CN108503638B - A kind of method of cobalt catalysis polyhalo imidodicarbonic diamide Dehalogenation reduction - Google Patents
A kind of method of cobalt catalysis polyhalo imidodicarbonic diamide Dehalogenation reduction Download PDFInfo
- Publication number
- CN108503638B CN108503638B CN201810381136.XA CN201810381136A CN108503638B CN 108503638 B CN108503638 B CN 108503638B CN 201810381136 A CN201810381136 A CN 201810381136A CN 108503638 B CN108503638 B CN 108503638B
- Authority
- CN
- China
- Prior art keywords
- imidodicarbonic diamide
- polyhalo
- dehalogenation
- method described
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/06—Peri-condensed systems
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a kind of methods of cobalt catalysis polyhalo imidodicarbonic diamide Dehalogenation reduction, it is in the reactor of inert atmosphere, under catalyst system containing catalytic amount cobalt dihromide, excessive manganese powder and excessive sodium formate, making polyhalo imidodicarbonic diamide class aromatic hydrocarbons, a step efficiently realizes the Dehalogenation reduction of polyhalo imidodicarbonic diamide class aromatic hydrocarbons in organic solvent.Synthetic route provided by the invention has many advantages, such as to be simple and efficient, raw material is cheap, synthesis cost is low, has repeatability well, can promote the use of the Dehalogenation reduction reaction of other halogenated aryl hydrocarbon derivatives.
Description
Technical field
The present invention relates to a kind of methods of cobalt catalysis polyhalo imidodicarbonic diamide Dehalogenation reduction.
Background technique
It is that pigment belongs to high-grade organic pigment, wherein as precursor structure be pigment being a kind of weight using imidodicarbonic diamide
The kind wanted, this kind of pigment have excellent sun-proof, heat resistance, are applied to high-grade paint, such as: car paint, metal surface
Coating, exterior coating etc..Halogenated imidodicarbonic diamide can be converted to as the intermediate for being pigment containing different substituents
Diimide derivative is greatly enriched paint color so that pigment be made to have different color difference.
However, halogenated imidodicarbonic diamide is extremely difficult by natural degradation.Since the 1980s, a large amount of halogen aromatic hydrocarbons are to ring
The harmfulness in border becomes more and more clear.People are as far as possible by this major class chemicals (such as Polychlorinated biphenyls, more halogen such as polybrominated biphenyls
For aromatic hydrocarbons) it is converted into harmless product, therefore people are dedicated to the degradation of halogen containing organic compound dehalogenation to reduce its toxic.In the past
40 years in, heterogeneous metal catalysis Dehalogenation reduction provide main dehalogenation method.But such methods used Noble Metal Rhodium,
Palladium etc., these noble metal script natural resources are very limited, expensive, and recycle difficulty, thus such methods gradually by
Industry is abandoned.The metal catalytic Dehalogenation reduction method for developing conventional low cost is imperative.Inorganic matter containing cobalt stores up in the earth's crust
Very abundant is measured, and cheap and easy to get.Therefore using cobalt as the catalyst of polyhalo aromatic hydrocarbons Dehalogenation reduction, there is extraordinary reality
Meaning and industrial prospect.
Summary of the invention
Technical problem to be solved by the present invention lies in during overcoming the more halogen aromatic hydrocarbons Dehalogenation reductions of existing precious metal catalyst
Existing shortcoming develops a kind of cheap, easily and efficiently Dehalogenation reduction method.
The present invention, which passes through, have been industrialized and cheap reagent cobalt dihromide is the catalyst of Dehalogenation reduction, it is opened up
New specific use realizes its higher industrial value.
The object of the present invention is to provide a kind of polyhalo imidodicarbonic diamide system easily and efficiently Dehalogenation reduction methods.
The invention is characterized in that the combination catalytic body containing catalytic amount cobalt dihromide, excessive manganese powder and excessive sodium formate simultaneously
It is the Dehalogenation reduction that a step efficiently realizes polyhalo imidodicarbonic diamide class aromatic hydrocarbons in organic solvent.
The present invention relates to the halogenated imidodicarbonic diamide of raw material four to occur to take off under cobalt dihromide, manganese powder and sodium formate collective effect
Halogen reduction reaction, a step efficiently produce the imidodicarbonic diamide of dehalogenation, and yield is up to 96%.Reaction in the present invention to raw material,
Reagent and condition be not harsh, easy to operate, and separation and purifying are easy.
Technical scheme is as follows:
A kind of method of cobalt catalysis polyhalo imidodicarbonic diamide Dehalogenation reduction, it is characterised in that: under inert atmosphere, polyhalo
The imidodicarbonic diamide class aromatic hydrocarbons combination catalyst system containing catalytic amount cobalt dihromide, excessive manganese powder and excessive sodium formate at the same time
Under, the Dehalogenation reduction of polyhalo imidodicarbonic diamide class aromatic hydrocarbons is realized in organic solvent.
Preferably, described method includes following steps: (1) polyhalo imidodicarbonic diamide class aromatic hydrocarbons, dibrominated is successively added
Cobalt, manganese powder, sodium formate and organic solvent, heating reaction；(2) after reaction, it is cooled to room temperature naturally；(3) reaction mixture is slow
Slowly it pours into saturated aqueous ammonium chloride to be quenched, be sufficiently stirred, then be extracted with dichloromethane, repeat extraction three times, merge organic phase,
Organic phase is washed with distilled water twice, and saturated common salt washing is primary, and anhydrous sodium sulfate is dry, is removed under reduced pressure by Rotary Evaporators
Organic solvent obtains concentration mixture；(4) concentration mixture is further purified by silica gel column chromatography, finally obtains purpose
Close object.
Preferably, the imide structure part of the polyhalo imidodicarbonic diamide class aromatic hydrocarbons nitrogen-atoms connection hydrogen atom,
Straight chained alkyl, branched alkyl, aryl.
It is further preferred that the organic solvent is n,N-Dimethylformamide, n,N-dimethylacetamide, N- methyl pyrrole
Pyrrolidone, pyridine, C1-C4The mixed solvent of alkyl substituted pyridines or these solvents.
It is further preferred that the organic solvent is that the mixing that n,N-dimethylacetamide/pyridine volume ratio is 1:1 is molten
Agent.
It is further preferred that the raw material polyhalo imidodicarbonic diamide, cobalt dihromide, manganese powder, sodium formate feed intake mole
Than being followed successively by 1:0.1-1:4-10:5-20.
It is further preferred that the raw material polyhalo imidodicarbonic diamide, cobalt dihromide, manganese powder, sodium formate feed intake mole
Than being followed successively by 1:0.2:6:10.
It is further preferred that the reaction temperature of the reaction is 50-110 DEG C, the reaction time is 4-24 hours.
It is further preferred that the reaction temperature of the reaction is 100 DEG C, the reaction time is 8 hours.
It is further preferred that the inert atmosphere is nitrogen atmosphere or argon atmosphere.
The present invention has the advantages that
1, method provided by the invention, can realize efficient Dehalogenation reduction with a step, reaction route have be simple and efficient, environment
Advantage friendly, cost of material is cheap；
2, method provided by the invention is not high to raw materials used, reagent and solvent requirement；
3, method provided by the invention, operating process are not necessarily to stringent Non-aqueous processing；
4, method provided by the invention, reproducible, yield is high, and up to 96%.
Detailed description of the invention
Fig. 1 is the reaction equation that preferred embodiment of the present invention cobalt is catalyzed differential responses object Dehalogenation reduction.
Specific embodiment
The present invention is further elaborated combined with specific embodiments below, but the present invention is not limited to following embodiments.Under
State method described in embodiment is conventional method unless otherwise instructed.The raw material unless otherwise instructed can be from open quotient
Industry approach and obtain.
According to Fig. 1, the Dehalogenation reduction method of the preferred embodiment of the present invention is as shown in general formula I:
Dehalogenation imidodicarbonic diamide product of the present invention is as shown in formula II:
Embodiment 1, by tetrachloro imidodicarbonic diamide prepare compound 2a
Under nitrogen protection, C is successively added into 50mL Schlenk reaction tube4Four chloro imidodicarbonic diamide substrate of alkyl
(1.0mmol), cobalt dihromide (0.2mmol), manganese powder (6.0mmol), sodium formate (10.0mmol), DMAC N,N' dimethyl acetamide
(10.0mL) and pyridine (10.0mL) is then heated to 100 DEG C, reacts 8 hours.After reaction, it is cooled to room temperature naturally.Reaction
Mixed liquor slowly pours into 100mL saturated aqueous ammonium chloride and is quenched, and is sufficiently stirred 30 minutes, then is extracted with 100mL methylene chloride,
It repeats extraction three times, merges organic phase, organic phase is washed with distilled water twice, and saturated common salt washing is primary, and anhydrous sodium sulfate is dry
It is dry, dichloromethane solvent is removed under reduced pressure by Rotary Evaporators, obtains concentration mixture.Product is further by silica gel column chromatography
Purifying, adsorbent: 300-400 mesh silica gel, eluant, eluent: anhydrous methanol and methylene chloride.Finally obtain compound 2a red solid
0.447g (yield: 89%).
The structure confirmation data of the product is as follows:
Mass spectrum: MS (MALDI-TOF): 502.2 (M+).
Nucleus magnetic hydrogen spectrum:1H NMR(400MHz,CDCl3) δ (ppm): δ=8.57 (d, 8H), 4.17 (t, 4H), 1.57-1.62
(m,4H),1.17–1.20(m,4H),0.93(t,6H).
Embodiment 2, by tetrabromo imidodicarbonic diamide prepare compound 2a
Substantially with embodiment 1, difference is preparation method: the corresponding tetrachloro imidodicarbonic diamide in embodiment 1 is replaced
For corresponding tetrabromo imidodicarbonic diamide, compound 2a red solid 0.457g (yield: 91%) is obtained.
The structure confirmation data of the product is as follows:
Mass spectrum: MS (MALDI-TOF): 502.2 (M+).
Nucleus magnetic hydrogen spectrum:1H NMR(400MHz,CDCl3) δ (ppm): δ=8.67 (d, 8H), 4.17 (t, 4H), 1.57-1.62
(m,4H),1.17–1.20(m,4H),0.93(t,6H).
Embodiment 3, by tetrachloro imidodicarbonic diamide prepare compound 2b
Substantially with embodiment 1, difference is preparation method: by the C in embodiment 14The replacement of alkyl tetrachloro imidodicarbonic diamide
For C6Alkyl tetrachloro imidodicarbonic diamide obtains compound 2b red solid 0.508g (yield: 91%).
The structure confirmation data of the product is as follows:
Mass spectrum: MS (MALDI-TOF): 558.3 (M+).
Nucleus magnetic hydrogen spectrum:1H NMR(400MHz,CDCl3) δ (ppm): δ=8.68 (d, 8H), 4.17 (t, 4H), 1.57-1.63
(m,4H),1.16–1.25(m,8H),0.91(t,6H).
Embodiment 4, by tetrabromo imidodicarbonic diamide prepare compound 2b
Substantially with embodiment 3, difference is preparation method: the corresponding tetrachloro imidodicarbonic diamide in embodiment 3 is replaced
For corresponding tetrabromo imidodicarbonic diamide.Obtain compound 2b red solid 0.514g (yield: 92%).
The structure confirmation data of the product is as follows:
Mass spectrum: MS (MALDI-TOF): 558.3 (M+).
Nucleus magnetic hydrogen spectrum:1H NMR(400MHz,CDCl3) δ (ppm): δ=8.68 (d, 8H), 4.17 (t, 4H), 1.57-1.63
(m,4H),1.16–1.25(m,8H),0.91(t,6H).
Embodiment 5, by tetrachloro imidodicarbonic diamide prepare compound 2c
Substantially with embodiment 3, difference is preparation method: by the C in embodiment 36The replacement of alkyl tetrachloro imidodicarbonic diamide
For C8Alkyl tetrachloro imidodicarbonic diamide obtains compound 2c red solid 0.535g (yield: 87%).
The structure confirmation data of the product is as follows:
Mass spectrum: MS (MALDI-TOF): 614.4 (M+).
Nucleus magnetic hydrogen spectrum:1H NMR(400MHz,CDCl3) δ (ppm): δ=8.67 (d, 8H), 4.18 (t, 4H), 1.74 (m,
4H),1.15–1.25(m,20H),0.89(t,6H).
Embodiment 6, by tetrabromo imidodicarbonic diamide prepare compound 2c
Substantially with embodiment 5, difference is preparation method: the corresponding tetrachloro imidodicarbonic diamide in embodiment 5 is replaced
For corresponding tetrabromo imidodicarbonic diamide.Obtain compound 2c red solid 0.566g (yield: 92%).
The structure confirmation data of the product is as follows:
Mass spectrum: MS (MALDI-TOF): 614.4 (M+).
Nucleus magnetic hydrogen spectrum:1H NMR(400MHz,CDCl3) δ (ppm): δ=8.67 (d, 8H), 4.18 (t, 4H), 1.74 (m,
4H),1.15–1.25(m,20H),0.89(t,6H).
Embodiment 7, by tetrachloro imidodicarbonic diamide prepare compound 2d
Substantially with embodiment 5, difference is preparation method: by the C in embodiment 58The replacement of alkyl tetrachloro imidodicarbonic diamide
For C12Alkyl tetrachloro imidodicarbonic diamide obtains compound 2d red solid 0.676g (yield: 93%).
The structure confirmation data of the product is as follows:
Mass spectrum: MS (MALDI-TOF): 726.5 (M+).
Nucleus magnetic hydrogen spectrum:1H NMR(400MHz,CDCl3) δ (ppm): δ=8.71 (d, 8H), 4.22 (t, 4H), 1.58-0.88
(m,46H).
Embodiment 8, by tetrabromo imidodicarbonic diamide prepare compound 2d
Substantially with embodiment 7, difference is preparation method: the corresponding tetrachloro imidodicarbonic diamide in embodiment 7 is replaced
For corresponding tetrabromo imidodicarbonic diamide.Obtain compound 2d red solid 0.698g (yield: 96%).
The structure confirmation data of the product is as follows:
Mass spectrum: MS (MALDI-TOF): 726.5 (M+).
Nucleus magnetic hydrogen spectrum:1H NMR(400MHz,CDCl3) δ (ppm): δ=8.71 (d, 8H), 4.22 (t, 4H), 1.58-0.88
(m,46H).
Embodiment 9, by tetrachloro imidodicarbonic diamide prepare compound 2e
Substantially with embodiment 7, difference is preparation method: by the C in embodiment 712The replacement of alkyl tetrachloro imidodicarbonic diamide
For 2,6-iPrC6H3Aryl tetrachloro imidodicarbonic diamide obtains compound 2e red solid 0.633g (yield: 89%).
The structure confirmation data of the product is as follows:
Mass spectrum: MS (MALDI-TOF): 710.4 (M+).
Nucleus magnetic hydrogen spectrum:1H NMR(400MHz,CDCl3) δ (ppm): δ=8.81 (d, 4H), 8.78 (d, 4H), 7.5 (t,
2H),7.35(d,4H),2.76(septet,4H),1.18(d,24H).
Embodiment 10, by tetrabromo imidodicarbonic diamide prepare compound 2e
Substantially with embodiment 9, difference is preparation method: the corresponding tetrachloro imidodicarbonic diamide in embodiment 9 is replaced
For corresponding tetrabromo imidodicarbonic diamide.Obtain compound 2e red solid 0.675g (yield: 95%).
The structure confirmation data of the product is as follows:
Mass spectrum: MS (MALDI-TOF): 710.4 (M+).
Nucleus magnetic hydrogen spectrum:1H NMR(400MHz,CDCl3) δ (ppm): δ=8.81 (d, 4H), 8.78 (d, 4H), 7.5 (t,
2H),7.35(d,4H),2.76(septet,4H),1.18(d,24H).
Embodiment 11, by tetrachloro imidodicarbonic diamide prepare compound 2e
Substantially with embodiment 9, difference is preparation method: by the n,N-dimethylacetamide (10.0mL) in embodiment 9
N,N-dimethylformamide (20.0mL) is replaced with pyridine (10.0mL).Obtain compound 2e red solid 0.639g (yield:
90%).
Embodiment 12, by tetrachloro imidodicarbonic diamide prepare compound 2e
Substantially with embodiment 9, difference is preparation method: by the n,N-dimethylacetamide (10.0mL) in embodiment 9
DMAC N,N' dimethyl acetamide (20.0mL) is replaced with pyridine (10.0mL).Obtain compound 2e red solid 0.646g (yield:
91%).
Embodiment 13, by tetrachloro imidodicarbonic diamide prepare compound 2e
Substantially with embodiment 9, difference is preparation method: by the n,N-dimethylacetamide (10.0mL) in embodiment 9
Pyridine (20.0mL) is replaced with pyridine (10.0mL).Obtain compound 2e red solid 0.618g (yield: 87%).
Embodiment 14, by tetrachloro imidodicarbonic diamide prepare compound 2e
Substantially with embodiment 9, difference is preparation method: by cobalt dihromide (0.2mmol), the manganese powder in embodiment 9
(6.0mmol), sodium formate (10.0mmol) replace with cobalt dihromide (0.1mmol), manganese powder (4.0mmol), sodium formate
(5.0mmol).Obtain compound 2e red solid 0.433g (yield: 61%).
Embodiment 15, by tetrachloro imidodicarbonic diamide prepare compound 2e
Substantially with embodiment 9, difference is preparation method: by cobalt dihromide (0.2mmol), the manganese powder in embodiment 9
(6.0mmol), sodium formate (10.0mmol) replace with cobalt dihromide (1.0mmol), manganese powder (10.0mmol), sodium formate
(20.0mmol).Obtain compound 2e red solid 0.639g (yield: 90%).
Embodiment 16, by tetrachloro imidodicarbonic diamide prepare compound 2e
Substantially with embodiment 9, difference is preparation method: will be heated to 100 DEG C in embodiment 9, reacts 8 hours and replace
To be heated to 50 DEG C, react 4 hours.Obtain compound 2e red solid 0.355g (yield: 50%).
Embodiment 17, by tetrachloro imidodicarbonic diamide prepare compound 2e
Substantially with embodiment 9, difference is preparation method: will be heated to 100 DEG C in embodiment 9, reacts 8 hours and replace
To be heated to 110 DEG C, react 24 hours.Obtain compound 2e red solid 0.689g (yield: 97%).
Nitrogen is changed to argon gas, as protection gas, principle is identical, repeats no more.
The above method also can be applied to dichloro (bromine) imidodicarbonic diamide, chlordene (bromine) imidodicarbonic diamide, eight chlorine (bromine)
The Dehalogenation reduction of imidodicarbonic diamide, principle is identical, just no longer repeats one by one.
Above-mentioned specific embodiment is only explained in detail technical solution of the present invention, the present invention not only only office
Be limited to above-described embodiment, it will be understood by those skilled in the art that it is all according to above-mentioned principle and spirit on the basis of the present invention
It improves, substitution, it all should be within protection scope of the present invention.
Claims (10)
1. a kind of method of cobalt catalysis polyhalo imidodicarbonic diamide Dehalogenation reduction, it is characterised in that: under inert atmosphere, polyhalo
Under combination catalyst system of the imidodicarbonic diamide class aromatic hydrocarbons at the same time containing catalytic amount cobalt dihromide, excessive manganese powder and excessive sodium formate,
The Dehalogenation reduction for realizing polyhalo imidodicarbonic diamide class aromatic hydrocarbons in organic solvent, obtains dehalogenation imidodicarbonic diamide product；
The dehalogenation imidodicarbonic diamide product is as shown in formula II:
(formula II).
2. according to the method described in claim 1, it is characterized by: described method includes following steps: (1) more halogen are successively added
For imidodicarbonic diamide class aromatic hydrocarbons, cobalt dihromide, manganese powder, sodium formate and organic solvent, heating reaction；(2) after reaction, natural
It is cooled to room temperature；(3) reaction mixture slowly pours into saturated aqueous ammonium chloride and is quenched, and is sufficiently stirred, then is extracted with dichloromethane,
It repeats extraction three times, merges organic phase, organic phase is washed with distilled water twice, and saturated common salt washing is primary, and anhydrous sodium sulfate is dry
It is dry, organic solvent is removed under reduced pressure by Rotary Evaporators, obtains concentration mixture；(4) concentration mixture passes through silica gel column chromatography
It is further purified, finally obtains purpose compound.
3. according to the method described in claim 1, it is characterized by: the acid imide knot of the polyhalo imidodicarbonic diamide class aromatic hydrocarbons
Nitrogen-atoms connection hydrogen atom, straight chained alkyl, branched alkyl or the aryl of structure part.
4. method described in any one of -3 according to claim 1, it is characterised in that: the organic solvent is N, N- dimethyl
Formamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, pyridine or C1-C4In alkyl substituted pyridines any one or
Any two or more any mixing.
5. according to the method described in claim 4, it is characterized by: the organic solvent is n,N-dimethylacetamide and pyridine
The solvent mixed according to the volume ratio of 1:1.
6. method described in any one of -3 according to claim 1, it is characterised in that: two acyl of raw material polyhalo is sub-
Amine, cobalt dihromide, manganese powder, sodium formate molar ratio be followed successively by 1: 0.1-1: 4-10: 5-20.
7. according to the method described in claim 6, it is characterized by: the raw material polyhalo imidodicarbonic diamide, cobalt dihromide, manganese
Powder, sodium formate molar ratio be followed successively by 1: 0.2: 6: 10.
8. method described in any one of -3 according to claim 1, it is characterised in that: the reaction temperature of the Dehalogenation reduction reaction
Degree is 50-110 DEG C, and the reaction time is 4-24 hours.
9. according to the method described in claim 8, it is characterized by: the Dehalogenation reduction reaction reaction temperature be 100 DEG C,
Reaction time is 8 hours.
10. method described in any one of -3 according to claim 1, it is characterised in that: the inert atmosphere is nitrogen atmosphere
Or argon atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810381136.XA CN108503638B (en) | 2018-04-25 | 2018-04-25 | A kind of method of cobalt catalysis polyhalo imidodicarbonic diamide Dehalogenation reduction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810381136.XA CN108503638B (en) | 2018-04-25 | 2018-04-25 | A kind of method of cobalt catalysis polyhalo imidodicarbonic diamide Dehalogenation reduction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108503638A CN108503638A (en) | 2018-09-07 |
| CN108503638B true CN108503638B (en) | 2019-11-26 |
Family
ID=63383413
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810381136.XA Active CN108503638B (en) | 2018-04-25 | 2018-04-25 | A kind of method of cobalt catalysis polyhalo imidodicarbonic diamide Dehalogenation reduction |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108503638B (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1036132C (en) * | 1993-07-08 | 1997-10-15 | 中国科学院上海有机化学研究所 | Reduction method for fluorohaloparaffin |
| CN103242312B (en) * | 2013-05-23 | 2015-09-02 | 中国科学院化学研究所 | A kind of efficient method preparing Bing bis-perylene diimides derivative |
| CN105749936A (en) * | 2016-04-05 | 2016-07-13 | 宁夏蓝丰精细化工有限公司 | Metal composite catalyst for selective dechloridation and preparation method thereof |
-
2018
- 2018-04-25 CN CN201810381136.XA patent/CN108503638B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN108503638A (en) | 2018-09-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108047107B (en) | The preparation method of diphenyl disenenide ether compound | |
| CN107188832A (en) | A kind of method that utilization carbon dioxide synthesizes the carbamate containing trifluoromethyl | |
| CN108164539B (en) | Green phthalocyanine compound and preparation method thereof | |
| CN105153237B (en) | Half sandwich Cyclometalated ruthenium complex and its preparation method and application | |
| CN108503638B (en) | A kind of method of cobalt catalysis polyhalo imidodicarbonic diamide Dehalogenation reduction | |
| Iqbal et al. | Synthesis of phthalonitriles using a palladium catalyst | |
| CN104098432B (en) | A kind of synthetic method of trifluoromethylation aromatic hydrocarbons | |
| CN109503547B (en) | Process for preparing benzodithiolane derivatives | |
| CN107235952A (en) | It is a kind of to help the synthetic method for pacifying moldin skeleton | |
| CN106146496A (en) | A kind of gulf district cyclization synthetic method of double imide derivative | |
| CN109651385A (en) | A kind of preparation method of pyrans [3,2-a] carbazole compound | |
| WO2015170688A1 (en) | Metal-supported porous coordination polymer catalyst | |
| CN105968374B (en) | A kind of copper (I) coordination polymer and its preparation method and application | |
| CN108129277A (en) | A kind of method for synthesizing 2,2 '-dinaphthyl ether | |
| CN109879792A (en) | A kind of polysubstituted isoindoles compound and preparation method thereof | |
| CN100545165C (en) | The method of synthesizing copper phthalocyanine in ionic liquid | |
| CN105198806B (en) | A kind of method using aromatic amine, diketone synthesis of quinoline derivatives | |
| CN108822107A (en) | A kind of method of nickel catalysis polyhalo imidodicarbonic diamide class aromatic hydrocarbons Dehalogenation reduction | |
| CN114560832A (en) | Method for synthesizing dibenzofuran compound | |
| CN114591148A (en) | Method for synthesizing bisphenol fluorene based on microreactor | |
| CN107641101A (en) | A kind of preparation method of phenanthridines ketone compounds | |
| CN114014805A (en) | Preparation method of trifluoromethylated 2, 4-quinolinedione compounds | |
| CN113072470A (en) | N-acetonitrile bis-benzenesulfonylimine derivative and preparation method and application thereof | |
| CN112939891A (en) | Method for preparing biphenyl benzothiazole compound | |
| CN106749315B (en) | 8- hexyl-thieno [3 ', 2 ':3,4] benzo [1,2-c] carbazole compound and its synthetic method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |