CN108276244A - A kind of method of the chloro- 2- iodine dihalo objects of one pot process 1- - Google Patents
A kind of method of the chloro- 2- iodine dihalo objects of one pot process 1- Download PDFInfo
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- CN108276244A CN108276244A CN201810135582.2A CN201810135582A CN108276244A CN 108276244 A CN108276244 A CN 108276244A CN 201810135582 A CN201810135582 A CN 201810135582A CN 108276244 A CN108276244 A CN 108276244A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/013—Preparation of halogenated hydrocarbons by addition of halogens
- C07C17/02—Preparation of halogenated hydrocarbons by addition of halogens to unsaturated hydrocarbons
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/22—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of halogens; by substitution of halogen atoms by other halogen atoms
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
- C07C67/287—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms
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Abstract
The invention discloses the synthetic methods of 1 chlorine shown in a kind of formula (IV), 2 iodine dihalo object：N hydroxy benzo triazoles shown in tert-butyl hydroperoxide, formula (III) shown in olefin(e) compound shown in formula (I) and propiodal, formula (II) are mixed in organic solvent, in room temperature at 50 DEG C, the reaction was complete obtains reaction solution A；Chloroacetic chloride is added into gained reaction solution A, the reaction was complete at room temperature, and gained reaction solution B is post-treated to obtain 1 chlorine, the 2 iodine dihalo compound.Method safety environmental protection of the present invention does not generate exhaust gas, more conducively its application in medicine synthesizes；Reaction condition is mild, and substrate adaptability is good, and a variety of substituent groups can realize that corresponding 1 chlorine, 2 iodine is halogenated.
Description
(1) technical field
Present invention relates particularly to a kind of methods of the chloro- 2- iodine dihalo objects of one pot process 1-.
(2) background technology
Dihalo object some natural products and drug molecule it is artificial synthesized in often crucial intermediate, while one
Halides are also highly useful synthon in organic synthesis a bit, so developing novel dihalide reaction either for section
It learns research or actual production is all of great significance.But up to the present, it is reported about the synthetic method of such compound
It is very few.Most common method is exactly directly to carry out halogenation to carbon-carbon double bond using halogen simple substance, although this method is simple,
This method is not easy to operate and easily causes environmental pollution, therefore greatly limits the large-scale application of this method.
(3) invention content
The object of the present invention is to provide a kind of new methods of the chloro- 2- iodine dihalo objects of 1-, with olefin(e) compound, iodine
Source, tert-butyl hydroperoxide and N- hydroxy benzo triazoles are raw material, excess acetyl chloride are directly added into without post-processing, in temperature
The synthesis of the chloro- 2- iodine dihalo objects of a variety of 1- may be implemented under the conditions of.
In order to achieve the above objectives, the technical solution adopted by the present invention is as follows：
The synthetic method of the chloro- 2- iodine dihalo objects of 1- shown in a kind of formula (IV), it is characterised in that：The synthetic method
Specifically prepared in accordance with the following steps：
(1) by tert-butyl hydroperoxide, formula (III) institute shown in olefin(e) compound shown in formula (I) and propiodal, formula (II)
The N- hydroxy benzo triazoles shown are mixed in organic solvent, under room temperature to 50 DEG C (preferably 40 DEG C), are tracked by TLC anti-
It answers, the reaction was complete obtains reaction solution A；Olefin(e) compound shown in the formula (I) and t-butyl peroxy shown in propiodal, formula (II)
The ratio between the amount for the substance that feeds intake for changing N- hydroxy benzo triazoles shown in hydrogen, formula (III) is 1:0.5-1:2-4:1.2-2 is (preferably
1:0.5:2:1.2)。
(2) chloroacetic chloride is added into reaction solution A obtained by step (1), the reaction was complete at room temperature, and gained reaction solution B is after
Processing obtains the chloro- 2- iodine dihalo compounds of 1-；The addition of the chloroacetic chloride and alkene shown in the formula (I)
The ratio between amount of substance of hydrocarbon compound is 4~6:1 (preferably 5:1)；
In formula (I) or formula (IV)：
R1For substituted-phenyl or naphthalene；The substituted-phenyl is by nitro, C1-5Alkyl, C1-5Alkoxy, C1-5Alkyl ester
Base or the phenyl of cyano substitution.
Further, in step (1), substituted olefine shown in the preferably described formula (I) is one of following：Styrene, 2- methyl
Styrene, 4- cyano styrenes, indenes, (amyl- 4- alkene -1- bases oxygroup) benzene or amyl- 4- alkene -1- yl benzoic acid esters.
Further, in step (1), substituted olefine shown in the more preferable formula (I) is styrene or 4- cyano benzene second
Alkene.
Further, in step (1), substituted olefine shown in the most preferably described formula (I) is styrene.
Further, in step (1), the propiodal is elemental iodine.
Further, in step (1), the organic solvent is dichloromethane or 1,2- dichloromethane.
Further, in step (1), the volumetric usage of the organic solvent shown in the formula (I) to replace alkene
The ratio between amount of substance of hydrocarbon compound is 3-3.3ml/mmol.
Further, in step (1), preferred reaction time 4-6h.
Further, in step (2), preferred reaction time 10-16h.
Further, in step (2), the post-processing approach of the reaction solution B is：After reaction, reaction solution B is first
Carry out being concentrated under reduced pressure to give grease, gained grease carries out column chromatography for separation again, with volume ratio for 6/1-20/1 petroleum ether/
Ethyl acetate mixtures are eluant, eluent, collect the eluent containing target compound, are dried to get the 1- after solvent is evaporated off
Chloro- 2- iodine dihalo object.
More specifically, synthetic method of the present invention is specifically prepared in accordance with the following steps：
(1) by tert-butyl hydroperoxide, formula shown in substituted olefine compound shown in formula (I) and propiodal, formula (II)
(III) N- hydroxy benzo triazoles shown in are mixed in organic solvent, react 4-6h at 40 DEG C, obtain reaction solution A；It is described
Substituted olefine compound shown in formula (I) and N- hydroxyls shown in tert-butyl hydroperoxide, formula (III) shown in propiodal, formula (II)
The ratio between amount for the substance that feeds intake of base benzotriazole is 1:0.5:2:1.2；Substituted olefine compound shown in the formula (I) is selected
From one of following：Styrene, 2-methyl styrene, 4- cyano styrenes, indenes, (amyl- 4- alkene -1- bases oxygroup) benzene or amyl- 4- alkene -
1- yl benzoic acid esters；The propiodal is elemental iodine；The solvent is dichloromethane or 1,2- dichloroethanes；The solvent
Volumetric usage shown in formula (I) to replace the amount of the substance of acetylene hydrocarbon compound to be calculated as 3-3.3ml/mmol；
(2) chloroacetic chloride (5 equivalents are calculated as with olefin(e) compound) is added into reaction solution A obtained by step (1), at room temperature
10-16h is reacted, first carries out being concentrated under reduced pressure to give grease after reaction by reaction solution B, gained grease is subjected to column layer again
Analysis separation, using the petrol ether/ethyl acetate mixed liquor of petroleum ether or volume ratio 20/1-6/1 as eluant, eluent, collects and merges containing mesh
The eluent for marking compound is dried after solvent is evaporated off to get the chloro- 2- iodine dihalo compounds of 1-；The chloroacetic chloride
Addition and the ratio between amount of substance of olefin(e) compound shown in the formula (I) be 5:1.
Compared with prior art, the beneficial effects of the invention are as follows：
(1) safety and environmental protection does not generate exhaust gas, more conducively its application in medicine synthesizes；
(2) compared with prior art, reaction condition is mild, and substrate adaptability is good, and a variety of substituent groups can be realized accordingly
The chloro- 2- iodine of 1- it is halogenated；
(3) directly using substituted olefine compound as raw material, using one kettle way, operation is simple, is a kind of synthesize containing each
The variation route of the different chloro- 2- iodine dihalide compounds of 1- of kind.
(4) specific implementation mode
With reference to specific embodiment, the present invention is described in further detail, but protection scope of the present invention and not only
It is limited to this.
The mass concentration of tert-butyl hydroperoxide used in the present embodiment is 70%.
Embodiment 1
Compound 1
By styrene (114.9 μ L, 1mmol), 70% tert-butyl hydroperoxide of iodine (26.9mg, 0.5mmol)
(257.5mg, 2mmol) and N- hydroxy benzo triazoles (166.6mg, 1.2mmol) are mixed in 3ml dichloromethane solvents and add
Enter into flask, reacts 4h at 40 DEG C.TLC is detected after reaction, is down to room temperature, be added chloroacetic chloride (353.7 μ L,
16h 5mmol) is reacted, TLC is detected after reaction, with column chromatography chromatogram method (eluent：Petroleum ether) isolated (chloro- 2- of 1-
Iodoethane base) benzene (compound 1) 133.9mg, yield 50.2%.
Characterization of The Products：White solid, m.p.47 DEG C.1H NMR(500MHz,CDCl3)δ 7.51–7.31(m,5H),5.08
(dd, J=9.6,5.8Hz, 1H), 3.91-3.66 (m, 2H)13C NMR(125MHz,CDCl3)δ139.15,129.19,
128.82,127.24,,61.72, 9.99.
Embodiment 2
Compound 2
By p-nitrophenyl ethylene (44.7mg, 0.3mmol), iodine (38.1mg, 0.15 mmol), 70% tertiary butyl mistake
Hydrogen oxide (77.25mg, 0.6mmol) and N- hydroxy benzo triazoles (49.1mg, 0.36mmol) are mixed in 1ml dichloromethane
Solvent is added in flask, reacts 6h at 40 DEG C.TLC is detected after reaction, is down to room temperature, and chloroacetic chloride (106.1 μ are added
L, 1.5mmol) 16h is reacted, TLC is detected after reaction, with column chromatography chromatogram method (eluent：Petroleum ether) isolated 1-
(the chloro- 2- iodoethane bases of 1-) -4- nitrobenzenes (compound 2) 56.3mg, yield 60.2%.
Characterization of The Products：Faint yellow solid, m.p.57 DEG C.1H NMR(500MHz,CDCl3)δ 8.38–8.18(m,2H),
7.64-7.58 (m, 2H), 5.07 (dd, J=8.8,5.7Hz, 1H), 3.98 (ddd, J=20.2,11.4,7.3Hz, 2H)13C
NMR(125MHz,CDCl3) δ 148.15 (s), 145.86 (s), 128.62 (s), 128.43 (s), 124.11 (d, J=
17.9Hz), 59.45(s),8.41(s).
Embodiment 3
Compound 3
By indenes (61.1mg, 0.5mmol), iodine (63.4mg, 0.25mmol), tert-butyl hydroperoxide (128.7mg,
1mmol) and N- hydroxy benzo triazoles (83.3 mg, 0.6mmol) are mixed in 2ml dichloromethane solvents and are added in flask,
4h is reacted at 40 DEG C.TLC is detected after reaction, and chloroacetic chloride (176.8 μ L, 2.5mmol) is added and reacts 16h, TLC detections
After reaction, with column chromatography chromatogram method (eluent：Petroleum ether) isolated iodo- 2, the 3- dihydros -1H- indenes of the chloro- 2- of 1- (changes
Close object 8) 17.1mg, yield 12.3%.
Characterization of The Products：Colourless liquid.1H NMR (500MHz, CDCl3) δ 7.46 (d, J=6.7 Hz, 1H), 7.37-7.27
(m, 3H), 5.35 (d, J=2.9Hz, 1H), 4.66 (dt, J=6.3,3.2Hz, 1H), 3.45 (ddd, J=20.1,16.8,
4.7Hz,2H).13C NMR(125MHz, CDCl3)δ139.84,129.71,127.94,125.50,125.11,67.62,
64.49, 40.75.HRMS(ESI)calcd for C9H8ClI(M+H+):278.52,found 277.94.
Embodiment 4
Compound 4
By (amyl- 4- alkene -1- bases oxygroup) benzene (48.6mg, 0.3mmol), iodine (38.1 mg, 0.15mmol), tertiary fourth
Base hydrogen peroxide (77.2mg, 0.6mmol) and N- hydroxy benzo triazoles (49.1mg, 0.36mmol) are mixed in 1ml dichloros
Methane solvent is added in flask, reacts 6h at 40 DEG C.TLC is detected after reaction, addition chloroacetic chloride (106.1 μ L,
16h 1.5mmol) is reacted, TLC is detected after reaction, with column chromatography chromatogram method (eluent：Petrol ether/ethyl acetate=9/1)
Isolated ((the chloro- 5- iodine amyls of 4-) oxygroup) benzene (compound 4) 39.4mg, yield 40.5%.
Characterization of The Products：Weak yellow liquid.1H NMR(500MHz,CDCl3) δ 7.34-7.28 (m, 2H), 6.97 (t, J=
7.4Hz, 1H), 6.94-6.90 (m, 2H), 4.32-4.26 (m, 1H), 4.08 (dd, J=11.2,4.5Hz, 1H), 4.02 (td,
J=5.8,3.0Hz, 2H), 3.85 (dd, J=11.1,10.0Hz, 1H), 2.28-2.19 (m, 1H), 2.13-2.04 (m, 1H),
1.99–1.84(m,2H).13C NMR(125MHz,CDCl3) δ 158.77 (s), 129.45 (s), 120.72 (d, J=
13.4Hz),114.47(s),66.60,49.92(s),33.40(s),32.51(s), 28.86(s).HRMS(ESI)calcd
for C11H14ClIO(M+H+):324.59,found 323.98.
Embodiment 5
Compound 5
By 2-methyl styrene (36.2mg, 0.3mmol), iodine (38.1mg, 0.15 mmol), tert-butyl hydroperoxide
Hydrogen (77.2mg, 0.6mmol) and N- hydroxy benzo triazoles (49.1mg, 0.36mmol) are mixed in 1ml dichloromethane solvents
It is added in flask, reacts 4h at 40 DEG C.TLC is detected after reaction, and chloroacetic chloride (106.1 μ L, 1.5mmol) is added and reacts
16h, TLC are detected after reaction, with column chromatography chromatogram method (eluent：Petroleum ether) isolated 1- (the chloro- 2- iodine ethyls of 1-)-
36.3 mg of 2- toluene (compound 5), yield 37.1%.
Characterization of The Products：Weak yellow liquid.1H NMR(500MHz,CDCl3) δ 7.53-7.50 (m, 1H), 7.23 (ddd, J=
14.2,7.2,1.8Hz, 2H), 7.16 (d, J=7.2Hz, 1H), 5.08 (dt, J=9.4,2.9Hz, 1H), 3.39 (ddd, J=
19.9,10.4,6.3Hz,2H),2.34 (s,3H).13C NMR(125MHz,CDCl3)δ136.55,136.44,130.87,
129.00, 126.86,126.26,46.83,34.16,19.24.HRMS(ESI)calcd for C9H10ClI (M+H+):
280.53,found 279.95.
Embodiment 6
Compound 6
By amyl- 4- alkene -1- yl benzoic acids ester (57.1mg, 0.3mmol), iodine (38.1 mg, 0.15mmol), tertiary fourth
Base hydrogen peroxide (77.2mg, 0.6mmol) and N- hydroxy benzo triazoles (49.1mg, 0.36mmol) are mixed in 1ml dichloros
Methane solvent is added in flask, reacts 4h at 40 DEG C.TLC is detected after reaction, addition chloroacetic chloride (106.1 μ L,
16h 1.5mmol) is reacted, TLC is detected after reaction, with column chromatography chromatogram method (eluent：Petrol ether/ethyl acetate=9/1)
Isolated bromo- 5- iodine amyl benzoic ether (compound 6) 58mg of 4-, yield 68.3%.
Characterization of The Products：Weak yellow liquid.1H NMR(500MHz,CDCl3) δ 8.05 (dd, J=8.3,1.3Hz, 2H),
7.59-7.54 (m, 1H), 7.48-7.42 (m, 2H), 4.38 (t, J=6.1Hz, 2H), 4.24 (ddt, J=9.0,7.7,
3.6Hz, 1H), 3.88 (dd, J=10.3,4.3 Hz, 1H), 3.64 (t, J=10.2Hz, 1H), 2.44-2.32 (m, 1H),
2.13–2.04(m, 1H),2.00–1.87(m,2H).13C NMR(125MHz,CDCl3)δ166.52,133.01, 130.15,
129.58,128.40,\63.87,51.96,35.92,32.78,26.25.HRMS(ESI) calcd for C12H14BrIO2(M+
H+):397.05,found 395.92.
Embodiment 7
Compound 7
By 4- cyano styrenes (38.7mg, 0.3mmol), iodine (38.1mg, 0.15 mmol), tert-butyl hydroperoxide
Hydrogen (77.2mg, 0.6mmol) and N- hydroxy benzo triazoles (49.1mg, 0.36mmol) are mixed in 1ml dichloromethane solvents
It is added in flask, reacts 4h at 40 DEG C.TLC is detected after reaction, and it is anti-that chloroacetic chloride (106.1 μ L, 1.5mmol) is added
16h, TLC is answered to detect after reaction, with column chromatography chromatogram method (eluent：Petroleum ether) isolated 4- (the chloro- 2- iodine second of 1-
Base) benzonitrile (compound 7) 56.8mg, yield 65.3%.
Characterization of The Products：Brown oil.1H NMR(500MHz,CDCl3)δ7.71–7.66 (m,2H),7.52–7.48(m,
2H), 5.07 (dd, J=10.1,5.3Hz, 1H), 3.79-3.65 (m, 2H)13C NMR(125MHz,CDCl3)δ143.95
(s),132.53(s),128.10(s), 118.13(s),112.94(s),59.86(s),8.53(s).HRMS(ESI)calcd
for C9H7ClIN(M+H+):291.52,found 290.93。
Claims (10)
1. the synthetic method of the chloro- 2- iodine dihalo objects of 1- shown in a kind of formula (IV), it is characterised in that：The synthetic method tool
Body is prepared in accordance with the following steps：
It (1) will be shown in tert-butyl hydroperoxide, formula (III) shown in olefin(e) compound shown in formula (I) and propiodal, formula (II)
N- hydroxy benzo triazoles are mixed in organic solvent, and in room temperature at 50 DEG C, the reaction was complete obtains reaction solution A；The formula (I)
Shown in olefin(e) compound and propiodal, three nitrogen of N- hydroxy benzos shown in tert-butyl hydroperoxide, formula (III) shown in formula (II)
The ratio between amount for the substance that feeds intake of azoles is 1:0.5-1:2-4:1.2-2.
(2) chloroacetic chloride is added into reaction solution A obtained by step (1), the reaction was complete at room temperature, and gained reaction solution B is post-treated
Obtain the chloro- 2- iodine dihalo compounds of 1-；The addition of the chloroacetic chloride with it is Olefination shown in the formula (I)
It is 4~6 to close the ratio between amount of substance of object:1；
In formula (I) or formula (IV)：
R1For substituted-phenyl or naphthalene；The substituted-phenyl is by nitro, C1-5Alkyl, C1-5Alkoxy, C1-5Carbalkoxy or
The phenyl of cyano substitution.
2. synthetic method as described in claim 1, it is characterised in that：In step (1), substituted olefine shown in the formula (I)
Selected from one of following：Styrene, 2-methyl styrene, 4- cyano styrenes, indenes, (amyl- 4- alkene -1- bases oxygroup) benzene or amyl- 4-
Alkene -1- yl benzoic acid esters.
3. synthetic method as claimed in claim 2, it is characterised in that：In step (1), substituted olefine shown in the formula (I)
Selected from one of following：Styrene or 4- cyano styrenes.
4. synthetic method as described in claim 1, it is characterised in that：In step (1), the propiodal is elemental iodine.
5. synthetic method as described in claim 1, it is characterised in that：In step (1), the organic solvent is dichloromethane
Or 1,2- dichloromethane.
6. the synthetic method as described in claim 1 or 5, it is characterised in that：In step (1), the volume of the organic solvent
Dosage is with the ratio between amount of substance of substituted olefine compound shown in the formula (I) for 3-3.3ml/mmol.
7. synthetic method as described in claim 1, it is characterised in that：In step (1), reaction time 4-6h.
8. synthetic method as described in claim 1, it is characterised in that：In step (2), reaction time 10-16h.
9. synthetic method as described in claim 1, it is characterised in that：In step (2), the post-processing side of the reaction solution B
Method is：After reaction, reaction solution B first being carried out being concentrated under reduced pressure to give grease, gained grease carries out column chromatography for separation again,
Using volume ratio for 6/1-20/1 petrol ether/ethyl acetate mixed liquor as eluant, eluent, collect the eluent containing target compound, steam
Except dry to get the chloro- 2- iodine dihalo objects of 1- after solvent.
10. synthetic method as described in claim 1, it is characterised in that：The synthetic method is prepared in accordance with the following steps：
(1) by tert-butyl hydroperoxide, formula (III) institute shown in substituted olefine compound shown in formula (I) and propiodal, formula (II)
The N- hydroxy benzo triazoles shown are mixed in organic solvent, react 4-6h at 40 DEG C, obtain reaction solution A；Formula (I) institute
The substituted olefine compound shown and N- hydroxy benzos three shown in tert-butyl hydroperoxide, formula (III) shown in propiodal, formula (II)
The ratio between amount for the substance that feeds intake of nitrogen azoles is 1：0.5：2：1.2；Substituted olefine compound shown in the formula (I) be selected from it is following it
One：Styrene, 2-methyl styrene, 4- cyano styrenes, indenes, (amyl- 4- alkene -1- bases oxygroup) benzene or amyl- 4- alkene -1- Ji Benjia
Acid esters；The propiodal is elemental iodine；The solvent is dichloromethane or 1,2- dichloroethanes；The volumetric usage of the solvent
To replace the amount of the substance of acetylene hydrocarbon compound to be calculated as 3-3.3ml/mmol shown in formula (I)；
(2) chloroacetic chloride is added into reaction solution A obtained by step (1), 10-16h is reacted at room temperature, after reaction by reaction solution
B first carries out being concentrated under reduced pressure to give grease, and gained grease is carried out column chromatography for separation again, with petroleum ether or volume ratio 20/1-
6/1 petrol ether/ethyl acetate mixed liquor is eluant, eluent, collects and merges the eluent containing target compound, after solvent is evaporated off
Drying is to get the chloro- 2- iodine dihalo compounds of 1-；Shown in the addition of the chloroacetic chloride and the formula (I)
The ratio between amount of substance of olefin(e) compound is 5:1.
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| CN107382884A (en) * | 2016-07-07 | 2017-11-24 | 浙江工业大学 | A kind of synthetic method of β iodos N alkoxy benzo triazole compounds |
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| CN115197046A (en) * | 2021-04-13 | 2022-10-18 | 华南理工大学 | Halogenation method of unsaturated hydrocarbon |
| CN115197046B (en) * | 2021-04-13 | 2023-12-15 | 华南理工大学 | Halogenation method of unsaturated hydrocarbon |
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