled to room temperature in air, and suction filtration obtains 4,6-diacetyl Resorcinol, and transformation efficiency is 89.1%.
Embodiment 24
150 ℃ of temperature, P
2o
5/ MSA/
aA/ Resorcinol(mol ratio)=0.74/2.2/
5/ 1,4,6-diacetyl Resorcinol is prepared in Resorcinol acetylize: take the Resorcinol of 5.5g, the P of 5.2g
2o
5in the there-necked flask of 100 mL, measure acetic acid 14 mL in above-mentioned there-necked flask, and add the methylsulfonic acid of 7 mL.Stirring and dissolving, and the temperature to 130 ℃ that raises.HPLC is in per sampling half an hour, and observing response, after completion of the reaction, is cooled to room temperature, adds water 15mL and methyl alcohol 10mL, is heated to 80 ℃ and stirs after half an hour, is cooled to room temperature in air, and suction filtration obtains 4,6-diacetyl Resorcinol, and transformation efficiency is 88.5%.
Embodiment 25
130 ℃ of temperature, P
2o
5/ MSA/
aA/ Resorcinol(mol ratio)=0.74/2.2/
3/ 1,4,6-diacetyl Resorcinol is prepared in Resorcinol acetylize: take the Resorcinol of 5.5g, the P of 5.2g
2o
5in the there-necked flask of 100 mL, measure acetic acid 8.6 mL in above-mentioned there-necked flask, and add the methylsulfonic acid of 7 mL.Stirring and dissolving, and the temperature to 130 ℃ that raises.HPLC is in per sampling half an hour, and observing response, after completion of the reaction, is cooled to room temperature, adds water 15mL and methyl alcohol 10mL, is heated to 80 ℃ and stirs after half an hour, is cooled to room temperature in air, and suction filtration obtains 4,6-diacetyl Resorcinol, and transformation efficiency is 88.1%.
Embodiment 26
130 ℃ of temperature, P
2o
5/ MSA/
aA/ Resorcinol(mol ratio)=0.74/2.2/
2/ 1,4,6-diacetyl Resorcinol is prepared in Resorcinol acetylize: take the Resorcinol of 5.5g, the P of 5.2g
2o
5in the there-necked flask of 100 mL, measure acetic acid 6.3 mL in above-mentioned there-necked flask, and add the methylsulfonic acid of 7 mL.Stirring and dissolving, and the temperature to 130 ℃ that raises.HPLC is in per sampling half an hour, and observing response, after completion of the reaction, is cooled to room temperature, adds water 15mL and methyl alcohol 10mL, is heated to 80 ℃ and stirs after half an hour, is cooled to room temperature in air, and suction filtration obtains 4,6-diacetyl Resorcinol, and transformation efficiency is 83.5%.
Embodiment 27
130 ℃ of temperature, P
2o
5/ MSA/
aA/ Resorcinol(mol ratio)=0.74/2.2/
1/ 1,4,6-diacetyl Resorcinol is prepared in Resorcinol acetylize: take the Resorcinol of 5.5g, the P of 5.2g
2o
5in the there-necked flask of 100 mL, measure acetic acid 3.0 mL in above-mentioned there-necked flask, and add the methylsulfonic acid of 7 mL.Stirring and dissolving, and the temperature to 130 ℃ that raises.HPLC is in per sampling half an hour, and observing response, after completion of the reaction, is cooled to room temperature, adds water 15mL and methyl alcohol 10mL, is heated to 80 ℃ and stirs after half an hour, is cooled to room temperature in air, and suction filtration obtains 4,6-diacetyl Resorcinol, and transformation efficiency is 42.3%.
Embodiment 28
130 ℃ of temperature, P
2o
5/
mSA/ AA/Resorcinol(mol ratio)=0.74/
5/ 5/1,4,6-diacetyl Resorcinol is prepared in Resorcinol acetylize: take the Resorcinol of 5.5g, the P of 5.2g
2o
5in the there-necked flask of 100 mL, measure acetic acid 14 mL in above-mentioned there-necked flask, and add the methylsulfonic acid of 16.2 mL.Stirring and dissolving, and the temperature to 130 ℃ that raises.HPLC is in per sampling half an hour, and observing response, after completion of the reaction, is cooled to room temperature, adds water 15mL and methyl alcohol 10mL, is heated to 80 ℃ and stirs after half an hour, is cooled to room temperature in air, and suction filtration obtains 4,6-diacetyl Resorcinol, and transformation efficiency is 86.9%.
Embodiment 29
130 ℃ of temperature, P
2o
5/
mSA/ AA/Resorcinol(mol ratio)=0.74/
1.1/ 5/1,4,6-diacetyl Resorcinol is prepared in Resorcinol acetylize: take the Resorcinol of 5.5g, the P of 5.2g
2o
5in the there-necked flask of 100 mL, measure acetic acid 14 mL in above-mentioned there-necked flask, and add the methylsulfonic acid of 3.5 mL.Stirring and dissolving, and the temperature to 130 ℃ that raises.HPLC is in per sampling half an hour, and observing response, after completion of the reaction, is cooled to room temperature, adds water 15mL and methyl alcohol 10mL, is heated to 80 ℃ and stirs after half an hour, is cooled to room temperature in air, and suction filtration obtains 4,6-diacetyl Resorcinol, and transformation efficiency is 87.1%.
Embodiment 30
130 ℃ of temperature, P
2o
5/
mSA/ AA/Resorcinol(mol ratio)=0.74/
0.5/ 5/1,4,6-diacetyl Resorcinol is prepared in Resorcinol acetylize: take the Resorcinol of 5.5g, the P of 5.2g
2o
5in the there-necked flask of 100 mL, measure acetic acid 14 mL in above-mentioned there-necked flask, and add the methylsulfonic acid of 1.8 mL.Stirring and dissolving, and the temperature to 130 ℃ that raises.HPLC is in per sampling half an hour, and observing response, after completion of the reaction, is cooled to room temperature, adds water 15mL and methyl alcohol 10mL, is heated to 80 ℃ and stirs after half an hour, is cooled to room temperature in air, and suction filtration obtains 4,6-diacetyl Resorcinol, and transformation efficiency is 74.2%.
Embodiment 31
130 ℃ of temperature, P
2o
5/ MSA/AA/Resorcinol(mol ratio)=0.37/1.1/5/1,4,6-diacetyl Resorcinol is prepared in Resorcinol acetylize: take the Resorcinol of 5.5g, the P of 2.6g
2o
5in the there-necked flask of 100 mL, measure acetic acid 14 mL in above-mentioned there-necked flask, and add 3.5 mL methylsulfonic acids.Stirring and dissolving, and the temperature to 130 ℃ that raises.HPLC is in per sampling half an hour, and observing response, after completion of the reaction, is cooled to room temperature, adds water 15mL and methyl alcohol 10mL, is heated to 80 ℃ and stirs after half an hour, is cooled to room temperature in air, and suction filtration obtains 4,6-diacetyl Resorcinol, and transformation efficiency is 36.4%.
Embodiment 32
The evaluation of 4,6-diacetyl Resorcinol.
From the hydrogen nuclear magnetic resonance spectrogram of Fig. 2, can find out, a, b, c, d be attributed to respectively proton hydrogen on the phenyl ring adjacent with phenolic hydroxyl group, with ethanoyl adjacent phenyl rings on the peak of methyl on hydrogen, ethanoyl on proton hydrogen, phenolic hydroxyl group.Each peak is unimodal, and the peak area ratio of a/b/c/d is 1/1/2/6, is consistent with the structure of 4,6-diacetyl Resorcinol.
Claims (2)
1. Resorcinol acetylize prepares 4, the method of 6-diacetyl Resorcinol, it is characterized in that: in reactor, add methylsulfonic acid as catalyzer, diacetyl oxide or acetic acid are as acetylizing agent, add Resorcinol, mol ratio is methylsulfonic acid/diacetyl oxide or acetic acid/Resorcinol=(0.5 ~ 5)/(1 ~ 5)/1; Mix and blend heating, temperature heated perimeter is 90 ~ 150 ℃; HPLC observing response is done in per sampling half an hour, after reaction finishes, is cooled to room temperature, adds water and methyl alcohol, again carries out heated and stirred, is finally cooled to room temperature, and product is separated out, and suction filtration obtains 4,6-diacetyl Resorcinol.
2. the method for 4,6-diacetyl Resorcinol is prepared in Resorcinol acetylize according to claim 1, it is characterized in that: described catalyzer also comprises P
2o
5, P
2o
5molar weight be less than or equal to the molar weight of 1.5 times of Resorcinols.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310735713.8A CN103709024B (en) | 2013-12-28 | 2013-12-28 | Method for preparing 4,6-diacetylresorcinol by acetylating resorcinol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310735713.8A CN103709024B (en) | 2013-12-28 | 2013-12-28 | Method for preparing 4,6-diacetylresorcinol by acetylating resorcinol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103709024A true CN103709024A (en) | 2014-04-09 |
| CN103709024B CN103709024B (en) | 2015-07-15 |
Family
ID=50402417
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310735713.8A Active CN103709024B (en) | 2013-12-28 | 2013-12-28 | Method for preparing 4,6-diacetylresorcinol by acetylating resorcinol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103709024B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104098590A (en) * | 2014-07-15 | 2014-10-15 | 南通大学 | Benzo [1, 2-d: 5, 4-d']-di-(oxazole)-2, 6-dithiol and preparation method thereof |
| CN107879910A (en) * | 2017-11-02 | 2018-04-06 | 武汉科技大学 | A kind of green synthesis process of 2,4 dihydroxy benaophenonel |
| CN108191678A (en) * | 2018-01-17 | 2018-06-22 | 长江师范学院 | A kind of method that 4,6- diamino resorcin hydrochlorates are prepared by resorcinol one kettle way |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5621146A (en) * | 1994-12-07 | 1997-04-15 | Kuraray Co., Ltd. | Process for producing 2,4-dihydroxyacetophenone |
| US5892118A (en) * | 1996-10-09 | 1999-04-06 | Daiwa Kasei Industry Co., Ltd. | Process for producing 4,6-diaminoresorcinols |
| WO2004080939A1 (en) * | 2003-03-11 | 2004-09-23 | Unilever Plc | Process for the preparation of a cosmetic active |
-
2013
- 2013-12-28 CN CN201310735713.8A patent/CN103709024B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5621146A (en) * | 1994-12-07 | 1997-04-15 | Kuraray Co., Ltd. | Process for producing 2,4-dihydroxyacetophenone |
| US5892118A (en) * | 1996-10-09 | 1999-04-06 | Daiwa Kasei Industry Co., Ltd. | Process for producing 4,6-diaminoresorcinols |
| WO2004080939A1 (en) * | 2003-03-11 | 2004-09-23 | Unilever Plc | Process for the preparation of a cosmetic active |
Non-Patent Citations (1)
| Title |
|---|
| TERUYUKI OKAYASU ET AL.: "Preparation of a novel poly(vinylsulfonic acid)-grafted solid phase acid catalyst and its use in esterification reactions", 《CHEM. COMMUN.》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104098590A (en) * | 2014-07-15 | 2014-10-15 | 南通大学 | Benzo [1, 2-d: 5, 4-d']-di-(oxazole)-2, 6-dithiol and preparation method thereof |
| CN104098590B (en) * | 2014-07-15 | 2016-08-24 | 南通大学 | Benzo [1,2-d:5,4-d`] two (azoles)-2,6-two mercaptan and preparation method thereof |
| CN107879910A (en) * | 2017-11-02 | 2018-04-06 | 武汉科技大学 | A kind of green synthesis process of 2,4 dihydroxy benaophenonel |
| CN107879910B (en) * | 2017-11-02 | 2021-06-11 | 武汉科技大学 | Green synthesis process of 2, 4-dihydroxy benzophenone |
| CN108191678A (en) * | 2018-01-17 | 2018-06-22 | 长江师范学院 | A kind of method that 4,6- diamino resorcin hydrochlorates are prepared by resorcinol one kettle way |
| CN108191678B (en) * | 2018-01-17 | 2020-07-28 | 长江师范学院 | Method for preparing 4, 6-diamino resorcinol hydrochloride by resorcinol one-pot method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103709024B (en) | 2015-07-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | Copper-mediated trifluoromethylation of arylboronic acids by trifluoromethyl sulfonium salts | |
| Yu et al. | A highly efficient Mukaiyama–Mannich reaction of N-Boc isatin ketimines and other active cyclic ketimines using difluoroenol silyl ethers catalyzed by Ph 3 PAuOTf | |
| CN103709024B (en) | Method for preparing 4,6-diacetylresorcinol by acetylating resorcinol | |
| Singh et al. | Environment-friendly green chemistry approaches for an efficient synthesis of 1-amidoalkyl-2-naphthols catalyzed by tannic acid | |
| Dawar et al. | One-pot esterification and Ritter reaction: chemo-and regioselectivity from tert-butyl methyl ether | |
| CN109020789B (en) | Method for preparing 2-methoxypropene | |
| CN109232178B (en) | Novel method for preparing high-purity hydroxytyrosol | |
| Yi et al. | Rh-Catalyzed aminative dearomatization of 2-naphthols | |
| CN101642717B (en) | Application of L-tryptophane being taken as catalyst of Knoevenagel reaction | |
| CN102531897B (en) | Method for preparing alpha-replacing malonic acid diacetoxyiodo derivative | |
| CN109761848B (en) | Method for preparing nitrile | |
| Gao et al. | NbCl5 as an efficient catalyst for chemoselective synthesis of 1, 1-diacetates under solvent-free conditions | |
| CN103724216B (en) | One kettle way prepares the method for 4,6-diaminoresorcinol hydrochloride | |
| CN107986970B (en) | Polysubstituted aromatic hydrocarbon derivative and preparation method thereof | |
| CN108046998B (en) | Preparation method of 3-methyl-4-isopropyl phenol | |
| CN106008265A (en) | Palladium-catalyzed benzyl quaternary ammonium salt C-N bond fission Suzuki coupling method | |
| CN103086898B (en) | Preparation method of diphenylamine or ring-substituted derivative thereof | |
| CN104327107A (en) | Preparation method of fluoroquinolone antibiosis medicine | |
| CN108191678B (en) | Method for preparing 4, 6-diamino resorcinol hydrochloride by resorcinol one-pot method | |
| CN113061072A (en) | Method for preparing 1-cyclopropyl naphthalene | |
| CN103274958B (en) | Method for preparing amide compound through catalysis of ligand-assisted zirconium oxychloride | |
| CN107056595B (en) | Preparation method of 3-bromofluorenone | |
| CN101775029A (en) | Convenient synthesis method for alkyl substitution phenyloboricacid | |
| CN113735799A (en) | Synthetic method of dyclonine hydrochloride | |
| CN103288605B (en) | Synthetic method of combretastatin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: CHONGQING INSTITUTE OF GREEN AND INTELLIGENT TECHN Free format text: FORMER OWNER: CHONGQING INSTITUTE OF GREEN AND INTELLIGENT TECHNOLOGY Effective date: 20150521 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20150521 Address after: 400714 Chongqing Road, Beibei District, No. 266 Applicant after: CHONGQING INSTITUTE OF GREEN AND INTELLIGENT TECHNOLOGY, CHINESE ACADEMY OF SCIENCES Address before: The town of Chongqing District of Beibei city and 400714 water park founder Road No. 266 Applicant before: Chongqing Institute of Green and Intelligent Technology, Chinese Academy of Sciences |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP02 | Change in the address of a patent holder | ||
| CP02 | Change in the address of a patent holder |
Address after: 402460 5-1 5-1 nineteen building Agricultural Hall, Changlong Avenue, Changzhou street, Rongchang District, Chongqing, China Patentee after: CHONGQING INSTITUTE OF GREEN AND INTELLIGENT TECHNOLOGY, CHINESE ACADEMY OF SCIENCES Address before: 400714 No. 266 Fangzheng Road, Pei Pei District, Chongqing Patentee before: CHONGQING INSTITUTE OF GREEN AND INTELLIGENT TECHNOLOGY, CHINESE ACADEMY OF SCIENCES |
|
| CP02 | Change in the address of a patent holder | ||
| CP02 | Change in the address of a patent holder |
Address after: 400714 No. 266 Fangzheng Road, Beibei District, Chongqing. Patentee after: CHONGQING INSTITUTE OF GREEN AND INTELLIGENT TECHNOLOGY, CHINESE ACADEMY OF SCIENCES Address before: 402460 5-1 5-1 nineteen building Agricultural Hall, Changlong Avenue, Changzhou street, Rongchang District, Chongqing, China Patentee before: CHONGQING INSTITUTE OF GREEN AND INTELLIGENT TECHNOLOGY, CHINESE ACADEMY OF SCIENCES |
|
| OL01 | Intention to license declared | ||
| OL01 | Intention to license declared |