CN109320555A - A kind of synthetic method of bis-phosphite - Google Patents
A kind of synthetic method of bis-phosphite Download PDFInfo
- Publication number
- CN109320555A CN109320555A CN201811350926.8A CN201811350926A CN109320555A CN 109320555 A CN109320555 A CN 109320555A CN 201811350926 A CN201811350926 A CN 201811350926A CN 109320555 A CN109320555 A CN 109320555A
- Authority
- CN
- China
- Prior art keywords
- xenols
- solution
- reaction solution
- organic solvent
- dissolved
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65744—Esters of oxyacids of phosphorus condensed with carbocyclic or heterocyclic rings or ring systems
Abstract
The invention discloses a kind of synthetic methods of bis-phosphite, this method is with the phosphorus trichloride of amount of reagent, 2,2 '-xenols and 3,3', 5,5'- tetra-tert -2,2'- xenol is raw material, and phosphorus trichloride is dissolved in organic solvent and forms solution, then it is added under stiring dissolved with 2, the solution of 2 '-xenols and catalyst, after phosphorus trichloride solution is added, reaction solution the reaction was continued a few hours；The solution dissolved with 3,3', 5,5'- tetra-tert -2,2'- xenols and organic base is added to above-mentioned reaction solution, after addition, reaction solution continues to stir a few hours, then raises temperature to 80-120 DEG C of reflux a few hours；Reaction solution is cooled to room temperature after the reaction was completed, is filtered, washed filter cake, and filtrate is concentrated by evaporation after merging and obtains solid, obtains product after washing.Present invention process has the characteristics that bis-phosphite yield is high, phosphorus trichloride dosage is few, by-product is few, the reaction time is short, post-processing is simple.
Description
Technical field:
The present invention is that is involved is a kind of synthetic methods of bis-phosphite.
Background technique:
Coordinating phosphorus atoms there are two containing in bisphosphite ligands molecular structure, can be coordinated to be formed with transition-metal catalyst
The metal complex of double chelating ligands, the ligand have important role in transition-metal catalysis.
Synthetic method disclosed in the prior art is broadly divided into two steps: (1) phosphorus trichloride reacts production 2 with 2,2 '-xenols,
2 '-bis- phenoxy group phosphine chloromethylated intermediates；(2) intermediate again with 3,3', tie up in organic base by 5,5'- tetra-tert -2,2'- xenol
Reaction generates bis-phosphite product under the action of sour agent.
Large excess of phosphorus trichloride is all made of in existing public technology to react as phosphorization reagent 2,2 '-xenol.So
And phosphorus trichloride gas is toxic, has strong impulse and strong corrosive, conjunctiva can be made to send out after sucking phosphorus trichloride gas
Inflammation, laryngalgia and eye tissue destroy, to lung and all irritating effect of mucous membrane.The above characteristic to be operated using phosphorus trichloride
Shi Shifen is difficult, can cause huge harm to operator and environment.A large amount of phosphorus trichloride waste liquid is had after the reaction was completed, it is difficult
With processing.
Summary of the invention:
The object of the present invention is to provide the synthetic methods that a kind of one-step method prepares bis-phosphite, to solve the prior art
In to adopt using significantly excessive phosphorus trichloride be raw material bring a series of problems.
The present invention provides a kind of synthetic method of bis-phosphite, comprising the following steps:
(a) phosphorus trichloride is dissolved in organic solvent and forms solution, 2,2 '-xenols and catalysis are then added under stiring
Agent is dissolved in the solution formed after organic solvent, and after addition, reaction solution is heated to 70-100 DEG C and continues stirring 1-6 hours,
The organic solvent is selected from one or more of tetrahydrofuran, toluene, and the catalyst is selected from pyridine, triethylamine, N, N- bis-
One or more of methylaniline, 1- methylimidazole, 1- ethyl imidazol(e), 2- picoline, n,N-Dimethylformamide, it is described
Phosphorus trichloride and 2, the molar ratios of 2 '-xenols are 1:1-1:1.5, the catalyst and 2, the molar ratio 0.01 of 2 '-xenols:
1-0.1:1；(b) 3,3', 5,5'- tetra-tert -2,2'- xenols and organic base are dissolved in organic solvent and form solution, then
The reaction solution that above-mentioned steps (a) is formed is added, after addition, reaction solution continues stirring 1-6 hours, then raises temperature to
70-120 DEG C reflux 1-5 hours, the organic solvent is selected from one or more of tetrahydrofuran, toluene, organic base choosing
From one or more of pyridine, triethylamine, n,N-Dimethylaniline, described 2,2 '-xenols and 3,3', 5,5'- tetra- tertiary fourths
The molar ratio of base -2,2'- xenol is 2:1-5:1, and the organic base and 2, the molar ratio of 2 '-xenols is 2:1-10:1；
(c) reaction solution is cooled to room temperature after the reaction was completed, is filtered, washed filter cake, and filtrate is concentrated by evaporation after merging is consolidated
Body, solid obtain product after being washed with acetonitrile.
Wherein, chemical equation is as follows:
According to preparation method of the present invention, it is characterised in that it the following steps are included:
(a) phosphorus trichloride is dissolved in organic solvent and forms solution, 2,2 '-xenols and catalysis are then added under stiring
Agent is dissolved in the solution formed after organic solvent, and after addition, reaction solution is heated to 70-100 DEG C and continues stirring 1-6 hours,
The organic solvent is one or more of tetrahydrofuran, toluene, and the catalyst is pyridine, 1- methylimidazole, N, N- bis-
One or more of methylformamide, the phosphorus trichloride and 2, the molar ratio of 2 '-xenols are 1:1.05-1:1.10, institute
State the molar ratio 0.02:1-0.05:1 of catalyst and 2,2 '-xenols；
(b) 3,3', 5,5'- tetra-tert -2,2'- xenols and organic base are dissolved in organic solvent and form solution, then
The reaction solution that above-mentioned steps (a) is formed is added, after addition, reaction solution continues stirring 1-6 hours, then raises temperature to
80-120 DEG C reflux 1-5 hours, the organic solvent be one or more of tetrahydrofuran, toluene, the organic base be pyrrole
One or more of pyridine, triethylamine, described 2,2 '-xenols and 3,3', mole of 5,5'- tetra-tert -2,2'- xenols
Than for 2:1-3:1, the organic base and 2, the molar ratio of 2 '-xenols is 3:1-5:1；
(c) reaction solution is cooled to room temperature after the reaction was completed, is filtered, washed filter cake, and filtrate is concentrated by evaporation after merging is consolidated
Body, solid obtain product after being washed with acetonitrile.
Synthetic method of the present invention prepares bis-phosphite with the phosphorus trichloride one-step method of amount of reagent, and there is bis-phosphite to produce
The advantages that product yield is high, by-product is few, the reaction time is short, environmental pollution is small, post-processing is simple.
Specific embodiment
The following examples will be described further technical solution of the present invention, but not thereby limiting the invention.
Embodiment 1
2,2 '-xenol of 1.00mol, 0.05mol 1- methylimidazole are dissolved in 2000mL toluene, under stirring in batches
It is added dropwise in the 200mL toluene solution dissolved with 1.05mol phosphorus trichloride, was added dropwise in 2 hours or so, reaction solution continues to add
Heat stirs 3 hours to 90 DEG C, is added then to above-mentioned reaction solution dissolved with 0.5mol3,3', 5,5'- tetra-tert -2,2'- connection
The toluene solution 3000mL of phenol and 4.00mol pyridine, was added dropwise in 2 hours or so, and reaction solution continues stirring 5 hours,
100 DEG C are then raised temperature to stir 4 hours.Reaction solution is cooled to room temperature after the reaction was completed, filter cake is filtered, washed, after filtrate merges
Evaporation and concentration obtains solid, and solid obtains bis-phosphite white crystal after being washed with acetonitrile, through nuclear magnetic resonance spectroscopy, phosphorus spectrum with
And efficient liquid phase chromatographic analysis is consistent with document report, product is diphosphite two (2,2'- xenol) -3,3', 5,5'- tetra- uncle
Butyl -2,2'- biphenyl phenolic ester, yield 99% (yield on the basis of 2,2 '-xenols to calculate).
Embodiment 2
2,2 '-xenol of 1.00mol, 0.10mol n,N-Dimethylformamide are dissolved in 2000mL tetrahydrofuran, stirred
It mixes down and is added dropwise in the 200mL tetrahydrofuran solution dissolved with 1mol phosphorus trichloride in batches, was added dropwise in 2 hours or so, instead
It answers solution to continue to be heated to 90 DEG C of stirrings 5 hours, is added then to above-mentioned reaction solution dissolved with 0.5mol3,3', 5, tetra- uncle of 5'-
The tetrahydrofuran solution 3000mL of butyl -2,2'- xenol and 4.00mol triethylamine, was added dropwise in 2 hours or so, reaction
Solution continues stirring 5 hours, then raises temperature to 100 DEG C and stirs 4 hours.Reaction solution is cooled to room temperature after the reaction was completed, is filtered, is washed
Filter cake is washed, filtrate is concentrated by evaporation after merging and obtains solid, and solid obtains bis-phosphite white crystal after being washed with acetonitrile, through core
Magnetic resonance hydrogen spectrum, phosphorus spectrum and efficient liquid phase chromatographic analysis are consistent with document report, and product is (2, the 2'- biphenyl of diphosphite two
Phenol) -3,3', 5,5'- tetra-tert -2,2'- biphenyl phenolic esters, yield 96% (yield on the basis of 2,2 '-xenols to calculate).
Embodiment 3
2,2 '-xenol of 1.00mol, 0.03mol pyridine are dissolved in 2000mL toluene, are added dropwise in batches under stirring
It dissolved in the 200mL toluene solution of 1.10mol phosphorus trichloride, was added dropwise in 2 hours or so, it is small that reaction solution continues stirring 3
When, it is added then to above-mentioned reaction solution dissolved with 3,3', 5,5'- tetra-tert -2,2'- xenol of 0.55mol and 5.00mol
The tetrahydrofuran solution 3000mL of pyridine, was added dropwise in 2 hours or so, and reaction solution continues stirring 3 hours, then raised temperature to
100 DEG C are stirred 4 hours.Reaction solution is cooled to room temperature after the reaction was completed, is filtered, washed filter cake, and filtrate is concentrated by evaporation after merging
To solid, solid obtains bis-phosphite white crystal after being washed with acetonitrile, through nuclear magnetic resonance spectroscopy, phosphorus spectrum and efficient liquid phase
Chromatography is consistent with document report, product be diphosphite two (2,2'- xenol) -33,3', 5,5'- tetra-tert -2,
2'- biphenyl phenolic ester, yield 95% (yield on the basis of 2,2 '-xenols to calculate).
Embodiment 4
2,2 '-xenol of 1.00mol, 0.05mol n,N-Dimethylaniline are dissolved in 2000mL tetrahydrofuran, stirred
Under be added dropwise in the 200mL tetrahydrofuran solution dissolved with 1.50mol phosphorus trichloride in batches, be added dropwise in 2 hours or so, instead
It answers solution to continue to be heated to 90 DEG C of stirrings 3 hours, is added then to above-mentioned reaction solution dissolved with 3,3', 5,5'- tetra- uncle of 0.3mol
The tetrahydrofuran solution 2000mL of butyl -2,2'- xenol and 5.00mol triethylamine, was added dropwise in 2 hours or so, reaction
Solution continues stirring 5 hours, then raises temperature to 100 DEG C and stirs 4 hours.Reaction solution is cooled to room temperature after the reaction was completed, is filtered, is washed
Filter cake is washed, filtrate is concentrated by evaporation after merging and obtains solid, and solid obtains bis-phosphite white crystal after being washed with acetonitrile, through core
Magnetic resonance hydrogen spectrum, phosphorus spectrum and efficient liquid phase chromatographic analysis are consistent with document report, and product is (2, the 2'- biphenyl of diphosphite two
Phenol) -3,3', 5,5'- tetra-tert -2,2'- biphenyl phenolic esters, (yield is with 3,3', 5,5'- tetra-terts -2,2'- for yield 91%
It is calculated on the basis of xenol).
Embodiment 5
By 2,2 '-xenol of 1.00mol, 0.01mol 2- picoline be dissolved in 2000mL toluene, under stirring in batches
It is secondary to be added dropwise in the 200mL toluene solution dissolved with 1.01mol phosphorus trichloride, it was added dropwise in 2 hours or so, reaction solution continues
It is heated to 100 DEG C to stir 6 hours, be added then to above-mentioned reaction solution dissolved with 0.55mol3,3', 5, tetra-tert -2 5'-,
The tetrahydrofuran solution 3000mL of 2'- xenol and 4.00mol pyridine, was added dropwise in 2 hours or so, and reaction solution continues to stir
It mixes 5 hours, then raises temperature to 100 DEG C and stir 4 hours.Reaction solution is cooled to room temperature after the reaction was completed, is filtered, washed filter cake, filter
Liquid is concentrated by evaporation after merging and obtains solid, and solid obtains bis-phosphite white crystal after being washed with acetonitrile, through hydrogen nuclear magnetic resonance
Spectrum, phosphorus spectrum and efficient liquid phase chromatographic analysis are consistent with document report, and product is diphosphite two (2,2'- xenol) -33,
3', 5,5'- tetra-tert -2,2'- biphenyl phenolic esters, yield 94% (yield on the basis of 2,2 '-xenols to calculate).
Claims (2)
1. a kind of synthetic method of bis-phosphite, which comprises the following steps:
(a) phosphorus trichloride is dissolved in organic solvent and forms solution, 2,2 '-xenols are then added under stiring and catalyst is molten
The solution formed after organic solvent, after addition, reaction solution is heated to 70-100 DEG C and continues stirring 1-6 hours, described
Organic solvent is selected from one or more of tetrahydrofuran, toluene, and the catalyst is selected from pyridine, triethylamine, N, N- dimethyl
One or more of aniline, 1- methylimidazole, 1- ethyl imidazol(e), 2- picoline, n,N-Dimethylformamide, the trichlorine
Change phosphorus and 2, the molar ratio of 2 '-xenols is 1:1-1:1.5, the catalyst and 2, the molar ratio 0.01:1- of 2 '-xenols
0.1:1；
(b) 3,3', 5,5'- tetra-tert -2,2'- xenols and organic base are dissolved in organic solvent and form solution, be then added
The reaction solution that above-mentioned steps (a) are formed, after addition, reaction solution continues stirring 1-6 hours, then raises temperature to 70-120
DEG C reflux 1-5 hour, the organic solvent be selected from one or more of tetrahydrofuran, toluene, the organic base selected from pyridine,
One or more of triethylamine, n,N-Dimethylaniline, described 2,2 '-xenols and 3,3', 5,5'- tetra-terts -2,2'-
The molar ratio of xenol is 2:1-5:1, and the organic base and 2, the molar ratio of 2 '-xenols is 2:1-10:1；
(c) reaction solution is cooled to room temperature after the reaction was completed, is filtered, washed filter cake, and filtrate is concentrated by evaporation after merging and obtains solid, Gu
Body obtains product after being washed with acetonitrile.
2. the method according to claim 1, wherein the following steps are included:
(a) phosphorus trichloride is dissolved in organic solvent and forms solution, 2,2 '-xenols are then added under stiring and catalyst is molten
The solution formed after organic solvent, after addition, reaction solution is heated to 70-100 DEG C and continues stirring 1-6 hours, described
Organic solvent is one or more of tetrahydrofuran, toluene, and the catalyst is pyridine, 1- methylimidazole, N, N- dimethyl
One or more of formamide, the phosphorus trichloride and 2, the molar ratio of 2 '-xenols is 1:1.05-1:1.10, described to urge
The molar ratio 0.02:1-0.05:1 of agent and 2,2 '-xenols；
(b) 3,3', 5,5'- tetra-tert -2,2'- xenols and organic base are dissolved in organic solvent and form solution, be then added
The reaction solution that above-mentioned steps (a) are formed, after addition, reaction solution continues stirring 1-6 hours, then raises temperature to 80-120
DEG C reflux 1-5 hour, the organic solvent be one or more of tetrahydrofuran, toluene, the organic base be pyridine, three second
One or more of amine, described 2, the molar ratio of 2 '-xenols and 3,3', 5,5'- tetra-tert -2,2'- xenols is 2:
1-3:1, the organic base and 2, the molar ratio of 2 '-xenols are 3:1-5:1；
(c) reaction solution is cooled to room temperature after the reaction was completed, is filtered, washed filter cake, and filtrate is concentrated by evaporation after merging and obtains solid, Gu
Body obtains product after being washed with acetonitrile.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811350926.8A CN109320555A (en) | 2018-11-14 | 2018-11-14 | A kind of synthetic method of bis-phosphite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811350926.8A CN109320555A (en) | 2018-11-14 | 2018-11-14 | A kind of synthetic method of bis-phosphite |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109320555A true CN109320555A (en) | 2019-02-12 |
Family
ID=65260926
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811350926.8A Pending CN109320555A (en) | 2018-11-14 | 2018-11-14 | A kind of synthetic method of bis-phosphite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109320555A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112010906A (en) * | 2020-08-31 | 2020-12-01 | 中国海洋石油集团有限公司 | Bisphosphite and preparation method and application thereof |
| CN114075244A (en) * | 2020-08-18 | 2022-02-22 | 中国石油化工股份有限公司 | Bidentate phosphite ester and purification method and application thereof |
| CN114075245A (en) * | 2020-08-18 | 2022-02-22 | 中国石油化工股份有限公司 | Bidentate phosphite ligand, preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU732269A1 (en) * | 1977-11-17 | 1980-05-05 | Предприятие П/Я А-7411 | Method of preparing phosphoric acid bisphenyl esters |
| CN105440081A (en) * | 2015-12-07 | 2016-03-30 | 中国海洋石油总公司 | Diphosphite synthesis method |
| CN108129515A (en) * | 2017-12-05 | 2018-06-08 | 中海油天津化工研究设计院有限公司 | A kind of synthetic method of bis-phosphite |
-
2018
- 2018-11-14 CN CN201811350926.8A patent/CN109320555A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU732269A1 (en) * | 1977-11-17 | 1980-05-05 | Предприятие П/Я А-7411 | Method of preparing phosphoric acid bisphenyl esters |
| CN105440081A (en) * | 2015-12-07 | 2016-03-30 | 中国海洋石油总公司 | Diphosphite synthesis method |
| CN108129515A (en) * | 2017-12-05 | 2018-06-08 | 中海油天津化工研究设计院有限公司 | A kind of synthetic method of bis-phosphite |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114075244A (en) * | 2020-08-18 | 2022-02-22 | 中国石油化工股份有限公司 | Bidentate phosphite ester and purification method and application thereof |
| CN114075245A (en) * | 2020-08-18 | 2022-02-22 | 中国石油化工股份有限公司 | Bidentate phosphite ligand, preparation method and application thereof |
| CN112010906A (en) * | 2020-08-31 | 2020-12-01 | 中国海洋石油集团有限公司 | Bisphosphite and preparation method and application thereof |
| CN112010906B (en) * | 2020-08-31 | 2021-09-28 | 中国海洋石油集团有限公司 | Bisphosphite and preparation method and application thereof |
| WO2022041617A1 (en) * | 2020-08-31 | 2022-03-03 | 中国海洋石油集团有限公司 | Diphosphite, preparation method therefor and use thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109320555A (en) | A kind of synthetic method of bis-phosphite | |
| CN108129515A (en) | A kind of synthetic method of bis-phosphite | |
| Cao et al. | Activation of carbodiimide and transformation with amine to guanidinate group by Ln (OAr) 3 (THF) 2 (Ln: Lanthanide and yttrium) and Ln (OAr) 3 (THF) 2 as a novel precatalyst for addition of amines to carbodiimides: Influence of aryloxide group | |
| CN105440081A (en) | Diphosphite synthesis method | |
| Bollermann et al. | Reactivity of [Zn2Cp* 2] toward transition-metal complexes: Synthesis and characterization of [Cp* M (ZnCp*) 3](M= Ni, Pd, Pt) | |
| Ma et al. | Tridecanuclear and docosanuclear manganese phosphonate clusters with slow magnetic relaxation | |
| Lugmair et al. | Di-tert-butyl phosphate complexes of titanium | |
| CN109369722A (en) | A kind of preparation method of bis-phosphite | |
| Hevia et al. | New octahedral rhenium (I) tricarbonyl amido complexes | |
| CN102286006A (en) | Ether-chain bridged bis-benzimidazole metal complexes and preparation method and application thereof | |
| Zhuravel et al. | Palladium (II) terminal phosphido complexes derived from cyclometalated dimesitylphosphine: synthesis, structure, and low-barrier phosphorus inversion | |
| Ju et al. | l-and d-[Ln (HCO2)(SO4)(H2O)] n (Ln= La, Ce, Pr, Nd, and Eu): Chiral Enantiomerically 3D Architectures Constructed by Double−[Ln–O] n–Helices | |
| CN104447700A (en) | Binaphthol-bridged n-heterocyclic bis-carbene metal complex as well as preparation method and application thereof | |
| CN113817174B (en) | Preparation method and application of in-situ hydrazide three-dimensional MOFs material | |
| Levine et al. | Direct Observation of P (O)− C Bond Formation from (N⌒ N) PdMe (P (O)(OPh) 2) Complexes. Rate Enhancement of Reductive Elimination by Addition of Triarylphosphines | |
| CN106366329A (en) | Terephthalic acid binuclear cadmium polymer and preparation method thereof | |
| Kovacik et al. | Regiochemistry of platinum-catalyzed hydrophosphination of a diene. Formation of the chiral diphosphine Et2PCH (CN) CH (CH2CH2CN) PEt2 via monophosphine intermediates | |
| Gan et al. | A three-dimensional framework structure constructed from 2-(2-pyridyl-N-oxide) ethylphosphonic acid and Nd (III) | |
| Zhuravel et al. | Synthesis and structure of dinuclear palladium (II) complexes with bridging hydrido and phosphido ligands | |
| JP2010510178A (en) | Process for producing 1,1,1,3,3-pentachlorobutane | |
| Tu et al. | Ligand electronic effects in the palladium catalyzed asymmetric allylic alkylation reaction with planar chiral diphosphine-oxazoline ferrocenyl ligands | |
| Pi et al. | Synthesis, Structural Characterization, and Reactivity of Lanthanide Complexes Containing a New Methylene-Bridged Indenyl− Pyrrolyl Dianionic Ligand | |
| CN103237796B (en) | Piperazine-N, N '-bis-dithionic acid salt brine solution and manufacture method thereof | |
| CN104031075A (en) | 1:1 type enol quinoline metal complexes as well as synthetic method and application thereof | |
| Teo et al. | Spacer-directed coordination polymers-of-oligomers (POLO) of silver |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190212 |