CN110002948A - The preparation method of halogenated cycloolefin - Google Patents
The preparation method of halogenated cycloolefin Download PDFInfo
- Publication number
- CN110002948A CN110002948A CN201910347975.4A CN201910347975A CN110002948A CN 110002948 A CN110002948 A CN 110002948A CN 201910347975 A CN201910347975 A CN 201910347975A CN 110002948 A CN110002948 A CN 110002948A
- Authority
- CN
- China
- Prior art keywords
- cyclobutane
- chloro
- raw material
- fluorine
- cis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/04—Systems containing only non-condensed rings with a four-membered ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to " preparation methods of halogenated cycloolefin ", belong to the field of chemical synthesis.Preparation method of the invention is in amide or alkyl amine solvent, using halogenated cycloalkane as raw material, dehalogenation reaction to occur, obtains the halogenated cycloolefin of target product.Not only reaction condition is mild for the method for the present invention, halogenated cycloolefin high income, does not need the reducing agent using the danger such as metal or hydrogen, and process safety is reliable, does not generate that metal halide etc. is useless solid, can be industrially effectively separated by common distillation means.
Description
Technical field
Metal is not needed the present invention relates to a kind of preparation method of halogenated cycloolefin more particularly to one kind or hydrogen exists,
It only needs under amide existence condition, the method that highly selective dehalogenation reaction synthesizing halogen cycloolefin occurs for halogenated cycloalkane.
Background technique
Dehalogenation reaction is a kind of important method of synthesizing halogen alkene.The conventional method generally used is metal or hydrogen
As reducing agent, Organic Ingredients synthesizing halogen cycloolefin is restored.
United States Patent (USP) US2436142 is reported in alcohol solvent, and 1,2- dichloro trans-1,1,2,2,3,4-Hexafluorocyclobutane and zinc powder are in reflux condition
It is reacted under part, obtains hexafluoro cyclobutane, yield 94%.
Document " Russian Journal of Organic Chemistry, 2010, vol.46,1290-1295 " report
At 180 DEG C, hydrogen and 1,2- dichloro trans-1,1,2,2,3,4-Hexafluorocyclobutane reacts 1 hour, obtains hexafluoro cyclobutane, yield 57%.
In above-mentioned prior art, (1) is had the following deficiencies: by the synthesis of the perhalogenated cyclopentene of representative of hexafluoro cyclobutane
When reducing agent is metal powder, it is useless solid to generate a large amount of metal halide etc., seriously pollutes environment；(2) when reducing agent is hydrogen,
Because there is the generation of by-product saturation cycloalkane, cause yield very low.
Summary of the invention
The technical problem to be solved by the present invention is to overcome deficiency present in background technique, providing a kind of amide, there are items
Under part, the method that dehalogenation reaction prepares halogenated cycloolefin occurs for halogenated cycloalkane, and not only reaction condition is mild for this method, Er Qiexuan
Selecting property height.
A kind of preparation method of halogenated cycloolefin is original with formula (I) halogenated cycloalkane in amide or alkyl amine solvent
Dehalogenation reaction occurs for material, and reaction equation is as follows:
Wherein, X=Cl, Br or I；
Y=H, F or Cl；
Z=H, F or Cl；
N=2,3 or 4；
M=0,1,2,3,4,5,6,7 or 8；
Q=0,1,2,3,4,5,6,7 or 8；
P=0,1,2,3,4,5,6,7 or 8；
And meet 2n=m+q+p.
The amide is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N, N- dimethylpropionamide, N, N- diformazan
Base butyramide, N, N- diethylformamide, N, N- diethyl acetamide or N, N- diethyl propionamide；The alkylamine is positive fourth
Amine, n-amylamine, n-hexylamine, positive heptyl amice, n-octyl amine, di-n-propylamine, di-n-butylamine, two n-amylamines, triethylamine or tri-n-butylamine.
The molar ratio of amide or alkylamine and halogenated cycloalkane is 1~10:1, reaction temperature 50 in the dehalogenation reaction
~300 DEG C, the reaction time is 2~30 hours.
It is preferred that: the molar ratio of amide or alkylamine and halogenated cycloalkane is 1~3:1, and reaction temperature is 100~200 DEG C, instead
It is 4~20 hours between seasonable.
The halogenated cycloolefin be the chloro- 2,3,3- trifluoro cyclobutane of 1-, five fluorine cyclobutane of 1- chlorine, hexafluoro cyclobutane, 3,3,
4,4- tetrafluoro cyclobutane, seven fluorine cyclopentene of 1- chlorine, octafluoro cyclopentene, 3,3,4,4,5,5- hexafluoro cyclopentene, nine fluorine hexamethylene of 1- chlorine
Alkene, decafluorocyclohexene and 3,3,4,4,5,5,6,6- octafluoro cyclohexene.
The starting halo cycloalkane is the chloro- 2,3,3- trifluoro cyclobutane of 1,1,2- tri-, the chloro- five fluorine ring fourth of 1,1,2- tri-
Alkane, cis- or/and anti-form-1, the chloro- trans-1,1,2,2,3,4-Hexafluorocyclobutane of 2- bis-, cis- or/and anti-form-1, the chloro- 3,3,4,4- ptfe ring fourth of 2- bis-
Alkane, cis- or/and anti-form-1, the bromo- 3,3,4,4- tetrafluoro cyclobutane of 2- bis-, cis- or/and anti-form-1, the iodo- 3,3,4,4- of 2- bis-
Tetrafluoro cyclobutane, the chloro- seven fluorine pentamethylene of 1,1,2- tri-, cis- or/and anti-form-1, the chloro- Octafluorocyclopentane of 2- bis-, it is cis- or/and
Anti-form-1, the chloro- 3,3,4,4,5,5- hexafluoro pentamethylene of 2- bis-, the chloro- nine fluorine hexamethylene of 1,1,2- tri-, cis- or/and anti-form-1,2-
Two chloro- ten fluorine hexamethylenes, cis- or/and anti-form-1, the chloro- 3,3,4,4,5,5,6,6- octafluoro hexamethylene of 2- bis-.
The raw material is 1,1,2- tri- chloro- 2, and 3,3- trifluoro cyclobutane prepare chloro- 2,3,3- trifluoro cyclobutane of 1-；
Or the raw material is 1,1,2- tri- chloro- five fluorine cyclobutane, prepares five fluorine cyclobutane of 1- chlorine；
Or the raw material is cis- or/and anti-form-1, the chloro- trans-1,1,2,2,3,4-Hexafluorocyclobutane of 2- bis- prepares hexafluoro cyclobutane；
Or the raw material is cis- or/and anti-form-1,2- bis- chloro- 3,3,4,4- tetrafluoro cyclobutane, preparation 3,3,4,4-
Tetrafluoro cyclobutane；
Or the raw material is cis- or/and anti-form-1,2- bis- bromo- 3,3,4,4- tetrafluoro cyclobutane, preparation 3,3,4,4-
Tetrafluoro cyclobutane；
Or the raw material is cis- or/and anti-form-1,2- bis- iodo- 3,3,4,4- tetrafluoro cyclobutane, preparation 3,3,4,4-
Tetrafluoro cyclobutane；
Or the raw material is 1,1,2- tri- chloro- seven fluorine pentamethylene, prepares seven fluorine cyclopentene of 1- chlorine；
Or the raw material is cis- or/and anti-form-1, the chloro- Octafluorocyclopentane of 2- bis- prepares octafluoro cyclopentene；
Or the raw material be cis- or/and anti-form-1,2- bis- chloro- 3,3,4,4,5,5- hexafluoro pentamethylene, preparation 3,3,
4,4,5,5- hexafluoro cyclopentene；
Or the raw material is 1,1,2- tri- chloro- nine fluorine hexamethylene, prepares nine fluorine cyclohexene of 1- chlorine；
Or the raw material is cis- or/and anti-form-1, the chloro- ten fluorine hexamethylene of 2- bis- prepares decafluorocyclohexene；
Or the raw material is cis- or/and anti-form-1,2- bis- chloro- 3,3,4,4,5,5,6,6- octafluoro hexamethylenes, preparation
3,3,4,4,5,5,6,6- octafluoro cyclohexene.
It after the dehalogenation reaction, is cooled to room temperature, then carries out air-distillation and obtain halogenated cycloolefin.
The reactor material of the dehalogenation reaction is glass material, stainless steel material or polytetrafluoroethylene (PTFE) material.
The present invention, by Liquid reduction reaction process, obtains halogenated cycloolefin using halogenated cycloalkane as raw material.Its key reaction is such as
Under:
Wherein, X=Cl, Br or I；
Y=H, F or Cl；
Z=H, F or Cl；
N=2,3 or 4；
M=0,1,2,3,4,5,6,7 or 8；
Q=0,1,2,3,4,5,6,7 or 8；
P=0,1,2,3,4,5,6,7 or 8；
And meet 2n=m+q+p.
Organic solvent N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N in reaction, N- dimethylpropionamide, N, N-
Amide dimethyl butyrate, N, N- diethylformamide, N, N- diethyl acetamide or N, N- diethyl propionamide, n-butylamine, positive penta
Amine, n-hexylamine, positive heptyl amice, n-octyl amine, di-n-propylamine, di-n-butylamine, two n-amylamines, triethylamine or tri-n-butylamine can make halogenated ring
Alkane occurs dehalogenation reaction and generates halogenated cycloolefin.
The present invention can carry out under normal pressure, can also carry out under high pressure.Due to being liquid phase reactor, do not relate in most cases
And phase feed or product, therefore, pressure influences reaction of the present invention little.
The present invention can carry out in the reactor of glass material, stainless steel material or polytetrafluoroethylene (PTFE) material.
The present invention provides a kind of methods that halogenated cycloalkane dehalogenation produces halogenated cycloolefin.Halogenated cycloalkane includes 1,1,
The chloro- 2,3,3- trifluoro cyclobutane of 2- tri-, the chloro- five fluorine cyclobutane of 1,1,2- tri-, cis- or/and anti-form-1, the chloro- hexafluoro ring fourth of 2- bis-
Alkane, cis- or/and anti-form-1, the chloro- 3,3,4,4- tetrafluoro cyclobutane of 2- bis-, cis- or/and anti-form-1, the bromo- 3,3,4,4- of 2- bis-
Tetrafluoro cyclobutane, cis- or/and anti-form-1, it is the iodo- 3,3,4,4- tetrafluoro cyclobutane of 2- bis-, the chloro- seven fluorine pentamethylene of 1,1,2- tri-, suitable
Formula or/and anti-form-1, the chloro- Octafluorocyclopentane of 2- bis-, cis- or/and anti-form-1, the chloro- 3,3,4,4,5,5- hexafluoro ring penta of 2- bis-
Alkane, 1,1,2- tri- chloro- nine fluorine hexamethylene prepare nine fluorine cyclohexene of 1- chlorine, cis- or/and anti-form-1, the chloro- ten fluorine hexamethylene of 2- bis-
Alkane, cis- or/and anti-form-1, the chloro- 3,3,4,4,5,5,6,6- octafluoro hexamethylene of 2- bis-.Halogenated cycloolefin includes 1- chloro- 2,3,
3- trifluoro cyclobutane, five fluorine cyclobutane of 1- chlorine, hexafluoro cyclobutane, 3,3,4,4- tetrafluoro cyclobutane, seven fluorine cyclopentene of 1- chlorine, octafluoro
Cyclopentene, 3,3,4,4,5,5- hexafluoro cyclopentene, nine fluorine cyclohexene of 1- chlorine, decafluorocyclohexene and 3,3,4,4,5,5,6,6- octafluoro
Cyclohexene.Raw material 1,1,2- tri- chloro- 2,3,3- trifluoro cyclobutane boiling points are 120 DEG C (760mmHg), cis- or/and anti-form-1,2-
Two chloro- trans-1,1,2,2,3,4-Hexafluorocyclobutane boiling points are 59.9 DEG C (760mmHg), cis- or/and anti-form-1, and the bromo- trans-1,1,2,2,3,4-Hexafluorocyclobutane boiling point of 2- bis- is
96.7 DEG C (760mmHg), cis- or/and anti-form-1, the chloro- ten fluorine hexamethylene boiling point of 2- bis- is 108 DEG C (760mmHg), etc.；It produces
Chloro- 2,3,3- trifluoro cyclobutane boiling point of object 1- is 51-52 DEG C (760mmHg), and hexafluoro cyclobutane boiling point is 5-6 DEG C (760mmHg),
3,3,4,4- tetrafluoro cyclobutane boiling points are 50-50.5 DEG C (629mmHg), and seven fluorine cyclopentene boiling point of 1- chlorine is 56-58 DEG C
(760mmHg), octafluoro cyclopentene boiling point are 27 DEG C (760mmHg), and 3,3,4,4,5,5- hexafluoro cyclopentene boiling points are 70-71 DEG C
(760mmHg), decafluorocyclohexene boiling point are 52-52.5 DEG C (760mmHg), etc..It can by above-mentioned raw materials and corresponding product
To find out, after halogenated cycloalkane sloughs a molecule halogen, the boiling point of the halogenated cycloolefin of products therefrom is than corresponding starting halo
Cycloalkane is 50 degree or even 70 degree low.Due between raw material and corresponding product there are bigger boiling-point difference away from, need to only divide
It is other that the post-processing such as air-distillation is carried out to the surplus stock of reaction system and corresponding product, the halogenated ring of high-purity can be obtained
Alkene.
Advantages of the present invention: technical method provided by the invention only needs amide or alkylamine as reaction dissolvent, is not required to
The reducing agent of the danger such as metal or hydrogen is added, not only process safety is reliable, and mild, the halogenated cycloolefin of reaction condition
High income, does not generate that metal halide etc. is useless solid, can be industrially effectively separated by common distillation means.
Specific embodiment
Analysis instrument: Shimadzu GC-2010, chromatographic column are DB-VRX capillary column (i.d.0.32mm；
length 30m；J&W Scientific Inc.).
GC analysis method: 250 DEG C of detector temperature, 250 DEG C of temperature of vaporization chamber, 40 DEG C of column initial temperature, holding 10 minutes, 15
DEG C/min is warming up to 230 DEG C, it is kept for 8 minutes.
It is following that the present invention is described in further detail in conjunction with the embodiments, but do not limit the scope of the invention.
Embodiment 1
In the autoclave of 1L, the n,N-Dimethylformamide of 2mol and 1, the 2- dichloro trans-1,1,2,2,3,4-Hexafluorocyclobutane of 1mol is added
(molar ratio of cis and trans is 60:40) reacts 6 hours at 160 degree, after reaction, carries out rectifying, obtain hexafluoro ring
Butylene (boiling point is 5-6 DEG C/760mmHg), yield 96.8%, purity 99.1%.
Embodiment 2
In the autoclave of 1L, the n,N-dimethylacetamide of 2mol and 1, the 2- dichloro trans-1,1,2,2,3,4-Hexafluorocyclobutane of 1mol is added
(molar ratio of cis and trans is 60:40) reacts 6 hours at 170 degree, after reaction, carries out rectifying, obtain hexafluoro ring
Butylene (boiling point is 5-6 DEG C/760mmHg), yield 95.8%, purity 99.2%.
Embodiment 3
In the autoclave of 1L, be added 1mol n,N-Dimethylformamide and 1mol 1,1,2- tri- chloro- 2,3,3- tri-
Fluorine cyclobutane reacts 6 hours at 160 degree, after reaction, carries out rectifying, obtain chloro- 2,3,3- trifluoro cyclobutane (boiling point of 1-
For 51-52 DEG C/760mmHg), yield 80.5%, purity 98.4%.
Embodiment 4
In the autoclave of 1L, be added 4mol n,N-dimethylacetamide and 1mol 1,1,2- tri- chloro- 2,3,3- tri-
Fluorine cyclobutane reacts 6 hours at 170 degree, after reaction, carries out rectifying, obtain chloro- 2,3,3- trifluoro cyclobutane (boiling point of 1-
For 51-52 DEG C/760mmHg), yield 74.4%, purity 98.5%.
Embodiment 5
In the autoclave of 1L, it is added the n,N-dimethylacetamide of 6mol and 1, the 2- bis- chloro- 3 of 1mol, 3,4,4- tetra-
Fluorine cyclobutane reacts 6 hours at 160 degree, after reaction, carries out rectifying, and obtaining 3,3,4,4- tetrafluoro cyclobutanes, (boiling point is
50-50.5 DEG C/629mmHg), yield 77.1%, purity 98.6%.
Embodiment 6
In the autoclave of 1L, the n,N-dimethylacetamide of 8mol and the chloro- Octafluorocyclopentane of 1,2- bis- of 1mol is added
(molar ratio of cis and trans is 50:50) reacts 6 hours at 170 degree, after reaction, carries out rectifying, obtain octafluoro ring
Butylene (boiling point is 27 DEG C/760mmHg), yield 75.5%, purity 98.3%.
Embodiment 7
In the autoclave of 1L, the n,N-dimethylacetamide of 10mol and the chloro- ten fluorine hexamethylene of 1,2- bis- of 1mol is added
(molar ratio of cis and trans is 50:50) reacts 6 hours at 170 degree, after reaction, carries out rectifying, obtain ten fluorine rings
Hexene (boiling point is 52-52.5 DEG C/760mmHg), yield 71.8%, purity 98.8%.
Embodiment 8
In the autoclave of 1L, the n,N-Dimethylformamide of 2mol and 1, the 2- dibromo trans-1,1,2,2,3,4-Hexafluorocyclobutane of 1mol is added
(molar ratio of cis and trans is 50:50) reacts 6 hours at 160 degree, after reaction, carries out rectifying, obtain hexafluoro ring
Butylene (boiling point is 5-6 DEG C/760mmHg), yield 98.6%, purity 99.4%.
Embodiment 9
In the autoclave of 1L, the n,N-Dimethylformamide of 2mol and 1, the 2- diiodo- trans-1,1,2,2,3,4-Hexafluorocyclobutane of 1mol is added
(molar ratio of cis and trans is 50:50) reacts 6 hours at 160 degree, after reaction, carries out rectifying, obtain hexafluoro ring
Butylene (boiling point is 5-6 DEG C/760mmHg), yield 99.5%, purity 99.6%.
Embodiment 10
In the autoclave of 1L, the n-octyl amine of 2mol and 1, the 2- dichloro trans-1,1,2,2,3,4-Hexafluorocyclobutane (cis and trans of 1mol is added
Molar ratio be 60:40), reacted at 170 degree 6 hours, after reaction, progress rectifying, obtaining hexafluoro cyclobutane, (boiling point is
5-6 DEG C/760mmHg), yield 91.2%, purity 99.3%.
Embodiment 11
In the autoclave of 1L, 1, the 2- dichloro trans-1,1,2,2,3,4-Hexafluorocyclobutane of di-n-butylamine and 1mol that 2mol is added is (cis- and anti-
The molar ratio of formula is 60:40), it is reacted at 170 degree 6 hours, after reaction, carries out rectifying, obtain hexafluoro cyclobutane (boiling point
For 5-6 DEG C/760mmHg), yield 86.7%, purity 99.1%.
Claims (8)
1. a kind of preparation method of halogenated cycloolefin, in amide or alkyl amine solvent, using formula (I) halogenated cycloalkane as raw material,
Dehalogenation reaction occurs, reaction equation is as follows:
Wherein, X=Cl, Br or I；
Y=H, F or Cl；
Z=H, F or Cl；
N=2,3 or 4；
M=0,1,2,3,4,5,6,7 or 8；
Q=0,1,2,3,4,5,6,7 or 8；
P=0,1,2,3,4,5,6,7 or 8；
And meet 2n=m+q+p.
2. preparation method according to claim 1, the amide is n,N-Dimethylformamide, N, N- dimethylacetamide
Amine, N, N- dimethylpropionamide, N, N- amide dimethyl butyrate, N, N- diethylformamide, N, N- diethyl acetamide or N, N-
Diethyl propionamide, the alkylamine be n-butylamine, n-amylamine, n-hexylamine, positive heptyl amice, n-octyl amine, di-n-propylamine, di-n-butylamine,
Two n-amylamines, triethylamine or tri-n-butylamine.
3. according to the method described in claim 1, in the dehalogenation reaction amide or alkylamine and halogenated cycloalkane molar ratio
For 1~10:1, reaction temperature is 50~300 DEG C, and the reaction time is 2~30 hours.
4. according to the method described in claim 3, the condition of the dehalogenation reaction are as follows: amide or alkylamine and halogenated cycloalkane
Molar ratio is 1~3:1, and reaction temperature is 100~200 DEG C, and the reaction time is 4~20 hours.
5. according to the method described in claim 1, wherein, the halogenated cycloolefin is chloro- 2,3,3- trifluoro cyclobutane of 1-, 1- chlorine
Five fluorine cyclobutanes, hexafluoro cyclobutane, 3,3,4,4- tetrafluoro cyclobutane, seven fluorine cyclopentene of 1- chlorine, octafluoro cyclopentene, 3,3,4,4,5,
5- hexafluoro cyclopentene, nine fluorine cyclohexene of 1- chlorine, decafluorocyclohexene and 3,3,4,4,5,5,6,6- octafluoro cyclohexene.
6. it is chloro- to prepare 1- for 3,3- trifluoro cyclobutane according to the method described in claim 5, the raw material is 1,1,2- tri- chloro- 2
2,3,3- trifluoro cyclobutane；
Or the raw material is 1,1,2- tri- chloro- five fluorine cyclobutane, prepares five fluorine cyclobutane of 1- chlorine；
Or the raw material is cis- or/and anti-form-1, the chloro- trans-1,1,2,2,3,4-Hexafluorocyclobutane of 2- bis- prepares hexafluoro cyclobutane；
Or the raw material is cis- or/and anti-form-1,2- bis- chloro- 3,3,4,4- tetrafluoro cyclobutane, 3,3,4,4- tetrafluoros of preparation
Cyclobutane；
Or the raw material is cis- or/and anti-form-1,2- bis- bromo- 3,3,4,4- tetrafluoro cyclobutane, 3,3,4,4- tetrafluoros of preparation
Cyclobutane；
Or the raw material is cis- or/and anti-form-1,2- bis- iodo- 3,3,4,4- tetrafluoro cyclobutane, 3,3,4,4- tetrafluoros of preparation
Cyclobutane；
Or the raw material is 1,1,2- tri- chloro- seven fluorine pentamethylene, prepares seven fluorine cyclopentene of 1- chlorine；
Or the raw material is cis- or/and anti-form-1, the chloro- Octafluorocyclopentane of 2- bis- prepares octafluoro cyclopentene；
Or the raw material be cis- or/and anti-form-1,2- bis- chloro- 3,3,4,4,5,5- hexafluoro pentamethylene, preparation 3,3,4,4,
5,5- hexafluoro cyclopentene；
Or the raw material is 1,1,2- tri- chloro- nine fluorine hexamethylene, prepares nine fluorine cyclohexene of 1- chlorine；
Or the raw material is cis- or/and anti-form-1, the chloro- ten fluorine hexamethylene of 2- bis- prepares decafluorocyclohexene；
Or the raw material be cis- or/and anti-form-1,2- bis- chloro- 3,3,4,4,5,5,6,6- octafluoro hexamethylenes, preparation 3,3,
4,4,5,5,6,6- octafluoro cyclohexene.
7. then carrying out air-distillation according to the method described in claim 6, being cooled to room temperature after the dehalogenation reaction
Obtain halogenated cycloolefin.
8. according to the method described in claim 1, the reactor material of the dehalogenation reaction be glass material, stainless steel material or
Polytetrafluoroethylene (PTFE) material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910347975.4A CN110002948B (en) | 2019-04-28 | 2019-04-28 | Process for preparing halogenated cycloolefins |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910347975.4A CN110002948B (en) | 2019-04-28 | 2019-04-28 | Process for preparing halogenated cycloolefins |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110002948A true CN110002948A (en) | 2019-07-12 |
| CN110002948B CN110002948B (en) | 2022-03-01 |
Family
ID=67174640
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910347975.4A Active CN110002948B (en) | 2019-04-28 | 2019-04-28 | Process for preparing halogenated cycloolefins |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110002948B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111423306A (en) * | 2020-02-21 | 2020-07-17 | 北京宇极科技发展有限公司 | Method for preparing hydrohalocycloalkene by hydrolyzing halogenated cycloalkene |
| CN112209805A (en) * | 2020-10-14 | 2021-01-12 | 中船重工（邯郸）派瑞特种气体有限公司 | Synthetic method of octafluorocyclopentene |
| CN112645792A (en) * | 2020-12-09 | 2021-04-13 | 中船重工（邯郸）派瑞特种气体有限公司 | Preparation method of octafluorocyclopentene |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040586A (en) * | 2010-11-10 | 2011-05-04 | 兰州安杰利生物化学科技有限公司 | Method for synthesizing 4,5-dichloro-1,2-dithiocyclopentenone |
| WO2017133675A1 (en) * | 2016-02-03 | 2017-08-10 | 大鹏药品工业株式会社 | Method for preparing high-purity cyclohexenone long-chain alcohol |
| CN107365244A (en) * | 2017-08-03 | 2017-11-21 | 北京宇极科技发展有限公司 | Organic solvent provides hydrogen source and the method that hydrogen halogen exchange reaction prepares 1H perhalogeno cycloolefins occurs |
| CN108911941A (en) * | 2018-05-25 | 2018-11-30 | 凯莱英生命科学技术(天津)有限公司 | 1,3- cyclohexadiene is continuously synthesizing to method |
-
2019
- 2019-04-28 CN CN201910347975.4A patent/CN110002948B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040586A (en) * | 2010-11-10 | 2011-05-04 | 兰州安杰利生物化学科技有限公司 | Method for synthesizing 4,5-dichloro-1,2-dithiocyclopentenone |
| WO2017133675A1 (en) * | 2016-02-03 | 2017-08-10 | 大鹏药品工业株式会社 | Method for preparing high-purity cyclohexenone long-chain alcohol |
| CN107365244A (en) * | 2017-08-03 | 2017-11-21 | 北京宇极科技发展有限公司 | Organic solvent provides hydrogen source and the method that hydrogen halogen exchange reaction prepares 1H perhalogeno cycloolefins occurs |
| CN108911941A (en) * | 2018-05-25 | 2018-11-30 | 凯莱英生命科学技术(天津)有限公司 | 1,3- cyclohexadiene is continuously synthesizing to method |
Non-Patent Citations (1)
| Title |
|---|
| KHURANA, JM ET AL.: "STEREOSELECTIVE DEBROMINATION OF VIC-DIBROMIDES TO E-ALKENES WITH DIMETHYLFORMAMIDE", 《SYNTHESIS》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111423306A (en) * | 2020-02-21 | 2020-07-17 | 北京宇极科技发展有限公司 | Method for preparing hydrohalocycloalkene by hydrolyzing halogenated cycloalkene |
| CN112209805A (en) * | 2020-10-14 | 2021-01-12 | 中船重工（邯郸）派瑞特种气体有限公司 | Synthetic method of octafluorocyclopentene |
| CN112645792A (en) * | 2020-12-09 | 2021-04-13 | 中船重工（邯郸）派瑞特种气体有限公司 | Preparation method of octafluorocyclopentene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110002948B (en) | 2022-03-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110002948A (en) | The preparation method of halogenated cycloolefin | |
| JP4864879B2 (en) | Method for synthesizing 1,3,3,3-tetrafluoropropene | |
| EP2536676B1 (en) | Process for producing 2-chloro-3,3,3-trifluoropropene | |
| KR101967822B1 (en) | Bis(1,1-dichloro-3,3,3-trifluoropropyl)ether and method for producing same | |
| US8404907B2 (en) | Process for cis-1-chloro-3,3,3-trifluoropropene | |
| KR20180038006A (en) | Catalytic isomerization of Z-1,1,1,4,4,4-hexafluoro-2-butene to E-1,1,1,4,4,4-hexafluoro-2-butene | |
| JP5694576B2 (en) | Method for producing difluoroacetonitrile and its derivatives | |
| CN103373896A (en) | Method for preparing 1,1,1,4,4,4-hexafluoro-2-butene | |
| JP2018533607A (en) | Process for producing 2,3,3,3-tetrafluoropropene and / or vinylidene fluoride | |
| JP2015120670A (en) | Method for producing 1-chloro-1,2-difluoroethylene | |
| CN111039778B (en) | Preparation method of HFPO tetramer | |
| JP2019127465A (en) | Method for producing 1h,2h-perfluorocycloalkene | |
| CN107365244A (en) | Organic solvent provides hydrogen source and the method that hydrogen halogen exchange reaction prepares 1H perhalogeno cycloolefins occurs | |
| CN108101754B (en) | Synthesis method of hydrofluoroether | |
| CN101128412B (en) | Synthesis of fluorinated ethers | |
| EP2580180B1 (en) | Producing short chain perfluoroalkyl iodides | |
| JP7184055B2 (en) | Method for producing 1,3-dioxolane compound and perfluoro(2,2-dimethyl-1,3-dioxole) | |
| JP5088254B2 (en) | Method for producing fluoroalkyl halide | |
| KR20090131049A (en) | Process for preparing hydrofluoroethers | |
| JPH11508893A (en) | Addition of trifluoromethane to fluoroolefins and isomerization of monohaloperfluoroalkanes | |
| JP5088253B2 (en) | Method for producing fluoroalkyl halide | |
| RU2807184C9 (en) | Method for obtaining cyclobutane | |
| RU2807184C2 (en) | Method for obtaining cyclobutene | |
| JP5266648B2 (en) | Process for producing perfluoro (exomethylenecycloalkene) compound | |
| CN108314624B (en) | Preparation method of polyfluoroaniline |
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 | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20210610 Address after: 362000 west side of 11 / F, youth building, 288 Tian'an North Road, Fengze District, Quanzhou City, Fujian Province Applicant after: Quanzhou Yuji New Material Technology Co.,Ltd. Address before: 100081 room 02, 15 / F, building 6, courtyard A2, Xisanhuan North Road, Haidian District, Beijing Applicant before: BEIJING YUJI SCIENCE AND TECHNOLOGY Co.,Ltd. |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |