CN107602528A - A kind of method for preparing five-membered ring list sulfocarbonate - Google Patents
A kind of method for preparing five-membered ring list sulfocarbonate Download PDFInfo
- Publication number
- CN107602528A CN107602528A CN201710873662.3A CN201710873662A CN107602528A CN 107602528 A CN107602528 A CN 107602528A CN 201710873662 A CN201710873662 A CN 201710873662A CN 107602528 A CN107602528 A CN 107602528A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- ammonium
- preparation
- epoxide
- membered ring
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of method for preparing five-membered ring list sulfocarbonate, specially using nitrogen-bridged three aryloxy group aluminium complex as catalyst, carbonyl sulfide is catalyzed in the presence of co-catalyst and prepares five-membered ring list sulfocarbonate with epoxide reaction, the formula of the nitrogen-bridged three aryloxy group aluminium complex is：LAl (THF), L represents nitrogen-bridged three aryloxy ligands in formula；Al represents metal aluminium ion；THF represents tetrahydrofuran；Co-catalyst is tetrabutylammonium chloride, TBAB, tetrabutylammonium iodide, double (dihalotriphenylphosphoranes base) ammonium chlorides, DTAB, 1, the carbene of 8 diazabicyclos [5.4.0] 11,1, one kind in the carbene of 5,7 diazabicyclos [5.4.0] 11.Raw material is easy to get in preparation method disclosed by the invention, and reaction condition is gentle, and reaction substrate epoxide universality is wide, and the reaction time is short, the high income of target product, and operation and last handling process are simple.
Description
Technical field
The present invention relates to technical field of organic chemistry, more particularly to a kind of method for preparing five-membered ring list sulfocarbonate.
Background technology
Five-membered ring list sulfocarbonate is the high folding of potential polar non-solute, drug synthesis intermediate, and preparation
Monomer of optical index resin Polythiocarbonate etc..Therefore the synthesis of research five-membered ring list sulfocarbonate has important valency
Value.
Carbonyl sulfide is atmosphere pollution, and is industrial waste gas, but is also a kind of important chemical synthesis raw material simultaneously, sharp
Five-membered ring list sulfocarbonate is prepared with carbonyl sulfide and epoxide reaction, on the one hand effectively can be closed using carbonyl sulfide
Into valuable Organic chemical products；On the other hand this reaction has very high Atom economy, meets Green Chemistry principle.
Thus tool has very important significance.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of method for preparing five-membered ring list sulfocarbonate, and it has
The advantages of catalyst synthesis is simple, high income, gentle reaction condition；And reaction substrate is wide, it is adapted to a variety of contain different substitutions
The epoxide of functional group.
In order to solve the above technical problems, technical scheme provided by the invention is as follows：One kind prepares five-membered ring list thiocarbonic acid
The method of ester, using epoxide and carbonyl sulfide as reactant, using nitrogen-bridged three aryloxy group aluminium complex as catalyst,
In the presence of co-catalyst, five-membered ring list sulfocarbonate is prepared by addition reaction.
Described co-catalyst is selected from quaternary ammonium salt, quaternary alkylphosphonium salts or organic base.
Preferably, described quaternary ammonium salt is selected from tetrabutyl ammonium halide, ten alkylpolyoxyethylenes, trimethyl
Ammonium halide, cetyl trimethyl ammonium halide, TBAH, tetraethyl ammonium acetate, benzyl triethyl ammonium ammonium halide, benzyl
Tripropyl ammonium acetate, benzyl tributyl ammonium acetate, double (dihalotriphenylphosphoranes base) ammonium halides, benzyl tripropyl ammonium halide, benzyl three
At least one of butyl ammonium halide, tetrabutyl ammonium nitrate, tetrapropyl ammonium acetate, benzyl triethyl ammonium acetic acid ammonium salt.
Preferably, described quaternary alkylphosphonium salt be selected from 4-phenyl phosphonium bromide, butyl triphenyl phosphonium iodide, tetraalkyl halogenation phosphonium salt,
At least one of benzyltriphenyl phosphonium halogenation phosphine, propyl group triphenyl phosphonium halides phosphine, tetraphenyl phosphonium halide.
Preferably, described organic base is selected from N- methylimidazoles, DMAP, 7- methyl isophthalic acids, 5,7- tri- azepines
Bicyclic [4.4.0] decyl- 5- the alkene, -7- carbenes of 1,8- diazabicyclos [5.4.0] 11,1,5,7- diazabicyclos [5.4.0]
At least one of 11-7- carbenes.
Preferably, described epoxide be selected from oxirane, expoxy propane, 1,2- epoxy butanes, C5-C20 α-
Oxyalkylene, epoxy methyl undecylenate, allyl glycidyl ether, epoxychloropropane, epoxy iso-butane, 7-oxa-bicyclo[4.1.0,4-
In vinyl epoxy cyclohexane, GMA, limonene oxide, cyclopentane epoxide, styrene oxide extremely
Few one kind.
Preferably, the chemical structural formula of the nitrogen-bridged three aryloxy group aluminium complex is as follows：
In formula, R H, Cl, Br, CH3、CH2CH3、C(CH3)3、OCH3、OCH2CH3Or NO2Any one in group.
Preferably, the co-catalyst is selected from tetrabutylammonium chloride (Bu4NCl), tetrabutylammonium iodide (Bu4NI), double (three
Phenyl phosphoranyl) ammonium chloride (PPNCl), -7- carbenes (DBU) of 1,8- diazabicyclos [5.4.0] 11,1,5,7- diazas
Bicyclic [5.4.0] 11-7- carbenes (TBD).
Under above-mentioned preferred ingredient, the mol ratio of described catalyst and co-catalyst is 1：0.5~1： 500；Further
Preferably 1:1~1：100.
Preferably, the mol ratio of the carbonyl sulfide and epoxide is 1：1~8：1；More preferably 2：1~5：
1, be advantageous to the quick progress of reaction and the complete conversion of epoxide using the carbonyl sulfide of excess.
Preferably, the catalyst and epoxide mol ratio are 1：50~1：5000.
Further preferably described epoxide is selected from oxirane, expoxy propane, styrene oxide, epoxy hexamethylene
At least one of alkane, phenyl glycidyl ether, allyl glycidyl ether.
Preferably, the reaction is carried out 0.5~12 hour under 50 DEG C~150 DEG C self-generated pressures.
Relative to prior art, the present invention has significant beneficial technique effect：
(1) raw material is simple and easy to get, and one step of reaction is completed, without multi-step synthetic process.Generated time is greatly shortened, reacts bottom
Thing universality is wide, is adapted to a variety of epoxides containing different substitution functional groups.Reaction time is short, and target product yield is high,
Operation and last handling process are simple.
(2) the five-membered ring list thiocarbonic acid ester structure that the present invention is prepared is clear and definite, and excellent performance is molten in aprotic, polar
The fields such as agent, electrolyte, pharmaceutical synthesis have a wide range of applications.
Embodiment
Such scheme is described further below in conjunction with specific embodiment.It should be understood that these embodiments are to be used to illustrate
The present invention and be not limited to limit the scope of the present invention.The implementation condition used in embodiment can be done according to the condition of specific producer
Further adjustment, unreceipted implementation condition is usually the condition in normal experiment.
Introduce and summarize
The present invention by way of example rather than provides the mode of limitation to illustrate.It should be noted that in present disclosure
Described " one " or " one kind " embodiment is not necessarily referring to same embodiment, and refers at least a kind of.
Various aspects of the invention are described below.However, as will be readily apparent to one of skill in the art, can
Implement the present invention according to the only some or all of aspects of the present invention.For purposes of illustration, provide herein specific numbering, material and
Configuration, enables one to thoroughly understand the present invention.However, be evident that for those of skill in the art,
The present invention can be implemented without concrete details.In other examples, not make the present invention is obscure many institutes have been omitted or simplified
Known feature.
Various operations are described successively as multiple discrete steps, and with most helpful in the side for understanding the present invention
Formula illustrates；However, in-order description should not be construed as to imply that these operations are necessarily dependent on order.
Reactant according to type species is illustrated to various embodiments.To show for those of skill in the art and
It is clear to, any number of different types of reactant can be used to implement for the present invention, and be more than those for the purpose of illustration
And the reactant provided herein.In addition, also it is evident that, the invention is not limited in any specific mixing is shown
Example.
Specific embodiment
In the present invention, the equation of synthetic method is shown below, and epoxides is with carbonyl sulfide in nitrogen-bridged three fragrant oxygen
The thio carbon of five-membered ring list corresponding to ring-opening reaction generation is coupled in the presence of base aluminium complex catalyst and co-catalyst
Acid esters, because carbonyl sulfide has unsymmetric structure, therefore the five-membered ring product for reacting formation has two kinds of different structures, following institute
Show, the concrete structure and ratio of product are determined by the nucleus magnetic hydrogen spectrum of product.
If epoxide is meso structure (i.e. with symmetrical structure) in above-mentioned reaction equation, such as epoxy hexamethylene
Alkane, cyclopentane epoxide etc., then cyclic products have exclusive architecture.When epoxide is not meso structure, R, R' can be with
It is any two kinds in the groups such as hydrogen atom, alkyl, alkoxy, phenyl, benzyl, phenoxy group, and R represents the larger base of molecular weight
Group, product 1 and product 2 are distinguished with this.
Use catalysis carbonyl sulfide/epoxide addition synthesizing five-membered ring list sulfocarbonate catalyst have with
Lower structure, the catalyst sequence number of different structure is as shown in following formula.
Catalyst be by part and the trimethyl aluminium of corresponding chemical structure in tetrahydrofuran solvent under the conditions of anhydrous and oxygen-free
Coordination prepares gained, and chemical equation is as follows：
The present invention is made with reference to embodiment into further describing：
If embodiment 1 adds the oxirane of dry mass into the autoclave of 10ml capacity successively, catalyst a and help
Catalyst tetrabutylammonium chloride, catalyst are 1 with co-catalyst mol ratio:0.5, the mol ratio of catalyst and epoxide is
1:5000.Then autoclave is closed, is passed through carbonyl sulfide gas to specified pressure, carbonyl sulfide and is rubbed with epoxide
You are than being 2:1, reactor is placed in 50 DEG C of oil baths and reacted 0.5 hour under self-generated pressure.Reaction is cooled to room temperature after terminating,
Emptying gas, sampling calculate yield by nucleus magnetic hydrogen spectrum, and test result is shown in Table 1.
If embodiment 2 adds the expoxy propane of dry mass into the autoclave of 10ml capacity successively, catalyst b and help
Catalyst tetrabutylammonium chloride, catalyst are 1 with co-catalyst mol ratio:1, the mol ratio of catalyst and epoxide is 1:
2000.Then autoclave is closed, is passed through carbonyl sulfide gas to specified pressure, carbonyl sulfide and epoxide mole
Than for 2:1, reactor is placed in 60 DEG C of oil baths and reacted 1 hour under self-generated pressure.Reaction is cooled to room temperature after terminating, and is vented
Gas, sampling calculate yield by nucleus magnetic hydrogen spectrum, and test result is shown in Table 1.
If embodiment 3 successively into the autoclave of 10ml capacity add dry mass styrene oxide, catalyst c and
Double (dihalotriphenylphosphoranes base) ammonium chlorides of co-catalyst, catalyst are 1 with co-catalyst mol ratio:10, catalyst and epoxy compound
The mol ratio of thing is 1:1000.Then autoclave is closed, is passed through carbonyl sulfide gas to specified pressure, carbonyl sulfide with
Epoxide mol ratio is 3:1, reactor is placed in 80 DEG C of oil baths and reacted 3 hours under self-generated pressure.After reaction terminates
Room temperature, emptying gas are cooled to, sampling calculates yield by nucleus magnetic hydrogen spectrum, and test result is shown in Table 1.
If embodiment 4 successively into the autoclave of 10ml capacity add dry mass epoxy hexane, catalyst d and
Co-catalyst tetrabutylammonium iodide, catalyst are 1 with co-catalyst mol ratio:50, the mol ratio of catalyst and epoxide
For 1:500.Then autoclave is closed, is passed through carbonyl sulfide gas to specified pressure, carbonyl sulfide and epoxide
Mol ratio is 4:1, reactor is placed in 100 DEG C of oil baths and reacted 3 hours under self-generated pressure.Reaction is cooled to room after terminating
Temperature, emptying gas, sampling calculate yield by nucleus magnetic hydrogen spectrum, and test result is shown in Table 1.
If embodiment 5 adds the phenyl glycidyl ether of dry mass, catalysis into the autoclave of 10ml capacity successively
Agent c and the -7- carbenes of 1,5,7- diazabicyclo [5.4.0] of co-catalyst 11, catalyst are 1 with co-catalyst mol ratio:
100, the mol ratio of catalyst and epoxide is 1:100.Then autoclave is closed, is passed through carbonyl sulfide gas extremely
Specified pressure, carbonyl sulfide are 4 with epoxide mol ratio:1, reactor is placed in 120 DEG C of oil baths under self-generated pressure
Reaction 6 hours.Reaction is cooled to room temperature, emptying gas after terminating, sampling calculates yield by nucleus magnetic hydrogen spectrum, and test result is shown in Table
1。
If embodiment 6 adds the allyl glycidyl ether of dry mass into the autoclave of 10ml capacity successively, urge
Agent f and co-catalyst tetrabutylammonium chloride, catalyst are 1 with co-catalyst mol ratio:500, catalyst and epoxide
Mol ratio be 1:50.Then autoclave is closed, is passed through carbonyl sulfide gas to specified pressure, carbonyl sulfide and epoxy
Compound mole ratio is 5:1, reactor is placed in 150 DEG C of oil baths and reacted 12 hours under self-generated pressure.Reaction terminates rear cold
But yield is calculated by nucleus magnetic hydrogen spectrum to room temperature, emptying gas, sampling, test result is shown in Table 1.
The reaction equation of embodiment 1~6
If epoxide is meso structure (i.e. with symmetrical structure) in above formula, such as 7-oxa-bicyclo[4.1.0, epoxy
Pentamethylene etc., then cyclic products have exclusive architecture.When epoxide is not meso structure, R, R' can be hydrogen originals
Any two kinds in the groups such as son, alkyl, alkoxy, phenyl, benzyl, phenoxy group, and R represents the larger group of molecular weight, with
This distinguishes product 1 and product 2.
Table 1：The test result of the reaction product of embodiment 1~6
1Catalyst type：Catalyst code name is consistent with code name in above catalyst structure formula in this form, and to it is related
Chemical constitution is corresponding；2Co-catalyst species：Bu4NCl is tetrabutylammonium chloride, Bu4NI is tetrabutylammonium iodide, PPNCl is double
(dihalotriphenylphosphoranes base) ammonium chloride, the DBU 1, -7- carbenes of 8- diazabicyclos [5.4.0] 11, TBD 1,5,7- diazas
Bicyclic [5.4.0] 11-7- carbenes；3The mol ratio of catalyst and co-catalyst；4The mol ratio of catalyst and epoxide；5
The mol ratio of sulphur carbonoxide and epoxide；6Yield 1：The yield of product 1 in reaction equation；Yield 2：Reaction equation
The yield of middle product 2, is determined by nucleus magnetic hydrogen spectrum.
Specific embodiment described above is only the preferred embodiment of the present invention, it is noted that for the art
For those of ordinary skill, under the premise without departing from the principles of the invention, some improvement or replacement can also be made, these improvement
Or replace and should also be as being considered as protection scope of the present invention.
Claims (10)
- A kind of 1. method for preparing five-membered ring list sulfocarbonate, it is characterised in that using epoxide and carbonyl sulfide be anti- Thing is answered, using nitrogen-bridged three aryloxy group aluminium complex as catalyst, in the presence of co-catalyst, is prepared into by addition reaction To five-membered ring list sulfocarbonate.
- 2. preparation method according to claim 1, it is characterised in that described co-catalyst is selected from quaternary ammonium salt, quaternary alkylphosphonium salts Or organic base.
- 3. preparation method according to claim 2, it is characterised in that described quaternary ammonium salt is selected from tetrabutyl ammonium halide, ten Alkylpolyoxyethylene, trimethyl ammonium halide, cetyl trimethyl ammonium halide, TBAH, four Ethyl ammonium, benzyl triethyl ammonium ammonium halide, benzyl tripropyl ammonium acetate, benzyl tributyl ammonium acetate, double (dihalotriphenylphosphoranes Base) ammonium halide, benzyl tripropyl ammonium halide, benzyl tributyl ammonium halide, tetrabutyl ammonium nitrate, tetrapropyl ammonium acetate, benzyl three At least one of ethyl ammonium salt.
- 4. preparation method according to claim 2, it is characterised in that the quaternary alkylphosphonium salts are selected from 4-phenyl phosphonium bromide, fourth Base triphenyl phosphonium iodide phosphine, tetraalkyl halogenation phosphonium salt, benzyltriphenyl phosphonium halogenation phosphine, propyl group triphenyl phosphonium halides phosphine, tetraphenyl phosphonium halide At least one of.
- 5. preparation method according to claim 2, it is characterised in that described organic base is selected from N- methylimidazoles, 4- bis- Methylamino pyridine, 7- methyl isophthalic acids, 5,7- tri- azabicyclo [4.4.0] decyl- 5- the alkene, -7- of 1,8- diazabicyclos [5.4.0] 11 At least one of carbene, the 1, -7- carbenes of 5,7- diazabicyclos [5.4.0] 11.
- 6. preparation method according to claim 1, it is characterised in that the nitrogen-bridged three aryloxy group aluminium complex Chemical structural formula is as follows：In formula, R H, Cl, Br, CH3、CH2CH3、C(CH3)3、OCH3、OCH2CH3Or NO2Any one in group.
- 7. preparation method according to claim 1, it is characterised in that the co-catalyst is selected from tetrabutylammonium chloride, four Butyl ammonium iodide, double (dihalotriphenylphosphoranes base) ammonium chlorides, -7- carbenes of 1,8- diazabicyclos [5.4.0] 11,1,5,7- phenodiazines Miscellaneous bicyclic [5.4.0] 11-7- carbenes.
- 8. preparation method according to claim 1, it is characterised in that described catalyst and the mol ratio of co-catalyst are 1：0.5~1：500.
- 9. preparation method according to claim 1, it is characterised in that the mol ratio of the carbonyl sulfide and epoxide For 1：1~8：1.
- 10. preparation method according to claim 1, it is characterised in that the catalyst is with epoxide mol ratio 1：50~1：5000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710873662.3A CN107602528A (en) | 2017-09-25 | 2017-09-25 | A kind of method for preparing five-membered ring list sulfocarbonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710873662.3A CN107602528A (en) | 2017-09-25 | 2017-09-25 | A kind of method for preparing five-membered ring list sulfocarbonate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107602528A true CN107602528A (en) | 2018-01-19 |
Family
ID=61058354
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710873662.3A Pending CN107602528A (en) | 2017-09-25 | 2017-09-25 | A kind of method for preparing five-membered ring list sulfocarbonate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107602528A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108358886A (en) * | 2018-04-04 | 2018-08-03 | 常熟理工学院 | A method of preparing trimethylene list sulfocarbonate with ionic liquid-catalyzed |
| CN109180937A (en) * | 2018-10-31 | 2019-01-11 | 浙江大学 | A method of preparing aliphatic poly thioether |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103275314A (en) * | 2013-05-27 | 2013-09-04 | 浙江大学 | Preparation method of polymonosulfo-carbonate with regular chain structure |
| CN103275313A (en) * | 2013-05-27 | 2013-09-04 | 浙江大学 | Polythiocarbonate and preparation method thereof |
| CN106243336A (en) * | 2016-08-15 | 2016-12-21 | 浙江大学 | A kind of crystalliferous Polythiocarbonate and preparation method thereof |
-
2017
- 2017-09-25 CN CN201710873662.3A patent/CN107602528A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103275314A (en) * | 2013-05-27 | 2013-09-04 | 浙江大学 | Preparation method of polymonosulfo-carbonate with regular chain structure |
| CN103275313A (en) * | 2013-05-27 | 2013-09-04 | 浙江大学 | Polythiocarbonate and preparation method thereof |
| CN106243336A (en) * | 2016-08-15 | 2016-12-21 | 浙江大学 | A kind of crystalliferous Polythiocarbonate and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| CHRISTOPHER J. WHITEOAK,ET AL.: "A Powerful Aluminum Catalyst for the Synthesis of Highly Functional Organic Carbonates", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108358886A (en) * | 2018-04-04 | 2018-08-03 | 常熟理工学院 | A method of preparing trimethylene list sulfocarbonate with ionic liquid-catalyzed |
| CN109180937A (en) * | 2018-10-31 | 2019-01-11 | 浙江大学 | A method of preparing aliphatic poly thioether |
| CN109180937B (en) * | 2018-10-31 | 2020-05-08 | 浙江大学 | Method for preparing aliphatic polythioether |
| US11440995B2 (en) | 2018-10-31 | 2022-09-13 | Zhejiang University | Method for preparing aliphatic polythioether |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1057991C (en) | Method for prepn. of 1-hexene | |
| CN105377828B (en) | The manufacture method of cyclic carbonate | |
| CN109382140B (en) | Carboxyl functionalized pyrazole ionic liquid, synthesis method and method for catalytically synthesizing cyclic carbonate by using same | |
| JP2010001443A (en) | Stereoselective alternating copolymerization of epoxide and carbon dioxide | |
| CN109180937A (en) | A method of preparing aliphatic poly thioether | |
| CN109134420A (en) | A kind of preparation method of cyclic carbonate ester | |
| CN111233816B (en) | Preparation method of cyclic carbonate | |
| CN107602528A (en) | A kind of method for preparing five-membered ring list sulfocarbonate | |
| CN107206370A (en) | Catalyst system for olefin oligomerization and the alkene oligomerization process using the catalyst system | |
| CN111303204B (en) | Two-dimensional metal organic complex containing thiazole functional group and preparation method and application thereof | |
| CN110204724A (en) | A method of preparing carbonyl sulfide co-production sulfur-containing polymer | |
| JP7480154B2 (en) | CATALYST SYSTEM FOR PRODUCING CYCLIC CARBONATES AND RELATED METHODS - Patent application | |
| KR20150037307A (en) | Novel neodymium compound and catalysts for polymerizing diene comprising the same | |
| CN113024787B (en) | Method for catalyzing ring-opening polymerization of epsilon-caprolactone by using [ OSSO ] type complex | |
| CN108395544B (en) | Large-scale preparation method of triazine skeleton covalent polymer | |
| CN106866718A (en) | A kind of preparation method of sesquialter aikyl aluminum halide | |
| CN105061513B (en) | A kind of organic phosphine molybdenum match, preparation method and application | |
| CN114276322A (en) | Method for preparing cyclic carbonate by photo-initiated polymerization of ionic liquid material | |
| CN104250317A (en) | Olefin polymerization catalyst | |
| KR101997692B1 (en) | N-Heterocyclic carbene metallocene compounds and method for preparing the same | |
| CN113200954B (en) | Preparation method of cyclic carbonate | |
| CN1948352B (en) | Catalyst components used for olefin hydrocarbon polymerization and its catalyst | |
| CN115350724A (en) | Preparation method of bifunctional polyion liquid catalyst for synthesizing oxazolidinone | |
| CN107629031A (en) | A kind of method for preparing ring list sulfocarbonate | |
| CN113996339A (en) | Catalyst for preparing cyclic carbonate and preparation method of cyclic carbonate |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180119 |